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CONTENTS

ACKNOWLEDGMENTS

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NOTATION

ix

ABSTRACT

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1 INTRODUCTION

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1.1 Interest in Algae

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1.2 Previous Life-Cycle Analyses of Algal Fuels

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1.3 GREET Model for Transportation Fuel Life-Cycle Analyses

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1.4 Goals of This Study

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2 METHOD

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2.1 Overview of Approach: Key Issues, Computational Framework, and GREET Expansion

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2.2 System Boundary

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2.3 Carbon Accounting

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2.4 Co-Product Treatment

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2.5 Reference Pathway, Baseline Pathway, and Functional Unit

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3 ALGAL OIL PRODUCTION MODEL

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3.1 Baseline Algal Fuel Pathway Overview

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3.2 Algae Growth and First Dewatering

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3.2.1 Nutrients

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3.2.2 Water Movement

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3.3 Secondary Dewatering

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3.3.1 Dissolved Air Flotation

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3.3.2 Dewatering Centrifuges

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3.4 Extraction

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3.4.1 Pressure Homogenization

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3.4.2 Hexane Extraction of Algal Lipids

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3.5 Fuel Production and Fuel Usage Models

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3.6 Energy and Nutrient Recovery: Co-Product Production

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3.6.1 Anaerobic Digestion

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3.6.2 Catalytic Hydrothermal Gasification for CH 4 Production

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3.6.3 Combined Heat and Power Systems

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3.7 Heating Values of Algae Biomass and Lipid-Extracted Algae

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3.8 Pathway Integration

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CONTENTS (Cont.)

4 WELL-TO-WHEELS RESULTS FOR ALGAL FUELS

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4.1 Baseline Scenario

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4.1.1 On-Site Balance of Co-Products, Electricity, and Heat

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4.1.2 Fossil Energy Use

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4.1.3 Petroleum Energy Use

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4.1.4 Greenhouse Gas Emissions

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4.1.5 Total Energy Use

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4.1.6 Sensitivity Analysis

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4.2 Reduced Emission Scenarios

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4.2.1 Low-A: Conservative Changes

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4.2.2 Low-B: Improved Extraction and CH 4 Handling

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4.2.3 Results for Reduced Emissions Scenarios

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4.3 Comparison with Other Fuels

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5 DISCUSSION AND CONCLUSIONS

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6 REFERENCES

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APPENDIX A: Process Scale and CO 2 Transport

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APPENDIX B: Nutrient Life-Cycle Analysis for Algae Growth

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FIGURES

1 Diagram of GREET Model, Which Includes More Than 100 Fuel Production Pathways from Various Energy Feedstocks

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2 Diagram of GREET Model Showing Many Potential Biofuel Production Pathways

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3 Life-Cycle Analysis Flowchart for Algal Fuels

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4 Carbon Flows in the Pathway

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5 Carbon Accounting

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

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7 Life-Cycle Analysis Flowchart for Gasoline and Diesel Production

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iv

FIGURES (Cont.)

8 Algal Lipid-Based Fuel Pathway

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9 Baseline Algae Lipid Production Process

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10 Flow of Nitrogen and Phosphorus in the System

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

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12 Carbon Mass Balance through Anaerobic Digestion

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

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14 Fossil Energy Use for the Baseline Scenario

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15 Contributions to Fossil Energy Use for the Baseline Scenario

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16 Petroleum Use for the Baseline Scenario

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17 GHG Emissions for the Baseline Scenario

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18 Contributions to WTP GHG Emissions

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19 Contributions to WTW GHGs from Fugitive CH 4 Emissions and Direct N 2 O Emissions from Digestate Solids Used as a Fertilizer Replacement

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

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21 Total Energy Use for the Baseline Scenario

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22 Sensitivity Analysis for Algae Baseline Scenario

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23 GHG Emissions for Two Reduced Emission Scenarios

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24 GHG Emissions for Renewable Diesel and Renewable Gasoline for a Reduced Emission Scenario

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

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v

FIGURES (Cont.)

A-1

Pipeline

65

A-2

Pressure with Friction Factor of 4 × 10 -3 and Density of 1.3 kg/m 3 in a 2-m-Diameter Pipeline

66

A-3

Velocity, Pressure, and Delivery Power for Flue-Gas Transport to

67

TABLES

1

Total Greenhouse Gas Emissions for Reference Pathways

15

2

Paddle Wheel Power Consumption

21

3

Self-Cleaning Disc-Stack Centrifuge Characteristics

22

4

Decanter-Bowl Centrifuge Characteristics

22

5

Literature Survey of Energy Inputs for Algae Oil Extraction Using Hexane as Solvent, per Kilogram of Extracted Oil

24

6

Wet Hexane Extraction Parameters Used in This Study, with Extraction Efficiency Assumed To Be 95%

24

7

Anaerobic Digester Performance, with Volumes at 0C and 1 Atmospheric Pressure

26

8

Energy Consumption for Biogas Cleanup for Several Processes

29

9

Carbon Content for Several Macromolecular Compositions

31

10

Technical Parameters for Catalytic Hydrothermal Gasification Process

35

11

Efficiencies and Emissions from Two CHP Technologies

38

12

Lower Heating Values for Macromolecules from Lardon et al. 2009

38

13

Direct Energy Consumption for Co-Product, Oil, and Fuel Transportation

39

14

On-Site Balances of Co-Product, Electricity, and Heat

41

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TABLES (Cont.)

15

Energy Intensities, Direct Energy Demand, and CO 2 Demand for Processes on Site

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B-1

Formulations for Algae Growth Media from the Literature

71

B-2

Inputs per Mass Unit of Nutrient Product

79

B-3

GREET Energy Inputs for Agriculture

80

B-4

Additional Energy Inputs for Remaining Feedstock and Intermediate Components

80

B-5

Overall Energy Inputs, Including Feedstock

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B-6

Energy Inputs for All Considered Algae Nutrients

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B-7

Energy Inputs for All Considered Algae Nutrients without Loss of Nitrogen in HNO 3 Conversion

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B-8

Energy for All Considered Algae Nutrients on a Molar Basis

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B-9

Energy Allocations Expressed as Fractions of Total Energy

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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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AD

AD residue

APD

BD

BOD

C

Ca(HPO 4 ) 2

CAPDET

CFM

CH 4

CHP

CIDI

CO

CO

2

CO

2 -e

COD

DAF

DAP

EPA

gCO 2 -e

GHG

GPM

GREET

HRSG

H 2 S

ICE

inWG

IPCC

LCA

LEA

LHV

NOTATION

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, (NH 4 ) 2 HPO 4

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

ix

MEA

mmBtu

monoethanolamine

million Btu

N

NH NO N 2 O

x

3

nitrogen ammonia mono-nitrogen oxides, NO and NO 2 nitrous oxide

P

PBR

PM

PM

PO 4

PSA pressure swing adsorption

psi pound(s) per square inch

psig pound(s) per square inch gauge

PTW pump to wheels (considers the usage by a vehicle portion of the life cycle)

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

10

2.5

SI

SO x

spark-ignited

sulfur oxides

TAG triacylglyceride

TS total solids

TSS total suspended solids

(NH 2 ) 2 CO

urea

VOC volatile organic compound

vol% percentage by volume

VS volatile solids

wt% percentage by weight, typically dry weight

WTP well to pump (considers fuel life cycle from resource acquisition through delivery of fuel at the fuel station)

WTW well to wheels (i.e., cradle to grave; considers entire fuel life cycle)

WWT wastewater treatment

x

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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 (CH 4 ) emissions during the production of biogas and nitrous oxide (N 2 O) 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 (gCO 2 -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 CH 4 losses from the biogas production and processing activities. This work may have implications for using agricultural- engineering 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.

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1.1 INTEREST IN ALGAE

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1 INTRODUCTION

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

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reductions were possible; however, if monoethanolamine (MEA) capture of carbon dioxide (CO 2 ) was employed to purify and concentrate the CO 2 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 CH 4 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 CH 4 emissions and emissions of nitrous oxide (N 2 O) when digestate is used as agricultural fertilizer as important factors for pathways using biogas produced by anaerobic digestion.

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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 Energy’s (DOE’s) 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 (CO 2 , CH 4 , and N 2 O), and emissions of six criteria pollutants: carbon monoxide (CO), volatile organic compounds (VOCs), mono-nitrogen oxides (NO x ), sulfur oxides (SO x ), particulate matter with a diameter no larger than 10 micrometers (PM 10 ), and particulate matter with a diameter no larger than 2.5 micrometers (PM 2.5 ).

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 algae- based biofuels, other biofuels, and other transportation fuels.

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6 FIGURE 1 Diagram of GREET Model, Which Includes More Than 100 Fuel Production Pathways from

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)

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7 FIGURE 2 Diagram of GREET Model Showing Ma ny Potential Biofuel Production Pathways
7 FIGURE 2 Diagram of GREET Model Showing Ma ny Potential Biofuel Production Pathways

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

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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, algal- nutraceutical 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-

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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 algae’s 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 large- scale 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 CO 2 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.

spark ignition (SI) engines for renewable gasoline fuels. FIGURE 3 Life-Cycle Analys is Flowchart for Algal

FIGURE 3 Life-Cycle Analysis Flowchart for Algal Fuels

2.3 CARBON ACCOUNTING

This work studied algae grown with CO 2 from power plant flue gas. Despite the fossil origin of this CO 2 , it is treated as atmospheric CO 2 in the analysis. The philosophy is that the power plant will operate whether algae are grown or not, and its CO 2 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 CO 2 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 CH 4 during biogas formation and back into CO 2 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 CO 2 can be emitted as CO, VOCs, and CH 4 . Conversion to CH 4 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 CO 2 emission. Biogenic carbon in CH 4 is added after the CH 4 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 CO 2 captured by the algae. The carbon accounting is summarized in Figure 5.

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C in C in Fuel Atmospheric CO2 Power Plant C in Emissions, C in Leaked
C in
C in
Fuel
Atmospheric CO2
Power
Plant
C in Emissions,
C in Leaked CO 2
C in
C in Emissions
Flue-Gas
Algae
C in
Oil
C in
C in
Fuel
Conversion
Growth
Algae
Extraction
Oil
Fuel
Combustion
C in LEA
C in Co-
products
Biogas
C in Biogas
Combustion
C in Emissions
Recovery
Upgrading
C
in LEA
C in Residue
C in
Electricity
Methane
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 CO 2 , 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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Emissions from processes, direct + upstream, are charged:

GHG Penalty
GHG Penalty

Pathway

 

Biogas and

 

Processes

Transport

Residue Combustion

Nutrients

Carbon from power plant (flue gas) is treated as atmospheric:

Zero
Zero
CO 2 Lost from Pond
CO 2 Lost from Pond
CO 2 Lost from Pond
CO 2 Lost from Pond
CO 2 Lost from Pond

CO 2 Lost from Pond

CO 2 Lost from Pond
CO 2 Lost from Pond
CO 2 Lost from Pond

Credits for CO 2 input and displaced fertilizer nutrients:

GHG Credit
GHG Credit
+ CO 2 Credit for Flue ‐ Gas Inputs Displaced Fertilizer Production
+
CO 2 Credit
for Flue ‐ Gas Inputs
Displaced
Fertilizer Production
for Flue ‐ Gas Inputs Displaced Fertilizer Production Net GHGs FIGURE 5 Carbon Accounting (Flue-gas CO
Net GHGs
Net GHGs

FIGURE 5 Carbon Accounting (Flue-gas CO 2 is treated as atmospheric, and back-end accounting is used to correctly account for the transformation of CO 2 to other emissions like CH 4 )

Imported Electricity, Natural Gas, and Nutrients

On-site processes On-Site Demand Recovered Power & heat Clean Recovered CHP E biogas nutrients AD
On-site processes
On-Site
Demand
Recovered
Power & heat
Clean
Recovered
CHP
E
biogas
nutrients
AD
Upgrade
E
Co ‐ methane
Raw biogas
Remnants
Algae Growth &
Oil Production
E
Algal oil

co-power

co-methane

oil

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 E lipid , E co-power , and E co-methane are the unallocated energies in the produced lipids, exported electricity, and exported CH 4 from the lipid production stage, then an allocation factor for the lipid production steps may be defined by Equation 1:

13

A lipid = E lipid / (E lipid + E co-power + E co-methane )

(1)

An allocation factor for the lipid conversion step can be defined similarly from E fuel, E glycerin , and E heavy , 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.

A conversion = E fuel / (E fuel + E glycerin + E heavy )

The whole-pathway emissions allocated to the final fuel product, GHG fuel

Allocated , are

(2)

calculated from the unallocated lipid-production emissions (GHG lipid ) and the unallocated conversion emissions (GHG conversion ) via Equation 3:

GHG fuel

Allocated = A conversion (A lipid (GHG lipid – GHG displaced-fertilizer ) + GHG conversion )

(3)

In this formula, A lipid (GHG lipid – GHG displaced-fertilizer ) are the emissions from the lipid production stage of the pathway that are allocated to the lipid intermediate. Multiplying them by A conversion 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 GHG displaced-fertilizer by A lipid and A conversion . 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 fuel

Allocated = A conversion (A lipid GHG lipid + GHG conversion ) – GHG displaced-fertilizer

(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 low- sulfur 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.

14

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 Transportation of Petroleum Refining Fuel Transport Recovery Crude and
Energy & Materials
Exploration and
Transportation of
Petroleum Refining
Fuel Transport
Recovery
Crude
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% CH 4 ) during crude oil production. The typical contributions for an average U.S.-processed barrel of oil are 3.37 m 3 of flared associated gas (typical flare efficiency of 98%) and 1.49 m 3 of vented associated gas. This adds up to 2,923 grams of carbon dioxide equivalent (g CO 2 -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 CO 2 -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 Pathways a

Share of Total (%)

 

Recovery,

Refining,

Total GHG

Including

Including

Vehicle

Emissions

Fuel

Transportation

Distribution

Operation

(gCO 2 -e/mmBtu Fuel)

Petroleum gasoline in SI engine Petroleum diesel in

6

15

79

97,986

CIDI engine

7

13

80

100,536

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.

16

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 to Air from all Fertilizer Production Algae & Lipid Lipid BD,
Energy & Materials
Emissions
to Air
from all
Fertilizer
Production
Algae & Lipid
Lipid
BD, RD,
Fuel
Fuel Combustion
Production
Transport
RG Production
Transport
in Vehicles
CO2
Supply
Residue
Transport
N 2 O from
Soil
Electricity,
Glycerin,
Soil Amendments,
Heavy Oils
Biogas,
Fuel Gas
Co-products
Feed

FIGURE 8 Algal Lipid-Based Fuel Pathway

Recovered H 2 O

Urea Bio ‐ DAF & Homogenizer, DAP Open Pond Flocculation Centrifuge Hexane Extraction Flue gas
Urea
Bio ‐
DAF &
Homogenizer,
DAP
Open Pond
Flocculation
Centrifuge
Hexane Extraction
Flue gas
0.5
10 g/L
200 g/L
g/L
Lipid-Extracted
Algae
Recovered CO 2
CHP
Biogas
Clean ‐ Up
Anaerobic
Digestion
N,P in liquid
N, P in Solids
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. CO 2 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/m 2 /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/m 2 /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 CO 2 , 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 (NH 3 ) 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 CO 2 per gram of algal biomass. CO 2 is delivered via 1.5-m sump with a utilization efficiency of 85%, resulting in a gross CO 2 requirement of 2.24 g per gram of algal biomass. Lundquist et al. (2010) estimates a CO 2 utilization efficiency of 75% for flue gas and 90% for pure CO 2 . The 85% utilization in this analysis is optimistic; however, power for CO 2 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 NH 3 . 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., (NH 2 ) 2 CO) 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(HPO 4 ) 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 P 2 O 5 ). 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

New Nutrients N P 0.014 g/g 0.0063 g/g Net Recovered to Culture Algae in Pond
New Nutrients
N
P
0.014
g/g
0.0063
g/g
Net Recovered to Culture
Algae in Pond
Loss of New Nutrients
N
P
N
P
N
P
0.0422
g/g
0.0063
g/g
0.0555
g/g
0.0125
g/g
0.0007 g/g
0 g/g
Lost in Return
Digester Supernatant
Residuals in Digester
N
P
N
P
N
P
0.0022 g/g
0 g/g
0.0444
g/g
0.0063
g/g
0.0555
g/g
0.0125
g/g
Digester Solids
N
P
0.0111
g/g
0.0063
g/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)

Makeup water 0.33 L/g

Evaporation

0.23 L/g 2 L/g Pond Settle
0.23 L/g
2 L/g
Pond
Settle

1.9 L/g

Pumping required0.33 L/g Evaporation 0.23 L/g 2 L/g Pond Settle 1.9 L/g 0.1 L/g FIGURE 11 Water

0.1 L/g

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

Lundquist’s 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

 

Power

Speed

Source

(W/ha)

(cm/s)

Benemann and Oswald 1996 Stephenson et al. 2010 Kadam 2001 Lundquist et al. 2010

1,226

20

3,670

30

2,344

2000

25

Pumping power, in principle, can be computed from the pumping velocity, pipeline characteristics (including length), pump efficiency, and elevation changes. In practice,

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/m 2 /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 85–97% are reported for self-cleaning disc stack centrifuges and of 85–95% 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 × 10 3 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 waste- activated 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

Value

Input total suspended solids (TSS) (%) Output TSS (%) Electrical power per volume flow (kWh/m 3 ) Liquid density (kg/1) Calculated electrical power per mass flow (kWh/kg)

0.1–1

5–12

1

1

1.0 × 10 -3

TABLE 4 Decanter-Bowl Centrifuge Characteristics (Mohn 1980; Grima, Fernández et al. 2007)

Parameter

Value

Input TSS (%) Output TSS (%) Electrical power per volume flow (kWh/m 3 ) Liquid density (kg/1) Calculated electrical power per mass flow (kWh/kg)

0.5–4

10–22

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

Stephenson

Lardon et al.

(2009)

Lundquist et al.

(2010)

Input per Kilogram of Oil

et al.

Dry,

Wet,

(2010)

Dry

Low N

Wet

Low N

Small

Large

Electricity (kWh) Heat (gross) (MJ) Hexane (loss) (kg)

0.056

0.417

0.194

2.333

1.083

0.092

0.045

1.700

7.100

3.200

22.400

10.200

3.579

2.686

0.003

0.015

0.007

0.055

0.025

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 kWh thermal /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%

Scenario

Natural Gas

(kWh thermal )/

kg-Oil)

Electricity

(kWh/kg-Oil)

Hexane Loss

(g/kg-Oil)

Baseline

1.7

0.54

5.2

High

3

1

10

Low

0.5

0.1

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.

25

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 CO 2 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 CH 4 and CO 2 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 CH 4 yield and gas production rate are important indicators of carbon conversion performance and overall process efficiency, CH 4 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 CH 4 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 CH 4 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 CH 4 Yield

The CH 4 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 CH 4 and CO 2 produces 0.35 L of CH 4 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 digester’s 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 CH 4 produced per gram of volatile solids (VS) in the feed (L-CH 4 /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 CH 4 potential via 0.35 L-CH 4 /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 CH 4 Yield, (L/g-VS)

CH 4

CH 4

 

Digestible

Ratio

Yield

Yield

Digestion

Source

Feed

Fraction

(g-VS/g-TS)

(L/g-VS)

(L/g-TS)

Time (d)

Ras et al.

Chlorella

33% of

0.85–0.90

0.15

0.15

16

2011

COD

51% of

0.85–0.90

0.24

0.22

28

COD

Samson

Spirulina

66% of VS

0.89

0.26

0.23

33, 70%

and

CH 4

Leduy

1982

Sialve

Chlorella

46% b of VS

0.63–0.79

0.31–

0.30 c

64

et al.

vulgaris

0.35

2009

Chlorella-

36% b of VS

0.59–0.79

0.17–

0.22

3–30

scenedesmus

0.32

(hydraulic

sludge

retention

 

time)

 

Dunaliella

65% b of VS

0.68

0.44

0.40

28

salina

Spirulina

38% b of VS

0.63–0.74

0.26

0.23

33

maxima

Collet

Chlorella

56% of

0.90

0.29

0.26

46, extrap- olated from Ras et al.

et al.

COD

2011

Ehimen

Chlorella

25%–65%

0.946

0.0–0.30

0–0.32

5–15

et al.

of VS

2011

a VS = volatile solids, TS = total solids, COD = chemical oxygen demand.

b Computed as the ratio of yield (VS)/theoretical.

c Assumes 0.9 g-VS/g-TS

27

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 CH 4 volume produced per gram of VS in the feed, and they reported the CH 4 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% CH 4 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 CH 4 volume per gram of VS in the feed. We computed the ratio of the experimental and theoretical CH 4 yields and display them as digestibility in the table. Sialve et al. (2009) also reports the CH 4 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 (25–40C) on CH 4 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 CH 4 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-CH 4 /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-CH 4 /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% CH 4 in the biogas, and VS destruction was between 50% and 55%.

Our objective is to estimate CH 4 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-CH 4 /g-TS and 0.4 L-CH 4 /g-TS were adopted as the

28

low and high points of the yield range. The midpoint, 0.3 L-CH 4 /g-TS, was used as the baseline value for CH 4 yield. The biogas volume was computed from the CH 4 yield based on 67 vol% CH 4 in the biogas. Note that in our approach, uncertainty in the CH 4 fraction produces uncertainty in the CO 2 recovery rate rather than uncertainty in the CH 4 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 kWh thermal /kg-TS and 0.11 kWh electrical /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 kWh electrical /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 kWh electrical /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 kWh electrical /kg-VS.

The process energy per volume of CH 4 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 (H 2 S), 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 CO 2 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.

29

Four types of technologies are commonly employed for removal of CO 2 , H 2 S, and other impurities: membrane separation, adsorption, absorption, and cryogenic distillation. Membrane separation separates CO 2 from the biogas stream by utilizing the differences in membrane permeability among CO 2 , H 2 S, and CH 4 . 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 CO 2 , H 2 S, and CH 4 to clean the gas stream. In PSA, contaminants are adsorbed more easily than CH 4 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 CO 2 (–59°F) in order to remove it from biogas. CO 2 Wash ® , developed by Acrion Technologies, is an example of cryogenic distillation that adopts absorption to remove other impurities by using the condensed CO 2 as absorbent. The CO 2 concentration of output gas (~27%) is still higher than that of pipeline- quality 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 300–500 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 lower-

pressure technology is chosen in future work, additional energy will be required.

TABLE 8 Energy Consumption for Biogas Cleanup for Several Processes (Potential fugitive CH 4 emissions do not account for CH 4 reduction in downstream processing of the process off-gas.) (Petersson and Wellinger 2009)

 

Organic

 

Water

Physical

Chemical

Parameter

PSA

Scrubbing

Scrubbing

Scrubbing

Electricity (kWh/Nm 3 -raw biogas) Temperature requirement (°C) Potential fugitive CH 4 emissions (%)

0.25

<0.25

0.24–0.33

<0.15

None <3%, 6–10% a

None

55–80

160

<1–2

2–4

<0.1

a Two sources reported different emissions.

30

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 C 4.43 H 7 O 1.44 N 1.16 and C 6 H 12 O 6 , 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 CH 4 and CO 2 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).

Total Solids

into Digester

(Weissman and Goebel 1987). Total Solids into Digester Digester Carbon = 44 wt% of dry solids
Digester

Digester

Carbon = 44 wt% of dry solids

Carbon = 44 wt% of dry solids

Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
Digester Carbon = 44 wt% of dry solids
into Digester Digester Carbon = 44 wt% of dry solids Carbon in CH 4 Carbon in

Carbon in CH 4 4

Carbon in CO 2 2

Carbon in Supernatant and Sludge (by difference)

FIGURE 12 Carbon Mass Balance through Anaerobic Digestion

31

New Nutrients Algae Process, Through Extraction Volatilization Loss Lipid Extracted Retained in Algae Extracted
New Nutrients
Algae Process,
Through Extraction
Volatilization
Loss
Lipid Extracted
Retained in
Algae
Extracted Oil
Digester Solids
Digester
Nutrients Added
Supernatant
to Digester
Returned to
Treatment and
Soil Amendment
Culture
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

Lipid

Protein

Carbohydrate

Carbon

Baseline

25

25

50

44

Low lipid

12.5

37.5

50

46

High lipid

50

2

25

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.

32

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 NH 3 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/NH 3

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 CH 4 Emissions from Anaerobic Digestion and Biogas Cleanup

Two studies of CH 4 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 CH 4 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% CH 4

33

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 CH 4 versus the CH 4 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 CH 4 production.

Liebetrau et al. (2010) identified several sources of CH 4