Utah State University DigitalCommons@USU All Graduate Theses and Dissertations Graduate Studies 7-2013 Nutrient and Carbon-Dioxide Requirements for Large-Scale Microalgae Biofuel Production Benjamin K. Shurtz Utah State University Follow this and additional works at: http://digitalcommons.usu.edu/etd Part of the Mechanical Engineering Commons Recommended Citation Shurtz, Benjamin K., "Nutrient and Carbon-Dioxide Requirements for Large-Scale Microalgae Biofuel Production" (2013). All Graduate Theses and Dissertations. Paper 1759. This Thesis is brought to you for free and open access by the Graduate Studies at DigitalCommons@USU. It has been accepted for inclusion in All Graduate Theses and Dissertations by an authorized administrator of DigitalCommons@USU. For more information, please contact [email protected]. NUTRIENT AND CARBON-DIOXIDE REQUIREMENTS FOR LARGE-SCALE MICROALGAE BIOFUEL PRODUCTION by Benjamin K. Shurtz A thesis submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE in Mechanical Engineering Approved: ________________________ Dr. Byard D. Wood Co-Major Professor ________________________ Dr. Jason C. Quinn Co-Major Professor ________________________ Dr. Rees R. Fullmer Committee Member ________________________ Dr. Mark R. McLellan Vice President for Research and Dean of the School of Graduate Studies UTAH STATE UNIVERSITY Logan, Utah 2013 ii Copyright © Benjamin K. Shurtz 2013 All Rights Reserved iii ABSTRACT Nutrient and Carbon-Dioxide Requirements for Large-Scale Microalgae Biofuel Production by Benjamin K. Shurtz, Master of Science Utah State University, 2013 Co-Major Professors: Byard D. Wood, Jason C. Quinn Department: Mechanical & Aerospace Engineering Growing demand for energy worldwide has increased interest in the production of renewable fuels, with microalgae representing a promising feedstock. The large-scale feasibility of microalgae-based biofuels has previously been evaluated through technoeconomic and environmental impact assessments, with limited work performed on resource requirements. This study presents the use of a modular engineering system process model, founded on literature, to evaluate the nutrient (nitrogen and phosphorus) and carbon dioxide resource demand of five large-scale microalgae to biofuels production systems. The baseline scenario, representative of a near-term large-scale production system, includes process models of growth, dewater, lipid extraction, anaerobic digestion, and biofuel conversion. Optimistic and conservative process scenarios are simulated to represent practical best and worst case system performance to bound the total resource demand of large-scale production. Baseline modeling results combined with current US nutrient availability from fertilizer and wastewater are used to perform a scalability iv assessment. Results show nutrient requirements represent a major barrier to the development of microalgae-based biofuels to meet the US Department of Energy 2030 renewable fuel goal of 30% of transportation fuel, or 60 billion gallons per year. Specifically, results from the baseline and optimistic fuel production systems show wastewater sources can provide sufficient nutrients to produce 3.8 billion gallons and 13 billion gallons of fuel per year, corresponding to 6% and 22% of the DOE goal, respectively. High resource demand necessitates nutrient recovery from the lipidextracted algae, thus limiting its use as a value-added co-product. Discussion focuses on system scalability, comparison of results to previous resource assessments, and model sensitivity of nutrient and carbon dioxide resource requirements to system parameter inputs. (79 pages) v PUBLIC ABSTRACT Nutrient and Carbon-Dioxide Requirements for Large-Scale Microalgae Biofuel Production by Benjamin K. Shurtz Ever-increasing fuel prices and a limited supply of oil worldwide are threatening our economy and way of life in both the near and distant future. In order to reduce oil dependence, the US Department of Energy (DOE) has established a goal that by the year 2030, 30% of the US transportation fuel will be renewable. The goal equates to approximately 60 billion gallons per year of renewable fuel. In an effort to reach the DOE renewable fuel goal, numerous types of plants are being studied, whose oil can be harvested and refined to serve as replacement fuel. Among the various plants under consideration for fuel production, microalgae have the greatest known potential yield in gallons of oil per acre of land. This study evaluates the nutrient requirements for large-scale microalgae production, sufficient to meet the DOE fuel goal. Five different production scenarios are considered, and the nutrient requirements for the baseline, or most expected scenario, are then compared to the availability of various nutrient sources. Results suggest that nutrient demand represents a major barrier to achievement of the DOE fuel production goal. A sensitivity analysis is used to determine which aspects of the fuel production process have the greatest impact on nutrient demand, which guides suggestions for future research. vi DEDICATION To my wonderful wife, Kyla, who keeps me motivated to persevere. vii ACKNOWLEDGMENTS The author gratefully acknowledges funding support from the Department of Energy, DE-EE0003114, Utah Science and Technology Initiative for Economic Development, and Utah State University. Thank you to my supervisory committee - Byard D. Wood, Jason C. Quinn, and Rees R. Fullmer - for their guidance throughout this research project. A special thanks to Byard and Jason for their numerous hours dedicated to the accomplishment of this work as coadvisors. Ben Shurtz viii CONTENTS Page ABSTRACT ....................................................................................................................... iii PUBLIC ABSTRACT ........................................................................................................ v DEDICATION ................................................................................................................... vi ACKNOWLEDGMENTS ................................................................................................ vii LIST OF TABLES .............................................................................................................. x LIST OF FIGURES ........................................................................................................... xi LIST OF ABBREVIATIONS ........................................................................................... xii BACKGROUND AND LITERATURE REVIEW ............................................................ 1 Introduction ................................................................................................................... 1 Previous Assessments ................................................................................................... 1 Statement of Need ......................................................................................................... 3 METHODS: MODEL DEVELOPMENT AND VALIDATION ....................................... 5 Baseline, Optimistic, and Conservative Scenarios ....................................................... 6 Growth .................................................................................................................... 7 Dewatering .............................................................................................................. 8 Lipid Extraction and Conversion ............................................................................ 8 Recycling – Anaerobic Digestion ........................................................................... 9 ix Alternative Process Scenarios ..................................................................................... 10 Lipid-extracted Algae (LEA) Co-product ............................................................. 10 Hydrothermal Liquefaction ................................................................................... 11 RESULTS AND DISCUSSION ....................................................................................... 14 Total Resource Requirements ..................................................................................... 14 Scalability Assessment Based on Nutrient Availability ............................................. 15 Comparison to Previous Nutrient Assessments .......................................................... 17 Sensitivity Analysis .................................................................................................... 19 CONCLUSION ................................................................................................................. 22 REFERENCES ................................................................................................................. 23 APPENDICES .................................................................................................................. 28 Appendix A. Research Proposal ................................................................................. 29 Appendix B. Detailed Process Block Diagrams ......................................................... 41 Appendix C. Model Calculations in Mathcad............................................................. 45 Appendix D. Complete Table of Model Parameter Values ........................................ 56 Appendix E. Calculations in Mathcad for Nutrient Source Availability .................... 59 x LIST OF TABLES Table Page 1 Summary of system parameter values for the five microalgae to biofuel production scenarios ......................................................................................13 2 Total biomass and corresponding nutrient requirements for the five scenarios at the DOE 60 BGY fuel production level .................................................15 3 Scalability assessment: Comparison of seawater, wastewater, and fertilizer availability and requirements to meet baseline system nutrient needs at a biofuel production level of 60 BGY.............................................16 A.1 Planned dates for completion of the proposed milestones .........................................39 D.1 Complete summary of system parameter values used for model mass balance calculations for the five production scenarios ...............................................58 xi LIST OF FIGURES Figure Page 1 Systems process model of the microalgae to biofuel production system, used to model five production scenarios. ........................................................5 2 Process model for baseline, optimistic, and conservative scenarios ............................6 3 Process model for the LEA co-product scenario ........................................................11 4 Process model for the HTL scenario ..........................................................................12 5 Results for (A) Nitrogen demand and (B) Phosphorus demand from various literature sources ............................................................................................18 6 Model output sensitivity to system parameters for (A) Nitrogen requirement, (B) Phosphorus requirement, and (C) CO2 requirement .......................20 A.1 Model of the process studied by Pate et al. (2011) ....................................................33 A.2 Model of the process to be studied .............................................................................36 B.1 Mass flow schematic of the complete microalgae to biofuel production process ......................................................................................................42 B.2 Growth process input/output diagram ........................................................................43 B.3 Harvest process input/output diagram ........................................................................43 B.4 Recycling process input/output diagram ....................................................................43 B.5 Extraction process input/output diagram ....................................................................44 B.6 Transesterification and end products process input/output diagram ..........................44 xii LIST OF ABBREVIATIONS AD Anaerobic Digestion BGY Billion gallons per year CO2 Carbon dioxide C:N:P Carbon:Nitrogen:Phosphorus DOE Department of Energy HTL Hydrothermal liquefaction LCA Life-cycle assessment LEA Lipid-extracted algae Mmt Million metric tons TEA Techno-economic analysis TGY Trillion gallons per year TS Total solids VS Volatile solids BACKGROUND AND LITERATURE REVIEW Introduction Increasing volatility in energy availability and cost, as well as the environmental impacts of fossil fuel use, has led to an elevated interest in the domestic production of renewable fuel. The US Department of Energy (DOE) has quantified the level of interest in, and need for, renewable fuel through the establishment of a goal for the year 2030 that 30% of US transportation fuel will be renewable, which corresponds to approximately 60 billion gallons per year (BGY) [1]. A variety of second and third generation terrestrial based feedstock options exist, but microalgae have several advantages, including higher solar energy conversion efficiency, abilities to be grown on non-arable land, utilization of salt or saline water, and integration with various low value nutrient (nitrogen and phosphorus) sources including seawater, wastewater, and point source carbon dioxide (CO2) [2,3]. Furthermore, microalgae are of interest in wastewater treatment for the removal of nitrogen and phosphorus [4-6]. The many advantages make microalgae one of the more promising feedstocks for production of renewable biofuels. Previous Assessments Researchers have evaluated the requirements, implications, and barriers to microalgae biofuel production at the scale required for the DOE 2030 goal via technoeconomic analysis (TEA), lifecycle assessment (LCA), and resource assessment, with discussion regarding the utilization of wastewater as a nutrient source. The majority 2 of the TEAs and LCAs to date have developed system models in an effort to quantify the energy and mass requirements, but limit results to financial costs and environmental impact without considering nutrient requirements at large-scale [7-22]. Results from TEAs have suggested that higher value co-products from the lipid extracted algae (LEA) could improve the economics of biofuel production, but fail to address the impact of this mass flow on the nutrient demand and availability [7,8]. Published LCAs contain results focused on energy use and carbon emissions, but include only minimal analysis and discussion regarding scale-up limitations based on nutrient requirements [9,10]. Resource assessments have evaluated the impact and availability of land, water, CO2, and nutrient requirements on the scalability of microalgae based biofuels with results derived from simplified models. Studies have shown that land does not currently represent a resource limitation, while water will be a limiting resource in some regions of the US [23-25]. Limitations on the economic transportation of CO2 combined with land availability represent another potential barrier for scale-up [24]. Pate et al. [26] perform a high-level, low-granularity evaluation of the water, land, CO2 and nutrient requirements for largescale production based on a mass balance assessment. Model details include only microalgae cultivation and omit all other steps of the biofuel production system. Their results provide the order of magnitude to expect for resource demand, but are inadequate due to the limited model scope. Additional nutrient assessments make claims that seawater and wastewater can potentially provide the nutrients necessary for large-scale microalgae production, but provide no justification for these claims [27,28]. The feasibility of integrating wastewater with microalgae cultivation as a source of water and nutrients for microalgae growth, as well as effective wastewater treatment has been 3 established [2-3, 29-31], but such studies have not extended results to scalability. Despite the knowledge gained through previous TEAs, LCAs, and resource assessments, a need remains for thorough evaluation of the nutrient demand of large-scale biofuel production. Statement of Need Based on the current state of the field, there exists a need to quantify the nutrient and CO2 requirements of the microalgae to biofuels system based on large-scale representative models and evaluate the potential for various nutrient sources such as fertilizer and wastewater to meet nutrient needs. This study assesses the large-scale resource requirements through the development of a large-scale engineering process model of the microalgae to biofuel production system. The baseline model, representative of a near-term large-scale system, includes growth, dewatering, lipid extraction, anaerobic digestion (AD), and biofuel conversion processes for a system boundary that is consistent with the “strain to pump.” Optimistic and conservative scenarios were developed to encompass the variability of process efficiencies within the baseline system, account for advancements in processing technology, and provide bounds for the resource requirements. Alternative production processes were assessed which include a system based on the production of fuel with LEA co-products and the utilization of an alternative extraction and nutrient recycling process through hydrothermal liquefaction (HTL). Total nutrient and CO2 input requirements were determined for an annual fuel production level of 60 billion gallons corresponding to the DOE renewable fuel goal. Nutrient requirement results were compared to US resource availability to evaluate system scalability. Discussion focuses on the results for resource 4 requirements for the five production scenarios, system scalability within the US, a comparison of results to previous resource assessments, and sensitivity of resource results to model inputs. This thesis reflects the completion of work proposed and approved, as contained in Appendix A. 5 METHODS: MODEL DEVELOPMENT AND VALIDATION A modular engineering system model, designed to track mass flow, was developed and validated in order to quantify the resource requirements of a large-scale microalgae to biofuels production system. The process model, shown in Fig. 1, includes 24 inputs used to characterize the production system with process losses and efficiencies in each step included. More detailed mass flow diagrams for each step are contained in Appendix B. The mass flow diagrams were used in the development of the calculations for the mass flow model, which are contained in Appendix C. Five production scenarios were modeled, with the following sections outlining the input values and justification for each system parameter. 1 Systems process model of the microalgae to biofuel production system, used to model five production scenarios. Fig. 1. Systems process model of the microalgae to biofuel production system, used to model five production scenarios 6 Baseline, Optimistic, and Conservative Scenarios The baseline scenario is intended to represent a near-term large-scale microalgae to biofuels production system, Fig. 2. The model includes growth, dewater, lipid extraction, biofuel conversion, and resource recycling through AD as the process steps [7,9,11,32]. In order to establish bounds on resource demand, optimistic and conservative scenarios are modeled. The optimistic scenario is comprised of the most efficient values reported in literature for each process, typically at bench or lab-scale, and represents the biofuel production system with the lowest possible resource consumption. The conservative scenario represents current technology, and results in the highest possible resource consumption. It is recognized that at commercial scale, processes will inherently have a loss to the environment or a waste stream, so a loss is included in each process and standardized due to uncertainty. The baseline process model loss was assumed to be 1% and was cut in half for the optimistic case and doubled for the conservative case, corresponding to 0.5% and 2%, respectively. 2 Process model for baseline, optimistic, and conservative scenarios Fig. 2. Process model for baseline, optimistic, and conservative scenarios 7 Growth The elemental composition of the microalgae is represented through the carbon : nitrogen : phosphorus (C:N:P) ratio, where the Redfield ratio, 106:16:1, was used for the baseline scenario [33]. The C:N:P ratio was assumed to be 166:20:1 for the optimistic case, as presented by Smith [34], which increases the C:N ratio by approximately 20% from the baseline. For the conservative case, 79:16:1 was selected to provide an equal but opposite deviation from the baseline as the optimistic scenario. A biomass carbon content of 50% was assumed for the baseline and unchanged for the optimistic and conservative scenarios as it is a generally accepted value [9,26,35,36]. The hydrogen content of the microalgae was selected to be 7.5%, 6%, and 9% for the baseline, optimistic, and conservative values, respectively [37]. Published values for lipid content cover a wide range. A lipid percentage of 30% was selected for the baseline as a mid-range, realistic value to expect from an actual large-scale growth system, with 40% and 20% representing the optimistic and conservative cases, respectively [7,9,26,38,39]. The percent of lipids that are phospholipids was assumed to be 25% for the baseline, the average value reported by Chen et al. [40], and was taken as 5% for the optimistic scenario and 30% for the conservative scenario [9,40]. Nutrient absorption in the growth phase is assumed to be 99% for nitrogen uptake, with the remainder being absorbed by competitive species or converted to nitrous oxide [41,42]. Nitrogen uptake in the optimistic and conservative scenarios was assumed to be 100% and 98%, respectively [41]. The growth system assumes additional carbon will be supplied to the growth medium in the form of gaseous CO2, and an associated utilization efficiency of 85% was selected for the baseline [8,9]. Sheehan et al. [43] report 90% CO2 8 absorption into the growth medium, which was used for the optimistic scenario. The conservative case was calculated based on the operation of outdoor cultivation systems and laboratory experimental work supporting a utilization of 2% [38,44-46]. Dewatering Multiple possible dewatering processes exist, and the baseline scenario of this study assumed dissolved air flotation with a 10% biomass loss followed by centrifugation with a 5% biomass loss, which were combined for an overall 14.5% biomass loss going from 1% solids to 20% solids [9]. The lost biomass was assumed to be caught by a filter and sent to the AD. The optimistic scenario considered only a centrifuge with a minimal biomass loss of 2%, and the conservative scenario assumed a 20% loss, increased based on low-energy harvesting technologies such as bio-flocculation. Lipid Extraction and Conversion The lipid extraction process contains two fundamental avenues for losses, first in biomass oil that is un-extracted and second in the incomplete recovery of the extracted lipid. For the baseline, the percent of biomass passing unaffected through the extraction process was assumed to be 10%. It is assumed the oil that is extracted but not recovered is 5% [9,43]. The unaffected biomass was assumed to be caught by a filter and sent to the AD. Both of the extraction parameters were varied by ±50% of their baseline values for the optimistic and conservative scenarios, which corresponds to 5% and 15% for the biomass passing through, and 2% and 8% for un-extracted oil [9]. For the conversion of extracted lipid to biofuel, transesterification was modeled with 99% of the lipid entering the process converted to biofuel [32,47]. It is important to note here that it was assumed that ‘lipid content’ in the biomass is referring to the lipids 9 only, and not to triacylglycerides (TAG), which means that any non-fuel output of transesterification is already accounted for. Thus, it was assumed that the fuel output from transesterification is equal to the lipid input with a standard process loss to the environment. Recycling – Anaerobic Digestion The baseline recycling process utilizes an AD for nutrient recovery and biogas generation from the LEA and whole biomass recovered from the filtration of the centrate in the dewatering step [32]. In describing the baseline performance of the AD, it was assumed that 76% of the nitrogen is recovered which includes a 5% volatilization [9]. Phosphorus is assumed to be recovered with a 70% efficiency for the baseline scenario [48]. For the optimistic and conservative cases, nitrogen and phosphorus recovery via AD was assumed to be 85% and 60%, respectively [9,48]. The biogas production of the AD system was modeled based on the volatile solids (VS), total solids (TS), methane yield per gram of volatile solids (g-VS), and percent methane (CH4) content in the biogas. A characteristic of 0.94 g-VS g- TS-1 for whole biomass, and 0.90 g-VS g- TS-1 for LEA was assumed and kept constant for all scenarios [49,50]. The biogas yield from whole biomass was assumed to be 0.43 L-CH4 g-VS-1 at 67% CH4, 0.80 L-CH4 g-VS-1 at 62% CH4, and 0.25 L-CH4 g-VS-1 at 72% CH4 for the baseline, optimistic, and conservative scenarios, respectively [50,51]. Similarly for the digestion of LEA, biogas yield and composition for the baseline, optimistic, and conservative scenarios were assumed to be 0.22 L-CH4 g-VS-1 at 59% CH4, 0.31 L-CH4 g-VS-1 at 49% CH4, and 0.14 L-CH4 g-VS-1 at 69% CH4, respectively [49,52,53]. It was assumed that all biogas would be burned in an on-site combined heat and power unit and 10 the produced CO2 reused in the growth phase, with a 10% CO2 loss assumed for the baseline scenario, then halved for the optimistic case and doubled for the conservative case to account for losses in recovery and transport. Alternative Process Scenarios Two alternative process scenarios were modeled and evaluated: a) the use of LEA as a co-product and b) hydrothermal processing of the biomass to bio-oil through HTL. The LEA co-product scenario provides further insight to claims made by previous TEAs in regard to the economic value of the LEA, and HTL represents a promising alternative processing technology due to the ability to process wet biomass and recover nutrients. For each of the alternative scenarios, the baseline assumptions are used unless otherwise detailed. Lipid-extracted Algae (LEA) Co-product Analyses of the economics of biofuel production typically include discussion in regard to higher-valued co-products derived from the LEA to improve the cost of biofuel production [7,8]. While the generation of revenue supplemental to that of biofuel through LEA co-products initially appears economically advantageous, its implications on resource demand must be assessed. In this study, an alternative scenario was modeled, considering the use of LEA as a co-product to evaluate the associated resource requirements, Fig. 3. The LEA co-product scenario assumes all of the lipid-extracted biomass is removed from the process stream as a product after extraction. It is assumed the minimal whole biomass recovered in the filtration of the centrate in the dewater step is added to the LEA product stream and not processed through anaerobic digestion. 11 3 Process model for the LEA co-product scenario Fig. 3. Process model for the LEA co-product scenario Hydrothermal Liquefaction Hydrothermal liquefaction (HTL) is a technology currently being evaluated which breaks down biological matter into lipid and elemental components, providing the advantages of processing wet biomass and the conversion of proteins and carbohydrates to bio-oil [54-57]. The outputs of this process are bio-oil (or biogas if a catalyst is used), nitrogen and potassium-rich water, and precipitated phosphorus and sulfur [57]. The modeled process replaces the extraction and the AD steps of the baseline production system, Fig. 4. The bio-oil yield from the process is assumed to be 50% based on recovery of the 30% algal lipid content and 20% additional bio-oil through the conversion of carbohydrates and proteins [54-57]. The percent phospholipid content was set to 0% because HTL strips the phosphates from any phospholipids in the processing of the feedstock [56,57]. The biomass caught by the filter in the dewater process is sent into the HTL process. Similar to AD, the literature describing the experimental performance of HTL report the amount of oil obtained in terms of output per input, which inherently accounts 12 4 Process model for the HTL scenario Fig. 4. Process model for the HTL scenario for any losses to the environment [54-57]. Therefore, as with AD in the previous scenarios, HTL was modeled utilizing recovery efficiencies with no additional process losses. Nutrient recovery was assumed to be 75% for nitrogen, with the remaining nitrogen being contained in the bio-oil, and 95% for precipitated phosphorus recovery and processing [57]. Table 1 provides a summary of the system parameters and assumptions for each of the five microalgae to biofuel production scenarios used in this study, presented in the order in which they were discussed previously. A more thorough table, with parameters presented in the order which they appear in the model, is contained in Appendix D. 13 1 Summary of system parameter values for the five microalgae to biofuel production scenarios Table 1 Summary of system parameter values for the five microalgae to biofuel production scenarios Parameter Process Loss (%) C:N:P Ratio Hydrogen (%) Lipid Content (%) Phospholipids (%) N Consumed by Microalgae (%) CO2 Absorbed (%) Biomass Unharvested (%) Biomass Unextracted (%) Extracted Lipid Lost (%) N Recovery (AD) (%) P Recovery (AD) (%) CH4 Prod. –Biomass (L-CH4 g-VS-1) CH4 Prod. – LEA (L-CH4 g-VS-1) CH4 in Biogas – Biomass (%) CH4 in Biogas – LEA (%) CO2 Combustion Loss (%) Baseline 1 106:16:1 7.5 30 25 99 85 14.5 10 5 76 70 0.43 0.22 67 59 10 Optimistic 0.5 166:20:1 6 40 5 100 90 2.0 5 2 85 85 0.80 0.31 62 49 5 Conservative 2 79:16:1 9 20 30 98 2 20.0 15 8 60 60 0.25 0.14 72 69 20 LEA coproduct 1 106:16:1 7.5 30 25 99 85 14.5 10 5 0 0 N/A N/A N/A N/A N/A HTL 1 106:16:1 7.5 30 0 99 85 2.0 0 0 66 95 N/A N/A N/A N/A N/A 14 RESULTS AND DISCUSSION Total Resource Requirements Mass flow calculations were performed for the five biofuel production scenarios, each at the DOE 60 BGY fuel production level, to quantify the supply of resources to be added to the system. In addition to nutrients and CO2 demand, water consumption was also calculated based on the hydrogen content of the grown biomass, which in this study is only referring to the fixation of hydrogen in the biomass and does not include evaporation or process losses. The total system requirements for each scenario are reported in Table 2. The lower and upper bounds for nutrient and CO2 requirements for large-scale microalgae production are illustrated through the optimistic and conservative results, with the baseline scenario portraying the expected resource demand from production that is realizable in the near-term. The mass balance calculations show that one billion metric tons of biomass will need to be grown in the baseline scenario to meet the 60 BGY fuel goal corresponding to a land area of 21 million hectares if a growth rate of 13 g m-2 day-1 is assumed [32]. This land requirement does not represent a resource constraint as concluded by previous assessments [23,39]. The total nutrient need for the optimistic scenario is approximately one-fourth that of the baseline scenario, with the conservative scenario requiring three times the phosphorus and four times the nitrogen compared to the baseline scenario. The large variation in nutrient demand can be attributed primarily to the range in efficiency of nutrient recovery in the AD. The LEA co-product scenario, characterized as the baseline scenario without AD, has roughly the same nutrient requirements as the conservative scenario. Alternatively, HTL has approximately half the 15 2 Total biomass and corresponding nutrient requirements for the five scenarios at the DOE 60 BGY fuel production level Table 2 Total biomass and corresponding nutrient requirements for the five scenarios at the DOE 60 BGY fuel production level. The unit Mmt represents millions of metric tons. Biomass produced (Mmt) Nitrogen required (Mmt) Phosphorus required (Mmt) CO2 required (Mmt) H20 Consumption (BGY) Baseline Optimistic Conservative LEA coproduct HTL 1002 23.1 5.2 1540 179 587 6.7 1.1 738 84 1850 96 14.4 161000 395 1002 89 12.2 2060 180 435 10.4 0.4 896 78 required biomass production and nitrogen demand from the baseline, and a phosphorus requirement less than one-tenth of the baseline, similar to the optimistic scenario. The ratio of nitrogen input to phosphorus input is much higher in the HTL scenario because of the high nitrogen content in the bio-oil, an issue that necessitates further downstream processing [55]. The system CO2 requirement shows higher variability across the scenarios than the other resources due to the wide range of utilization efficiency. Through the variation apparent in Table 2, bounds have been determined for the resource requirements to meet the DOE 2030 fuel goal via microalgae biodiesel with the baseline scenario representing a near-term realizable production facility and the optimistic and conservative cases used to bound the analysis. Scalability Assessment Based on Nutrient Availability System scalability was assessed through a comparison of the total input requirements and current nutrient resource availability. Growth nutrients for the cultivation of microalgae can be in the form of fertilizer or by utilizing a growth medium that already contains nutrients such as wastewater or seawater [26,27]. Total source 16 3 Scalability assessment: Comparison of seawater, wastewater, and fertilizer availability and requirements to meet baseline system nutrient needs at a biofuel production level of 60 BGY Table 3 Scalability assessment: Comparison of seawater, wastewater, and fertilizer availability and requirements to meet baseline system nutrient needs at a biofuel production level of 60 BGY. The unit TGY is trillion gallons per year. Seawater Wastewater Fertilizer Wastewater & Fertilizer Input Needed % of the Great Salt Lake[58] Nitrogen 19 TGY 280% Phosphorus 28 TGY 430% Input Needed % of total Available WW in U.S.[59,60] 186 TGY 1600% 173 TGY 1500% Input Needed % of U.S. Consumption[61] 23.1 Mmt 98% 5.2 Mmt 125% 92% 117% % of U.S. Fertilizer Consumption after use of 100% of U.S. Wastewater[58-61] supply to meet the baseline nutrient requirements was determined for three nutrient sources - seawater, wastewater, and fertilizer, Table 3. In the case of seawater, since the supply is seemingly limitless, a volumetric comparison is provided. Detailed calculations related to the results in Table 3 are provided in Appendix E. The scalability assessment shows nutrient requirements are a current barrier to meeting DOE 2030 production goals strictly through microalgae based biofuels. If seawater is used as the nutrient source, it would be necessary in amounts equivalent to more than four times the volume of the Great Salt Lake in Utah. This would represent a major economic barrier due to pumping requirements, and limit production facility locations geographically. The nutrients available from wastewater correspond to a fuel production level of 3.8 BGY or 6% of the DOE fuel goal. Meeting the DOE goal would require sixteen times the available wastewater in the US, therefore illustrating wastewater to be a possible supplement, but not the ultimate source for nutrients. Commercial 17 fertilizer represents a viable nutrient supply, but scaling to the levels discussed would require the entire current US fertilizer market. Technological advancement in the various processes can improve performance and the corresponding scalability. If achieved, the optimistic scenario would bring the nutrient requirements to within the availably supply, with a fertilizer demand of 28% of the current US market to meet the DOE goal. A production level of 13 BGY could be achieved from wastewater nutrients, with 17% of the US fertilizer market supplementing the wastewater to achieve 60 BGY total fuel production. Additionally, HTL as an extraction and nutrient recycling process shows potential value in biofuel production due to the inherent ability to process non-lipid organic material into bio-oil while recovering nutrients. The nutrient demands for the LEA co-product scenario are an order of magnitude greater than availability and show that for biofuel production sufficient to meet the DOE 2030 goal, nutrient from the LEA must be recycled. Results from the scalability assessment show that nutrient management represents an important aspect of microalgae scalability. Comparison to Previous Nutrient Assessments A variety of microalgae based TEA and LCA studies have reported nutrient requirements for the cultivation of microalgae but have failed to evaluate the large-scale demand [9,10,12,13,32]. The majority of the previous assessments are founded on models which are constructed with small-scale laboratory-based growth and lipid production data [10,13,27,28], but this type of analysis has been shown to misrepresent microalgae production at large-scale [11]. The simplistic scaling of small-scale laboratory based data 18 leads to erroneous assumptions about industrial growth facility function, and is a source of uncertainty in microalgae biofuels economic, sustainability, and resource assessments. Incomplete resource assessments have led to a large uncertainty in the current requirements for large scale production [9,10,12,13,26-28,32]. Results from previous studies were normalized to the baseline units of this study, 60 billion gallons of fuel production annually from 1002 Mmt of biomass. Normalized values reported in surveyed literature range from 14 Mmt of nitrogen and 4.1 Mmt of phosphorus [9,32] to 147 Mmt of nitrogen and 21 Mmt of phosphorus [10,27] as shown in Fig. 5. The nutrient requirements in this study are 1.6 and 1.3 times the lowest values and 0.16 and 0.25 times the highest values reported in the literature surveyed for nitrogen and phosphorous requirements, respectively. Interestingly, when compared to the high 5 Results for (A) Nitrogen demand and (B) Phosphorus demand from various literature sources 140 120 100 80 60 40 20 0 25 (B) Phosphorus Input (Mmt) (A) Nitrogen Input (Mmt) 160 20 15 10 5 0 Fig. 5. Results for (A) Nitrogen demand and (B) Phosphorus demand from various literature sources. The black dotted line represents the baseline requirement from this study. 19 productivity scenario from Pate et al. [26], the most comparable scenario to this study, the baseline requirements are 63% and 105% of their results for nitrogen and phosphorus. The differences and similarities in results occur through a combination of factors, specifically that Pate et al. [26] only consider the growth phase, neglect losses, and assume high algal productivity which introduces uncertainty. Compared to literature, the baseline results obtained in this study are similar with results from previous studies, falling between the high and low values reported. Results from this study, however, are derived from an improved model which describes a complete production system including process details and system losses. Sensitivity Analysis A sensitivity analysis was performed to illustrate which process parameters have the greatest effect on resource demand and to ultimately guide future research. The sensitivity analysis was performed by independently varying each system parameter by ±20% from the baseline and recording the nitrogen, phosphorus, and CO2 requirements. Fig. 6 shows the results from the sensitivity to process parameters in order of greatest impact on resource requirements. Results were analyzed using a one tail distribution with a 95% confidence interval, resulting in a critical t-ratio of 2.1. The critical t-ratio provides the boundary through which system parameters are deemed as sensitive or non-sensitive. The parameters whose t-ratio magnitude are above the critical, and thus whose bar extends beyond the confidence interval in Fig. 6, were deemed sensitive. Although twenty-four system parameters were varied, only those parameters deemed as sensitive according to their t-ratio were included in the figure. 20 N Recovered from AD (76%, -47) P Recovered from AD (70%, -29) C:N:P Ratio - N (16, 16) C:N:P Ratio - P (1, 16) Carbon Content (50%, 16) Carbon Content (50%, 16) C:N:P Ratio - C (116, -17) C:N:P Ratio - C (116, -17) Lipid Content (30%, -17) Lipid Content (30%, -17) N Consumed by Algae (99%, -13) Phospholipids (25%, 5.8) Biomass Unharvested (14.5%, 2.7) Biomass Unharvested (14.5%, 2.7) Process Loss (1%, 2.4) Process Loss (1%, 2.3) -60 -30 0 30 60 -60 0 30 60 (B) Percent Deviation from Baseline Input of 5.2 Million Metric Tons (A) Percent Deviation from Baseline Input of 23.1 Million Metric Tons Legend Parameter (x,y) – x- Baseline parameter value y- t-ratio of parameter Carbon Content (50%, 20) CO2 Absorbtion (85%, -20) Lipid Content (30%, -15) Output for parameter deviation of +20% from baseline value CH4 Content - Whole (62%, 2.7) CH4 Content - LEA (50%, 2.4) CH4 Prod. - Whole (0.43 L g-VS-1, -2.6) Output for parameter deviation of -20% from baseline value CH4 Prod. - LEA (0.22 L g-VS-1, -2.3) -60 -30 -30 0 30 60 95% Confidence Interval (C) Percent Deviation from Baseline Input of 1540 Million Metric Tons Fig. 6. Model output sensitivity to system parameters for (A) Nitrogen requirement, (B) Phosphorus requirement, and (C) CO2 requirement 6 Model output sensitivity to system parameters for (A) Nitrogen requirement, (B) Phosphorus requirement, and (C) CO2 requirement The two parameters whose variation has the greatest impact on system nutrient demand are the nitrogen and phosphorus recovery rates of the AD. Any advancement in nutrient recovery in recycling, whether it be improvement in anaerobic digester 21 performance or by use of an alternative technology such as HTL, will decrease the nitrogen and phosphorus supply requirements. The next group of parameters most capable of driving down resource demand are those describing the composition of the microalgae strain. This demonstrates that the microalgae strain characteristics including C:N:P ratio, lipid content, phospholipid content, and carbon content must be thoroughly understood and even optimized through synthetic biology or other means for efficient nutrient use in microalgae growth. The utilization efficiency of CO2 also has a large effect on the input requirement, which becomes especially important when coupled with the variability of this parameter. As explained in the methods section, and shown in Table 1, the CO2 absorption rate has varied from as low as 2% to as high as 90% in built systems. There is high variability in the absorption, and the input requirement is highly sensitive to this variance, so it will be imperative to maximize the utilization efficiency when designing a commercial-scale production system. Resource requirements for largescale microalgae production can be reduced through technological improvements affecting these sensitive system parameters. 22 CONCLUSION A detailed and modular engineering system model was developed, validated, and used to determine total system resource requirements for five microalgae to biofuel production scenarios at a production level of 60 BGY. Optimistic and conservative process scenarios were modeled in an effort to bound the nutrient and CO2 requirements for large-scale microalgae production with a baseline scenario intended to represent a near-term commercial system. Baseline nutrient requirements for attaining the DOE 2030 goal exceed the nutrients available in wastewater and are equivalent to the current fertilizer consumption in the US. Utilization of wastewater as the sole source of nutrients limits biofuel production to 3.8 BGY for the baseline scenario and 13 BGY for the optimistic scenario. Wastewater alone cannot provide the necessary nutrient supply to meet the DOE 2030 goal based on a microalgae to biofuel production system. The heavy nutrient demand for large-scale production requires nutrients to be recovered from the LEA, and thus LEA cannot be used as an economically beneficial co-product. Sensitivity analysis shows that resource demand can be impacted through improvements in nutrient recycling, microalgae strain characteristics, and the CO2 utilization efficiency. Current nutrient requirements for microalgae production limit the ability to meet the DOE 2030 renewable fuel goal, but system improvements can potentially make the goal attainable, as illustrated with the optimistic scenario. 23 REFERENCES [1] DOE. Alternative fuel transportation program; replacement fuel goal modification. Federal Register 2007;72(50):12041-60. [2] Pittman JK, Dean AP, Osundeko O. The potential of sustainable algal biofuel production using wastewater resources. 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Nutrient requirements have been assessed for large-scale cultivation, but rely on lab-scale research data which is not applicable. The use of laboratory data introduces a large uncertainty regarding the resource requirements for large-scale production. The proposed research will aim to fill the knowledge gap associated with resource requirements for the scaling of microalgae biofuels to large-scale levels. Sensitivity analysis will be performed on a systems level to identify areas for further research and development. Results from this study will provide values for nutrient input requirements and water consumption of a commercial-scale microalgae production system. Results will then be extended into a scalability assessment through a comparison of resource requirements to the geographic resolution of resource availability. This information will be essential for future economic and environmental analyses related to large-scale microalgae production. Background Ever-growing demand for fuel world-wide has generated instability in the supply chain. The increase in fuel demand –and thus fuel prices – has increased the volatility of economies worldwide. One option for decreasing market variability is to find alternative forms of fuel, whose added supply and competition will naturally drive prices down. Additionally, fossil fuels are a limited resource that will eventually be depleted, which creates a long-term need for alternative fuel sources. These immediate and long-term fuel needs have sparked much interest and research in finding possible alternatives to 31 fossil fuel. There are many potential sources of fuel, and the final solution will likely use multiple sources. A variety of alternative fuel feedstocks are actively being investigated. One promising option is growing microalgae and harvesting its oil, which can be refined to serve as a drop in diesel fuel replacement. Microalgae is especially appealing because of its abilities to be grown on non-arable land, to use water sources other than freshwater, and to absorb and use CO2. These advantages combined with uncertainty in global energy supply have led to interest in microalgae as an alternative fuel feedstock. Research has provided much scientific insight about the possibilities as well as the foreseeable obstacles to be overcome for commercial-scale biofuel production via microalgae. When considering resource requirements, much of the focus of the research to date has been into sunlight availability, associated productivity rates, land consumption, and water consumption. The nutrient requirement for algae growth, however, is a topic often neglected or minimalized in available literature and in scalability assessments. Two key nutrients microalgae require are nitrogen and phosphorus. Terrestrial crops require these nutrients also, as fertilizer, so microalgae and food crops could potentially have to compete for the same supply of fertilizers. This makes understanding the required nutrient inputs a key component for accurate scalability assessments that needs to be addressed. In order to accurately assess a large-scale growth facility to meet production goals, and in order to predict the cost of biofuel production, the required system input for the desired production must be accurately known. This presents an opportunity and a need for further research. 32 Current State of Applicable Research Introduction Extensive research has already been done regarding the scalability of microalgae production, but knowledge is still lacking regarding resource requirements. The proposed research aims to fill this knowledge gap, and the information that has become available through previous research will serve as an essential foundation for the proposed research. The previous research that will be utilized can be broken into three categories: 1. Nutrient Requirements, 2. Process Losses and Efficiencies, and 3. Wastewater and Nutrient Removal. The current state of research in each category is presented here. Nutrient Requirements Some studies discuss the nutrient and water requirements for algae growth, but conclusions are only discussed at a laboratory scale (Yang et al., 2011; Woertz et al. 2009). Pate et al. (2011) took a first step towards understanding the implications of large-scale microalgae production and the corresponding nutrient requirements. In their study, percentages (15%, 30%, 80%, 150%) of DOE goals for lipid production were used as a reference point to determine how much microalgae would need to be grown annually for the different scenarios. Each production scenario was considered in four different regions of the United States to determine the necessary land, water, and nutrients. It will be shown that their study provides useful information, but is lacking in scope due to crude assumptions. Figure A.1 was created as a visual representation of the system studied by Pate et al. (2011). Each numbered location in the figure has a mass flow associated with it that 33 will be discussed. The desired level of lipid production at location 3 was determined as a percentage of DOE goals. The results of the study describe the level of resources required at location 2. Using freshwater supplemented with the required nutrients, and with no considerations made for losses and recycling, the results found to describe location 2 are assumed to also be the requirements at location 1. The conclusion is that the amount of resources required for large-scale biofuel production through microalgae growth is unattainably high. This model is simple, and provides a good starting point for understanding the implications of large-scale algae production, but the results are highly inaccurate for an actual process when discussing the resource inputs at location 1 because production systems will include recycle processes. Fig. A.1. Model of the process studied by Pate et al. (2011) 7A.1 Model of the process studied by Pate, et al. (2011) Process Losses and Efficiencies There will be losses and efficiencies at each step throughout the complete process, but only a few will be discussed in any detail here. First, some nutrients will be contained in the extracted lipids. Frank et al. (2011), in their life-cycle report, assumed that the phosphorus and nitrogen content within the lipids is small enough to be neglected without affecting calculations. They do recognize, though, that there will be a small 34 amount of nutrients contained in the lipids. In a separate study, Li-Beisson (2012) discusses the biomass composition of various strains of microalgae, as well as TAG makeup. Next, nutrients can be recycled through anaerobic digestion or hydrothermal liquefaction, each with efficiency rates. Frank et al. (2011) provide several references for nutrient recovery rates through anaerobic digesters, and conclude to use 80% nutrient recovery in their study. Currently, information regarding each of the process steps is available, but scattered. This information needs to be compiled and utilized to understand the nutrient flow throughout the entire process, which is the goal of the proposed research. Wastewater and Nutrient Removal Wastewater is considered a potentially valuable resource by those interested in biofuel production via microalgae (Yang et al., 2011; Menetrez, 2012; Pittman et al., 2011). Wastewater contains both water and nutrients that are necessary for algae growth, but these nutrients are considered pollutants in wastewater treatment that are expensive to remove (Abdel-Raouf et al., 2012). As a result of this, many researchers in wastewater treatment are interested in using microalgae as a water treatment process (Abdel-Raouf et al., 2012; Woertz et al., 2009). Microalgae present a potentially less-expensive method of pollutant removal, combined with the advantage of producing bioproducts from harvested lipids. The studies done on microalgae use for wastewater cleanup have produced a range of values for the percentage of pollutant removal from the water. Abdel-Raouf et al. (2012) cites several studies using Chlorella vulgaris which reported 50.2% - 86% nitrogen removal and 70% - 97.8% phosphorus removal. Woertz et al. 35 (2009) were able to remove >98% of ammonium and >96% of phosphorus with microalgae. Although information is available on wastewater composition and nutrient/pollutant removal rates, whether wastewater has the potential to be the sole nutrient source for microalgae growth is still unknown because the exact nutrient input required for the complete production process is unknown. Summary Information is available on different stages of the production process, showing what the resource consumption and losses will be. This information, however, is only available for individual stages and research has not been done which combines these pieces of information into a process evaluation. A study has conducted a zeroth order assessment which reported the nutrients contained in a given quantity of microalgae, but did not include any process factors. Finally, wastewater has great potential as a nutrient source for microalgae production, but whether this source alone will be sufficient is unknown because the nutrient input requirements are unknown. Proposal of Thesis Topic and Completion Steps Overview Based on the inconsistency and low level of detail in previous studies, the proposed research is to move beyond a simple model like the one utilized by Pate et al. (2011). The proposed model will include more of the process details that will be involved in an actual system. The study will focus on nutrient consumption and losses, along with water consumption in order to provide detailed information for this key aspect 36 of a scalability assessment. The model architecture is presented in Figure A.2. This model includes nutrient losses during growth and harvesting, losses in lipid extraction, losses in the recycling process, and nutrient recovery through recycling. The model will be constructed in such a way to critically evaluate a variety of nutrient sources, system processes, microalgae strains, and end products from biofuel to bioproducts. 8A.2 Model of the process to be studied Fig. A.2. Model of the process to be studied The numbered locations in Figure A.2 correspond to the same numbered locations in Figure 1. The results obtained by Pate et al. (2011) give nutrient levels at location 2 based on a given level of lipid production at location 3. The proposed research will then use this information, along with information about each step of the process, to determine the required nutrient input at location 1. A sensitivity analysis will be performed to determine the variability that can be expected from the obtained results, and especially which steps of the process most greatly impact input requirements. The results will then be compared to the amount of available nutrients and nutrient sources at various locations 37 throughout the country. Evaluations will also be made for different recycling processes, microalgae strains, and additional bioproducts. Research Challenge and Question Challenge: The Energy Independence and Security Act of 2007 stipulates a 36 billion gallon biofuel production by 2022. Researchers have shown that scalability of microalgae biofuels is dependent on, and potentially limited by, available resources. In order to quantify the exact limits of large-scale microalgae production imposed by nutrient availability, lab-scale models of algae growth must be connected to system-scale modeling. This challenge inspires a key question to be answered by this research: What is the required nutrient input for a commercial-scale, microalgae production process when considering losses, efficiencies, and recycling? Additional Discussion Points: a. How does this input requirement compare to nutrient availability via wastewater and other sources? b. How do different system processes affect the overall system performance and nutrient input? c. How will additional end products affect the nutrient requirement of the system? d. Will different strains of microalgae significantly change the nutrient input requirements? e. What is the non-recoverable, elemental water consumption due to microalgae growth? 38 Description of Tasks for Completion In order to answer the research question proposed, the following information will need to be gathered or determined: 1. Nutrient losses during growth and harvesting. This includes nutrients not absorbed from the water during growth as well as algae missed during harvest that escapes. 2. Nutrient content in lipids 3. Biomass losses during extraction 4. Losses in the recycling process. This includes biomass losses throughout the process and the nutrient recovery rate. 5. Wastewater composition and supply at locations throughout the country 6. Characteristics of recycling processes (AD, Hydrothermal Liquefaction) 7. C:N:P Ratios for microalgae strains 8. Any other systems validation data The first step will be to generate mass balance calculations which reproduce the results found by Pate et al. (2011). This can be used to evaluate different C:N:P ratios. The next step will be to generate mass balance calculations for the full system model. The information listed above will be gathered, completed in parallel with the creation of mass balance equations. The mass balance equations will then be used to determine which aspects of the process will have great impact or little impact on the system input requirements. Those pieces of the process that have the greatest effect will 39 then be analyzed in greater detail to determine how much variability can be expected and to identify needs for future research. Four production levels will be used - the same levels used by Pate et al. (2011). A written summary of the process and results will be provided, as well as tables and graphs containing the complete results. Condensed results, displaying maximum, minimum, and mid-range results will also be provided. Work Plan 4A.1 Planned dates for completion of the proposed milestones Table A.1 Planned dates for completion of the proposed milestones Task Completion Date Determine Process Values 11/15/2012 Write Mass Balance Equations to Mathcad 11/15/2012 Run Scenarios and Gather Results 12/15/2012 Create Tables and Graphs for Results 1/15/2013 Write Summary of Results for Publication (First Draft) 2/5/2013 Write Complete Report for Thesis (First Draft) 3/20/2013 Submit Publication 4/10/2013 Thesis Defense 4/20/2013 40 References Abdel-Raouf, N., Al-Homaidan, A.A., Ibraheem, I.B.M.. 2012. Microalgae and wastewater treatment. Saudi Journal of Biological Sciences. 19, 257-275. Davis, Ryan, Aden, Andy, Pienkos, Philip T.. 2011. Techno-economic analysis of autotrophic microalgae for fuel production. Applied Technology. 88, 3524-3531. Frank, E.D., Han, J., Palou-Rivera, I., Elgowainy, A., Wang, M.Q.. 2011. 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Bioresource Technology. 102, 17-25. Wijffels, Rene H., Barbosa, Maria J. 2010. An Outlook on Microalgal Biofuels. Science. 329, 796-799. Woertz, Ian, Fulton, Laura, Lundquist, Tryg. 2009. Nutrient Removal & Greenhouse Gas Abatement with CO2 Supplemented Algal High Rate Ponds. WEFTEC. 79247936. Yang, Jia, Xu, Ming, Zhang, Xuezhi, Hu, Qiang, Sommerfeld, Milton, Chen, Yongsheng. 2011. Life-cycle analysis on biodiesel production from microalgae: Water footprint and nutrients balance. Bioresource Technology. 102, 159-165. 41 Appendix B. Detailed Process Block Diagrams 42 This appendix contains input/output diagrams for each process within the microalgae to biofuel production system that was modeled. The individual block diagrams were used to generate the mass balance calculations of the model, which appear in Appendix C. Figure B.1 shows the system as a whole, with each flow stream numbered, and corresponding numbers are contained in each subdiagram. There is one subdiagram for each process block within the system, which comprise Figures B.2 through B.6. Legend N - Nutrients (N,P,C/CO2) L - Lipid B - Biomass Leaving the system Input/output that remains within the system 6 Inputs Growth 4 Harvest Extraction 5 3 Filte r 9 2 2 End Product 7 Filter 8 9 10 1 Recycling Fig. B.1. Mass flow schematic of the complete microalgae to biofuel production process 9B.1 Mass flow schematic of the complete microalgae to biofuel production process 43 System Inputs: N Growth 1.From Recycling: N 2.From Harvest: N Loss to Env.: N,B 4.To Harvest: N,B 3.From Extraction: N Fig. B.2. Growth process input/output diagram 10B.2 Growth process input/output diagram Harvest Loss to Env.: N,B 4.From Growth: N,B 5.To Extraction: N,B 6.To End Product: B 9.To Recycle: B Filter1: N,B 2.To Growth: N Fig. B.3. Harvest process input/output diagram 11B.3 Harvest process input/output diagram 8.From Extraction: B Recycling Solids: N 9.From Filter1: B 10.From Filter2: B,L 1.To Growth: N Fig. B.4. Recycling process input/output diagram 12B.4 Recycling process input/output diagram 44 Loss to Env.: N,B,L Extraction 7.To End Product: L 5.From Harvest: N,B Ash: B 8.To Recycling: B Filter2: N,B,L 10.To Recycling: B,L 3.To Growth: N Fig. B.5. Extraction process input/output diagram 14B.6 Transesterification and end products process input/output diagram 6.From Harvest: B End Products 7.From Extraction: L Biomass Product Glycerine Transesterification: L Loss to Env.: L Fuel Product Fig. B.6. Transesterification and end products process input/output diagram 13B.5 Extraction process input/output diagram 45 Appendix C. Model Calculations in Mathcad 46 47 48 49 50 51 52 53 54 55 56 Appendix D. Complete Table of Model Parameter Values 57 Table D.1 is intended to serve as a supplement to Table 1 of the main text and also as an aid in understanding and utilizing the model developed (Appendix C). Whereas Table 1 provides a summary of the parameter values used for each scenario in terms consistent with the description of work contained in the text body and omits any information that is unessential for conceptual understanding, Table D.1 provides a complete summary of all model variables in terms consistent with the mass balance calculations in Appendix C. The variables listed in Table D.1 correspond to all of the terms highlighted in blue in the model. T 58 5D.1 Complete summary of system parameter values used for model mass balance calculations for the five production scenarios Table D.1 Complete summary of system parameter values used for model mass balance calculations for the five production scenarios CNP Lip_cont (%) H_perc (%) C_perc (%) Fuel_prod (BGY) Trans_Loss (%) NF_Lip (BGY) PL_Perc (%) NL_Biom (Mmt) Extr_Lip (%) Extr_Paste (%) Lip_extr_water (%) Biom_extr_water (%) Harv_Loss (%) Har_Biom (%) N_Rec_Eff (%) P_Rec_Eff (%) Whole_VS_Rat (g-VS g-TS-1) LEA_VS_Rat (g-VS g-TS-1) CH4_WholeVS (L g-VS-1) CH4_LEAVS (L g-VS-1) CH4_Burn (%) CO2_Conv Whole_CH4% (%) LEA_CH4% (%) CO2_Loss (%) Gro_Loss (%) N_Alg (%) CO2_abs (%) Baseline Optimistic Conservative 106:16:1 30 7.5 50 60 1 0 25 0 1 1 5 10 1 14.5 76 70 0.94 0.90 0.43 0.22 100 1 67 59 10 1 99 85 166:20:1 40 6 50 60 0.5 0 5 0 0.5 0.5 2 5 0.5 2 60 60 0.94 0.90 0.80 0.31 100 1 62 49 5 0.5 100 90 79:16:1 20 9 50 60 2 0 30 0 2 2 8 15 2 20 85 85 0.94 0.90 0.25 0.14 100 1 72 69 20 2 98 2 LEA coproduct 106:16:1 30 7.5 50 60 1 0 25 0 1 1 5 10 1 14.5 0 0 0.94 0.90 0.43 0.22 100 1 67 59 100 1 99 85 HTL 106:16:1 50 7.5 50 60 1 0 0 0 0 0 0 0 2 0 75 95 0.94 0.90 0.43 0.22 100 1 67 59 100 1 99 85 59 Appendix E. Calculations in Mathcad for Nutrient Source Availability 60 This appendix contains calculations to determine the level of nutrient source supply required to meet baseline system demands. These calculations serve as the intermediate step between the information supplied from the sources [59-61], and the values reported in Table 3. Throughout the research and writing process, several comparisons were attempted (i.e. Seawater required was originally reported as % of Colorado River annual flow, then later reported as % of Great Salt Lake). The information in the ultimately unused calculations could potentially be of value in future work, so all of the various calculations are included here. 61 62 63 64 65 66 67
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