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CONTENTS ACKNOWLEDGMENTS ........................................................................................................ viii NOTATION .............................................................................................................................. ABSTRACT .............................................................................................................................. 1 INTRODUCTION .............................................................................................................. 1.1 1.2 1.3 1.4 2 Interest in Algae ........................................................................................................ Previous Life-Cycle Analyses of Algal Fuels ........................................................... GREET Model for Transportation Fuel Life-Cycle Analyses .................................. Goals of This Study ................................................................................................... ix 1 3 3 3 5 5 8 8 9 10 11 13 16 16 18 18 19 21 21 22 22 22 23 24 25 25 35 36 38 39

METHOD ........................................................................................................................... 2.1 Overview of Approach: Key Issues, Computational Framework, and GREET Expansion................................................................................................................... 2.2 System Boundary ...................................................................................................... 2.3 Carbon Accounting ................................................................................................... 2.4 Co-Product Treatment ............................................................................................... 2.5 Reference Pathway, Baseline Pathway, and Functional Unit ...................................

3 ALGAL OIL PRODUCTION MODEL ............................................................................. 3.1 3.2 3.3 3.4 3.5 3.6 Baseline Algal Fuel Pathway Overview.................................................................... Algae Growth and First Dewatering ......................................................................... 3.2.1 Nutrients ........................................................................................................ 3.2.2 Water Movement ........................................................................................... Secondary Dewatering .............................................................................................. 3.3.1 Dissolved Air Flotation ................................................................................. 3.3.2 Dewatering Centrifuges................................................................................. Extraction .................................................................................................................. 3.4.1 Pressure Homogenization .............................................................................. 3.4.2 Hexane Extraction of Algal Lipids................................................................ Fuel Production and Fuel Usage Models .................................................................. Energy and Nutrient Recovery: Co-Product Production ........................................... 3.6.1 Anaerobic Digestion ...................................................................................... 3.6.2 Catalytic Hydrothermal Gasification for CH4 Production ............................ 3.6.3 Combined Heat and Power Systems ............................................................. Heating Values of Algae Biomass and Lipid-Extracted Algae ................................. Pathway Integration...................................................................................................

3.7 3.8

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CONTENTS (Cont.) 4 WELL-TO-WHEELS RESULTS FOR ALGAL FUELS .................................................. 4.1 Baseline Scenario ...................................................................................................... 4.1.1 On-Site Balance of Co-Products, Electricity, and Heat ................................ 4.1.2 Fossil Energy Use.......................................................................................... 4.1.3 Petroleum Energy Use ................................................................................... 4.1.4 Greenhouse Gas Emissions ........................................................................... 4.1.5 Total Energy Use ........................................................................................... 4.1.6 Sensitivity Analysis ....................................................................................... Reduced Emission Scenarios .................................................................................... 4.2.1 Low-A: Conservative Changes ..................................................................... 4.2.2 Low-B: Improved Extraction and CH4 Handling .......................................... 4.2.3 Results for Reduced Emissions Scenarios .................................................... Comparison with Other Fuels ................................................................................... 40 40 40 40 41 44 46 48 49 49 50 50 50 54 58 63 71

4.2

4.3 5 6

DISCUSSION AND CONCLUSIONS .............................................................................. REFERENCES ...................................................................................................................

APPENDIX A: Process Scale and CO2 Transport .................................................................... APPENDIX B: Nutrient Life-Cycle Analysis for Algae Growth ............................................. FIGURES 1 2 Diagram of GREET Model, Which Includes More Than 100 Fuel Production Pathways from Various Energy Feedstocks ....................................................................... Diagram of GREET Model Showing Many Potential Biofuel Production Pathways ........

6 7 10 11 12 12 14

3 Life-Cycle Analysis Flowchart for Algal Fuels .................................................................. 4 5 6 7 Carbon Flows in the Pathway ............................................................................................. Carbon Accounting ............................................................................................................. Flowchart Showing How Energy and Nutrients Returned to the Process Decrease Inputs to the Pathway System and Are Not Treated as Co-Products .................. Life-Cycle Analysis Flowchart for Gasoline and Diesel Production..................................

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FIGURES (Cont.) 8 9 Algal Lipid-Based Fuel Pathway ........................................................................................ Baseline Algae Lipid Production Process ........................................................................... 17 17 20 20 30 31 43 43 44 45 45 46 47 47 48 51 52 53

10 Flow of Nitrogen and Phosphorus in the System................................................................ 11 Water Movement during Growth and First Dewatering per Gram of Harvested Algae ..... 12 Carbon Mass Balance through Anaerobic Digestion .......................................................... 13 Mass Flows Used to Compute Nitrogen and Phosphorus Flows through the System ........ 14 Fossil Energy Use for the Baseline Scenario ...................................................................... 15 Contributions to Fossil Energy Use for the Baseline Scenario ........................................... 16 Petroleum Use for the Baseline Scenario............................................................................ 17 GHG Emissions for the Baseline Scenario ......................................................................... 18 Contributions to WTP GHG Emissions .............................................................................. 19 Contributions to WTW GHGs from Fugitive CH4 Emissions and Direct N2O Emissions from Digestate Solids Used as a Fertilizer Replacement .......................... 20 Contributions to the Fertilizer Credit for Digestate Solids Applied to Agricultural Fields .............................................................................................................. 21 Total Energy Use for the Baseline Scenario ....................................................................... 22 Sensitivity Analysis for Algae Baseline Scenario .............................................................. 23 GHG Emissions for Two Reduced Emission Scenarios ..................................................... 24 GHG Emissions for Renewable Diesel and Renewable Gasoline for a Reduced Emission Scenario ................................................................................................ 25 Comparison of GHG Emissions and Fossil Energy Use between Algal Biodiesel Scenarios and Other Biofuel Scenarios...............................................................................

FIGURES (Cont.) A-1 Pipeline Geometry. .......................................................................................................... A-2 Pressure with Friction Factor of 4 10-3 and Density of 1.3 kg/m3 in a 2-m-Diameter Pipeline. .................................................................................................... A-3 Velocity, Pressure, and Delivery Power for Flue-Gas Transport to Site. ........................ TABLES 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Total Greenhouse Gas Emissions for Reference Pathways ............................................. Paddle Wheel Power Consumption ................................................................................. Self-Cleaning Disc-Stack Centrifuge Characteristics ...................................................... Decanter-Bowl Centrifuge Characteristics ...................................................................... Literature Survey of Energy Inputs for Algae Oil Extraction Using Hexane as Solvent, per Kilogram of Extracted Oil ........................................................................... Wet Hexane Extraction Parameters Used in This Study, with Extraction Efficiency Assumed To Be 95% ...................................................................................... Anaerobic Digester Performance, with Volumes at 0C and 1 Atmospheric Pressure ............................................................................................................................ Energy Consumption for Biogas Cleanup for Several Processes .................................... Carbon Content for Several Macromolecular Compositions ........................................... Technical Parameters for Catalytic Hydrothermal Gasification Process ......................... Efficiencies and Emissions from Two CHP Technologies .............................................. Lower Heating Values for Macromolecules from Lardon et al. 2009 ............................. Direct Energy Consumption for Co-Product, Oil, and Fuel Transportation .................... On-Site Balances of Co-Product, Electricity, and Heat ................................................... 15 21 22 22 24 24 26 29 31 35 38 38 39 41 65 66 67

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TABLES (Cont.) 15 Energy Intensities, Direct Energy Demand, and CO2 Demand for Processes on Site ..............................................................................................................

42 71 79 80 80 81 81 82 83 84 84

B-1 Formulations for Algae Growth Media from the Literature ............................................ B-2 Inputs per Mass Unit of Nutrient Product ........................................................................ B-3 GREET Energy Inputs for Agriculture ............................................................................ B-4 Additional Energy Inputs for Remaining Feedstock and Intermediate Components ...... B-5 Overall Energy Inputs, Including Feedstock ................................................................... B-6 Energy Inputs for All Considered Algae Nutrients.......................................................... B-7 Energy Inputs for All Considered Algae Nutrients without Loss of Nitrogen in HNO3 Conversion ............................................................................................................ B-8 Energy for All Considered Algae Nutrients on a Molar Basis ........................................ B-9 Energy Allocations Expressed as Fractions of Total Energy........................................... B-10 Energy Allocations on a Molar Basis for Nitrogen and Phosphorus ...............................

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ACKNOWLEDGMENTS This study was supported by the Office of Biomass Program within the Office of Energy Efficiency and Renewable Energy of the U.S. Department of Energy) under Contract Number DE- AC02-06CH11357. We would like to thank Zia Haq and Joyce Yang from the Office of Biomass Program for their support. We are also grateful to Meltem Urgun Demirtas, Richard Doctor, Jennifer Dunn, Cristina Negri, Seth Snyder, and May Wu from Argonne National Laboratory for their contributions regarding anaerobic digestion, process modeling, combined heat and power, and wastewater treatment. We are also grateful to John Benemann of Benemann Associates, Trg Lundquist of California Polytechnic State University, Ryan Davis of National Renewable Energy Laboratory, and Richard Oyler of Genifuel Corporation for their insights and helpful discussions.

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NOTATION AD AD residue APD BD BOD C Ca(HPO4)2 CAPDET CFM CH4 CHP CIDI CO CO2 CO2-e COD DAF DAP EPA gCO2-e GHG GPM GREET HRSG H2S ICE inWG IPCC LCA LEA LHV anaerobic digestion digestate solids Algae Process Description biodiesel biochemical oxygen demand carbon superphosphate Computer-Assisted Procedure for Design and Evaluation of Wastewater Treatment Systems cubic foot (feet) per minute methane combined heat and power compressed ignition, direct injection carbon monoxide carbon dioxide carbon dioxide equivalent chemical oxygen demand dissolved air flotation di-ammonium phosphate, (NH4)2HPO4 U.S. Environmental Protection Agency gram(s) of carbon dioxide equivalent greenhouse gas gallons per minute Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (model) heat recovery steam generator hydrogen sulfide internal combustion engine inch(es) water gauge Intergovernmental Panel on Climate Change life-cycle analysis lipid-extracted algae lower heating value

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MEA mmBtu N NH3 NOx N2O P PBR PM10 PM2.5 PO4 PSA psi psig PTW SI SOx TAG TS TSS (NH2)2CO VOC vol% VS wt% WTP WTW WWT

monoethanolamine million Btu nitrogen ammonia mono-nitrogen oxides, NO and NO2 nitrous oxide phosphorus photobioreactor particulate matter with a diameter no larger than 10 micrometers particulate matter with a diameter no larger than 2.5 micrometers sulfuric acid pressure swing adsorption pound(s) per square inch pound(s) per square inch gauge pump to wheels (considers the usage by a vehicle portion of the life cycle) spark-ignited sulfur oxides triacylglyceride total solids total suspended solids urea volatile organic compound percentage by volume volatile solids percentage by weight, typically dry weight well to pump (considers fuel life cycle from resource acquisition through delivery of fuel at the fuel station) well to wheels (i.e., cradle to grave; considers entire fuel life cycle) wastewater treatment

LIFE-CYCLE ANALYSIS OF ALGAL LIPID FUELS WITH THE GREET MODEL by Edward D. Frank, Jeongwoo Han, Ignasi Palou-Rivera, Amgad Elgowainy, and Michael Q. Wang ABSTRACT A life-cycle analysis (LCA) of greenhouse gas (GHG) emissions and energy use was performed to study algae-based pathways for producing biofuels such as biodiesel, renewable diesel, and renewable gasoline. For this analysis, the GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation) model developed at Argonne National Laboratory was expanded to include algae-based fuel production pathways. The analysis considers a putative production pathway. Attention was paid to energy recovery through biogas production from the residual biomass after lipid extraction, including fugitive methane (CH4) emissions during the production of biogas and nitrous oxide (N2O) emissions during the use of digestate (solid residue from anaerobic digestion) as agricultural fertilizer. The baseline scenario GHG emissions were 55,400 grams of carbon dioxide equivalent (gCO2-e) per million Btu of biodiesel produced from algal oil. Two lower-emission scenarios were also developed and evaluated. In general, the process improvements that are needed to improve economic viability also improve life-cycle GHG emissions; however, careful consideration must be given to controlling CH4 losses from the biogas production and processing activities. This work may have implications for using agriculturalengineering approaches for algae processes. Future LCA work will require better data from better engineering estimates for water transfer on site; better estimates of facility size (combined heat and power efficiency, especially); additional data on the fate of all the nitrogen in the process, including organic nitrogen in the digestate; and data on fugitive emissions. Results from future techno-economic comparisons between anaerobic digestion with appropriately low fugitive emissions and from other technologies (e.g., catalytic hydrothermal gasification) will be important for future studies, as will the results from a site-level assessment of water delivery energy needs.

1 INTRODUCTION 1.1 INTEREST IN ALGAE Many countries hope to displace petroleum transportation fuels with sustainable liquid fuels from plants (biofuels), thereby not only improving their energy and economic security but also reducing their greenhouse gas (GHG) emissions and slowing global climate change. Liquid fuels will be needed for some time to power motor vehicles, and they will still be required in some sectors, like aviation, even when electric vehicles based on sustainable power sources are deployed. Liquid biofuels have some unique advantages. They can be used in internal combustion engines (ICEs) that have benefited from more than 100 years of development and still have room to improve. Liquid fuels, by and large, can be transported and distributed by using the current liquid transportation fuel distribution infrastructure. The land, water, and nutrient needs of crops used for biofuels, combined with the needs of crops used for feed and food, must be consistent with the resources available. Interest in algae is high because algae may address some of the concerns related to plant-based biofuels. The potential productivity (dry-mass accumulation rate) of algae appears to be large when compared to that of cellulosic plants like grasses, grains, and trees. This trait, if realized in an agricultural process, offers large biomass yields per acre to increase net fuel production per unit of land used. Algae can store energy in intracellular lipid depots. These lipids show promise for being processed into diesel and gasoline equivalents at current petroleum refineries. Algal biomass can be converted to fuel in several ways. Lipid-based fuels are produced by transesterification or catalytic treatment (cracking, hydrogenation, and deoxygenation) of lipids extracted from the algae. The remaining biomass is considered for conversion to biogas and then further considered for generating power and heat. Alternatively, algal biomass can be processed wet with thermal processes like hydrothermal liquefaction to produce a mixture of oils, gases, solids and an aqueous phase. This report focuses on algal-lipid-based fuels that require lipid extraction from the biomass. 1.2 PREVIOUS LIFE-CYCLE ANALYSES OF ALGAL FUELS Life-cycle analysis (LCA) has become an integral part of assessing the energy and environmental effects of products in general and energy products in particular. Extensive LCAs have been performed for plant-based biofuels (see, for example, Wang 2011a), and several LCAs have been performed for algae-based biofuel pathways. This section, although it is not a comprehensive review, highlights key factors identified by these LCAs that provide context for the present work and guide the modeling. Kadam (2001) considered a coal power plant co-fired with algal biomass grown using flue gas from the power plant itself for algae growth. Kadam concluded that GHG emission

reductions were possible; however, if monoethanolamine (MEA) capture of carbon dioxide (CO2) was employed to purify and concentrate the CO2 in the flue gas, many of the benefits were lost because of the high steam requirements for regenerating the MEA. Campbell et al. (2009) studied scenarios for algal fuel production from flue gas in Australia. Seven of the nine power plants considered in the report did not have adequate land nearby for algae ponds. Therefore, the authors considered flue gas distribution and concluded that higher-pressure distribution required unacceptably high operating power, while low-pressure distribution introduced challenges related to capital, pipeline size, and routing. Lardon et al. (2009) studied four scenarios, two with dry hexane extraction of algal oil (like soy oil extraction) and two with hypothetical wet hexane extraction. The dry extraction scenarios required drying the wet biomass to 10% moisture, similar to soybeans. This drying required more energy than was available in the harvested algae biomass. It was hypothesized that the wet extraction process used a solvent extraction method for the wet biomass. The study emphasized the importance of increasing the lipid fraction of algae biomass and avoiding drying. It demonstrated that much of the algal biomass energy (heating value) remains in the biomass remnants after oil extraction. Clarens et al. (2010) compared the production of algae with that of several energy crops (corn, switchgrass, and canola). The study emphasized the importance of controlling nutrient demand for algae growth because of the high upstream life-cycle emissions. The authors pointed out that such demands, unless mitigated, could cause algal biomass production to have higher emissions on a life-cycle basis than do corn, switchgrass, or canola. Stephenson et al. (2010) compared algae production in paddlewheel-mixed ponds with its production in tubular photobioreactors. The analysis considered a two-stage growth model in which an initial nutrient-replete culture with high productivity was grown, followed by a nitrogen-limited stage to increase the lipid fraction of the biomass. The authors pointed out that mixing to keep the algae suspended required a significant amount of electric power. Moreover, the power consumption for paddlewheel mixing in a pond was eight times less than air-lift mixing in the photobioreactor when the circulation speed was 30 cm/s. Collet et al. (2011) studied the production of bio-methane from algae rather than the production of liquid fuels. Although this study did not consider the production of a liquid fuel, it included more detail on anaerobic digestion than did other studies, including digestion CH4 yields, nitrogen recovery, and digester power and heat requirements. Moller et al. (2009) reported on an LCA of anaerobic digestion and digestate use. The authors did not study algae, but they identified fugitive CH4 emissions and emissions of nitrous oxide (N2O) when digestate is used as agricultural fertilizer as important factors for pathways using biogas produced by anaerobic digestion.

1.3 GREET MODEL FOR TRANSPORTATION FUEL LIFE-CYCLE ANALYSES The GREET (Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation) model was developed at Argonne National Laboratory with support from the U.S. Department of Energys (DOEs) Office of Energy Efficiency and Renewable Energy. It is a publicly available LCA tool with more than 15,000 registered users designed to investigate numerous fuel and vehicle cycles (see Wang 1999a and b and the GREET Web site at http://greet.es.anl.gov/main). In the GREET model suite, the fuel-cycle model for transportation fuels considers the operations involved in producing and using fuels, while the vehicle-cycle model considers operations involved in manufacturing and decommissioning vehicles, including recycling. GREET is used to compute fossil, petroleum, and total energy use (including renewable energy in biomass), emissions of greenhouse gases (CO2, CH4, and N2O), and emissions of six criteria pollutants: carbon monoxide (CO), volatile organic compounds (VOCs), mono-nitrogen oxides (NOx), sulfur oxides (SOx), particulate matter with a diameter no larger than 10 micrometers (PM10), and particulate matter with a diameter no larger than 2.5 micrometers (PM2.5). GREET contains many vehicle/fuel systems. Fuel types include gasoline, diesel, biofuels, hydrogen, natural-gas-based fuels, and electricity. See Figure 1 for fuel production options in GREET and Figure 2 for biofuel production options in GREET. Vehicle technologies include gasoline engines, diesel engines, hybrid electric vehicles with gasoline and diesel engines, plug-in hybrid electric vehicles with gasoline and diesel engines, battery-powered electric vehicles, and fuel cell vehicles. Because of the wide array of fuels and vehicles analyzed under a shared methodological umbrella, shared upstream and downstream emissions, and shared co-product models, GREET provides a framework for consistently examining and comparing life-cycle energy use and emissions of many vehicle/fuel systems. 1.4 GOALS OF THIS STUDY GREET was expanded to include algal-lipid-based fuel pathways to allow systematic comparisons between algal biofuels and transportation fuels analyzed previously with GREET. The approach produced an easily configured tool that can compare many algae pathway options. This report describes the approach and LCA results for one particular pathway configuration. Another goal of the study was to integrate process details for anaerobic digestion, nutrient recovery, and soil application of digester residues into the algal liquid fuel LCA. By expanding GREET, algae fuel production pathways become available for GREET users and algae researchers and stakeholders to use in evaluating the different technical options of key algae pathway stages with regard to their LCA effects and in cross-comparing LCA results for algaebased biofuels, other biofuels, and other transportation fuels.

FIGURE 1 Diagram of GREET Model, Which Includes More Than 100 Fuel Production Pathways from Various Energy Feedstocks (Yellow boxes list feedstocks; red boxes list fuels produced from feedstocks)

FIGURE 2 Diagram of GREET Model Showing Many Potential Biofuel Production Pathways

2 METHOD 2.1 OVERVIEW OF APPROACH: KEY ISSUES, COMPUTATIONAL FRAMEWORK, AND GREET EXPANSION Several key issues affect an LCA of transportation fuels. The system boundary defines the scope within which resource consumption and emissions will be considered. Related to system boundary, the choice between a consequential or attributional analysis determines how side-effects of the operation, like changes in land use or redistribution of usage within the market, are addressed. For example, a consequential LCA relies primarily on economic relationships to address both direct and indirect effects. An attributional LCA addresses both types of effects primarily through technical steps, by allocating aggregate effects into different subprocesses or products. With the attributional LCA, when several products are produced simultaneously (e.g., algal oil and electricity), emissions and energy burdens must be allocated among the products. The choice of co-product treatment can affect the results significantly (Wang et al. 2011b). One objective of this work is to compare algal biofuels with petroleum fuels. Therefore, a reference scenario for the petroleum fuel must be specified. The GREET model was expanded and used as the computational framework for this study because it has been used by many researchers and used to study many transportation fuels, including many biofuels (Wang 2001). Algal biofuel pathways are theoretical rather than mature, demonstrated processes. The proposed unit operations are a mixture of established wastewater treatment (WWT) operations extrapolated to new applications, bench-scale experiments extrapolated to larger scales, algalnutraceutical operations, and some purely theoretical operations. The LCA methodology must reflect these large uncertainties. Therefore, the analysis presented here is based on energy and material consumption as reported in the literature and, in some instances, from estimates described in this report rather than on process audits or fully speciated data. Another consequence of the theoretical nature of algal biofuels is that the analysis must build the pathway from unit operations interconnected by estimated efficiencies for utilizing inputs in the production of outputs. The large degree of uncertainty in the pathway configuration itself introduces combinatorial complexity that must be handled by the computational framework. A helper tool called the Algae Process Description (APD) was constructed to facilitate the collection of different unit processes for algae pathways and to summarize and transfer the selected operations to GREET, where they could be integrated into a well-to-wheel (WTW) algal pathway. The information transferred for each process included inputs, outputs, and yields, as well as materials and fuels consumed. GREET was extended to allow configuration of algal co-product treatment, fuel production method, end use, transportation modes, and transportation distances. Then, after accounting for the upstream energy and emissions for input fuels and materials in the algae processes as well as the other steps, GREET estimated WTW energy and emissions. The use of the helper-tool isolated GREET from this combinatorial complexity, the intent being to support many process configurations and facilitate the integration of data coming in over time from disparate researchers. Details on this helper-

tool, the GREET modifications, and the GREET/APD interface are provided in Frank et al. (2011). Together, the expanded GREET model and new helper tool allow for process integration and facilitate iterative parameter studies while ensuring consistent treatment of upstream and downstream resource consumption between algae scenarios and between algal fuels and other transportation fuels. The analysis reported here was not based on detailed process modeling of the end-to-end pathway. Strict mass and energy balances were not attempted. However, all major energy inputs within the system boundary were sought, and approximate balances were used for key nutrients. For example, the algaes carbon, nitrogen, and phosphorus contents were used stoichiometrically to determine fertilizer consumption for algae growth. Flows of nitrogen and phosphorus were followed through harvesting and digestion to predict flows to soil amendment co-products. The absolute concentrations of these nutrients in the amendment will not be correct because a true mass balance on all elements was not possible; nevertheless, this approach should estimate the mass of nutrients in the amendment quite well. Furthermore, since the bulk of the amendment mass is from water, transport costs can be estimated quite well. Data were collected from published literature, LCA inventories, government reports, conference reports, and discussions with researchers. Emphasis was placed on reports of largescale processes, but process models were often used because no empirical or published data were available. The process models were entered into APD, and key process parameters were factored out for sensitivity analysis. The following sections describe the system boundary, co-product treatment, and reference scenario definitions for this study. 2.2 SYSTEM BOUNDARY Figure 3 depicts the system boundary for this analysis. The boundary defines a cradle to grave (i.e., WTW) fuel-cycle analysis. The vehicle cycle that describes the construction and end of life of the vehicle is not included. Construction, replacement, and decommissioning of equipment and facilities for the algae fuel cycle are also excluded from the analysis. With regard to nonfuel materials consumed, only fertilizers are considered at this time because they account for most material-related energy. Other materials (e.g., coagulants and short-life plastics) will be added in the future. The present LCA effort included direct effects from the algae pathway and from the operational activities of the pathway. Indirect effects (e.g., indirect land use changes and infrastructure preparation, such as pond preparation) are not included. Also, transportation of water to the site is excluded from the system boundary, but water movement on site is included. Water delivery to the site and other indirect effects and nonoperational activities will be included in updated results on the basis of resource assessment data that are newly available. Several narrowing choices were made with regard to the LCA flowchart. Algae can be grown in several ways. Autotrophic growth requires only CO2 as a substrate, while heterotrophic growth requires more complex carbon substrates (e.g., sugars). Mixotrophic growth modes can use both substrate classes. In this analysis, nutrient inputs were restricted to key nutrients needed

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for autotrophic growth modes. Heterotrophic and mixotrophic modes were not considered. The algal lipid production model is restricted to suspended planktonic cultivation followed by lipid extraction. Attached growth approaches were excluded, as were thermochemical conversions that bypass lipid extraction. Fuels were restricted to biodiesel via transesterification and renewable diesel and renewable gasoline via hydrotreating produced from the algal lipids. Vehicle operations considered only compression ignition, direct injection (CIDI) engines for diesel fuels and spark ignition (SI) engines for renewable gasoline fuels.

FIGURE 3 Life-Cycle Analysis Flowchart for Algal Fuels

2.3 CARBON ACCOUNTING This work studied algae grown with CO2 from power plant flue gas. Despite the fossil origin of this CO2, it is treated as atmospheric CO2 in the analysis. The philosophy is that the power plant will operate whether algae are grown or not, and its CO2 will be emitted into the air (at least in the foreseeable future). One way to view the situation is that the algal process is opportunistic, collecting the CO2 at the source before it is dispersed in the atmosphere. Figure 4 shows carbon flows in the algae pathway. Carbon originates in the fossil fuels combusted in a power plant or industrial operation. That carbon is captured in the algal biomass and flows through the pathway with the lipid and nonlipid portions of the biomass. It also can be transformed into CH4 during biogas formation and back into CO2 during combustion of biogas or combustion of the final fuel. Carbon can also be exported to fields in soil amendment co-products, exported in bio-methane co-products, and exported in lipid-extracted algae (LEA) if used for feed. Since the emission profiles of the original flue gas source and the emission profiles of the processes in the figure differ, carbon in the original CO2 can be emitted as CO, VOCs, and CH4. Conversion to CH4 is possible when carbon in the algae is converted to biogas. Back-end accounting is used to correctly handle this situation. In back-end accounting, the biogenic carbon emissions are determined via the emission factors for the various processes in the pathway. Carbon in VOCs and CO are weighted appropriately into the total CO2 emission. Biogenic carbon in CH4 is added after the CH4 emission mass is scaled by the corresponding Intergovernmental Panel on Climate Change (IPCC) global warming potential factor. After all emissions are charged in this way, a credit is taken for the original CO2 captured by the algae. The carbon accounting is summarized in Figure 5.

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C in Fuel C in Atmospheric CO2

Power Plant C in Flue-Gas Algae Growth

C in Emissions, C in Leaked CO2 C in Emissions C in Algae Oil Extraction C in Oil Conversion C in Fuel Fuel Combustion C in Coproducts C in Biogas Upgrading Combustion C in Emissions

C in LEA Biogas Recovery

C in LEA

C in Residue

C in Methane

Electricity

C in Atmosphere from Fugitive CH 4

FIGURE 4 Carbon Flows in the Pathway

2.4 CO-PRODUCT TREATMENT Co-products are treated with a hybrid approach that combines energy allocation and displacement methods. In theory, scenarios could have large fractions of co-produced electricity because the lipids are only a fraction of the biomass energy. Displacement methods could give misleading results when co-product credits are large (Wang et al. 2011b). On the other hand, fertilizer co-products would be mistreated if they were considered on an energy basis, because their energy values do not determine their effect on whole-system emissions. Therefore, a hybrid approach is used, in which electricity from biogas combustion and glycerin and heavy oils from conversion steps are treated by energy allocation, while fertilizer co-products are treated by displacement. Glycerin is treated as an energy product rather than a feedstock for specialty chemicals because of the market saturation of glycerin in the large-scale production of algal oil, together with oil seed-based biodiesel production. When the process uses electricity from on-site biogas or uses recovered nutrients, recovered CO2, or recovered heat, the net consumption of these nutrients and fuels by the algae pathway system is simply reduced accordingly (Figure 6).

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Emissionsfromprocesses,direct+upstream,arecharged: GHGPenalty Pathway Processes Transport Biogasand ResidueCombustion Nutrients

Carbonfrompowerplant(fluegas)istreatedasatmospheric: Zero CO2Lost fromPond

CreditsforCO 2inputanddisplacedfertilizernutrients: + CO2Credit forFlueGasInputs Displaced FertilizerProduction

GHGCredit

NetGHGs

FIGURE 5 Carbon Accounting (Flue-gas CO2 is treated as atmospheric, and back-end accounting is used to correctly account for the transformation of CO2 to other emissions like CH4)

On-site processes Imported Electricity, Natural Gas, and Nutrients On-Site Demand Recovered Power & heat Recovered nutrients AD Rawbiogas Remnants Algae Growth & Oil Production Algaloil Eoil Clean biogas Upgrade Comethane CHP Eco-power Eco-methane

FIGURE 6 Flowchart Showing How Energy and Nutrients Returned to the Process Decrease Inputs to the Pathway System and Are Not Treated as Co-Products

Emissions and energy consumption were allocated among co-products as follows. The pathway has two stages: lipid production and lipid conversion to fuel. Each stage has associated co-products and emissions. If Elipid, Eco-power, and Eco-methane are the unallocated energies in the produced lipids, exported electricity, and exported CH4 from the lipid production stage, then an allocation factor for the lipid production steps may be defined by Equation 1:

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Alipid = Elipid / (Elipid + Eco-power + Eco-methane)

(1)

An allocation factor for the lipid conversion step can be defined similarly from Efuel, Eglycerin, and Eheavy, the unallocated energies in the final fuel, glycerin, and the various heavy oil co-products (Equation 2). Heavy oil co-products occur if renewable diesel or gasoline is being made. Aconversion = Efuel / (Efuel + Eglycerin + Eheavy) The whole-pathway emissions allocated to the final fuel product, GHG Allocated , are fuel calculated from the unallocated lipid-production emissions (GHGlipid) and the unallocated conversion emissions (GHGconversion) via Equation 3: GHG Allocated = Aconversion (Alipid (GHGlipid GHGdisplaced-fertilizer) + GHGconversion) fuel (3) (2)

In this formula, Alipid (GHGlipid GHGdisplaced-fertilizer) are the emissions from the lipid production stage of the pathway that are allocated to the lipid intermediate. Multiplying them by Aconversion allocates a portion of them to the final fuel product. This is not the only possible treatment, especially with regard to the displaced fertilizer. We chose to share the displaced fertilizer credit among the fuel and fuel co-products by multiplying GHGdisplaced-fertilizer by Alipid and Aconversion. In an equally valid treatment, the nonfuel outputs may be treated as by-products, and the entire credit for the fertilizer may be assigned to the final fuel; for example: GHG Allocated = Aconversion (Alipid GHGlipid + GHGconversion) GHGdisplaced-fertilizer fuel (4)

Our choice of sharing the fertilizer credit among co-products (Equation 3) facilitates a future comparison of scenarios that may have different distributions of products than those used in this analysis. For example, if an alternative scenario produced mostly co-power, then Equation 4 would assign the fertilizer credit entirely to the fuel even though the pathway really was a power plant operation rather than liquid fuel production. The emissions allocated to the fuel might seem artificially low. Our intent in choosing Formula 3, then, is that it will dilute the allocation effects and facilitate comparisons of the scenarios. Allocations for other emissions and energy consumption are computed in a similar way. 2.5 REFERENCE PATHWAY, BASELINE PATHWAY, AND FUNCTIONAL UNIT In this report, reference pathway refers to the petroleum-based fuel pathway that is being displaced by the algal alternative. For biodiesel and renewable diesel fuels, this is lowsulfur diesel. For renewable gasoline, it is gasoline. Baseline pathway refers to a particular set of process options chosen as the default algae scenario. A sensitivity analysis is performed relative to the baseline pathway parameter values. A few alternative scenarios with different approaches to algal fuels are also considered.

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Petroleum gasoline and diesel, the reference pathways, are shown in Figure 7. For upstream GHG emissions (before vehicle operation), crude recovery and transportation account for roughly one-third of the emissions, and refining accounts for the remaining two-thirds. Recovery emissions arise mostly from natural gas combustion in pumps and vented or flared light gases in the production fields. Emissions from transportation of crude arise from residual oil for tanker transport and a mixture of residual oil, natural gas, and diesel for pipeline transport. Recovery emissions are three times larger than those from crude transport. Refinery emissions arise mostly from combustion of process fuels (largely natural gas), from hydrogen production, and from combustion of intermediate materials like heavy fractions and petroleum coke. Emissions from transportation of the final fuel to market are relatively small.

Energy & Materials

Exploration and Recovery

Transportation of Crude

Petroleum Refining

Fuel Transport and Distribution

Co-products

Gasoline and Diesel Combustion

FIGURE 7 Life-Cycle Analysis Flowchart for Gasoline and Diesel Production (Emissions to water, land, and air, which occur for all stages, are not shown)

A new report updating the energy efficiencies and emissions of the conventional crude oil production and refining industries (Palou-Rivera et al. 2011) is available. It emphasizes the emissions due to flaring and venting of associated gas (dissolved light gases, with about 82% CH4) during crude oil production. The typical contributions for an average U.S.-processed barrel of oil are 3.37 m3 of flared associated gas (typical flare efficiency of 98%) and 1.49 m3 of vented associated gas. This adds up to 2,923 grams of carbon dioxide equivalent (g CO2-e) per million Btu (mmBtu) of crude oil. The cited report also updates the energy efficiencies of conventional gasoline and diesel production in U.S. refineries, equal for both fuels at 89.9%, by considering the hydrogen balance within typical refineries. Refinery GHG emission results were updated to 13,215 g CO2-e per mmBTU of fuel by considering the latest available data for fuel consumption at U.S. refineries. GHG emissions for the reference pathway, including vehicle operation, are shown in Table 1.

15 TABLE 1 Total Greenhouse Gas Emissions for Reference Pathwaysa Share of Total (%) Recovery, Including Transportation 6 7 Refining, Including Distribution 15 13 Vehicle Operation 79 80 Total GHG Emissions (gCO2-e/mmBtu Fuel) 97,986 100,536

Fuel Petroleum gasoline in SI engine Petroleum diesel in CIDI engine


a

SI = spark ignited; CIDI = compression ignition, direct injection.

The functional unit employed by an LCA defines a common basis for emission and energy use computations among scenarios. There are several options, and the one chosen affects the interpretation of the analysis. For energy products, an energy functional unit (e.g., mmBtu of fuel) is a common choice. When fuels with similar combustion technologies and end-use efficiencies (e.g., petroleum diesel, biodiesel, and renewable diesel) are compared, the energy functional unit is clear because end-use efficiencies are constant across the scenarios; however, when scenarios include various fuels that use different combustion technologies and have different efficiencies, the energy functional unit may not be appropriate. For example, algal oils may be converted to both renewable diesel and renewable gasoline, but diesel vehicles are typically 20% more efficient than gasoline vehicles. In such cases, a service functional unit (e.g., 1 vehicle mile) may give clearer results, even though the results depend on fuel economy via factors like vehicle type, powertrain technology, and driving-cycle time. For biofuels, a unit of biomass input (e.g., mass or heating value of the biomass) can be a useful functional unit when the objective of the analysis is to reflect technological constraints on the biomass production potential (e.g., maximum productivity, such as 2,000 tons of biomass per day). Therefore, a biomass functional unit can compare different fuel production technologies by showing how much energy and how many emissions are saved relative to a reference case per unit of biomass resource consumed. In the present analysis, an energy functional unit is employed: 1 mmBtu of fuel produced.

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3 ALGAL OIL PRODUCTION MODEL 3.1 BASELINE ALGAL FUEL PATHWAY OVERVIEW A generic production pathway for lipid-based fuel is summarized in Figure 8. This pathway includes transport of lipid to regional conversion centers and transport of fuel to market. Some analyses (e.g., Lundquist et al. 2010) consider solar drying of algae biomass and subsequent transport to regional extraction centers. The present analysis focuses on wet processes in which transport of the wet algae (20% solids) would not be economical or efficient. Thus, extraction must be done on site proximal to the growth pond or reactor. Wet processes avoid the land footprint required for solar drying and avoid possible climate constraints. In addition, solar drying requires knowledge of site layout and biomass turning to estimate energy for moving the wet biomass and also knowledge of potential air emissions during drying. A wet process is thus considered for contrast and to eliminate these uncertainties. The core of the model, Algae and Lipid Production, is elaborated in Figure 9. Planktonic algae may be grown in both open ponds and photobioreactors (PBRs). Planktonic algae require continuous mixing to remain in suspension at high culture densities, careful control of gas exchange, and thermal management to maintain suitable culture temperatures. The latter is handled naturally in ponds by evaporation, while in PBRs, it must be engineered in various ways, including spray cooling or partial immersion in a water bath. Review of the literature revealed tremendous variations in the approaches for PBRs yet unclear or contradictory requirements for cooling and mixing power. This analysis therefore focused on open ponds mixed by paddle wheel for which previous detailed economic analyses and scale-up analyses were available. Most extraction processes require the cell to be lysed (cellular disruption), and this requires partial dewatering of the culture. The baseline pathway dewaters the culture in several progressive steps (bio-flocculation, dissolved air flotation [DAF], and centrifugation) to manage energy consumption. Many algae carry a negative surface charge and can be made to flocculate around added flocculants that attract them electrostatically. Flocculants, however, can upset downstream processes and constitute a large input if added to the initial harvest because it is so dilute. A common assumption is that a bio-flocculation process that allows flocculation and settling of the algae without chemical inputs will be demonstrated. This is the approach taken here. Inefficiencies in the homogenizer and in recovery during dewatering lead to flows of biomass, along with the LEA after hexane extraction, to the anaerobic digester. Energy in these residues is partially recovered as biogas through anaerobic digestion (AD) and converted to electricity and heat by a combined heat and power (CHP) installation on site. Recovered electricity and nutrients are returned to the process to reduce process costs and energy consumption. Excesses are exported as co-products. In the model, heat from the CHP is available for use on site (e.g., by the digester itself). Excess CHP heat is discarded. The digester products are separated into supernatant and solids by centrifuge. The supernatant is returned to the culture on site, and the solid residues (digestate) are transported to fields for use as fertilizer. Lipids are transported to regional centers for conversion to fuel.

17

Energy & Materials

Emissions toAir

from all Fertilizer Production Algae&Lipid Production CO2 Supply Residue Transport N2Ofrom Soil Lipid Transport BD,RD, RGProduction Fuel Transport FuelCombustion inVehicles

Electricity, Soil Amendments, Biogas, Feed

Glycerin, Heavy Oils Fuel Gas

Co-products

FIGURE 8 Algal Lipid-Based Fuel Pathway

Recovered H2O Urea DAP Flue gas

OpenPond

0.5 g/L

Bio Flocculation

10 g/L

DAF& Centrifuge

200 g/L

Homogenizer, HexaneExtraction

Lipid-Extracted Algae Recovered CO2 CHP Biogas CleanUp Anaerobic Digestion N, P in Solids

N,P in liquid

Transport

Electricity

Soil Amendment

FIGURE 9 Baseline Algae Lipid Production Process

18

The efficiencies for the steps in Figure 9 are as follows. Water recovery from first-level dewatering (bio-flocculation) is assumed to be 100% except for the water that flows downstream with the algae at 10 g/L. Other losses (e.g., to control salt and growth inhibitor buildup) were not modeled. Algae that do not settle would be returned to the pond with the recovered water; thus, it is assumed they are eventually harvested. CO2 loss is 15%. DAF retains 90% of the algae, and the balance is sent to the digester. Centrifugation is treated similarly, but with 95% algae retention. The homogenizer disrupts 90% of the algae, and the balance flows through extraction (with no lipid recovery) to the digester with the residues. Lipid extraction retains 95% of lipids. 3.2 ALGAE GROWTH AND FIRST DEWATERING Productivity is the specific rate of biomass accumulation in the culture. In open ponds, light attenuation in the culture causes growth to quench rapidly with depth. Therefore, productivity for ponds is given per unit area in g/m2/d rather than volumetrically in g/L/d as in PBRs. Data and assumptions about productivity vary widely in the literature. High rates are reported in laboratory experiments, but corroboration at scale is lacking. The lipid fraction, expressed as weight percent (wt%), is the dry-weight fraction of the algal mass from lipids. As is the case for productivity, there is no clear value to choose for this parameter: It depends on the species and growth method. In principle, one should distinguish between the total lipid fraction, the triacylglyceride (TAG) fraction, and various other contributions to the total algal lipids, depending on the downstream conversion process; however, given the uncertainties in growth rate and total lipids, we do not distinguish between the various fractions in this analysis. These two key parameters, then, are largely a matter of choice. The analysis presented here follows the techno-economic analysis of Davis et al. (2011), which employs 25 dry-g/m2/d and 25 wt% for the productivity and lipid fraction, corresponding to 2,700 gal-lipid/acre/yr for a 365-day growing season. Sensitivity studies will examine values of half and twice these baseline choices and span the majority of the reported values. 3.2.1 Nutrients Nutrients, except for CO2, are assumed to be consumed stoichiometrically, based on a carbon : nitrogen : phosphorus (C : N : P) composition of 103 : 10 : 1. For comparison, the corresponding ratios observed in marine biomass, 106 : 16 : 1, are relatively uniform over regions and species (Redfield 1958). The lower value used here reflects the expectation of nitrogen limitation during growth to stimulate lipid accumulation. Other studies use similar values. For example, Christi (2007) uses 100 : 11 : 1. Note that although the media may contain excess nutrient concentrations relative to the algae concentration, water is recycled in this analysis, and it is only the nutrient consumption that is considered. There are mechanisms for nutrient loss that would increase demand. Volatilization of ammonia (NH3) can cause nitrogen loss, and Christi (2007) points out that phosphates can

19

complex with metal ions. Loss of media to pond failures, and loss from flushing to control the accumulation of salts or growth inhibitors, would also increase nutrient consumption. This analysis includes 5% loss of nitrogen to volatilization (see also Section 3.6.1.4). The overall biomass is assumed to contain 50 dry wt% carbon (Chisti 2007) and to therefore require 1.9 g of CO2 per gram of algal biomass. CO2 is delivered via 1.5-m sump with a utilization efficiency of 85%, resulting in a gross CO2 requirement of 2.24 g per gram of algal biomass. Lundquist et al. (2010) estimates a CO2 utilization efficiency of 75% for flue gas and 90% for pure CO2. The 85% utilization in this analysis is optimistic; however, power for CO2 transport and transfer will be seen to account for a minor fraction of the total process energy. A sensitivity analysis studies values of 75% and 95%. An LCA of nutrients commonly employed in algal cultures at bench scale was performed (see Appendix B). This work showed that most nitrogen fertilizers have comparable upstream energy demand because they ultimately rely on the manufacture of NH3. When there were exceptions, it was because the nitrogen source was mined, like Chilean saltpeter. We assumed that algae production will use commodity agricultural chemicals to minimize cost and that these lower-energy nutrients are thus not likely to be used. For these reasons, urea (i.e., (NH2)2CO) and diammonium phosphate (DAP) were used as nutrient sources. In some scenarios with high nitrogen recovery relative to phosphorus recovery, DAP supplied too much nitrogen. In those scenarios, superphosphate (Ca(HPO4)2, anhydrous) was used. These chemicals were already in GREET and were used for other biofuel LCAs. Therefore, comparisons with other biofuels involving these nutrients will share identical methodologies for upstream emissions from nutrient production. In summary, in the baseline scenario, the gross nutrient demand per dry gram of algae was 55.5 mg N and 12.5 mg P (28.6 mg P2O5). The gross demand was met from new nutrients (14 mg N, 6.3 mg P) and recovered nutrients (42.2 mg N and 6.3 mg P) (see Figure 10). Nutrient recovery is described in Section 3.6.1.4. 3.2.2 Water Movement Growth and first dewatering account for almost all water movement in the pathway. Water movement occurs when the ponds are mixed to keep the algae in suspension, when culture is moved to first dewatering for settling, when the supernatant is returned from settling back to the growth ponds, and when water lost to evaporation is replaced. In this study, culture is returned to the pond from settling without loss. Future work will consider further losses to manage the accumulation of salt and growth inhibitors and media loss to culture failures when these data become available. Figure 11 summarizes these activities per gram of algae for the baseline scenario. As illustrated, each gram of harvested algae corresponded to 2 L of culture, and, of this, 0.1 L passed to downstream operations. Thus, 95% of the process volume resided in the growth and first dewatering activities. In this study, water demand was determined from the

20

NewNutrients N P 0.014g/g 0.0063g/g

NetRecoveredto Culture N P 0.0422g/g 0.0063g/g

AlgaeinPond N P 0.0555g/g 0.0125g/g

LossofNewNutrients N P 0.0007g/g 0g/g

LostinReturn N P 0.0022g/g 0g/g

DigesterSupernatant N P 0.0444g/g 0.0063g/g

ResidualsinDigester N P 0.0555g/g 0.0125g/g

DigesterSolids N P 0.0111g/g 0.0063g/g

FIGURE 10 Flow of Nitrogen (N) and Phosphorus (P) in the System (The numbers display the grams of N and P per dry-gram of algae)

Evaporation 0.23L/g 2L/g Pond Settle 0.1L/g

Makeupwater 0.33L/g

1.9L/g Pumpingrequired

FIGURE 11 Water Movement during Growth and First Dewatering per Gram of Harvested Algae

evaporative loss of 0.225 in./d from the open pond. This value was computed from an average pan evaporation of 0.3 in./d, typical of Arizona, and a lake/pan correction factor of 0.75. Circulation power for paddle wheel mixing (driven by electric power) was analyzed in several sources (Weissman and Goebel 1987; Weissman et al. 1988; Benemann and Oswald 1996; Kadam 2001; Lundquist et al. 2010; Stephenson et al. 2010) (see Table 2). The Benemann and Oswald value is listed as representative of both the Weissman and Goebel and Weissman et al. detailed analyses that consider various speeds and conditions. The circulation power scales with the cube of the mixing velocity, which is typically between 20 and 30 cm/s and depends on the alga species. Lundquist et al. extends the Benemann estimate by considering the power savings possible from reducing the mixing when possible. This study model uses

21

Lundquists number. Sensitivity analyses scale this by the cube of the velocity to consider mixing speeds of 20 and 30 cm/s.

TABLE 2 Paddle Wheel Power Consumption Source Power (W/ha) Speed (cm/s)

Pumping power, in principle, can be Benemann and Oswald 1996 1,226 20 computed from the pumping velocity, pipeline Stephenson et al. 2010 3,670 30 characteristics (including length), pump Kadam 2001 2,344 efficiency, and elevation changes. In practice, Lundquist et al. 2010 2000 25 this computation depends a great deal on good engineering practice to define the parameters that are consistent with a robust system. Some rules of thumb for good design in WWT are in Guyer (2011), as follows: Solids below 2% may be treated as water, but when they are above 2%, friction is 1.5 to 4 times higher, and pumping speeds must be at least 2 ft/s to maintain solids in suspension. Pumps that consume 2.4 10-5 kWh/L and move 300 gallons per minute (GPM) and meet these constraints can be found, but additional factors must be considered in a design. CAPDET, a detailed process design and cost estimating system for the design of WWT plants, represents accepted practice for WWT (Harris et al. 1982). Algae suspensions meet the criteria for intermediate water pumping (low solids, relatively clean, amendable to more efficient pumps) in CAPDET, for which power consumption is 4.8 10-5 kWh/L and total head is 15 ft. On one hand, CAPDET represents design principles for processes similar to those used for algae. On the other hand, no optimization or tradeoff has been made to account for the scale of algal operations. Nevertheless, the CAPDET value is adopted for the baseline design, and the value of 2.4 10-5 kWh/L will be considered in the sensitivity analysis. 3.3 SECONDARY DEWATERING 3.3.1 Dissolved Air Flotation Dissolved air flotation was described in several sources (Harris et al. 1982; Sim et al. 1988; Uduman et al. 2010). Harris et al. and Sim et al. reported similar energy numbers for DAF (1.33 10-4 kWh/dry-g and 1.48 1 0-4 kWh/dry-g), but the Uduman et al. estimate was 10 times higher (1.67 10-3 kWh/dry-g). Harris et al. computed the power consumption from the total dry weight of the solids recovered by the DAF system. The value above, 1.33 10-4 kWh/dry-g, corresponds to processing the algae produced by 2,000 ha with 25 g/m2/d productivity, but the result depends only weakly upon the total biomass processed, increasing by 4% if the DAF throughput is halved and decreasing by 4% if it is doubled. The Harris et al. value was used for this study, and an algae retention efficiency of 90% was assumed. Lost algae flow to anaerobic digestion. Coagulant consumption was neglected.

22

3.3.2 Dewatering Centrifuges Energy consumption and dewatering performance vary considerably depending on the type of centrifuge employed. Two types characterized for algal biomass dewatering are shown in Tables 3 and 4. Mass retention efficiencies of 8597% are reported for self-cleaning disc stack centrifuges and of 8595% for a decanter bowl (EPA 1979). Harris et al. (1982) reports a rule of thumb of 1 horsepower (HP) per GPM (i.e., 3.298 10-3 kWh per gram of suspended matter). Since this falls between the disc stack and decanter bowl, the analysis uses 95% algae retention and 3.3 103 kWh/g-algae of electricity. Lost algae flow to anaerobic digestion. 3.4 EXTRACTION 3.4.1 Pressure Homogenization Pressure homogenization is an established process used to disrupt bacteria in wasteactivated sludge. GEA Niro Soavi manufactures homogenizers ranging from 100 to 1,500 bar and up to 5,000 L/h and has reported some experiments with algae. It observed 79% homogenization of Chlorella per pass at 600 bar and 2,000 L/h. At 10 wt% solids, this is 365 kWh/dry ton for two passes. The Stephenson et al. (2010) process model assumes 22 wt%
TABLE 3 Self-Cleaning Disc-Stack Centrifuge Characteristics (Mohn 1980; Grima et al. 2007) Parameter Input total suspended solids (TSS) (%) Output TSS (%) Electrical power per volume flow (kWh/m3) Liquid density (kg/1) Calculated electrical power per mass flow (kWh/kg) Value 0.11 512 1 1 1.0 10-3

TABLE 4 Decanter-Bowl Centrifuge Characteristics (Mohn 1980; Grima, Fernndez et al. 2007) Parameter Input TSS (%) Output TSS (%) Electrical power per volume flow (kWh/m3) Liquid density (kg/1) Calculated electrical power per mass flow (kWh/kg) Value 0.54 1022 8 1 8.0 10-3

23

from the decanter centrifuge (i.e., 168 kWh/dry ton for homogenization); however, discussions with GEA Niro Soavi indicate that it is unusual to work above 20% solids because of pumping difficulties and homogenizing efficiency. In EPA (2006), pressure homogenization energy consumption was 750 kWh/dry-ton for 4 to 7 wt% solids, and it was 200 kWh/dry-ton with 90% disruption efficiency in Davis (2010). This analysis uses 183 kWh per dry metric ton and 90% efficiency, corresponding to 20 wt% input and some reduction in efficiency for the higher solids content. This treatment assumes that undisrupted cells flow to recovery, downstream, for digestion. The reasoning is that although no separation is done, the undisrupted algae will flow through lipid extraction and be present in the LEA cake that is sent to recovery. 3.4.2 Hexane Extraction of Algal Lipids Algal lipid extraction with solvents has not been demonstrated at scale or for a broad range of species. The Aquatic Species Program close-out report included an experimental study conducted by Nagle and colleagues (Sheehan 1998). Those researchers studied solvent extraction of algal lipids with n-butanol, ethanol, and hexane/2-propanol and found the highest extraction efficiencies occurred with n-butanol (90%), followed by hexane/2-propanol and ethanol. The experiments used slurries with 15% solids, 90-minute reactions, 1,200 g of solvent, and 400 g of wet biomass, giving a 3:1 solvent to biomass ratio. For comparison, soybean oil extraction mixes volumes of solvent and soybean meal that are approximately equal. The soybean meal typically contains 18.5 wt% oil. A few papers describe models of algal oil extraction with hexane; they are summarized in Table 5. Stephenson et al. (2010), on the basis of preliminary data (Stephenson et al. cites a private communication), assumed that a 1:2 solvent-to-biomass volumetric ratio would recover 99% of the algal triacylglycerides. The authors then simulated solvent recovery with the HYSYS process simulation software. The low solvent-to-slurry ratio is reflected in the low thermal demand in Table 5 for Stephenson et al. (2010). Note that in the simplest approximation, the thermal demand derives from the need to vaporize hexane, so the process heat demand should be related to the total hexane in the process. Lardon et al. (2009) assumed that the energy demand for a wet process would scale with the reaction volume to estimate energy from established soybean oil extraction. The authors appear to have assumed that the energy demand per process volume would be independent of the lipid concentration, and they then scaled the result by the lipid fraction to prepare two scenarios, one with 17.5 wt% lipids, and the other with 38.5 wt% lipids. The latter is listed as low N in the table. Lundquist et al. (2010) considered extraction from algae flakes produced by solar drying. The authors thus used data for hexane extraction of soybean oil from dry meal. They considered a regional extraction facility that would operate at larger scale in order to increase efficiency and allocate costs over the algal growth facilities served.

24 TABLE 5 Literature Survey of Energy Inputs for Algae Oil Extraction Using Hexane as Solvent, per Kilogram of Extracted Oil Lardon et al. (2009) Dry 0.417 7.100 0.015 Dry, Low N 0.194 3.200 0.007 Wet 2.333 22.400 0.055 Wet, Low N 1.083 10.200 0.025 Lundquist et al. (2010) Small 0.092 3.579 Large 0.045 2.686

Input per Kilogram of Oil Electricity (kWh) Heat (gross) (MJ) Hexane (loss) (kg)

Stephenson et al. (2010) 0.056 1.700 0.003

The present study considered all these authors and derived a low-energy scenario from Stephenson et al. (2010). Because that study assumed such a low solvent-to-biomass ratio compared to the ratio used in either soybean oil extraction or Nagle and colleagues, the electricity was rounded up from 0.05 to 0.1 kWh/kg-oil, and the thermal requirement was rounded to one digit: 0.5 kWhthermal/kg-oil produced. A high-energy scenario was derived from the Lardon et al. (2009) wet low-N case by rounding the value to a single digit. The baseline scenario was defined by the average of these two (see Table 6). Extraction efficiency was assumed to be 95%. In the baseline scenario, heat for extraction comes from on-site power generation, as described in Section 3.6.3.
TABLE 6 Wet Hexane Extraction Parameters Used in This Study, with Extraction Efficiency Assumed To Be 95% Natural Gas (kWhthermal)/ kg-Oil) 1.7 3 0.5

Scenario Baseline High Low

Electricity (kWh/kg-Oil) 0.54 1 0.1

Hexane Loss (g/kg-Oil) 5.2 10 2.5

3.5 FUEL PRODUCTION (CONVERSION) AND FUEL USAGE MODELS Extracted lipids are transported and converted to biodiesel by transesterification in the baseline model. Alternative scenarios consider conversion to renewable diesel and renewable gasoline via hydrotreating. Fuels are transported to market and used in CIDI or spark-ignition vehicles. The transesterification, renewable diesel, and renewable gasoline models are the standard GREET models developed for processing soy-oil fuels (Huo et al. 2008). Conversion co-products are treated by energy allocation.

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3.6 ENERGY AND NUTRIENT RECOVERY: CO-PRODUCT PRODUCTION The recovery model estimates nutrient and energy recovery from material sent to the recovery process. This material is a mixture of algae lost upstream plus LEA from extraction. Two recovery processes are considered in the analysis: anaerobic digestion (baseline) and catalytic hydrothermal gasification, modeled via the Genifuel Corporation process (alternative scenario). In both cases, biogas is combusted via a CHP plant to produce electricity, recoverable process heat, and CO2 that can be returned to the pond. 3.6.1 Anaerobic Digestion In a WWT plant, the primary purpose of the AD is waste solids reduction and waste stabilization. In conventional AD processes used in WWT, sufficient carbon is usually provided by organics contained in the wastewater and waste solids, which is measured as chemical oxygen demand (COD). In the digestion process, organics in the feed solids are removed through conversion to CH4 and CO2 via anaerobic microbial metabolism. In this way, volatile content is reduced to meet U.S. Environmental Protection Agency (EPA) discharge limits. Several issues must be considered during the design and operation of a digester, including solid and hydraulic residence times, influent nutrient and carbon contents, microbial biomass yield, biogas yield, biogas rate, biogas composition, operating temperature, and digester configuration. Although the CH4 yield and gas production rate are important indicators of carbon conversion performance and overall process efficiency, CH4 production per se is only a secondary objective for WWT. With regard to algal fuel production, it is the opposite: The focus is on energy and carbon recovery through CH4 production as well as nitrogen and phosphorus nutrient recovery from the LEA. The WWT design parameters, mentioned above, are not a focus of this investigation unless they are critical for determining energy demand and emissions. Therefore, the discussion below focuses on CH4 yield and its prediction based on total LEA mass sent to the digester. Process energy for the digester is also considered because it affects emissions. The analysis is relatively insensitive to the thermal demand because it is obtained from waste heat from the CHP system. Also, thermophilic digesters, considered here, operate at 35C, so the heat required is low quality. 3.6.1.1 CH4 Yield The CH4 yield depends on the digester substrate. Theoretically, yield is calculated on the basis of biochemical oxygen demand (BOD), and complete conversion of a gram of BOD to CH4 and CO2 produces 0.35 L of CH4 at standard conditions (temperature of 0C, atmospheric pressure). In practice, the yield is less than this, partly because some of the BOD supports growth of the anaerobic microbial culture, and partly because only a portion of the BOD is digested. Digestibility varies with the feed and the anaerobic digesters design and operating conditions, like temperature and digestion time.

26

Table 7 summarizes several studies of AD performance with algae feeds. These experimental studies report yields empirically as the volume of CH4 produced per gram of volatile solids (VS) in the feed (L-CH4/g-VS). Ras and associates studied digestion of Chlorella at bench scale and measured VS with standard methods defined by the American Public Health Association, and they measured COD calorimetrically (Eaton and Franson 2005; Ras et al. 2011). They then assumed equality between COD and BOD to estimate the theoretical CH4 potential via 0.35 L-CH4/g-COD. This defines the values for digestibility as seen in the table: 33% and 51% of COD for 16- and 28-day digestion times. The data from
TABLE 7 Anaerobic Digester Performance, with Volumes at 0C and 1 Atmospheric Pressure (Samson and Leduy 1982; Sialve et al. 2009; Lundquist et al. 2010; Collet et al. 2011; Ras et al. 2011)a
Theoretical CH4 Yield, (L/g-VS) CH4 Yield (L/g-VS) 0.15 0.24 0.26 CH4 Yield (L/g-TS) 0.15 0.22 0.23

Source Ras et al. 2011

Feed Chlorella

Digestible Fraction 33% of COD 51% of COD 66% of VS

Ratio (g-VS/g-TS) 0.850.90 0.850.90 0.89

Digestion Time (d) 16 28 33, 70% CH4

Samson and Leduy 1982 Sialve et al. 2009

Spirulina

Chlorella vulgaris Chlorellascenedesmus sludge Dunaliella salina Spirulina maxima

46%b of VS 36%b of VS

0.630.79 0.590.79

0.31 0.35 0.17 0.32 0.44 0.26 0.29

0.30c 0.22

64 330 (hydraulic retention time) 28 33 46, extrapolated from Ras et al. 515

65%b of VS 38%b of VS 56% of COD 25%65% of VS 0.90

0.68 0.630.74

0.40 0.23 0.26

Collet et al. 2011 Ehimen et al. 2011


a b c

Chlorella

Chlorella

0.946

0.00.30

00.32

VS = volatile solids, TS = total solids, COD = chemical oxygen demand. Computed as the ratio of yield (VS)/theoretical. Assumes 0.9 g-VS/g-TS

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Collet et al. (2011) in the table were derived similarly. Indeed, the results reported by Collet et al. (2011) are from Ras et al. (2011) but extrapolated to a different digestion time by those authors. Samson and Leduy (1982) studied Spirulina maxima digestion. They studied a semicontinuous process in a 10-L reactor for 14 weeks. The digester was inoculated with sludge from a municipal sewage digester that had been adapted for two months on a Spirulina feed. The digester was operated at 35C with daily feeds, periodic mixing, and a 33-day digestion time. Samson and Leduy reported the total change in VS achieved by the experiment, and this is listed in the table as the digestibility. They also reported the CH4 volume produced per gram of VS in the feed, and they reported the CH4 fraction in the produced gas. This fraction was plotted as a function of time over the course of the digestion period. The value stabilized after several days at 70% CH4 by volume (70 vol%). Sialve et al. (2009) discuss theoretical yields for several algae computed from the macromolecular composition of the biomass (lipid, carbohydrate, and protein fractions) and tabulate experimental results for several species and AD conditions reported by other authors. The results were reported as CH4 volume per gram of VS in the feed. We computed the ratio of the experimental and theoretical CH4 yields and display them as digestibility in the table. Sialve et al. (2009) also reports the CH4 fraction in the biogas, which ranged from 62 to 76 vol%. Ehimen et al. (2011) studied digestion of Chlorella residues after lipid extraction. By contrast, all of the other reports discussed so far studied whole algae. Ehimen and associates worked with continuously stirred 1.5-L semicontinuous reactors and studied the effect of the retention period, carbon-to-nitrogen (C/N) ratio, substrate concentration, and reactor temperature (2540C) on CH4 yield, gas composition, and reactor stability. The C/N ratio in the LEA feed was 5.4. The C/N ratio was increased to a value as high as 25 by co-digesting with glycerin. The proportion of glycerin relative to the feed was consistent with the amount of glycerin that might be co-produced during transesterification of the algal lipids. Ehimen and colleagues found the largest CH4 yields at the lowest substrate concentration, namely 5 g/L. For all variables considered, the best performance occurred at maximum digestion time, 15 days. When reactor stability was defined by VS destruction exceeding 50%, feed concentrations were constrained to be between 5 and 20 g/L. This is dilute: Digesters usually operate between 50 and 100 g/L. Peak yield occurred at 35C, a feed concentration of 5 g/L, and a C/N ratio of 8.53. In that case, the yield was 0.302 L-CH4/g-VS. The feed in the study had 0.946 g-VS per gram of total solids (g-TS), so this peak value is 0.32 L-CH4/g-TS when expressed on a TS basis. Increasing the temperature did not improve performance; however, the authors noted that they did not adapt the digester inoculum to the higher temperature and used an inoculum developed at 35C for all experiments. Stable configurations of the digester had 67 vol% CH4 in the biogas, and VS destruction was between 50% and 55%. Our objective is to estimate CH4 production from the LEA mass flow into the digester. Most cited studies report approximately 90% of total algal solids were VS. We therefore converted the VS-based yields to TS-based yields, as shown in the next-to-last column of Table 7. On the basis of these values, 0.2 L-CH4/g-TS and 0.4 L-CH4/g-TS were adopted as the

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low and high points of the yield range. The midpoint, 0.3 L-CH4/g-TS, was used as the baseline value for CH4 yield. The biogas volume was computed from the CH4 yield based on 67 vol% CH4 in the biogas. Note that in our approach, uncertainty in the CH4 fraction produces uncertainty in the CO2 recovery rate rather than uncertainty in the CH4 production rate. 3.6.1.2 Process Energy Requirements The digester requires thermal and electrical energy. Values are taken from Collet et al. (2011) for a mesophilic, completely stirred tank reactor; they are 0.68 kWhthermal/kg-TS and 0.11 kWhelectrical/kg-TS. The heat requirement corresponds to 30% of the heat value of the biogas in Collet et al. (2011). The energy consumption depends on the retention time, which is 46 days in Collet et al. Moller et al. (2009) reports 35 kWhelectrical/ton-wastewater for AD operations, and other values in the paper imply 0.19 tons of VS per ton of wastewater (source separated organics from municipal waste); hence, 0.18 kWhelectrical/kg-VS, 63% higher than the Collet et al. (2011) value. The Collet et al. numbers will be used, since the values and conditions are explicit. Nitrogen is recovered largely by mineralization to ammonium in the aqueous phase plus organic nitrogen in the sludge. Therefore, additional electric power, comparable to a disc-stack centrifuge, is added to account for concentrating solids from the digestate to 30% solids. This increases the electrical requirement to 0.136 kWhelectrical/kg-VS. The process energy per volume of CH4 produced or nutrient recovered depends on the digestion time and digester size. Digesters for WWT applications are typically designed with a 20-day solids retention time. Longer times slightly increase performance, but not on par with increased costs from increased digester size. Shorter times slightly decrease performance when only the change in COD is considered, but the higher flows can wash out the microbial biomass and make the digester unstable. The digestion times in the table, then, are long compared to those associated with current WWT practice; therefore, the process energy estimates above may be high. In the model, thermal energy is obtained from the CHP operation. 3.6.1.3 Biogas Cleanup Biogas from landfills contains many impurities, such as hydrogen sulfide (H2S), siloxanes, halogenated organics, particulates, and moisture, that must be removed prior to combustion to avoid corrosion and deposits in the engine or turbine (Mintz et al. 2010). Because of the lack of data for algae-derived biogas, this analysis assumes cleanup required for algae biogas will be similar. We used the landfill biogas cleanup model already in GREET to compute energy demand for this basic cleanup required for combustion on site. Further cleanup is required to remove CO2 when biogas is converted to pipeline-quality bio-methane. This requires additional processing beyond that required for combustion in CHP turbines and engines. This additional energy is not required in the scenarios analyzed here.

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Four types of technologies are commonly employed for removal of CO2, H2S, and other impurities: membrane separation, adsorption, absorption, and cryogenic distillation. Membrane separation separates CO2 from the biogas stream by utilizing the differences in membrane permeability among CO2, H2S, and CH4. Membrane separation produces gas from 200 to 600 psig (Pomerantz and Turcote 2004; Air Liquide 2008). Pressure swing adsorption (PSA) utilizes the different adsorbabilities of CO2, H2S, and CH4 to clean the gas stream. In PSA, contaminants are adsorbed more easily than CH4 under high pressure. Once the adsorbent is saturated, adsorbed contaminants are removed by reducing the pressure. PSA produces upgraded gas from 100 to 200 pounds per square inch gauge (psig) (Sperling Hansen Associates 2007). Absorption processes separate molecules in the gas phase by absorbing them in a liquid phase. The amine process, common in the natural gas industry, uses aqueous solutions of alkanolamines. Water scrubbing is common for biogas. Absorption processes are suitable for large-scale processing units. In cryogenic distillation, biogas is cooled to condense the CO2 (59F) in order to remove it from biogas. CO2 Wash, developed by Acrion Technologies, is an example of cryogenic distillation that adopts absorption to remove other impurities by using the condensed CO2 as absorbent. The CO2 concentration of output gas (~27%) is still higher than that of pipelinequality natural gas or transportation fuel, which requires further treatment or post-purification (Cook et al. 2005). Energy consumption for several cleanup technologies is summarized in Table 8. Energy consumption for PSA is adopted for this analysis. The pressure of gas delivered by PSA approximately satisfies the inlet pressure requirements for CHP engines, which vary from 100 psig for small gas turbines to 300500 psig for 10- to 25-MW turbines. Therefore, energy for further pressurization prior to combustion in the turbine was not added in the analysis. If a lowerpressure technology is chosen in future work, additional energy will be required.
TABLE 8 Energy Consumption for Biogas Cleanup for Several Processes (Potential fugitive CH4 emissions do not account for CH4 reduction in downstream processing of the process off-gas.) (Petersson and Wellinger 2009) Organic Physical Scrubbing 0.240.33 5580 24

Parameter Electricity (kWh/Nm3-raw biogas) Temperature requirement (C) Potential fugitive CH4 emissions (%)
a

PSA 0.25 None <3%, 610%a

Water Scrubbing <0.25 None <12

Chemical Scrubbing <0.15 160 <0.1

Two sources reported different emissions.

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3.6.1.4 Nutrient Recovery from Anaerobic Digestion Nutrient recovery was modeled via an approximate mass flow for carbon (C) (Figure 12) and for nitrogen (N) and phosphorus (P) (Figure 13). The C wt% for LEA was estimated by considering it to be a mixture of protein and carbohydrate (represented by glucose) with molecular formulas of C4.43H7O1.44N1.16 and C6H12O6, respectively (Lardon et al. 2009). Carbon wt% was computed for three macromolecular compositions, and the value for the baseline composition was used for the analysis (Table 9). As shown in Figure 12, the C flows to CH4 and CO2 were computed from the biogas yield and composition, and the C in the digestate was determined by difference. C was assumed to split evenly between supernatant and digestate (Weissman and Goebel 1987).

TotalSolids intoDigester

Digester Carbon=44wt% ofdrysolids CarboninCH4 CarboninCO2 Carbonin SupernatantandSludge (bydifference)


FIGURE 12 Carbon Mass Balance through Anaerobic Digestion

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NewNutrients

AlgaeProcess, ThroughExtraction LipidExtracted Algae DigesterSolids Digester Supernatant Retainedin ExtractedOil

Volatilization Loss

NutrientsAdded toDigester

Returnedto Culture

SoilAmendment

Treatmentand Discharge

FIGURE 13 Mass Flows Used to Compute Nitrogen and Phosphorus Flows through the System

TABLE 9 Carbon Content (wt%) for Several Macromolecular Compositions Composition Baseline Low lipid High lipid Lipid 25 12.5 50 Protein 25 37.5 2 Carbohydrate 50 50 25 Carbon 44 46 47

N and P are found in the protein fraction of the biomass. Given the large uncertainty in total lipids and lipid distribution, the small fraction of P in phospholipids was neglected. Thus, it was approximated that all N and P in the biomass went to the LEA and flowed into the digestate. Several flows are considered in the mass balance in Figure 13. The starting point is the box with the bold font, Algae Process, Through Extraction. N and P per dry-gram of algae are computed for this box from the C : N : P ratio of 103 : 10 : 1 and 50 wt% C in the whole biomass. (The C, N, and P composition is described in Section 3.2.1.) Loss of N and P during extraction can be accounted for via flows to Retained in Extracted Oil, although zero was assumed in this analysis. (See also discussion of uncertainties in total lipid fraction versus phospholipid subfraction in Section 3.2.) Splits from N and P in the LEA feed to N and P in the digestate solids and to N and P in the supernatant after digestion are considered next. After that, consideration is given to splits of the supernatant among that returned to the algae culture, that applied to soil, and that discharged after any regulatory-mandated treatment. In this analysis, the supernatant was returned to the culture: None was applied as fertilizer in the fields or discharged.

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Although nutrients may sometimes be added to digesters, this analysis assumed none would be needed because of high N levels in the LEA. The solids were used as soil amendments and carry a portion of the nutrients to fields. Weissman et al. (1987) estimated that 25% of the N would reside in the sludge and 75% would reside in the supernatant, while the P would be split 50/50 between the solid and liquid phases. Weissman et al. also estimated that 30% volatilization of NH3 would occur when the supernatant was returned to a pond. Ras et al. (2011) measured 68% retention of N in the supernatant when Chlorella was anaerobically digested at a retention time of 28 days. Collet et al. (2011) extrapolated this to 90% recovery if the retention time was extended to 42 days and estimated that only 5% loss to volatilization would occur if the pond pH was below 7. Recovery of P was not mentioned in these references. The baseline scenario in this study assumes 80% of the N is retained as ammonium/NH3 in the supernatant that is returned to the pond, with only 5% volatilization resulting in 76% recovery to the algae culture. The 20% fraction of N remaining in the solids is treated as organic N with a bioavailability of 40% (Tchobanoglous et al. 2003; Bruun et al. 2006) that is exported as a fertilizer replacement co-product that displaces the average emissions for N and P production for corn farming. In the baseline scenario, P is split 50/50 between supernatant and solids and utilized at 100%. P is important economically and for sustainability considerations because of concerns about supply; however, N production is the major energy consumer, and the P recovery rate will be shown to have little effect on the LCA results (see also Section 4.1.6). The C in the digestate solids applied to fields provides a C sequestration credit. Bruun et al. (2006) used a computational model to extrapolate soil emission data to application of AD residues on arable land over periods of up to 100 years. Their modeling indicated that 8% to 16% of the C in AD residues would remain in the soil; however, they commented that their expectation was that all applied C should return to the atmosphere over time and that the sequestration seen in their modeling likely reflects uncertainties in the experimental data for long-term studies when emissions have become small. Nevertheless, the baseline analysis uses the 8% figure. Sensitivity analyses will consider sequestration fractions of 0% and 16%. 3.6.1.5 CH4 Emissions from Anaerobic Digestion and Biogas Cleanup Two studies of CH4 emissions from digesters were found in the literature. Flesch et al. (2011) measured emissions from a state-of-the-art digester with a rated capacity of 1 MW in Canada that digests manure and organic substrates to make biogas for power generation. Liebertrau et al. (2010) measured emissions at 10 German biogas facilities with capacities ranging from 0.5 to 1.5 MW that process various energy crops and manure. Flesch et al. (2011) determined that emissions differed according to activities at the site and could be separated into three categories: normal operations, flaring, and maintenance. During normal operations, fugitive emissions were 3.1% of the CH4 production rate; however, this rose to 19% when there was flaring of excess gas and fell to 1.2% during maintenance. Biogas flaring efficiency was observed to be less than usually expected, averaging 81% CH4

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combustion in the flare with a range of 48% to 99%. This range is usually assumed to be 90% to 95%. Note that flare efficiency was based on measured uncombusted CH4 versus the CH4 in the feed, but the authors indicated significant uncertainty in the magnitude of the result. In this study, the major source of emissions was from the hopper, where new substrate was added to the digester. When the hopper was reconfigured to have a negative pressure relative to the environment, normal operational emissions fell to 1.7% of total CH4 production. Liebetrau et al. (2010) identified several sources of CH4 emissions. The substrate feed system, corresponding to the hopper in Flesch et al. (2011), had 0.27% emissions when operated in open air and 0.1% with direct intake systems. Leaks from the digester cover were zero when it was made of concrete and were typically zero for membrane systems but were 0.17% for one that had developed leaks. On the other hand, at one facility, 5.5% of all CH4 was lost through a service opening from improper maintenance. Digestate must be stored until it is used as a fertilizer because application is seasonal. Emissions of CH4 from digestate stored in open tanks ranged from 1.4% to 10.4% of the CH4 produced by the digester, with a mean of 5%. The authors pointed out that digestion is never complete and cited a study that determined that the remaining digestible VS in the discharged digestate can produce an additional biogas volume totaling 1.5% to 3.5% of total production. The power co-generation units at the sites studied by Liebetrau and colleagues produced an average CH4 discharge of 1.73% of total produced CH4. Biogas cleanup can also produce CH4 emissions. Potential emissions are shown in Table 8. Two different loss rates were reported for PSA by different sources (<3% and 610%). Although the difference in estimates is large, it does not affect the present analysis because the cleanup process off-gas containing the emissions can be processed to mitigate emissions. One example would be including the off-gas in the CHP gas turbine air intake to combust the CH4 emitted during cleanup. The potential emissions from cleanup are called out to emphasize that techno-economic analysis must include mitigation of these emissions. Moller et al. (2009) estimates that 0.2% net fugitive emissions are associated with upgrading biogas to vehicle-quality gas. Vehicle-quality bio-methane requires more upgrading than algae fuels need for power co-generation, so emissions for biogas cleanup during algal fuel production would not be higher than this, given the Moller et al. analysis. On the other hand, when considering the whole biogas production pathway, Moller et al. (2009) considered fugitive emissions up to 3% of total CH4 production. Since most of the pathway studied by Moller and associates was similar to the one used in the present analysis, the Moller et al. analysis would estimate that up to 3% of total CH4 production in the algal fuel pathway would be emitted. Borjesson and Berglund (2006) considered emissions from biogas systems. They reported that emissions from stored digestate could be 520% of total digester CH4 production if emissions are not captured during storage. They reported that LCA studies of biogas production commonly assume a loss of 23% over the whole pathway. Considering all these sources, this analysis assumes a total fugitive CH4 loss of 2% for the whole pathway associated with biogas production, cleanup, and digestate handling. Sensitivity analyses will examine total fugitive CH4 emissions of 0% and 4%, although there

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appears to be the potential for substantially more. Emissions of CH4 are considered more in the discussion in Section 5. 3.6.1.6 Nitrous Oxide Emissions from Soil Application of Digestate Solids The method used by the IPCC Task Force on Greenhouse Inventories estimates that direct N2O emissions from organic fertilizers total 1% of the N applied to managed soil. More specifically, 0.01 kg N2O-N is emitted per kilogram of applied N. Each kilogram of N2O-N equates to 44/14 g of N2O (IPCC 2006). In 2010, an IPCC expert working group revisited this topic in light of the more than 1,000 publications released since that 2006 report on N2O emissions from soils (IPCC 2010) The expert panel concluded that the 2006 guidelines are clear and correct; however, the data indicate that disaggregating the emission factor by region, climate, and soil may introduce significant variations in emissions. Furthermore, the panel commented that only 10% of the studies considered organic fertilizers and that the relationships among the mineral/organic N fractions in the fertilizer, C/N ratio, and quality of organic C may have strong effects on N2O emissions. There is some question whether the IPCC treatment, which is based on applied N, is accurate or if only the bioavailable N should be the basis. Brown et al. (2010) developed a computational tool to determine GHG emissions from biosolids processing and end use. The Brown et al. literature review concluded that emissions from biosolids are lower than those from mineral fertilizer. Considering the lower emissions yet higher N application rate (to counter lower bioavailability), the model in Brown et al. assumes N2O emissions from biosolids are equivalent to those from the mineral fertilizers they replace when they are considered on the basis of meeting plant N demand. On the other hand, Brunn (2006) developed a detailed simulation of emissions from soilapplication of processed organic municipal waste on agricultural land, including the application of anaerobic digester residues. The computation included a detailed schedule for crop rotation, fertilizer application, and application of manure and digestate according to Danish regulations. The computation included soil processes (e.g., soil microbial biomass, soil organic biomass, tile drainage, leaching, and mineralization kinetics). The study considered a reference scenario in which N needs are met via animal waste and mineral fertilizers. In one alternative scenario, digested organic municipal waste displaced a portion of the mineral fertilizer on a bioavailable-N basis. The animal waste portion was held constant between the two scenarios. Integrating all factors over 100 years, Bruun et al. (2006) computed that the scenario with digestate substituting for a portion of the mineral fertilizer had additional emissions of 0.013 to 0.017 kg N2O-N per kilogram of applied N when compared to the scenario without digestate application. The analysis presented here considers these studies and uses the IPCC method for estimating N2O emissions from solids used as fertilizer. Thus, direct emissions of 0.01 kg N2O-N occur for each kilogram of N in the AD residue solids applied to soil. For sensitivity analysis, a low value case assumes that direct N2O emissions from digestate solids exactly equal those from the mineral fertilizers they displace.

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3.6.2 Catalytic Hydrothermal Gasification for CH4 Production A nonbiological process was considered as an alternative to anaerobic digestion for CH4 production. Pacific Northwest National Laboratory devised a process for gasification of wet biomass that is being commercialized by Genifuel Corporation for the production of renewable natural gas (Genifuel Corporation 2011; Elliott et al. 1993, 1996). The process converts wet biomass slurries to biogas, with a C conversion efficiency of 99%. The biogas is a mixture of CH4 and CO2 without N, sulfur, or siloxanes. The slurry feed should be between 1% and 40% solids, with 10% to 20% being optimal. The process has been applied to wastewater solids, bottoms from beer and ethanol fermentation, food processing wastes, dairy wastes, and algal biomass. N in the feedstock is recovered as ammonium in sterile water near neutral pH. P is recovered in an apatite-like precipitate. The calculations described here were developed through conversations with Genifuel Corporation. The process data in Table 10 are for slurry with a 15% solids content. We converted the yields to a dry-mass basis and assumed that yields on a dry-mass basis for other moisture levels would be similar. The process energy consumption is reported as an aggregated energy expressed as a fraction of gross CH4. The energy demand is largely for electricity, and the reduction in gross gas accounts for the electric power generators efficiency. In the future, a more detailed treatment will disaggregate the energy consumption into thermal and electrical; meanwhile, we estimate that the error from aggregation is no more than 2% of total energy consumed by this unit process. Biogas cleanup is performed on the catalytic hydrothermal gasification product, identical to the cleanup described for AD biogas.
TABLE 10 Technical Parameters for Catalytic Hydrothermal Gasification Process Parameter CH4 yield (m3/wet metric ton) Reduction in CH4 yield for LEA (%) Slurry solids content for yield specification (wt%) CO2/CH4 volumetric ratio (%) Fraction of CH4 used for process energy (%) Net CH4 (L/dry-g solids) Net CO2 (L/dry-g solids) CH4 produced (g/dry-g solids) CO2 produced (g/dry-g solids) Value 55 15 15 67 10 0.2805 0.2078 0.2009 0.4081

3.6.2.1 Nutrient Recovery from Catalytic Hydrothermal Gasification Genifuel Corporation reports over 95% recovery of the N and P that enter the gasifier. N is recovered as ammonium/NH3 in water, and P is recovered with other salts in a clayish apatite precipitate. N recovery was assumed to match the numbers reported by Genifuel, since

36

N assays on the liquid fraction have been done; however, P recovery from the precipitate has not been demonstrated, so a more conservative approach was taken. The analysis here assumes 95% recovery of N as ammonium and considers two scenarios with 0% or 90% recovery of P as PO4 in solution. The P recovery is achieved via addition of sulfuric acid stoichiometrically via the following reaction: 3 Ca3(PO4)2 + 6 H2SO4 6 CaSO4 + 3 Ca(H2PO4)2 Recovered N and P are both returned to the culture since they are recovered in solution. Energy for sulfuric acid production was obtained from GREET and is 0.64 Btu/ton-H2SO4. 3.6.3 Combined Heat and Power Systems This section describes how heat and electricity production via on-site CHP systems are determined. The heat characteristics (temperature and pressure) and suitability for the lipid extraction and anaerobic digestion processes are assessed. The total heat and electricity produced and their ability to meet demand are described in the results section. All efficiencies in this section are expressed on an LHV basis. The primary purpose of the CHP component is to reduce the imported power demand by combusting the biogas obtained from the unused algae fractions. In addition, heat is recovered to reduce fossil energy requirements for lipid extraction and anaerobic digestion. The critical parameters, then, are the electricity generation efficiency and heat recovery efficiency. In general, there is a trade-off between the electrical efficiency and quality (temperature) of the recovered heat in CHP applications. Regenerators and combined cycles can increase the electrical efficiency, but the combustion gases may become too cool for a heating application. In addition, the power plant size, operating conditions (altitude and ambient temperature), and load factor affect electrical efficiency. The facility size estimation in Appendix A indicates the need for electric power generation at the 1040 MW scale for 4,712 ha of cultivation at 25 g/m2/d, 25% lipids, and 0.30 L-CH4/g-TS CH4 yield from the digester at 0C and 1 atmosphere. The EPA CHP Partnership reviewed several kinds of distributed power generation systems (EPA 2008). Gas turbines match the electricity needs of this application, and, at the 10-MW scale, the typical electrical efficiency is 32% on an LHV basis. This falls to 30% at 5 MW and increases to 38% at 25 MW. These performances are at standard conditions (15C, sea level) and optimal load. Performance decreases with increases in temperature and altitude and at part-load operation. Operating at 100F reduces power and efficiency by 10%. Higher altitude decreases power and efficiency by 4% per 1,000 ft. These effects derive from reduced mass flow per volume of the working gas (air). Part-load performance affects efficiency nonlinearly. Four percent is a typical de-rating when operations are at 80% of maximum load. Pond operations at 80% of maximum load at 90C reduce efficiency by 7%. This changes the pond electrical efficiency at 5, 10, and 25 MW to 27.9%, 29.8%, and 35.3%, respectively. Note that the pond circulation power is

37

computed by assuming circulation is reduced in the evenings, and it is unclear at this time whether other operations on site will be continuous or intermittent: The part-load factor is unknown. The turbine exhaust temperature of the 10-MW representative turbine is 916F. When combined with a heat recovery steam generation (HRSG) system, the exhaust temperature drops to 322F, near the minimum temperature (300F) recommended to avoid condensation of water vapor from the exhaust. Under these conditions, the total CHP efficiency(Heat + Electricity)/ Fuelis 76%. The principle heat demand during lipid extraction is for solvent recovery. Hexane boils at 69C, but efficient separations often require an additional temperature increase of 2550C to drive the vaporization process as the solvent fraction in the mixture decreases. If an additional 10C is required across the surface of a heat exchanger, the process will require steam above 129C (264F). The HRSG exhaust temperature, 322F, will satisfy these process conditions. Desulfurization of the biogas might allow for a lower stack gas temperature and higher total CHP efficiency because operation would take place closer to the condensation temperature of the water vapor in the combustion gas stream. For the GE LM6000 40-MW generator, reducing the temperature of flue gases exiting the HRSG to just above the water vapor condensation temperature changes the total CHP efficiency from 77% to 85% (EPA 2008). To be conservative and to allow for the higher temperature requirement by nonhexane solvents, this possible efficiency gain is not included in the analysis. Heat transfer can easily be accomplished in the anaerobic digester since it operates at 35C. On the basis of the above considerations, the baseline scenario employs a gas turbine for CHP and assumes electrical efficiency of 33% and total CHP efficiency 76%. Sensitivity analyses will consider electrical efficiencies of 28% and 38%. ICEs can also be used for CHP, although the practical electric power output is limited to about 5 MW. Electrical efficiencies for ICEs range from 33% to 41%. Heat is available in both engine jacket cooling fluids and the exhaust gases. The former are 30% of the heat and have temperatures near, but below, the boiling point of water, which is too low to drive the entire extraction process. However, this heat might be combined with the higher-quality heat from the exhaust stream to meet the total process heating demand. This analysis assumes that an ICE can meet the process heating conditions for extraction and anaerobic digestion. A total CHP efficiency of 76% is assumed. ICEs are included in the analysis as an alternative scenario because they might be attractive for smaller algae farms; however, ICEs have significantly higher emissions in the untreated exhaust gases. Table 11 lists emissions and efficiencies for CHP technologies as used in this study.

38 TABLE 11 Efficiencies and Emissions from Two CHP Technologies (All efficiencies are based on the LHV value of the fuel) Gas Turbine Efficiency Electrical (%) Total CHP (%) Pollutant VOC CO NOx PM10 PM2.5 SOx CH4 N2O CO2 Low 28 76 Baseline 33 76 High 38 80 Internal Combustion Engine 37 76

Amount of Emissions (g/mmBtu of Fuel Input) 1.00 24.0 113 3.10 3.10 0.269 4.26 1.50 59,360 41.1 342 1,200 5.53 5.53 0.269 369 1.50 57,732

3.7 HEATING VALUES OF ALGAE BIOMASS AND LIPID-EXTRACTED ALGAE The whole-algae biomass LHV was used to calculate the total renewable energy that was input to the production process via the algal biomass. Emissions and energy consumption allocations are based on the co-product energy content, so renewable energy input to the process does not affect the emissions or energy consumption analyses. Lower heating values (LHVs) per macromolecule from Lardon et al. (2009) were used to compute the LHV of the whole biomass on the basis of its protein, carbohydrate, and lipid composition. The LHV value employed in the analysis, 18,591,000 Btu/ton, corresponds to the baseline scenario biomass composition: 25 wt% lipid, 25 wt% protein, and 50 wt% carbohydrate.
TABLE 12 Lower Heating Values for Macromolecules from Lardon et al. 2009 Macromolecule Protein Carbohydrate Lipid LHV (MJ/kg) 15.5 13 38.3 LHV (Btu/ton) 13,356,312 11,202,068 33,003,016

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3.8 PATHWAY INTEGRATION Co-produced electricity is consumed on site for process needs. If the amount of electricity produced on site is less than required, emissions and energy demand corresponding to the U.S. mix are added to supply the deficit. Heat from the combustion of biomass/biogas is available for reuse on site. If the produced heat is not sufficient to cover the heat required by the processes, a natural gas boiler with 80% efficiency provides the deficit. GREET compares the total CO2 from biogas combustion with the CO2 demand of the algae culture to determine how much flue gas must be delivered from off site. CO2 from off site incurs both transport (to site) and transfer (into culture) energy costs. Recovered CO2 incurs only energy costs for transfering CO2 to the culture. Transportation of co-products, intermediates, and final fuel is summarized in Table 13. AD digestate solids are transported for field application by assuming 30 wt% solids in water. Backhaul travel is included in the table. Algal oil was transported 600 mi by rail to reach a transesterification facility or refinery. This value is similar that associated with the case of soybean-oil transportation, in which the soybean oil is moved in a mixed transportation mode (barge for 520 mi and rail for 700 mi) for conversion to biodiesel. The algal oil case values were chosen because they are plausible and facilitate comparison with soybean-oil biodiesel. The transportation modes and distances for final fuel transportation and distribution exactly match those used for soybean-oil biodiesel.

TABLE 13 Direct Energy Consumption for Co-Product, Oil, and Fuel (Product) Transportation (Energy intensities include backhaul of the vehicle when appropriate) Energy Intensity (Btu/ton mi) Share (%) Distance (mi)

Transportation Mode Digestate solids transported to fields Heavy heavy-duty truck Medium heavy-duty truck Algal oil transported to fuel production Rail Fuel transported to terminal Barge Rail Heavy heavy-duty truck Fuel transported to station Heavy heavy-duty truck

1,028 2,200 370 403 370 1,028 1,028

100 0 100 8 29 63 100

50 50 600 520 800 50 30

40

4 WELL-TO-WHEELS RESULTS FOR ALGAL FUELS 4.1 BASELINE SCENARIO The portion of the pathway that includes all steps through delivery of fuel to the filling station is called the well-to-pump (WTP) portion. The remainder of the pathway (i.e., using the fuel in a vehicle) is called the pump-to-wheels (PTW) portion. The discussion below reports the energy consumption and emissions separately for the WTP and PTW portions. Results for the whole pathway, called the well-to-wheels (WTW) pathway, are also reported. Figure 3 illustrated the relationships between the WTP, PTW, and WTW portions of the pathway. 4.1.1 On-Site Balance of Co-Products, Electricity, and Heat Table 14 shows the on-site balance of electricity and heat. The amount of electricity demanded exceeds that produced from the LEA; however, the on-site thermal demand consumes only 69% of the heat recovered in the CHP. There is potential, then, to co-locate other thermal operations on site. Since all CHP power is consumed and none is exported as a co-product, the energy allocation method described in Section 2.4 assigns 100% of the emissions to the algal fuel. Indeed, only 75% of the electrical needs are met with on-site power, and the remaining balance must be imported, increasing the (upstream) fossil fuel consumption. Additional details on the on-site energy and CO2 balance are provided in Table 15. For that table, energy demand was computed from energy intensity by considering the yield of each step and by combining steps to produce 1 kg of algal lipids. CO2 demand was computed similarly. The table does not show off-site electricity demand for CO2 delivery to the site. The nutrient energy balance was presented in Figure 10. 4.1.2 Fossil Energy Use The WTW fossil energy consumption for algal biodiesel in this scenario is 45% of lowsulfur petroleum diesel, as shown in Figure 14. This occurs despite the fact that fossil energy consumption for algal fuel production (the WTP stage) is 2.6 times higher than for low-sulfur petroleum diesel production. The WTW savings occur because the energy in the algal fuel is considered to be biogenic, not fossil. Figure 15 shows the contribution of each process to total fossil energy use. The results are net values for which all recovered energy, including recovered nutrients, has been subtracted. In this scenario, 75% of N and 50% of P were recovered from the digester, while 25% of N and 50% of P were supplied with fresh urea and DAP. The single largest contribution, by stage, was from the growth and first dewatering stage, which mostly involved fertilizer manufacturing, mixing, and pumping. Mixing and pumping consume fossil energy when electric power is obtained from the grid.

41 TABLE 14 On-Site Balances of Co-Product, Electricity, and Heata CHP Electricity Total on-site generation On-site electricity requirement On-site use of generated electricity Discarded electricity Exported electricity Deficit imported CHP Heat Total on-site generation On-site heat requirement On-site use of generated heat Discarded heat Exported heat Deficit imported AD Residue Total produced On-site use Discarded residue Exported residue CO2 Total produced Discarded CO2 Recovered CO2 for algae growth use
a

Btu/kg-oil 14,620 19,450 14,620 0 0 4,830 Btu/kg-oil 18,911 12,996 12,996 5,916 0 0 kg/kg-oil 2.60 0 0 2.60 kg/kg-oil 3.47 0 3.47

Btu/Btu-BD 0.387 0.514 0.387 0.000 0.000 0.128 Btu/Btu-BD 0.500 0.344 0.344 0.156 0.000 0.000 kg/kg-BD 68.7 0.0 0.0 68.7 kg/mmBtu-BD 91.7 0.0 91.7

BD = biodiesel.

Fossil energy use in the conversion stage (transesterification) was from natural gas combustion and chemical use. Soil amendment transport consumes diesel fuel when digestate solids are transported to fields. The remaining portions in the pie chart correspond to fossil energy for electric power generation for electricity obtained from the grid. 4.1.3 Petroleum Energy Use Petroleum use is a subcategory of fossil energy use. Figure 16 compares petroleum use for petroleum diesel with algal biodiesel. When compared with low-sulfur petroleum diesel, algal biofuels have large petroleum savings. Transportation activities account for 44% of the petroleum consumption. The rest is consumed upstream (e.g., as part of the U.S. electricity mix).

42 TABLE 15 Energy Intensities, Direct Energy Demand, and CO2 Demand for Processes on Site (All energies are net.)
Direct Energy Intensity Process Growth and first dewatering Remaining dewatering Lipid extraction Anaerobic digester Off-site CO2, transfer into pond Recovered CO2, transfer into pond Biogas cleanup 0 0 4,695 Btu/kg lipid yield 1,856 Btu/dry-kg feed 0 0 0 Thermal Electrical 1,348 Btu/dry-kg algae 649 Btu/dry-kg yield 4,772 Btu/kg lipid yield 464 Btu/dry-kg feed 72.2 Btu/kg CO2 72.2 Btu/kg CO2 1,406 Btu/kg CH4 cleaned

Direct Energy Demand (Btu/kg lipid) Process Growth and first dewatering Remaining dewatering Lipid extraction Anaerobic digester Off-site CO2, transfer into pond Recovered CO2, transfer into pond Biogas cleanup Total direct demand on site Recovered on site Imported Process Inputs 2.24 kg CO2/kg algae 1.17 kg algae/ kg dewatered algae 4.68 kg dewatered algae/kg lipids 4.47 kg feed/kg lipids Thermal 0 0 4,695 8,301 0 0 0 12,996 18,911 0 Electrical 7,375 3,036 4,772 2,075 632 250 1,310 19,450 14,620 4,830 12.23 3.47 8.76 CO2 Demand (kg CO2/kg lipid) 12.23

43

Fossil Energy Use


1400000 1200000 1000000 800000 1,000,000 600000 400000 548,329 200000 215,388 0 Conventional LS Diesel Algae BD 0

PTW WTP

FIGURE 14 Fossil Energy Use for the Baseline Scenario

FIGURE 15 Contributions to Fossil Energy Use for the Baseline Scenario (Contributions are before a 55,500 Btu/mmBtu-BD fertilizer credit.)

BTU / mmBTU-BD

44

Petroleum Energy Use


1200000

PTW WTP

1000000

BTU / mmBTU-BD

800000

600000

1,000,000

400000

200000 0 0 79,681 Conventional LS Diesel 73,469 Algae BD

FIGURE 16 Petroleum Use for the Baseline Scenario

4.1.4 Greenhouse Gas Emissions WTW GHG emissions in the baseline scenario (Figure 17) are 55% of those from lowsulfur petroleum diesel. Figure 18 breaks down the WTP portion of the emissions shown in Figure 17. The WTP portion is negative only because the carbon in the biodiesel, captured from power plant flue gas, is treated as biogenic, which cancels out the substantial emissions related to the algae growth and processing. Figure 19 shows the effect of fugitive CH4 emissions and direct N2O emissions on the WTW GHG emissions. Fugitive CH4 and N2O emissions contribute 23% and 14% of the GHG emissions, respectively. The fugitive CH4 emissions are from anaerobic digestion, including subsequent handling of the digestate, and from biogas cleanup, as discussed in Section 3.6.1.5. These emissions might be controlled by choosing appropriate technologies and by rigorous maintenance of the facility. On the other hand, they could be substantially increased if monitoring and maintenance are insufficient.

45

GHG Emissions
120000 101,234 100000 80000 60000 40000 20000 0 -20000 -40000 Conventional LS Diesel Algae BD
-20000 100000 120000

PTW WTP WTW

80000

gCO2-e / mmBTU-BD

55,440

60000

40000

20000

-40000

FIGURE 17 GHG Emissions for the Baseline Scenario

WTP GHG Emissions


80000 60000 40000
80000

Biogenic Carbon Credit (Fuel)


60000

Displaced Fertilizer Credit


40000

gCO2-e/mmBTU-BD

WTP Emissions Before Credits


20000 0 -20000 -40000 -60000 -80000 -100000
20000

WTP, Net
0

-20000

-40000

-60000

-80000

-100000

Algae BD, WTP

FIGURE 18 Contributions to WTP GHG Emissions

46

Contributions to WTW GHGs...


60000 All Other Sources N2O from Soil Amendment Fugitive CH4 35,313

50000 gCO2-e/mmBTU-BD

40000

30000

20000 7,562 10000 12,566 0 Algae BD, WTW

FIGURE 19 Contributions to WTW GHGs from Fugitive CH4 Emissions and Direct N2O Emissions from Digestate Solids Used as a Fertilizer Replacement

The displaced fertilizer (soil amendment) credit is shown in detail in Figure 20. The fertilizer credit for avoided nitrogen manufacturing is reduced by N2O emissions from nitrogen in the digestate solids computed by using the IPCC methodology. Emissions from transporting the wet digestate contribute as well. There is also a substantial credit from sequestration of carbon in the digestate solids; however, if the carbon sequestration credit were reduced from 8% of the C in the digestate solids to 4.6%, the GHG benefit from fertilizer displacement would be lost. 4.1.5 Total Energy Use Figure 21 illustrates the total energy, including renewable energy, used to make algal biodiesel. Renewable energy includes the LHV of the algae biomass minus the heating value of co-produced glycerin. Energy in the biomass lost to heat in the CHP system is counted as renewable energy consumed in the process, whether it is recoverable but unused or whether it was thermodynamically unavailable. The recoverable but unused energy was 156,000 Btu per mmBtu-BD, 4% of the WTW total energy (6% of the WTP). The total energy use for algal biodiesel is three times higher than it is for petroleum lowsulfur diesel.

47

Contributions to Soil Amendment Credit


15000
15000.0

10000

10000.0

Fertilizer credit C Sequestration Transport Direct N2O Net

gCO2e/mmBTU-BD

5000

5000.0

0.0

-5000

-5000.0

-10000

-10000.0

-15000

-15000.0

FIGURE 20 Contributions to the Fertilizer Credit for Digestate Solids Applied to Agricultural Fields

Total Energy Use


4000000 3500000 3000000 BTU / mmBTU-BD 2500000 2000000 1500000 2,589,441 1000000 1,000,000 500000 0 219,183 Conventional LS Diesel Algae BD 1,000,000

PTW WTP

FIGURE 21 Total Energy Use for the Baseline Scenario

48

4.1.6 Sensitivity Analysis A sensitivity analysis was performed to determine key parameters affecting LCA results (see Figure 22). A sensitivity analysis is clearest when all parameters are varied over equal confidence intervals. In that circumstance, the change in the objective function (here, the GHG emissions) when each parameter is varied is equally likely, parameter to parameter, and the parameters may be ranked by change in the objective function to assess sensitivities. Statistical intervals are not available for the parameters in this study. The intervals were chosen to reflect intervals that were interesting in some regard, as explained later. The legend for each parameter includes three numbers in parentheses that indicate the parameter value used in the low, baseline, and high scenarios. The bars labeled low and high show the corresponding change in emissions. The mixing power variations correspond to mixing speeds of 20, 25, and 30 cm/s. The hexane extraction scenarios were defined in Table 6. The volatilization study considered different rates of NH3 loss from the pond. The CO2 efficiency study considered the ability of the culture to utilize the CO2 in the flue gas for algae growth before it escaped from the pond. Some studies considered alternative scenarios to explore a few choices defining the baseline scenario. The Wet Gasification scenario replaced the anaerobic digester with the catalytic hydrothermal gasification process and assumed 95% N recovery and either 0% (low) or 95% (high) P recovery. The gasification scenarios had lower emissions, partly because the N recovery was higher (compared to AD). The No Additional N2O from Digestate Solids

Lipid wt%, (12.5, 25, 50) Pumping to/from Pond, kWh/L, (2.4, 4.8, 9.6)x10-5 CH4 Yield, L/g-TS, (0.20, 0.30, 0.40) Productivity, g/m2/d, (12.5, 25, 50) CHP Electrical Efficiency (28%, 33%, 38%) Extraction Without CHP Heat Recovery Wet Gasification, 95%N, (0%P, 90%P) Mixing Power, kWh/ha/d, (25, 48, 83) Fraction of Total CH4 Emitted, (0.2%, 2%, 4%) Hexane Extraction Power. (See Table 6) No Additional N2O from Digestate Solids Fraction of N Recoved to Culture (66%, 76%, 86%) Fraction of C in Solids Sequestered, (0%, 8%, 16%) Internal Combustion Engine CHP instead of turbine Total Loss of N by Volatilization, (0%, 5%, 10%) CO2 Retention Efficiency in Pond, (25%, 15%, 5%) -30000 Low High Alternative Scenario -20000 -10000 0 10000 20000 30000

Emissions - 55,440, gCO2-e / mmBTU-BD

FIGURE 22 Sensitivity Analysis for Algae Baseline Scenario

49

scenario assumed equal N2O emissions from the digestate and from the displaced fertilizer, regardless of how much total N was in the digestate and regardless of the N bioavailability. This assumption contrasts with the IPCC methodology used in the baseline results. The ICE CHP scenario replaced the gas turbine with a biogas-fired ICE in the CHP system. The Extraction without CHP Heat Recovery scenario indicates the additional emissions that would occur if heat for solvent recovery during lipid extraction could not be obtained from the CHP system. This would be the case if, for example, the extraction operation was at a separate regional facility. 4.2 REDUCED EMISSION SCENARIOS 4.2.1 Low-A: Conservative Changes The baseline scenario was adjusted with two sets of changes. The first set of changes increases emissions in favor of more conservative process assumptions, as follows: Reduces the CHP electrical efficiency from 33% to 29% and Assumes the DAF dewatering produced 8% rather than 10% solids.

The CHP efficiency depends on the turbine size. This, in turn, depends on the size of the algae facility. The process-scale computation in Appendix A estimated a farm size of 4,712 ha on the basis of the assumption that 50% of the land adjacent to the power plant would be available. This corresponds to electric power generation of roughly 30 MW from the biomass residuals. The actual amount of land available, however, will likely be substantially less. In addition, as the lipid fraction increases to make the pathway viable, the energy in the residuals will decrease. These considerations push the analysis toward a smaller CHP size. In addition, the turbine may operate at a higher temperature and under a lower load factor than the standard operating conditions predicated for 33% efficiency. Reduced load could occur when the mixing speed is reduced to conserve power when possible. The 29% efficiency value reflects these possibilities. The lower DAF performance is more plausible, it but increases the mass that must be handled by the centrifuge, thereby increasing electricity use. Several changes offset these conservative choices: The lipid fraction was increased from the original 25 to 35 wt%. The anaerobic digester was replaced with the catalytic hydrothermal gasification process with 95% N recovery and 90% P recovery. Total CH4 fugitive emissions were reduced from the original 2% to 0.2%.

Discussions at recent conferences suggested that it may be easier to increase the lipid fraction than to increase productivity; hence, the choice was made to leave the productivity

50

unchanged. The catalytic hydrothermal gasification process might provide some benefits to an LCA. First, it might reduce the potential for fugitive CH4 emissions by eliminating the large process volumes and hold times for the digestate. The process also eliminates all biological N and recovers the resulting inorganic N as NH3 in sterile water. This eliminates N2O emissions from the digestate solids used as a fertilizer replacement and reduces the processs demand for N. The fugitive CH4 emissions were reduced to 0.2% because AD emission processes, including digestate storage, were avoided. 4.2.2 Low-B: Improved Extraction and CH4 Handling This scenario changed the baseline as follows: The lipid fraction was increased from the original 25 to 35 wt%. The productivity was increased from 25 to 30 g/m2/d. Total CH4 fugitive emissions were reduced from the original 2% to 0.2%. The hexane extraction energy demand was set halfway between the baseline scenario and the Low scenario in Table 6. Sequestration of carbon in the digestate solids was assumed to be zero.

Because the hexane extraction thermal demand is met with the CHP heat recovery, the savings from that operation came from reduced consumption of electric power. The assumption that sequestration of carbon in the digestate solids will be zero increases emissions, but it is included to be conservative. 4.2.3 Results for Reduced Emissions Scenarios Both scenarios achieve reductions of more than 50% in GHG emissions, as shown in Figure 23. Changing several parameters at once makes interpretation complex. For example, increasing the lipid fraction increases the lipid yield per mass of consumed nutrients. This partly dilutes the high nutrient recovery advantage of the gasification process viewed in terms of GHG or energy use; however, the higher nutrient efficiency would still offer economic and sustainability benefits. 4.3 COMPARISON WITH OTHER FUELS GHG results for biodiesel production in the Low-A reduced emissions scenario were compared with emissions for renewable diesel and renewable gasoline (Figure 24). Renewable diesel and renewable gasoline are produced catalytically (cracking and deoxygenation) from the algal lipid, while biodiesel is produced by transesterification. All three fuels have comparable

51

emissions; however, this occurs partly because renewable gasoline and renewable diesel fuels have large co-product credits from the other fractions produced with them. The three biodiesel scenarios are compared with other biofuels in Figure 25. The algal fuels consume more fossil fuel and have higher GHG emissions than other biofuels on the basis of the assumptions made in this study. It is important to note that some of the other biofuels use different co-product treatments. This factor is only one of many that affect the comparisons of the various fuels.

Reduced Emission Scenarios


100000 80000 gCO2-eq/mmBTU-BD 60000 40000 20000 0 Low-A -20000 -40000 -60000 Low-B
-20000 100000

PTW WTP WTW

80000

60000

39,628

36,246

40000

20000

-40000

-60000

FIGURE 23 GHG Emissions for Two Reduced Emission Scenarios (See text for definitions)

52

Renewable Diesel and Renewable Gasoline


100000
100000

GHG Emissions, gCO2-e/mmBTU

PTW
80000

80000 60000 40000 20000 0 Low-A, Biodiesel -20000 -40000 -60000 Low-A, RD Low-A, RG 39,628

WTP WTW

60000

45,908

39,786
40000

20000

-20000

-40000

-60000

FIGURE 24 GHG Emissions for Renewable Diesel and Renewable Gasoline for a Reduced Emission Scenario (Low-A is defined in the text)

53

GHG Emissions
150000 PTW 101,234 WTP WTW 55,440 50000 39,628 36,246
50000 100000 150000

gCO2-e / mmBTU-fuel

100000

22,494 5,909

21,801
0

0 -6,316 -50000 -6,112

-50000

-100000 Conventional LS Diesel Algae BD, baseline Low-A, Biodiesel Low-B, Biodiesel Soy BD EtOH, Woody EtOH, Biomass Herbaceous Biomass EtOH, Corn Stover EtOH, Forest Residue

-100000

Fossil Energy Use


1400000 1200000 PTW WTP

BTU / mmBTU-fuel

1000000 800000 600000 400000 200000 0 -200000 Conventional LS Diesel Algae BD, baseline Low-A, Biodiesel Low-B, Biodiesel Soy BD EtOH, Woody EtOH, Biomass Herbaceous Biomass EtOH, Corn Stover EtOH, Forest Residue

FIGURE 25 Comparison of GHG Emissions and Fossil Energy Use between Algal Biodiesel Scenarios and Other Biofuels Scenarios

54

5 DISCUSSION AND CONCLUSIONS Several process parameters affected the results only weakly. For example, pressure swing adsorption (PSA) was assumed for biogas cleanup. PSA is more electricity intensive than other options; nevertheless, fossil consumption from biogas cleanup was only 3% of the total. The study assumed that 85% of the CO2 in the flue gas would be retained in the algal biomass. This parameter is uncertain, and likely too high, but the sensitivity analysis showed it had a negligible effect on the LCA results. The analysis calculated energy recovery on the basis of the CH4 yield during anaerobic digestion and catalytic hydrothermal gasification rather than from biogas yield and biogas composition. The result of this parameterization is that the uncertainty in the biogas composition manifests itself as uncertainty in the CO2 recovery rate. Since the fossil energy consumption for CO2 transport and transfer from off site was only 5% of the total, the effect of uncertainty in the CO2 recovery rate on the analysis is small. That being said, the CH4 yield from LEA is highly uncertain, since few experiments have been done, and those were done at bench scale only. Evaporation accounted for 0.23 L out of a total of 4.23 L of water movement (not including mixing) per gram of harvested algae (see Figure 11). Thus evaporation, while a critical parameter for water consumption and sustainability, is only 5% of total pumped volume. Murphy and Allen (2011) estimated water delivery energy from U.S. Department of Agriculture irrigation data and found that it is 3.8 10-4 kWh/L to deliver groundwater for irrigation, and it is 9.8 104 kWh/L to pump water from the 180-m average depth of aquifers in the United States. The on-site pumping energy in our work was 4.8 10-5 kWh/L. Combining these numbers with the flows just described, each gram of harvested algae would require 731 J for pumping on site, 314 J to deliver groundwater, and 811 J to lift water from an aquifer, if needed. Since pumping on site accounted for 9% of the cumulative fossil energy consumption, adding water delivery to the site might then increase total fossil energy consumption by 4% to 14%. On the other hand, this may be an overestimation of energy demand if the water was delivered at sufficient pressure so that less on-site pumping was required. More detailed analysis is required in future work; however, two comments can be made now. First, the delivery of water will be site dependent and will complicate the analysis and the presentation of results. Second, remote pumping to deliver water will not be able to use electricity generated on site. The parameters with the largest consequences were related to energy and nutrient recovery and associated direct emissions. Algal biofuel production, as modeled in this study with the assumptions given, is energy intensive. New technologies could reduce the energy demand of the unit operations significantly, but a great deal of the energy demand derives from water movement to maintain the culture in suspension and to move it to and from the first stage of dewatering. Algal oil extraction and nutrient manufacturing are other large sources of energy demand.

55

The LCA conducted in this study showed that large amounts of on-site power need to be recovered from the biomass residuals if GHG emissions are to be kept low. High nutrient recovery rates from the residuals left after lipid extraction are also required. Therefore, on-site power production is a key to achieving low GHG emissions for algal biofuels. Even when the lipid content of algae is 35 wt%, roughly half the heating value of the whole algae biomass is left in the LEA, and this energy can be used to meet much of the electrical demand for algae system operation. A 4,700-ha algae farm, estimated under optimistic assumptions to be the largest farm that can receive flue gas from a single coal-fired electric power plant, would produce approximately 25 million gal of algal fuel per year and 30 MW of electricity, all of which would be used to (partially) satisfy on-site power needs. Biogas production by anaerobic digestion for the system defined by the baseline scenario would be roughly 10 times larger than the largest current biogas operations, yet there are significant concerns about CH4 losses during biogas production and handling. On one hand, fossil-based natural gas processing has demonstrated a much larger scale of gas handling, with CH4 emissions being below 0.2% of total CH4 flow. On the other hand, anaerobic digesters subjected to emission evaluations have demonstrated substantially higher fugitive emissions, by several percentage points. Some emissions were related to design, and some were related to maintenance. A 2% loss rate would release 1.6 million kg of CH4 per year per site. It is important to understand that regulatory agencies would be unlikely to allow such large emissions. These emissions are included to illustrate the potential risk of what appears to be the state of the art today, and to emphasize that economic analyses must account for costs to manage and monitor these emissions. There is a precedent for specific emission rates (i.e., leak percentages) to decrease as operational sizes scale up so that the total emissions remain capped or decrease. With regard to algal fuel production, technologies that are consistent with this need will need to be chosen. For techno-economic modeling of algal processes, technologies that consider environmental as well as economic concerns must be chosen. For example, additional equipment (e.g., off-gas recovery from digestate storage and off-gas handling from biogas upgrade operations) may be needed. One study substantiated estimates that 1.53.5% of the CH4 potential remains in the waste digestate (Liebetrau et al. 2010). If technology and procedures are not included to mitigate these emissions, substantial additional GHG emissions would be added to the current analysis. Future LCAs require better data on these emissions in terms of their magnitude and likelihood. Agricultural construction techniques offer an opportunity to reduce capital costs substantially (Lundquist et al. 2010); however, surveys of digesters indicate that there is a potential for leaks from the seals of membrane-topped digesters and that there is a potential for large leaks from missed or improper maintenance and perhaps from flaring (Flesch et al. 2011). Agricultural construction techniques will need careful evaluation with regard to these potential leaks in order to support future LCAs.

56

These observations lead to the conclusion that many key parameters driving algal biofuel LCA results center on biogas production: yields from digesters, yields from wet gasification, fugitive emissions, nutrient recovery rates, and electrical efficiency of the CHP generator. With regard to nutrient recovery, the fate of all nitrogen in the process must be understood better, especially organic nitrogen in LEA residuals and digestate. Although nitrogen transported to the fields to displace mineral fertilizers could result in N2O emissions in the fields, the literature is unclear on the emission rates for organic nitrogen in AD residues. If treated on a total-N basis with IPCC emission factors, digestate applied to fields causes more GHG emissions than it displaces if sequestration of the remaining carbon is less than approximately 5% of total carbon in the digestate. Future LCAs will require better data and more analysis with regard to this issue. With regard to algae growth and lipid production operations, the movement of water requires further attention. This study utilized wastewater engineering rules of thumb for good practice (Guyer 2011). As a result, pumping accounts for a substantial fraction of the electricity demand. The pumping activity simply transfers water to first-level dewatering and returns recovered water to the culture. It is possible that the rules of thumb in Harris et al. (1982) are not adequately optimized for algal sites, where different tradeoffs that will affect the engineering optimization probably exist. The baseline and low-emission scenarios did not include these possible optimizations for reducing the energy demand for water movement. They also did not include the energy demand to deliver water to the site and they did not include the energy demand for moving any water, sludge, or material after secondary dewatering (including sludge being moved for digestion or gasification). Wastewater treatment of potential process discharge was not considered, nor were the energy costs for inoculum production. Future work must consider these issues in order to determine whether these effects cancel, reduce, or increase the net energy demand reported on here. Although this study did not consider emissions from land use change (either direct or indirect), the effect should be small per unit of fuel because algal productivities are so high (approximately 2,500 gal/acre in this study) compared to those of other crops. These considerations indicate that a more detailed engineering analysis is required, which should include a conceptual site layout to help reveal the tradeoffs between moving large volumes of water-like but murky culture a long distance versus moving smaller volumes of more concentrated sludge. Another important outcome from engineering analysis should be the determination of the maximum farm size and the electric power load variability. These issues determine the size and de-rating factor of the CHP generator set and thereby affect the production of electrical power. Rough considerations in the Low-A scenario reduced power generation by almost 10% for these effects. Two lower-emission scenarios were considered in the study. New technologies could reduce energy consumption and GHGs further, although a large part of the emissions arose from the infrastructure connecting these technologies (i.e., from water movement, power generation, and CH4 loss). Nevertheless, it is encouraging to note that the changes required for achieving economic viability are often those that also reduce emissions. For example, increased lipid

57

fractions allow higher yields from a given capital expenditure; reductions in pumping energy decrease operating expenses; and reductions in CH4 emissions increase net power generation, again decreasing operating costs. This study focused on lipid-based fuels grown in ponds from flue gas. Future work will consider a broader spectrum of pathways, including heterotrophic growth from hydrolysates, growth in photobioreactors, and nonlipid conversion techniques like hydrothermal liquefaction. Further details will be added to the analysis, including information on infrastructure materials and consumed materials like coagulants and short-lived plastics. The key parameters for LCA of the algal lipid-based fuels identified in this study were the CH4 yield from anaerobic digestion, the CHP electrical efficiency, the on-site electrical energy demand, the rate for fugitive CH4 emissions (including handling of digestate), the emission factor for N2O from digestate solids, and, more generally, the fate of any nitrogen not recovered from the process and the rate of nitrogen recovery to avoid the manufacturing of NH3 upstream. Thermal demand on site is not yet a concern, if it can be integrated with the CHP system. However, there are questions about the size constraints affecting thermal process efficiencies when the process is located on site either to recover heat from CHP or to avoid shipping wet biomass.

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6 REFERENCES Air Liquide, 2008, Biogas Recovery System, http://www.airliquideadvancedtechnologies. com/file/otherelement/pj/plaquette-biogaz57164.pdf. Accessed Sept. 2009. Benemann, J.R., et al., 1982, Microalgae as a Source of Liquid Fuels, Final Technical Report, U.S. Department of Energy, Washington, D.C. Benemann, J.R., and W.J. Oswald, 1996, Systems and Economic Analysis of Microalgae Ponds for Conversion of CO2 to Biomass, Final Report, Pittsburgh Energy Technology Center. Borjesson, P., and M. Berglund, 2006, Environmental Systems Analysis of Biogas Systems, Part I: Fuel-Cycle Emissions, Biomass and Bioenergy 30(5):469485. Brown, S., et al., 2010, Calculator Tool for Determining Greenhouse Gas Emissions for Biosolids Processing and End Use, Environmental Science and Technology 44(24):95099515. Bruun, S., et al., 2006, Application of Processed Organic Municipal Solid Waste on Agricultural LandA Scenario Analysis, Environmental Modeling and Assessment 11(3):251265. Campbell, P.K., et al., 2009, Greenhouse Gas Sequestration by AlgaeEnergy and Greenhouse Gas Life-Cycle Studies. Chambers, A., et al., 2006, DIAL Measurement of Fugitive Emissions from Natural Gas Plants and the Comparison with Emission Factor Estimates, U.S. Environmental Protection Agency. Chisti, Y., 2007, Biodiesel from Microalgae, Biotechnology Advances 25(3):294306. Clarens, A.F., et al., 2010, Environmental Life-Cycle Comparison of Algae to Other Bioenergy Feedstocks, Environmental Science and Technology 44(5):18131819. Collet, P., et al., 2011, Life-Cycle Assessment of Microalgae Culture Coupled to Biogas Production, Bioresource Technology 102(1):207214. Cook, W., et al., 2005, Production of Liquid CH4 Truck Fuel from Landfill Gas, Final Report. Brookhaven National Laboratory, Upton, N.Y. Davis, R., 2010, Techno-Economic Analysis of Microalgae-Derived Biofuel Production, Report EPA-HQ-OAR-2005-0161-2642, U.S. Environmental Protection Agency. Davis, R., 2011, Techno-Economic Analysis of Autotrophic Microalgae for Fuel Production, Applied Energy 88(10):35243531. Eaton, A.D., and M.A.H. Franson, 2005, Standard Methods for the Examination of Water and Wastewater, American Public Health Association.

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Ehimen, E.A., et al., 2011, Anaerobic Digestion of Microalgae Residues Resulting from the Biodiesel Production Process, Applied Energy 88(10):34543463. Elliott, D.C., and L.J. Sealock, Jr., 1996, Chemical Processing in High-Pressure Aqueous Environments: Low-Temperature Catalytic Gasification, Chemical Engineering Research and Design 74a:563566. Elliott, D.C., et al., 1993, Chemical Processing in High-Pressure Aqueous Environments, 2: Development of Catalysts for Gasification, Industrial & Engineering Chemistry Research 32(8):15421548. EPA (U.S. Environmental Protection Agency), 1979, Process Design Manual for Sludge Treatment and Disposal. EPA, 2006, Emerging Technologies for Biosolids Management, Washington, D.C. EPA, 2008, Catalog of CHP Technologies. Flesch, T.K., et al., 2011, Fugitive CH4 Emissions from an Agricultural Biodigester, Biomass and Bioenergy, in press, corrected proof. Frank, E.D., et al., 2011, User Manual for Algae Life-Cycle Analysis with GREET: Version 0.0, Draft, Argonne National Laboratory, Argonne, Ill. Genifuel Corporation, 2011, Genifuel Corporation, http://www.genifuel.com/. Accessed July 2011. Grima, E.M., et al., 2007, Downstream Processing of Cell-Mass and Products, Blackwell Publishing Ltd. Guyer, J.P., 2011, Introduction to Sludge Handling, Treatment and Disposal, training course, Continuing Education and Development, Inc., Stony Point, N.Y. Harris, R.W., et al., 1982, Process Design and Cost Estimating Algorithms for the Computer Assisted Procedure for Design and Evaluation of Wastewater Treatment Systems (CAPDET), U.S. Environmental Protection Agency. Huo, H., et al., 2008, Life-Cycle Assessment of Energy Use and Greenhouse Gas Emissions of Soybean-Derived Biodiesel and Renewable Fuels, Environmental Science and Technology 43(3):750756. IPCC (Intergovernmental Panel on Climate Change), 2006, N2O Emissions from Managed Soils, and CO2 Emissions from Lime and Urea Application, in 2006 IPCC Guidelines for National Greenhouse Gas Inventories, Vol. 4, Chapter 11.

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IPCC, 2010, IPCC Expert Meeting on HWP, Wetlands and Soil N2O, http://www.ipccnggip.iges.or.jp/meeting/pdfiles/1010_GenevaMeetingReport_FINAL.pdf. Accessed August 14, 2011. Kadam, K.L., 2001, Microalgae Production from Power Plant Flue Gas: Environmental Implications on a Life-Cycle Basis, National Renewable Energy Laboratory. Lardon, L., et al., 2009, Life-Cycle Asessment of Biodiesel Production from Microalgae, Environmental Science and Technology 43(17):64756481. Liebetrau, J., et al., 2010, CH4 Emissions from Biogas-Producing Facilities within the Agricultural Sector, Engineering in Life Sciences 10(6):595599. Lundquist, T.J., et al., 2010, Realistic Technology and Engineering Assessment of Algae Biofuel Production, Energy Biosciences Institute, Berkeley, Calif. McPherson, M.J., 1993, Subsurface Ventilation Engineering, MVS Engineering. Mintz, M., et al., 2010, Well-to-Wheels Analysis of Landfill Gas-Based Pathways and Their Addition to the GREET Model, Argonne National Laboratory, Argonne, Ill. Mohn, F.H., 1980, Experiences and Strategies in the Recovery of Biomass from Mass Cultures of Microalgae, pp. 547571 in Algae Biomass, Elsevier/North-Holland Biomedical Press. Moller, J., et al., 2009, Anaerobic Digestion and Digestate Use: Accounting of Greenhouse Gases and Global Warming Contribution, Waste Management and Research 27(8):813824. Murphy, C.F., and D.T. Allen, 2011, Energy-Water Nexus for Mass Cultivation of Algae, Environmental Science & Technology 45(13):58615868. Palou-Rivera, I., et al., 2011, Update to Petroleum Refining and Upstream Emissions, Argonne National Laboratory, Argonne, Ill., in preparation. Petersson, A., and A. Wellinger, 2009, Biogas Upgrading TechnologiesDevelopments and Innovations, IEA Bioenergy. Pomerantz, M., and L. Turcote, 2004, Production of Pipeline Gas from Landfill Gas in Canada, presented at Wastecon 2004, Phoenix, Ariz., Sept. 2123. Ras, M., et al., 2011, Experimental Study on a Coupled Process of Production and Anaerobic Digestion of Chlorella vulgaris, Bioresource Technology 102(1):200206. Redfield, A.C., 1958, The Biological Control of Chemical Factors in the Environment, American Scientist 46:205211.

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Samson, R., and A. Leduy, 1982, Biogas Production from Anaerobic Digestion of Spirulina maxima Algal Biomass, Biotechnology and Bioengineering 24(8):19191924. Sheehan, J., 1998, A Look Back at the U.S. Department of Energys Aquatic Species Program: Biodiesel from Algae, National Renewable Energy Laboratory, Golden, Colo. Sialve, B., et al., 2009, Anaerobic Digestion of Microalgae as a Necessary Step to Make Microalgal Biodiesel Sustainable, Biotechnology Advances 27(4):409416. Sim, T. S., et al., 1988, Comparison of Centrifugation, Dissolved Air Flotation and Drum Filtration Techniques for Harvesting Sewage-Grown Algae, Biomass 16(1):5162. Sperling Hansen Associates, 2007, Highland Valley Center for Sustainable Waste Management Landfill Gas Utilization Options, SHAPRJ06014, http://a100.gov.bc.ca/appsdata/epic/html/ deploy/epic_project_doc_index_263.html. Accessed July 2009. Stephenson, A. L., et al., 2010, Life-Cycle Assessment of Potential Algal Biodiesel Production in the United Kingdom: A Comparison of Raceways and Air-Lift Tubular Bioreactors,. Energy and Fuels 24(7):40624077. Tchobanoglous, G., et al., 2003, Wastewater Engineering: Treatment and Reuse, McGraw-Hill, Boston, Mass. Uduman, N., et al., 2010, Dewatering of Microalgal Cultures: A Major Bottleneck to AlgaeBased Fuels, Journal of Renewable and Sustainable Energy 2(1):012701-1 through -15. Wang, M.Q., 1999a, The Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) Model Version 1.5, Argonne National Laboratory, Argonne, Ill., Aug. Wang, M.Q., 1999b, GREET 1.5Transportation Fuel-Cycle Model, Volume 1: Methodology, Development, Use, and Results, ANL/ESD-39, Vol. 1, Argonne National Laboratory, Argonne, Ill., Aug. Wang, M.Q., 2001, Development and Use of GREET 1.6 Fuel-Cycle Model for Transportation Fuels and Vehicle Technologies, Argonne National Laboratory, Argonne, Ill. Wang, M.Q., et al., 2011a, Energy and Greenhouse Gas Emission Effects of Corn and Cellulosic Ethanol with Technology Improvements and Land Use Changes, Biomass and Bioenergy 35(5):18851896. Wang, M., et al., 2011b, Methods of Dealing with Co-Products of Biofuels in Life-Cycle Analysis and Consequent Results within the U.S. Context, Energy Policy, in press, corrected proof.

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Weissman, J.C., and R.P. Goebel, 1987, Design and Analysis of Microalgal Open Pond Systems for the Purpose of Producing Fuels: A Subcontract Report, SERI/STR-231-2840, Solar Energy Research Institute, Golden, Colo., prepared for U.S. Department of Energy. Weissman, J.C., et al., 1988, Photobioreactor Design: Mixing, Carbon Utilization, and Oxygen Accumulation, Biotechnology and Bioengineering 31(4):336344.

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APPENDIX A: PROCESS SCALE AND CO2 TRANSPORT Life-cycle analyses (LCAs) are affected by the supply chain, manufacturing, and distribution network architectures that transport feedstocks, intermediates, and products. Unitprocess sizes affect LCAs by causing changes in energy efficiency. Constraints on production facility size can affect the network architecture: the need to aggregate resources to reach sufficient production scale can force the transport of resources. Conversely, if transporting an unrefined resource is too expensive, co-processes may be split apart. Separation makes heat recycling impossible and may increase the overall economic and environmental costs. The work reported in this section studied constraints on production scale from transportation of carbon dioxide (CO2) in flue gas to the algae farm. Several studies indicate that low-pressure transport of CO2 is the most plausible transportation option available as it does not currently exceed the energy or cost constraints particular to biofuels. Regan and Gartside (1983) studied the transport of 15% CO2 flue gas by volume (15 vol%), evaluating both compressed and low-pressure transport. The authors rejected the compressed gas case as too energy intensive because they had estimated that it could consume two-thirds of the energy of the produced algae. For the low-pressure case, the authors used a 6-ft diameter pipeline that was 50-km long and operated at a velocity of 50 ft/s. The operating point was 5.8 psi pressure drop (40 kPa) and discharge was at atmospheric pressure. Benemann et al. (1982) and Benemann and Oswald (1996) evaluated low-pressure CO2 supply for a 100-ha module of raceway ponds with paddle wheel mixing and concluded that, even with large-diameter (2-m) pipelines, transport was limited to 2.5 to 5 km. Consistent with Benemann and Oswalds (1996) analysis, Zhang et al. (2006) commented that gas-phase transport is not used for pipelines of any significant capacity or length because of the large pressure drops incurred and the disadvantages of a large-diameter pipeline; hence, supercritical CO2 pipelines are used for enhanced oil recovery, which does not suffer from the cost and energy constraints as acutely as does biofuel production (Zhang et al. 2006). One way to increase the total amount of transported CO2 is to concentrate it from the flue gas source prior to transport. Kadam (1997) compared the economics of monoethanolamine (MEA) extraction of CO2, compression to 1,500 pounds per square inch (psi), and transportation by pipeline over 100 km versus only the compressing, dehydrating, and piping of flue gas (14 vol% CO2). The compressed flue gas scenario was 40% more expensive than was MEA extraction because of the larger gas volume and compression costs; however, in a 2001 LCA study of a coal power plant that was co-fired with algae grown from its CO2 emissions, Kadam (2001) showed that steam requirements for MEA regeneration canceled out much of the greenhouse gas and energy benefits of using the algae fuel. Ultimately, the compressed gas transfer scenario was rejected as unlikely, and thus only uncompressed, short-distance transfer of flue gas was considered, a result that was similar to Benemann et al.s (1982) and Benemann and Oswalds (1996) results. Considering this prior work, the flue gas delivery model will assume low-pressure pipeline transport. The economic constraints found by Benemann and Oswald (1996) are

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reflected by requiring the algae farms to be proximal to the flue gas source so that increments in pipeline length are accompanied by increments in produced biomass. A.1 METHODS Low-pressure pipelines were evaluated at constant diameter with regard to power consumed and required velocity and pressure as compared to commercial blowers. The constantdiameter constraint is a proxy for constraints from pipeline cost and requirements for routing and permitting. Algae production costs arising from pipeline costs are reduced when algae facilities are located as close as possible to the CO2 source. Therefore, the analysis first relates pipeline length to total farm area and then determines flow-velocity limits for plausible blowers from which maximum transport distance is determined and, consequently, the maximum algae farm size that is possible when fed by pipelined CO2. The result is used to compute energy for CO2 transport for the LCA. A.2 LOW-PRESSURE CO2 PIPELINE MODEL A pipeline model was constructed in four steps. First, pipeline length was related to farm area served. The farm area determines CO2 demand, which, in turn, determines transport velocity for a pipeline with a given diameter. Second, maximum flow velocity was estimated from similar applications. Third, maximum fan pressure and velocity were estimated from fan data. Finally, power consumption was computed from these data. Each of these is explained below. A.2.1 Pressure Drop In the model, pressure losses (P) from friction were estimated with the Fanning equation: P = 4f(v2/2)(L/D) where: f is a friction factor (4 10-3, corresponding to a surface roughness of 0.9 mm, typical of concrete, and a Reynolds number of from 105 to 106), is the gas density (1.3 kg/m3 and CO2 mass fraction of 0.211), v is the gas velocity, L is the pipeline effective length, and D is the pipeline diameter. The flue gas is not dehydrated prior to transport. Transport power for the compressible gas was computed via Power = Pout Q X/ (FM), where F and M are the fan and motor efficiencies, Pout is the outlet pressure, X = (Pin/Pout)0.263 1, and the upstream pressure Pin = Pout + P. Calculations assumed that FM = 0.5 to account roughly for the following: age,

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detuning of the blower from optimum to match application needs, and absence of bends or other losses in the current computations. In the model, central blowers at the CO2 source generate sufficient pressure to overcome pipeline pressure drops and deliver the flue gas at atmospheric pressure (Pout = 101,325 Pa). A second compressor near the culture achieved pressure needed for transfer into the culture, assumed to be 1.5 m of water equivalent (2.1 psi gauge [psig]) (Benemann and Oswald 1996). The total power was the sum of transport plus transfer. A.2.2 Pipeline Geometry The pinwheel geometry in Figure A-1 related pipeline length to algae farm area. The pinwheel has four pipeline networks, one per pinwheel quadrant, with ponds arranged along the pipelines filling the available area. Each quadrant is driven by a fan assembly located at the common central flue gas dc L source. Each quadrant has a main trunk line of length L plus several branches arranged such that any point in the network can be reached with one bend at most and such that each branch has length L from the terminus back to the CO2 source. The distance between branches will be determined by the pond FIGURE A-1 Pipeline Geometry (A central source is size. Let dc be the stay-clear distance surrounded by four trunks, each feeding one quadrant. Each trunk feeds a sequence of branches around the power plant, represented by such that the total distance from source to terminus of the central box in the figure. Then, the any branch is L and has, at most, one bend.) total area of the pinwheel available for a given maximum pipeline length, L, is A = 2 L (L2 2 dc2), where L is the land-use efficiency outside of the stay-clear zone. L accounts for land availability and suitability within the area covered by the network and may be small. A.2.3 Pipeline Velocity and Fan Pressure Mine ventilation was used as prior-art to establish maximum pipeline velocity since mine ventilation moves large, uncompressed gas volumes over substantial distances. The Hard Rock Miners Handbook and the associated rules of thumb list several case histories and good practices (Vergne 2003). Typical design velocity for open concrete-lined shafts is 16 m/s. The not to exceed velocity is 20 m/s. Mine shafts may have a higher level of surface roughness as compared to fabricated pipeline; however, McPherson (1993) lists 0.005 as the coefficient of friction, f, for mine shafts, which is similar to the 0.004 value used here. On one hand, a concrete pipeline will be smoother than a mine drift, suggesting that higher velocities might be possible. On the other hand, mine drifts are several times larger in diameter than are an economic, routable

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pipelines, and the friction factor depends upon the roughness divided by diameter. The dependence is weak, for example, in a Moody diagram, there is a 60% change-in-friction factor for a ten-fold change in roughness-to-diameter ratio (Reynolds number = 4 105, r/D = 10-4 to 10-3). Computations that follow assume a 15-m/s limit for the flue-gas velocity in the pipeline. Figure A-2 shows the pressure and velocity ratings of several commercial fans. The fan nearest to the 15-m/s target is rated 16 m/s, 5,838 Pa (23 in. water gauge [inWG]), 2.98 105 W, with a flow of 30.7 m3/s (64,000 cubic feet per minute or CFM) and a fan diameter of 1.52 m (60 in.).

FIGURE A-2 Pressure with Friction Factor of 4 10-3 and Density of 1.3 kg/m3 in a 2-m-Diameter Pipeline (Sample fans are plotted at rated static pressure, and outlet velocity is corrected to 500 ft altitude and 200F. Data were taken from New York Blower [2010], Northern Blower [2010], and TLT Co-Vent, Inc. [2010] literature.)

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A.2.4 Pipeline Diameter and Maximum Flow Two meters is assumed to be the largest feasible diameter for a pipeline, similar to those of Benemann and Oswald (1996) and Regan and Gartside (1983). The baseline pipeline model (15 m/s velocity, 2-m diameter) has a flow of 47 m3/s per pinwheel leaf and a whole-pinwheel flow of 188 m3/s. For comparison, a 450-MW pulverized coal power plant produces 450 m3/s. At the extreme case of a 20-m/s velocity and a 3-m diameter, the pipeline flow is 141 m3/s, and the whole-pinwheel flow is 564 m3/s. A.3 MAXIMUM PIPELINE LENGTH The pipeline model was used to compute the served farm area as a function of pipeline length from which the required flow was obtained for a productivity of 40 g/m2/d and 2 g of CO2 per g algae. The velocities for these flows in 2-m and 3-m pipelines were used to compute pressure losses, as shown in Figure A-3. Algae biomass typically has a heating value of 18,000 J/dry-g. Thus, the algae productivity times the farm area can be expressed as biomass power (biomass heat value produced per unit of time), allowing Figure A-3 to also show the total power required for CO2 transport and transfer as a percentage of the this algal biomass power. The maximum length of the 2-m pipeline for 5,800-Pa fan pressure is 7 km and requires v = 13 m/s, values that are consistent with the commercial fan survey and suggesting that a detailed engineering treatment might match a blower to this operating point.

FIGURE A-3 Velocity, Pressure, and Delivery Power for Flue-Gas Transport to Site

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It is likely that some of the land within the served area will either be unsuitable or already in use. Without a full site analysis at each power plant, one can only hypothesize concerning a number. Many power plants are in areas that have already been developed, urban areas, or next to woodlands and farmland that would not qualify as nonproductive land. The present analysis will proceed with an arbitrarily chosen value of L = 0.5 for land-use efficiency, giving 4,712 ha for the maximum algae area per CO2 source and 1.8 MW of power for transport and 3.3 MW for transfer. The central stay-clear distance for the power plant, dc, was 1 km. A value of 0.5 is most likely to be high for many power plants. An earlier study by Benemann and Oswald (1996) concluded that transport was limited to 2.5 to 5.0 km, with 2.5 km more likely; however, if a distance of 5 km were possible, then a maximum of four 100-ha modules on each side of the pipeline could be deployed, giving a maximum of 800 ha per CO2 source. This configuration could be replicated to serve four quadrants, an approach that is similar to what is used in this study and achieves 3,200 ha. The primary difference between the Benemann and Oswald (1996) result and that presented here is that the Benemann result more carefully considers the economic cost of each additional length of pipeline, which adds to the capital costs and thus to the cost of the product. A.4 CO2 TRANSPORT AND TRANSFER POWER The transport pressure was computed by using a pressure drop of 5.8 kPa as described in the previous section, a ratio of specific heats k = cp/cv = 1.395, and delivery at atmospheric pressure: Transport power = Pa k/(k 1) [(Pa + P) / Pa ](k-1)/k The quantity = 0.5 is the combined compressor and motor efficiency, which is somewhat reduced to reflect the lack of real treatment of losses in bends. For the flue-gas properties stated above, this gives 1.16 10-5 kWh/g-CO2. Power to transfer the CO2 into the culture was computed as above but with a pressure drop of 1.5-m water equivalent (corresponding to transfer sump depth) and combined efficiency of 0.67. This approach produces 2.12 10-5 kWh/g-CO2 to transfer the CO2 into the pond (before consideration of CO2 uptake efficiency). Thus, transfer power dominates transport power in this model. A.5 REFERENCES FOR APPENDIX A Benemann, J.R., et al., 1982, Microalgae as a Source of Liquid Fuels, Final Technical Report, U.S. Department of Energy, Washington, D.C. Benemann, J.R., and W.J. Oswald, 1996, Systems and Economic Analysis of Microalgae Ponds for Conversion of CO2 to Biomass, Final Report, Pittsburgh Energy Technology Center.

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Kadam, K.L., 1997, Power Plant Flue Gas as a Source of CO2 for Microalgae Cultivation: Economic Impact of Different Process Options, Energy Conversion and Management 38 (Supplement 1):S505S510. Kadam, K.L., 2001, Microalgae Production from Power Plant Flue Gas: Environmental Implications on a Life-Cycle Basis, National Renewable Energy Laboratory. McPherson, M.J., 1993, Subsurface Ventilation Engineering, MVS Engineering. Northern Blower, Inc., 2010, Custom Fans for Industrial Applications, home page, http://www.northernblower.com/. New York Blower Company, 2010, The Leading Manufacturer of Industrial Fans and Blowers, home page, http://www.nyb.com/. Pomerantz, M., and L. Turcote, 2004, Production of Pipeline Gas from Landfill Gas in Canada, presented at Wastecon 2004, Phoenix, Ariz., Sept. 2123. Regan, D.L., and G. Gartside, 1983, Liquid Fuels from Micro-Algae in Australia, CSIRO, South Melbourne, Australia. TLT Co-Vent, Inc., 2010, World Leader in Heavy-Duty Centrifugal Fans, home page, http://www.tltcovent.com/en/. Vergne, D., 2003, Hard Rock Miners Handbook, McIntosh Engineering. Zhang, Z.X., et al., 2006, Optimization of Pipeline Transport for CO2 Sequestration, Energy Conversion and Management 47(6):702715.

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APPENDIX B: NUTRIENT LIFE-CYCLE ANALYSIS FOR ALGAE GROWTH B.1 NUTRIENTS FOR ALGAE GROWTH Table B-1 summarizes several formulations for algae growth media reported in the literature. While these media come more from the research domain than the mass culture domain, the list contains the major chemical constituents that might be included in an algal life-cycle analysis (LCA).
TABLE B-1 Formulations for Algae Growth Media from the Literature (grams per liter)
Substance NH4Cl NaNO3 KNO3 Ca(NO3)24H2O (NH2)2CO (NH4)2HPO4 K2HPO43H2O K2HPO4 KH2PO4 K2SO4 BG 11a Modified Allensa Bolds Basala Sorokin/ Kraussa Zarroucka Ben-Amotz & Avrona Chu 13b

1.5

1.5 0.02

0.25 1.25

2.5 0.505 0.2

0.04

0.039

0.075 0.175 1.25

0.5

0.014

0.04

Substance

Kratz & Myers, Cc,d

Modified Hughesc

Kesslerc

Sueokac

GPMd

NRELe

NH4Cl 0.05 NaNO3 1.5 KNO3 1 0.81 0.025 Ca(NO3)24H2O (NH2)2CO (NH4)2HPO4 K2HPO43H2O K2HPO4 1 0.039 0.72 KH2PO4 0.36 K2SO4 a Source: Richmond (2007). b Source: Dayanada et al. (2007). c Source: Starr (1971). d Source: Kratz and Myers (1955). e Source: Barclay et al. (1986). NREL = National Renewable Energy Laboratory.

2 0.049 0.028 0.2

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B.2 NUTRIENT LIFE CYCLE The life-cycle energy demand for each of the nutrient substances identified above was determined as follows: 1. The common industrial processes for manufacturing these compounds were determined. 2. The compounds in the media were related to feedstocks and intermediates that already had a full LCA in the Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model or to other feedstock and intermediate components comparable to those in GREET.1 3. Energy inputs were calculated from the GREET LCA of feedstocks and intermediates by apportioning them to the media constituents (described below). 4. Energy inventories for each media reagent were then computed. B.2.1 Ammonia (NH3) Ammonia is the main synthetic source of nitrogen. It is manufactured by using the HaberBosch process (a high-energy process) from syngas. Its LCA is already in GREET.

B.2.2 Ammonium Chloride (NH4Cl) Ammonium chloride is manufactured as a by-product of the soda and synthetic ammonia industries (Weston et al. 2003). The main reaction is: NH3 + CO2 + NaCl + H2O NaHCO3 + NH4Cl, where NaHCO3 is the main valuable product and NH4Cl is the less valuable by-product. The ammonia LCA is already in GREET, and the NaCl LCA is computed as a mining product.

This point is especially important for mining products, as explained in the assumptions section.

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B.2.3 Sodium Chloride (NaCl) Sodium chloride is produced from mining operations. B.2.4 Sodium Nitrate (NaNO3) Also known as Chilean saltpeter, it is produced from mining (85%) and as a by-product of nitric acid manufacturing. The LCA is based on the mining pathway.

B.2.5 Nitric Acid (HNO3) This is obtained by the catalytic oxidation of ammonia with air: 3 NH3 to 2 HNO3 and 1 NO (Clarke and Mazzafro 2005). (Whether the extra NO molecule and its reduction of the nitric acid from ammonia yield are taken into account will significantly modify the energy inputs of nitric acid and its derived products. See the difference between Tables B-6 and B-7 (which appear later). Its LCA is already in GREET. B.2.6 Potassium Nitrate (KNO3) Potassium nitrate is produced by a reaction between potassium chloride and nitric acid (Freilich and Petersen 2005). The potassium chloride (potash) comes from mining, and the nitric acid from ammonia oxidation: KCl + HNO3 KNO3 + HCl, or, in an aqueous environment, the reaction is as follows: 4 KCl + 4 HNO3 + O2 4 KNO3 + 2 H2O + 2 Cl2, which produces Cl2 as a valuable by-product. The LCA for HNO3 is already in GREET, and the LCA for KCl is computed as a mining product.

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B.2.7 Potassium Chloride (KCl) This mining product is often mined together with K2O (Freilich and Petersen 2005). B.2.8 Calcium Nitrate (Ca(NO3)2, Ca(NO3)24 H2O) Calcium nitrate is manufactured by the neutralization of nitric acid with limestone (CaCO3) (Taylor 2004) and is obtained from mining operations: 2 HNO3 + CaCO3 Ca(NO3)2 + CO2 + H2O. The LCAs for both HNO3 and CaCO3 are already present in GREET.

The LCAs for the anhydrous (Ca(NO3)2) and hydrated (Ca(NO3)24 H2O) forms differ only because of the mass allocation procedure employed by the LCA, which is based upon molecular weight. B.2.9 Calcium Carbonate (CaCO3) Limestone is obtained from mining operations. Its LCA is already in GREET. B.2.10 Urea (NH2)2CO Urea is manufactured from ammonia. Its LCA is already in GREET.

B.2.11 Potassium Phosphates (K2HPO4, K2HPO43 H2O, KH2PO4) Orthophosphates, from monopotassium phosphate (KH2PO3) to tripotassium phosphate (K3PO4), are manufactured from phosphoric acid neutralized with KOH (Freilich and Petersen 2005): H3PO4 + 2 KOH K2HPO4 + 2 H2O,

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H3PO4 + KOH KH2PO4 + H2O. The LCA for H3PO4 is already included in GREET, and that for KOH is specified below.

B.2.12 Potassium Hydroxide (KOH) Potassium hydroxide is produced by the electrolysis of KCl and is then concentrated by evaporation and cooling (Freilich and Petersen 2005). It is a high-energy-use process: 2 KCl + 2 H2O 2 KOH + H2 + Cl2. The KCl comes from mining operations. B.2.13 Phosphoric Acid (H3PO4) Phosphoric acid is produced by the wet process manufacturing for fertilizer production: digestion of phosphate rock (calcium phosphate) with sulfuric acid (Gard 2005). Phosphoric acid is separated from the resultant calcium sulfate slurry by filtration. Its LCA is already in GREET. B.2.14 Di-ammonium Phosphate, DAP ((NH4)2HPO4) DAP is produced by a reaction between ammonia and phosphoric acid (Gard 2005): 2 NH3 + H3PO4 (NH4)2HPO4. Both reactants LCAs are already included in GREET.

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B.2.15 Potassium Sulfate (K2SO4) Potassium sulfate is produced by using several processes, depending on which sulfate salts are available, by reacting them with potassium chloride and also from mining (Freilich and Petersen 2005). Langbeinite (K2SO42 MgSO4) is the top mined sulfate salt in the United States and the chosen pathway for this LCA: K2SO42 MgSO4 + 4 KCL 3 K2SO4 + MgCl2. Both the Langbeinite and KCl LCAs are calculated as those of mining products.

B.2.16 Langbeinite (K2SO42 MgSO4) Langbeinite is produced from mining operations and is the dominant magnesium sulfate salt mined in the United States. B.2.17 Superphosphate (Ca(H2PO4)2 + 2 CaSO4) Superphosphate is produced by the action of concentrated sulfuric acid on powdered phosphate rock: 3 Ca3(PO4)2 + 6 H2SO4 6 CaSO4 + 3 Ca(H2PO4)2. Both of the LCAs for phosphate rock and sulfuric acid are already present in GREET.

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B.2.18 Sulfuric Acid (H2SO4) Sulfuric acid is manufactured by using the contact process and using elemental sulfur, spent acid, or H2S as the raw material. It gets oxidized to SO2; then, through a catalytic oxidation step, becomes SO3; and finally, through absorption with spent acid, reaches 9899% purity (Muller 2006). It is a very exothermic process at high temperature but is often coupled with steam generation, electricity production, etc. Its LCA is already in GREET. B.2.19 Triple Superphosphate (Ca(H2PO4)2, Ca(H2PO4)2H2O) Triple superphosphate is produced by the action of concentrated phosphoric acid on ground phosphate rock. Ca3(PO4)2 + 4 H3PO4 3 Ca(H2PO4)2. Both of the LCAs for phosphate rock and phosphoric acid are already present in GREET.

B.2.20 Assumptions for Energy Inputs Before calculating the energy inputs for each of the nutrient components, we must specify some assumptions regarding the feedstock and intermediate components: The split of reactants energy inputs between the reaction products is an important issue for several components. We can distinguish several cases: When there is a single reaction product, it receives the total energy inputs of the reactants. When some of the products escape from the process or are clear subproducts (gases or water in solid reactions, etc.), the main product receives the total energy inputs of the reactants. Other cases (such as the NH4Cl manufacturing reaction above) are more complicated. As a first approximation, we have assigned the energy inputs of the reactants by mass allocation on the basis of the molecular weight of the products.

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In terms of weighting the mining versus manufacturing energy inputs from the existing energy inputs in GREET for agricultural components, we understand that, in most cases, mining energy requirements dominate the result, except in cases where a particularly energy-intensive manufacturing process is needed, such as high pressure (e.g., ammonia, urea) or electrolysis (KOH below). GREET already contains two feedstock types of materials from mining: KO2 and CaCO3. GREET assumes the energy inputs for both of them to be identical, with the values in the CaCO3 column in Table B-3 (appears later). There are four more mining components needed as inputs to algae nutrient manufacturing. We assume the energy required for each of these to be equal to the values already in GREET for mining of K2O and CaCO3: KCl is often mined together with K2O. This practice further supports the assumption of using the same energy inputs for both of these components. NaCl and KCl are very similar components, both in mining and usage. Therefore, the energy inputs for these components should be similar.

NaNO3 is mined almost exclusively in Chile. Therefore, one can argue for using higher values for its energy inputs to account for transportation uses. KOH (later in Table B-2) is the only manufactured component (intermediate or nutrient) that is not already in GREET and that requires a substantial energy input in its manufacturing. KOH is produced by the electrolysis of KCl, a notoriously high-energy process. Therefore, the energy inputs for KOH (later in Table B-4) are calculated as those resulting from KCl mining plus the energy used in the electrolytic process. The value of 8.5 million Btu/ton of product for the electrolytic manufacturing of KOH has been extracted from the report, Energy Use and Energy Intensity of the U.S. Chemical Industry (Worrell et al. 2000).

B.2.21 Nutrients from Feedstock and Intermediates Table B-2 summarizes the contribution of all of the feedstock and intermediate materials (either from GREET or mining) to each of the considered algae growth nutrients on a mass basis.

79 TABLE B-2 Inputs per Mass Unit of Nutrient Product (Data are from GREET and manufacturing reactions.)
Product Input NH3 NH4Cl NaNO3 KNO3 Ca(NO3)2 Ca(NO3)24H2O (NH2)2CO K2HPO4 K2HPO43H2O KH2PO4 (NH4)2HPO4 K2SO4 Ca(H2PO4)2 + 2 CaSO4 Ca(H2PO4)2 Ca(H2PO4)2H2O NH3 (GREET) 1.000 0.318 0.623 0.768 0.534 1.000 0.815 0.622 1.043 1.075 0.387 0.809 0.751 0.613 0.442 0.410 HNO3 (GREET) (NH2)2CO (GREET) H3PO4 (GREET) CaCO3 (GREET) H2SO4 (GREET) Ca3(PO4)2 (GREET)

0.610 0.424

0.258

Product Input NH3 NH4Cl NaNO3 KNO3 Ca(NO3)2 Ca(NO3)24H2O (NH2)2CO K2HPO4 K2HPO43H2O KH2PO4 (NH4)2HPO4 K2SO4 Ca(H2PO4)2 + 2 CaSO4 Ca(H2PO4)2 Ca(H2PO4)2H2O NaCl (Mining) KCl (Mining) KOH (From KCl) NaNO3 (Mining) K2SO42MgSO4 (Mining)

1.093 1.000 0.737

0.653 0.856 0.548 0.570 0.794

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B.3 ENERGY INPUTS OF NUTRIENTS The energy consumption for nutrient manufacture is computed in three steps. First, the direct consumption of process fuels and chemical inputs for the chemical intermediates used in nutrient manufacture is tabulated (Tables B-3 and B-4). Next, the process fuels required to manufacture each chemical feedstock used in Tables B-3 and B-4 are identified, and the amounts consumed are computed from the feedstock masses. This upstream fuel use is added to the direct fuel consumption (Table B-5). Table B-5 lists the total energy demand for chemical intermediates used in nutrient manufacturing. Finally, the intermediates are combined to obtain the total energy demand, categorized by process fuel, for nutrient manufacturing (Table B-6). Table B-7 presents a variation of the data in Table B-6 without accounting for the loss of the nitrogen atom in the manufacturing of nitric acid, as explained previously.
TABLE B-3 GREET Energy Inputs for Agriculture (mmBtu/ton product)a
Agricultural Product Energy Input Total energy input Natural gas Electricity Residual oil Diesel fuel Coal Ammonia (ton) Nitric acid (ton) Sulfuric acid (ton) Phosphoric rock (ton)
a

NH3 27.490 26.370 1.120

HNO3 0.532 0.526 0.006

(NH2)2CO 2.269 2.140 0.129

H3PO4 4.637 4.173 0.464

CaCO3 3.900 1.053 1.638 1.209

H2SO4 0.108 0.045 0.064

Ca3(PO4)2 0.245 0.000 0.245

0.405

0.567 2.674 3.525

Energies expressed as mmBtu/ton correspond to millions of Btu per short ton (2,000 lb).

TABLE B-4 Additional Energy Inputs for Remaining Feedstock and Intermediate Components (mmBtu/ton product)
Intermediate Component NaCl Total energy input Natural gas Electricity Residual oil Diesel fuel Coal Ammonia (ton) Nitric acid (ton) Sulfuric acid (ton) Phosphoric rock (ton) 3.900 1.053 1.638 1.209 KCl 3.900 1.053 1.638 1.209 KOH 12.400 1.053 10.138 1.209 NaNO3 3.900 1.053 1.638 1.209 K2SO42MgSO4 3.900 1.053 1.638 1.209

81 TABLE B-5 Overall Energy Inputs, Including Feedstock (mmBtu/ton product)


Chemical Intermediate Energy Input Total energy input Natural gas Electricity Residual oil Diesel fuel Coal NH3 27.490 26.370 1.120 HNO3 11.665 11.206 0.460 (NH2)2CO 17.856 17.092 0.764 H3PO4 5.789 4.292 1.497 CaCO3 3.900 1.053 1.638 1.209 H2SO4 0.108 0.045 0.064 Ca3(PO4)2 0.245 0.000 0.245

Chemical Intermediate Energy Input Total energy input Natural gas Electricity Residual oil Diesel fuel Coal NaCl 3.900 1.053 1.638 1.209 KCl 3.900 1.053 1.638 1.209 KOH 12.400 1.053 10.138 1.209 NaNO3 3.900 1.053 1.638 1.209 K2SO42MgSO4 3.900 1.053 1.638 1.209

TABLE B-6 Energy Inputs for All Considered Algae Nutrients (mmBtu/ton product)a
Energy Input Nutrient NH3 NH4Cl NaNO3 KNO3 Ca(NO3)2 Ca(NO3)24H2O (NH2)2CO K2HPO4 K2HPO43H2O KH2PO4 (NH4)2HPO4 K2SO4 Ca(H2PO4)2 + 2 CaSO4 Ca(H2PO4)2 Ca(H2PO4)2H2O
a

Total Energy Input 27.490 13.014 3.900 10.146 11.338 7.878 17.856 12.818 14.214 12.832 13.312 5.321 0.192 4.790 4.448

Natural Gas 26.370 9.546 1.053 7.760 9.249 6.426 17.092 4.185 3.570 5.054 11.414 1.437 0.017 3.471 3.223

Electricity 1.120 2.146 1.638 1.494 1.352 0.940 0.764 7.843 9.609 7.116 1.898 2.235 0.175 1.319 1.225

Residual Oil

Diesel Fuel 0.000 1.321 1.209 0.891 0.737 0.512 0.000 0.790 1.035 0.662 0.000 1.649 0.000 0.000 0.000

Coal

Energies expressed as mmBtu/ton correspond to millions of Btu per short ton (2,000 lb).

82 TABLE B-7 Energy Inputs for All Considered Algae Nutrients without Loss of Nitrogen in HNO3 Conversion (mmBtu/ton product)
Energy Input Total Energy Input 27.490 13.014 3.900 7.831 8.485 5.895 17.856 12.818 14.214 12.832 13.312 5.321 0.192 4.790 4.448 Natural Gas 26.370 9.546 1.053 5.539 6.511 4.524 17.092 4.185 3.570 5.054 11.414 1.437 0.017 3.471 3.223 Residual Oil Diesel Fuel 0.000 1.321 1.209 0.891 0.737 0.512 0.000 0.790 1.035 0.662 0.000 1.649 0.000 0.000 0.000

Nutrient NH3 NH4Cl NaNO3 KNO3 Ca(NO3)2 Ca(NO3)24H2O (NH2)2CO K2HPO4 K2HPO43H2O KH2PO4 (NH4)2HPO4 K2SO4 Ca(H2PO4)2 + 2 CaSO4 Ca(H2PO4)2 Ca(H2PO4)2H2O

Electricity 1.120 2.146 1.638 1.400 1.236 0.859 0.764 7.843 9.609 7.116 1.898 2.235 0.175 1.319 1.225

Coal

B.4 LCA RESULTS ON A MOLAR BASIS The LCA results can be expressed, approximately, on a molar basis per mole of N and mole of P. To this end, Table B-8 recapitulates Table B-6 but expresses the total LCA energy per mole of either N or P in the compound. This presentation is helpful when an elemental mass balance is used in lieu of a compound mass balance. This approach might be taken in a model that uses the biomass stoichiometry and production rate to account for the flow of N and P despite the absence of detailed process information. There are two kinds of N sources, ammonia-derived and Chilean saltpeter-derived, with the latter being substantially lower in energy use. Averaging the ammonia-derived sources gives 236 Wh/mol-N. The P numbers are more diverse. Ignoring the highest and lowest and averaging the rest yields 412 Wh/mol-P.

83 TABLE B-8 Energy for All Considered Algae Nutrients on a Molar Basis
Energy Content Substance NH3 NH4Cl NaNO3 KNO3 Ca(NO3)24 H2O (NH2)2CO (NH4)2HPO4 K2HPO4 K2HPO43 H2O KH2PO4 K2SO4 Ca(H2PO4)2 + 2 CaSO4 Ca(H2PO4)2 Ca(H2PO4)2H2O g/mol 17.03 53.49 84.99 101.1 236.15 60.06 132.06 228.22 174.18 136.09 174.26 506.33 234.05 252.07 mmBtu/ton 27.49 13.014 3.9 10.146 7.878 17.856 13.312 14.214 12.818 12.832 5.321 0.192 4.79 4.448 Wh/g 8.88 4.20 1.26 3.28 2.54 5.77 4.30 4.59 4.14 4.14 1.72 0.06 1.55 1.44 Wh/mol-N 151.2 224.8 107.1 331.3 300.5 173.2 1,047.8 721.1 564.1 15.7 181.1 181.1 Wh/mol-P

Obtaining total energy values, as in Table B-8, is not sufficient for performing a full LCA. The distribution over process fuels is needed to determine emissions. Table B-9 shows the distribution over process fuels expressed as a fraction of total energy input, as derived from Table B-6. Residual oil and coal are zero in all cases. Ignoring the NaNO3 again, the allocations are similar among the nitrogen sources. Averaging (but skipping the hydrated form of Ca(NO3)2 to avoid double counting) yields the following: 0.846 (natural gas), 0.103 (electricity), and 0.051 (diesel), where the 0.051 is not an average but is the balance required to sum with the natural gas and diesel averages to obtain 1.0. The phosphate sources are similar, except for the superphosphate, Ca(H2PO4)2 + 2 CaSO4. The others are averagedskipping the hydrated form of K2HPO4 and hydrated Ca(H2PO4)2 to avoid double countingwhich yields results of 0.481 (natural gas), 0.480 (electricity), and 0.039 (diesel fuel). Results are shown in Table B-10. These computations are used to allocate the molar total energy for N and P.

84 TABLE B-9 Energy Allocations Expressed as Fractions of Total Energy (Derived from Table B-6)
Nutrient NH3 NH4Cl NaNO3 KNO3 Ca(NO3)2 Ca(NO3)2.4 H2O (NH2)2CO K2HPO4 K2HPO4.3H2O KH2PO4 (NH4)2HPO4 K2SO4 Ca(H2PO4)2 + 2 CaSO4 Ca(H2PO4)2 Ca(H2PO4)2.H2O Natural Gas 0.959 0.734 0.270 0.765 0.816 0.816 0.957 0.326 0.251 0.394 0.857 0.270 0.089 0.725 0.725 Electricity 0.041 0.165 0.420 0.147 0.119 0.119 0.043 0.612 0.676 0.555 0.143 0.420 0.911 0.275 0.275 Diesel Fuel 0.000 0.102 0.310 0.088 0.065 0.065 0.000 0.062 0.073 0.052 0.000 0.310 0.000 0.000 0.000

TABLE B-10 Energy Allocations on a Molar Basis for Nitrogen and Phosphorus Wh/mol Element N P Natural Gas 200 198 Electricity 24 198 Diesel 12 16

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B.5 REFERENCES FOR APPENDIX B Barclay, W., Jet al., 1986, Microalgae Culture Collection, 19861987, Solar Energy Research Institute, Golden, Colo. Clarke, S., and W. Mazzafro, 2005, Nitric Acid, pp. 127 in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 17, Wiley. Dayanada, C., et al., 2007, Autotrophic Cultivation of Botryococcus braunii for the Production of Hydrocarbons and Exopolysaccharides in Various Media, Biomass and Bioenergy 31(1):87 93. Freilich, M., and R. Petersen, 2005, Potassium Compounds, pp. 142 in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 20, Wiley. Gard, D., 2005, Phosphoric Acids and Phosphates, pp. 155 in Kirk-Othmer Encyclopedia of Chemical Technology, Wiley. Kratz, W., and J. Myers, 1955, Nutrition and Growth of Several Blue-Green Algae, American Journal of Botany 42(3):282287. Muller, T., 2006, Sulfuric Acid and Sulfur Trioxide, pp. 152 in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 23, Wiley. Richmond, A., 2007, Handbook of Microalgal Culture: Biotechnology and Applied Phycology, Blackwell Science, Oxford, U.K. Starr, R., 1971, Algal CulturesSources and Methods of Cultivation, pp. 2953 in Methods in Enzymology, Photosynthesis, and Nitrogen Part A, Vol. 23, Academic Press. Taylor, A., 2004, Fertilizers, pp. 111128 in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 11, Wiley. Weston, C., et al., 2003, Ammonium Compounds, pp. 711762 in Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 2, Wiley. Worrell, E., et al., 2000, Energy Use and Energy Intensity of the U.S. Chemical Industry, Lawrence Berkeley National Laboratory, Berkeley, Calif.

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