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CONTENTS
ACKNOWLEDGMENTS ........................................................................................................ viii
NOTATION ..............................................................................................................................

ix

ABSTRACT ..............................................................................................................................

INTRODUCTION ..............................................................................................................

1.1
1.2
1.3
1.4

Interest in Algae ........................................................................................................


Previous Life-Cycle Analyses of Algal Fuels ...........................................................
GREET Model for Transportation Fuel Life-Cycle Analyses ..................................
Goals of This Study ...................................................................................................

3
3
5
5

METHOD ...........................................................................................................................

2.1

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


Expansion...................................................................................................................
2.2 System Boundary ......................................................................................................
2.3 Carbon Accounting ...................................................................................................
2.4 Co-Product Treatment ...............................................................................................
2.5 Reference Pathway, Baseline Pathway, and Functional Unit ...................................

8
9
10
11
13

3 ALGAL OIL PRODUCTION MODEL .............................................................................

16

3.1
3.2
3.3
3.4
3.5
3.6

3.7
3.8

Baseline Algal Fuel Pathway Overview....................................................................


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

iii

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18
18
19
21
21
22
22
22
23
24
25
25
35
36
38
39

CONTENTS (Cont.)
4 WELL-TO-WHEELS RESULTS FOR ALGAL FUELS ..................................................
4.1

40

Baseline Scenario ......................................................................................................


4.1.1 On-Site Balance of Co-Products, Electricity, and Heat ................................
4.1.2 Fossil Energy Use..........................................................................................
4.1.3 Petroleum Energy Use ...................................................................................
4.1.4 Greenhouse Gas Emissions ...........................................................................
4.1.5 Total Energy Use ...........................................................................................
4.1.6 Sensitivity Analysis .......................................................................................
Reduced Emission Scenarios ....................................................................................
4.2.1 Low-A: Conservative Changes .....................................................................
4.2.2 Low-B: Improved Extraction and CH4 Handling ..........................................
4.2.3 Results for Reduced Emissions Scenarios ....................................................
Comparison with Other Fuels ...................................................................................

40
40
40
41
44
46
48
49
49
50
50
50

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

54

REFERENCES ...................................................................................................................

58

APPENDIX A: Process Scale and CO2 Transport ....................................................................

63

APPENDIX B: Nutrient Life-Cycle Analysis for Algae Growth .............................................

71

4.2

4.3

FIGURES
1

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

Diagram of GREET Model Showing Many Potential Biofuel Production Pathways ........

3 Life-Cycle Analysis Flowchart for Algal Fuels ..................................................................

10

Carbon Flows in the Pathway .............................................................................................

11

Carbon Accounting .............................................................................................................

12

Flowchart Showing How Energy and Nutrients Returned to the Process


Decrease Inputs to the Pathway System and Are Not Treated as Co-Products ..................

12

Life-Cycle Analysis Flowchart for Gasoline and Diesel Production..................................

14

iv

FIGURES (Cont.)
8

Algal Lipid-Based Fuel Pathway ........................................................................................

17

Baseline Algae Lipid Production Process ...........................................................................

17

10 Flow of Nitrogen and Phosphorus in the System................................................................

20

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

20

12 Carbon Mass Balance through Anaerobic Digestion ..........................................................

30

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

31

14 Fossil Energy Use for the Baseline Scenario ......................................................................

43

15 Contributions to Fossil Energy Use for the Baseline Scenario ...........................................

43

16 Petroleum Use for the Baseline Scenario............................................................................

44

17 GHG Emissions for the Baseline Scenario .........................................................................

45

18 Contributions to WTP GHG Emissions ..............................................................................

45

19 Contributions to WTW GHGs from Fugitive CH4 Emissions and Direct


N2O Emissions from Digestate Solids Used as a Fertilizer Replacement ..........................

46

20 Contributions to the Fertilizer Credit for Digestate Solids Applied to


Agricultural Fields ..............................................................................................................

47

21 Total Energy Use for the Baseline Scenario .......................................................................

47

22 Sensitivity Analysis for Algae Baseline Scenario ..............................................................

48

23 GHG Emissions for Two Reduced Emission Scenarios .....................................................

51

24 GHG Emissions for Renewable Diesel and Renewable Gasoline for a


Reduced Emission Scenario ................................................................................................

52

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

53

FIGURES (Cont.)
A-1 Pipeline Geometry. ..........................................................................................................

65

A-2 Pressure with Friction Factor of 4 10-3 and Density of 1.3 kg/m3 in a
2-m-Diameter Pipeline. ....................................................................................................

66

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

67

TABLES
1

Total Greenhouse Gas Emissions for Reference Pathways .............................................

15

Paddle Wheel Power Consumption .................................................................................

21

Self-Cleaning Disc-Stack Centrifuge Characteristics ......................................................

22

Decanter-Bowl Centrifuge Characteristics ......................................................................

22

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

24

Wet Hexane Extraction Parameters Used in This Study, with Extraction


Efficiency Assumed To Be 95% ......................................................................................

24

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


Pressure ............................................................................................................................

26

Energy Consumption for Biogas Cleanup for Several Processes ....................................

29

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

6
7

vi

TABLES (Cont.)
15

Energy Intensities, Direct Energy Demand, and CO2 Demand for


Processes on Site ..............................................................................................................

42

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 ...................................................................

81

B-6 Energy Inputs for All Considered Algae Nutrients..........................................................

81

B-7 Energy Inputs for All Considered Algae Nutrients without Loss of Nitrogen in
HNO3 Conversion ............................................................................................................

82

B-8 Energy for All Considered Algae Nutrients on a Molar Basis ........................................

83

B-9 Energy Allocations Expressed as Fractions of Total Energy...........................................

84

B-10 Energy Allocations on a Molar Basis for Nitrogen and Phosphorus ...............................

84

vii

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.

viii

NOTATION
AD
AD residue
APD

anaerobic digestion
digestate solids
Algae Process Description

BD
BOD

biodiesel
biochemical oxygen demand

C
Ca(HPO4)2
CAPDET
CFM
CH4
CHP
CIDI
CO
CO2
CO2-e
COD

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

DAF
DAP

dissolved air flotation


di-ammonium phosphate, (NH4)2HPO4

EPA

U.S. Environmental Protection Agency

gCO2-e
GHG
GPM
GREET

gram(s) of carbon dioxide equivalent


greenhouse gas
gallons per minute
Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation
(model)

HRSG
H2S

heat recovery steam generator


hydrogen sulfide

ICE
inWG
IPCC

internal combustion engine


inch(es) water gauge
Intergovernmental Panel on Climate Change

LCA
LEA
LHV

life-cycle analysis
lipid-extracted algae
lower heating value

ix

MEA
mmBtu

monoethanolamine
million Btu

N
NH3
NOx
N2O

nitrogen
ammonia
mono-nitrogen oxides, NO and NO2
nitrous oxide

P
PBR
PM10
PM2.5
PO4
PSA
psi
psig
PTW

phosphorus
photobioreactor
particulate matter with a diameter no larger than 10 micrometers
particulate matter with a diameter no larger than 2.5 micrometers
sulfuric acid
pressure swing adsorption
pound(s) per square inch
pound(s) per square inch gauge
pump to wheels (considers the usage by a vehicle portion of the life cycle)

SI
SOx

spark-ignited
sulfur oxides

TAG
TS
TSS

triacylglyceride
total solids
total suspended solids

(NH2)2CO

urea

VOC
vol%
VS

volatile organic compound


percentage by volume
volatile solids

wt%
WTP

percentage by weight, typically dry weight


well to pump (considers fuel life cycle from resource acquisition through
delivery of fuel at the fuel station)
well to wheels (i.e., cradle to grave; considers entire fuel life cycle)
wastewater treatment

WTW
WWT

LIFE-CYCLE ANALYSIS OF ALGAL LIPID FUELS


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

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

reductions were possible; however, if monoethanolamine (MEA) capture of carbon dioxide


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

1.3 GREET MODEL FOR TRANSPORTATION FUEL LIFE-CYCLE ANALYSES


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

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

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

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

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

10

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

FIGURE 3 Life-Cycle Analysis Flowchart for Algal Fuels

2.3 CARBON ACCOUNTING


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

11
C in
Fuel

C in
Atmospheric CO2

Power
Plant

C in Emissions,
C in Leaked CO2

C in
Flue-Gas

C in Emissions
Algae
Growth

C in
Algae

Oil
Extraction

C in
Oil

Conversion

Fuel
Combustion
C in Coproducts

C in LEA
Biogas
Recovery

C in
Fuel

C in Biogas

Combustion

C in Emissions

Upgrading
C in LEA

C in Residue

C in
Methane

Electricity

C in Atmosphere
from Fugitive CH 4

FIGURE 4 Carbon Flows in the Pathway

2.4 CO-PRODUCT TREATMENT


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

12
Emissionsfromprocesses,direct+upstream,arecharged:
GHGPenalty
Pathway
Processes

Biogasand
ResidueCombustion

Transport

Nutrients

Carbonfrompowerplant(fluegas)istreatedasatmospheric:
Zero
CO2Lost
fromPond

CreditsforCO 2inputanddisplacedfertilizernutrients:

GHGCredit
+

CO2Credit
forFlueGasInputs

Displaced
FertilizerProduction
NetGHGs

FIGURE 5 Carbon Accounting (Flue-gas CO2 is treated as atmospheric, and back-end


accounting is used to correctly account for the transformation of CO2 to other emissions
like CH4)

On-site processes
Imported
Electricity, Natural
Gas, and Nutrients

On-Site
Demand
Recovered
Power & heat
Clean
biogas

Recovered
nutrients

CHP

Upgrade

AD
Rawbiogas

Comethane

Eco-power
Eco-methane

Remnants
Algae Growth &
Oil Production

Algaloil

Eoil

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

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

13

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

(1)

An allocation factor for the lipid conversion step can be defined similarly from Efuel,
Eglycerin, and Eheavy, the unallocated energies in the final fuel, glycerin, and the various heavy oil
co-products (Equation 2). Heavy oil co-products occur if renewable diesel or gasoline is being
made.
Aconversion = Efuel / (Efuel + Eglycerin + Eheavy)

(2)

, are
The whole-pathway emissions allocated to the final fuel product, GHG Allocated
fuel
calculated from the unallocated lipid-production emissions (GHGlipid) and the unallocated
conversion emissions (GHGconversion) via Equation 3:
GHG Allocated
= Aconversion (Alipid (GHGlipid GHGdisplaced-fertilizer) + GHGconversion)
fuel

(3)

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

(4)

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

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
Recovery

Transportation of
Crude

Petroleum Refining

Co-products

Fuel Transport
and Distribution

Gasoline and Diesel


Combustion

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

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

15
TABLE 1 Total Greenhouse Gas Emissions for Reference Pathwaysa
Share of Total (%)

Fuel
Petroleum gasoline
in SI engine
Petroleum diesel in
CIDI engine
a

Recovery,
Including
Transportation

Refining,
Including
Distribution

Vehicle
Operation

Total GHG
Emissions
(gCO2-e/mmBtu Fuel)

15

79

97,986

13

80

100,536

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
toAir

from all
Fertilizer
Production
Algae&Lipid
Production

Lipid
Transport

BD,RD,
RGProduction

Fuel
Transport

FuelCombustion
inVehicles

Residue
Transport

N2Ofrom
Soil

CO2
Supply

Electricity,
Soil Amendments,
Biogas,
Feed

Glycerin,
Heavy Oils
Fuel Gas

Co-products

FIGURE 8 Algal Lipid-Based Fuel Pathway

Recovered H2O
Urea
DAP
Flue gas

OpenPond

0.5
g/L

Bio
Flocculation

10 g/L

DAF&
Centrifuge

200 g/L

Homogenizer,
HexaneExtraction

Lipid-Extracted
Algae
Recovered CO2

CHP

Biogas
CleanUp

Anaerobic
Digestion

N,P in liquid

N, P in Solids

Transport

Electricity

FIGURE 9 Baseline Algae Lipid Production Process

Soil Amendment

18

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

19

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

20

NewNutrients
N
P
0.014g/g 0.0063g/g

LostinReturn
N
P
0.0022g/g
0g/g

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

AlgaeinPond
N
P
0.0555g/g 0.0125g/g

DigesterSupernatant
N
P
0.0444g/g 0.0063g/g

ResidualsinDigester
N
P
0.0555g/g 0.0125g/g

LossofNewNutrients
N
P
0.0007g/g
0g/g

DigesterSolids
N
P
0.0111g/g 0.0063g/g

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

Evaporation
0.23L/g

Makeupwater
0.33L/g

2L/g
Pond

Settle

0.1L/g

1.9L/g
Pumpingrequired

FIGURE 11 Water Movement during Growth and First


Dewatering per Gram of Harvested Algae

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

21

Lundquists number. Sensitivity analyses scale


this by the cube of the velocity to consider
mixing speeds of 20 and 30 cm/s.

TABLE 2 Paddle Wheel Power Consumption


Source

Power
(W/ha)

Speed
(cm/s)

Pumping power, in principle, can be


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

22

3.3.2 Dewatering Centrifuges


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

Value
0.11
512
1
1
1.0 10-3

TABLE 4 Decanter-Bowl Centrifuge Characteristics


(Mohn 1980; Grima, Fernndez et al. 2007)
Parameter

Value

Input TSS (%)


Output TSS (%)
Electrical power per volume flow (kWh/m3)
Liquid density (kg/1)
Calculated electrical power per mass flow (kWh/kg)

0.54
1022
8
1
8.0 10-3

23

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

24
TABLE 5 Literature Survey of Energy Inputs for Algae Oil Extraction Using Hexane as Solvent,
per Kilogram of Extracted Oil
Lardon et al.
(2009)

Lundquist et al.
(2010)

Input per
Kilogram of Oil

Stephenson
et al.
(2010)

Dry

Dry,
Low N

Wet

Wet,
Low N

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

0.056
1.700
0.003

0.417
7.100
0.015

0.194
3.200
0.007

2.333
22.400
0.055

1.083
10.200
0.025

Small

Large

0.092
3.579

0.045
2.686

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

Scenario
Baseline
High
Low

Natural Gas
(kWhthermal)/
kg-Oil)

Electricity
(kWh/kg-Oil)

Hexane Loss
(g/kg-Oil)

1.7
3
0.5

0.54
1
0.1

5.2
10
2.5

3.5 FUEL PRODUCTION (CONVERSION) AND FUEL USAGE MODELS


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

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

26

Table 7 summarizes several studies of AD performance with algae feeds. These


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

Source

Feed

Ras et al.
2011

Chlorella

Digestible
Fraction

Ratio
(g-VS/g-TS)

Theoretical
CH4 Yield,
(L/g-VS)

CH4
Yield
(L/g-VS)

CH4
Yield
(L/g-TS)

Digestion
Time (d)

33% of
COD
51% of
COD

0.850.90

0.15

0.15

16

0.850.90

0.24

0.22

28

0.89

0.26

0.23

33, 70%
CH4

0.31
0.35
0.17
0.32

0.30c

64

0.22

Samson
and
Leduy
1982

Spirulina

66% of VS

Sialve
et al.
2009

Chlorella
vulgaris
Chlorellascenedesmus
sludge

46%b of VS

0.630.79

36%b of VS

0.590.79

Dunaliella
salina
Spirulina
maxima

65%b of VS

0.68

0.44

0.40

330
(hydraulic
retention
time)
28

38%b of VS

0.630.74

0.26

0.23

33

Collet
et al.
2011

Chlorella

56% of
COD

0.90

0.29

0.26

46, extrapolated from


Ras et al.

Ehimen
et al.
2011

Chlorella

25%65%
of VS

0.946

0.00.30

00.32

515

a
b
c

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


Computed as the ratio of yield (VS)/theoretical.
Assumes 0.9 g-VS/g-TS

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

28

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

29

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

Parameter

PSA

Electricity (kWh/Nm3-raw biogas)


Temperature requirement (C)
Potential fugitive CH4 emissions (%)

0.25
None
<3%, 610%a

Two sources reported different emissions.

Water
Scrubbing
<0.25
None
<12

Organic
Physical
Scrubbing
0.240.33
5580
24

Chemical
Scrubbing
<0.15
160
<0.1

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 C4.43H7O1.44N1.16 and C6H12O6, respectively (Lardon et al. 2009). Carbon
wt% was computed for three macromolecular compositions, and the value for the baseline
composition was used for the analysis (Table 9). As shown in Figure 12, the C flows to CH4 and
CO2 were computed from the biogas yield and composition, and the C in the digestate was
determined by difference. C was assumed to split evenly between supernatant and digestate
(Weissman and Goebel 1987).

TotalSolids
intoDigester

Digester
Carbon=44wt%
ofdrysolids
CarboninCH4
CarboninCO2
Carbonin
SupernatantandSludge
(bydifference)
FIGURE 12 Carbon Mass Balance through
Anaerobic Digestion

31

NewNutrients

AlgaeProcess,
ThroughExtraction
LipidExtracted
Algae

Volatilization
Loss

Retainedin
ExtractedOil

DigesterSolids
Digester
Supernatant

Returnedto
Culture

NutrientsAdded
toDigester

SoilAmendment

Treatmentand
Discharge

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

TABLE 9 Carbon Content (wt%) for Several Macromolecular


Compositions
Composition
Baseline
Low lipid
High lipid

Lipid

Protein

Carbohydrate

Carbon

25
12.5
50

25
37.5
2

50
50
25

44
46
47

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

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 NH3 would occur when the
supernatant was returned to a pond. Ras et al. (2011) measured 68% retention of N in the
supernatant when Chlorella was anaerobically digested at a retention time of 28 days.
Collet et al. (2011) extrapolated this to 90% recovery if the retention time was extended to
42 days and estimated that only 5% loss to volatilization would occur if the pond pH was
below 7. Recovery of P was not mentioned in these references.
The baseline scenario in this study assumes 80% of the N is retained as ammonium/NH3
in the supernatant that is returned to the pond, with only 5% volatilization resulting in 76%
recovery to the algae culture. The 20% fraction of N remaining in the solids is treated as organic
N with a bioavailability of 40% (Tchobanoglous et al. 2003; Bruun et al. 2006) that is exported
as a fertilizer replacement co-product that displaces the average emissions for N and P
production for corn farming. In the baseline scenario, P is split 50/50 between supernatant and
solids and utilized at 100%. P is important economically and for sustainability considerations
because of concerns about supply; however, N production is the major energy consumer, and the
P recovery rate will be shown to have little effect on the LCA results (see also Section 4.1.6).
The C in the digestate solids applied to fields provides a C sequestration credit.
Bruun et al. (2006) used a computational model to extrapolate soil emission data to application
of AD residues on arable land over periods of up to 100 years. Their modeling indicated that 8%
to 16% of the C in AD residues would remain in the soil; however, they commented that their
expectation was that all applied C should return to the atmosphere over time and that the
sequestration seen in their modeling likely reflects uncertainties in the experimental data for
long-term studies when emissions have become small. Nevertheless, the baseline analysis uses
the 8% figure. Sensitivity analyses will consider sequestration fractions of 0% and 16%.
3.6.1.5 CH4 Emissions from Anaerobic Digestion and Biogas Cleanup
Two studies of CH4 emissions from digesters were found in the literature.
Flesch et al. (2011) measured emissions from a state-of-the-art digester with a rated capacity of
1 MW in Canada that digests manure and organic substrates to make biogas for power
generation. Liebertrau et al. (2010) measured emissions at 10 German biogas facilities with
capacities ranging from 0.5 to 1.5 MW that process various energy crops and manure.
Flesch et al. (2011) determined that emissions differed according to activities at the site
and could be separated into three categories: normal operations, flaring, and maintenance.
During normal operations, fugitive emissions were 3.1% of the CH4 production rate; however,
this rose to 19% when there was flaring of excess gas and fell to 1.2% during maintenance.
Biogas flaring efficiency was observed to be less than usually expected, averaging 81% CH4

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

34

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

35

3.6.2 Catalytic Hydrothermal Gasification for CH4 Production


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

Value
55
15
15
67
10
0.2805
0.2078
0.2009
0.4081

3.6.2.1 Nutrient Recovery from Catalytic Hydrothermal Gasification


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

36

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

37

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

38
TABLE 11 Efficiencies and Emissions from Two CHP
Technologies (All efficiencies are based on the LHV value of the
fuel)
Gas Turbine
Efficiency

Low

Baseline

High

Internal
Combustion
Engine

Electrical (%)
Total CHP (%)

28
76

33
76

38
80

37
76

Pollutant

Amount of Emissions (g/mmBtu of Fuel Input)

VOC
CO
NOx
PM10
PM2.5
SOx
CH4
N2O
CO2

1.00
24.0
113
3.10
3.10
0.269
4.26
1.50
59,360

41.1
342
1,200
5.53
5.53
0.269
369
1.50
57,732

3.7 HEATING VALUES OF ALGAE BIOMASS AND LIPID-EXTRACTED ALGAE


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

LHV (MJ/kg)

LHV (Btu/ton)

15.5
13
38.3

13,356,312
11,202,068
33,003,016

39

3.8 PATHWAY INTEGRATION


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

TABLE 13 Direct Energy Consumption for Co-Product, Oil, and Fuel (Product)
Transportation (Energy intensities include backhaul of the vehicle when appropriate)

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

Energy Intensity
(Btu/ton mi)

Share
(%)

Distance
(mi)

1,028
2,200

100
0

50
50

370

100

600

403
370
1,028

8
29
63

520
800
50

1,028

100

30

40

4 WELL-TO-WHEELS RESULTS FOR ALGAL FUELS


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

41
TABLE 14 On-Site Balances of Co-Product, Electricity, and Heata
CHP Electricity
Total on-site generation
On-site electricity requirement
On-site use of generated electricity
Discarded electricity
Exported electricity
Deficit imported

Btu/kg-oil
14,620
19,450
14,620
0
0
4,830

Btu/Btu-BD
0.387
0.514
0.387
0.000
0.000
0.128

CHP Heat
Total on-site generation
On-site heat requirement
On-site use of generated heat
Discarded heat
Exported heat
Deficit imported

Btu/kg-oil
18,911
12,996
12,996
5,916
0
0

Btu/Btu-BD
0.500
0.344
0.344
0.156
0.000
0.000

AD Residue
Total produced
On-site use
Discarded residue
Exported residue

kg/kg-oil
2.60
0
0
2.60

kg/kg-BD
68.7
0.0
0.0
68.7

kg/kg-oil
3.47
0
3.47

kg/mmBtu-BD
91.7
0.0
91.7

CO2
Total produced
Discarded CO2
Recovered CO2 for algae growth use
a

BD = biodiesel.

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

42
TABLE 15 Energy Intensities, Direct Energy Demand, and CO2 Demand
for Processes on Site (All energies are net.)
Direct Energy Intensity
Process

Thermal

Electrical

Growth and first dewatering

1,348 Btu/dry-kg algae

Remaining dewatering

649 Btu/dry-kg yield

Lipid extraction

4,695 Btu/kg lipid yield

Anaerobic digester

1,856 Btu/dry-kg feed

4,772 Btu/kg lipid yield


464 Btu/dry-kg feed

Off-site CO2, transfer into pond

72.2 Btu/kg CO2

Recovered CO2, transfer into pond

72.2 Btu/kg CO2

Biogas cleanup

1,406 Btu/kg CH4 cleaned

Direct Energy Demand


(Btu/kg lipid)
Process

Process Inputs

Thermal

Electrical

CO2 Demand
(kg CO2/kg lipid)

Growth and first dewatering

2.24 kg CO2/kg algae

7,375

Remaining dewatering

1.17 kg algae/
kg dewatered algae

3,036

Lipid extraction

4.68 kg dewatered
algae/kg lipids

4,695

4,772

Anaerobic digester

4.47 kg feed/kg lipids

8,301

2,075

Off-site CO2, transfer into pond

632

Recovered CO2, transfer into pond

250

Biogas cleanup

1,310

Total direct demand on site

12,996

19,450

12.23

Recovered on site

18,911

14,620

3.47

4,830

8.76

Imported

12.23

43

PTW
WTP

Fossil Energy Use


1400000

BTU / mmBTU-BD

1200000
1000000
800000
1,000,000
0

600000
400000

548,329
200000
215,388
0
Conventional LS Diesel

Algae BD

FIGURE 14 Fossil Energy Use for the Baseline Scenario

FIGURE 15 Contributions to Fossil Energy Use for the Baseline Scenario


(Contributions are before a 55,500 Btu/mmBtu-BD fertilizer credit.)

44

Petroleum Energy Use


1200000

PTW
WTP

BTU / mmBTU-BD

1000000

800000

600000

1,000,000

400000

200000
0
79,681

73,469

Conventional LS Diesel

Algae BD

FIGURE 16 Petroleum Use for the Baseline Scenario

4.1.4 Greenhouse Gas Emissions


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

45

PTW
WTP
WTW

GHG Emissions
120000

120000

101,234
100000

100000

gCO2-e / mmBTU-BD

80000

80000

55,440

60000

60000

40000

40000

20000

20000

0
-20000

Conventional LS
Diesel

Algae BD
-20000

-40000

-40000

FIGURE 17 GHG Emissions for the Baseline Scenario

WTP GHG Emissions


80000

80000

60000

60000

40000

40000

20000

20000

Biogenic Carbon Credit (Fuel)

gCO2-e/mmBTU-BD

Displaced Fertilizer Credit


WTP Emissions Before Credits
WTP, Net
0

-20000

-20000

-40000

-40000

-60000

-60000

-80000

-80000

-100000

-100000

Algae BD, WTP

FIGURE 18 Contributions to WTP GHG Emissions

46

Contributions to WTW GHGs...


60000

All Other Sources


N2O from Soil
Amendment
Fugitive CH4

gCO2-e/mmBTU-BD

50000

40000

35,313

30000

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

FIGURE 19 Contributions to WTW GHGs from Fugitive CH4


Emissions and Direct N2O Emissions from Digestate Solids Used
as a Fertilizer Replacement

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

47

gCO2e/mmBTU-BD

Contributions to Soil Amendment Credit


15000

15000.0

10000

10000.0

5000

Fertilizer credit
C Sequestration
Transport
Direct N2O
Net

5000.0

0.0

-5000

-5000.0

-10000

-10000.0

-15000

-15000.0

FIGURE 20 Contributions to the Fertilizer Credit for Digestate Solids Applied


to Agricultural Fields

Total Energy Use


4000000
3500000
1,000,000

BTU / mmBTU-BD

3000000
2500000
2000000
1500000

2,589,441
1000000
1,000,000
500000
0

219,183
Conventional LS Diesel

Algae BD

FIGURE 21 Total Energy Use for the Baseline Scenario

PTW
WTP

48

4.1.6 Sensitivity Analysis


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

Lipid wt%, (12.5, 25, 50)


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

Low
High
Alternative Scenario
-20000

-10000

10000

20000

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

FIGURE 22 Sensitivity Analysis for Algae Baseline Scenario

30000

49

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

Reduces the CHP electrical efficiency from 33% to 29% and


Assumes the DAF dewatering produced 8% rather than 10% solids.

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

The lipid fraction was increased from the original 25 to 35 wt%.

The anaerobic digester was replaced with the catalytic hydrothermal gasification process
with 95% N recovery and 90% P recovery.

Total CH4 fugitive emissions were reduced from the original 2% to 0.2%.

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

50

unchanged. The catalytic hydrothermal gasification process might provide some benefits to an
LCA. First, it might reduce the potential for fugitive CH4 emissions by eliminating the large
process volumes and hold times for the digestate. The process also eliminates all biological N
and recovers the resulting inorganic N as NH3 in sterile water. This eliminates N2O emissions
from the digestate solids used as a fertilizer replacement and reduces the processs demand for N.
The fugitive CH4 emissions were reduced to 0.2% because AD emission processes, including
digestate storage, were avoided.
4.2.2 Low-B: Improved Extraction and CH4 Handling
This scenario changed the baseline as follows:

The lipid fraction was increased from the original 25 to 35 wt%.

The productivity was increased from 25 to 30 g/m2/d.

Total CH4 fugitive emissions were reduced from the original 2% to 0.2%.

The hexane extraction energy demand was set halfway between the baseline scenario and
the Low scenario in Table 6.

Sequestration of carbon in the digestate solids was assumed to be zero.

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

51

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

Reduced Emission Scenarios

gCO2-eq/mmBTU-BD

100000

100000

WTP

80000

80000

60000

60000

40000

PTW

39,628

36,246

20000

WTW

40000

20000

Low-A

Low-B

-20000

-20000

-40000

-40000

-60000

-60000

FIGURE 23 GHG Emissions for Two Reduced Emission


Scenarios (See text for definitions)

52

Renewable Diesel and Renewable Gasoline

GHG Emissions, gCO2-e/mmBTU

100000

100000

PTW

80000

80000

60000

60000

40000

WTP
WTW

39,628

45,908

39,786
40000

20000

20000

Low-A, Biodiesel

Low-A, RD

Low-A, RG

-20000

-20000

-40000

-40000

-60000

-60000

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

53

GHG Emissions

gCO2-e / mmBTU-fuel

150000

100000

PTW

150000

WTP

101,234

WTW

100000

55,440
39,628

50000

36,246

50000

22,494

21,801
5,909

-6,112

-6,316
-50000

-50000

-100000

-100000

Conventional
LS Diesel

Algae BD,
baseline

Low-A,
Biodiesel

Low-B,
Biodiesel

Soy BD

EtOH, Woody
EtOH,
Biomass
Herbaceous
Biomass

EtOH, Corn
Stover

EtOH, Forest
Residue

Fossil Energy Use


1400000

PTW
WTP

BTU / mmBTU-fuel

1200000
1000000
800000
600000
400000
200000
0
-200000
Conventional
LS Diesel

Algae BD,
baseline

Low-A,
Biodiesel

Low-B,
Biodiesel

Soy BD

EtOH, Woody
EtOH,
Biomass
Herbaceous
Biomass

EtOH, Corn
Stover

EtOH, Forest
Residue

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

54

5 DISCUSSION AND CONCLUSIONS


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

55

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

56

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

57

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

58

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63

APPENDIX A: PROCESS SCALE AND CO2 TRANSPORT


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

64

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

65

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

66

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

FIGURE A-2 Pressure with Friction Factor of 4 10-3 and Density of


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

67

A.2.4 Pipeline Diameter and Maximum Flow


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

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

68

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

69

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

70

71

APPENDIX B: NUTRIENT LIFE-CYCLE ANALYSIS FOR ALGAE GROWTH


B.1 NUTRIENTS FOR ALGAE GROWTH
Table B-1 summarizes several formulations for algae growth media reported in the
literature. While these media come more from the research domain than the mass culture domain,
the list contains the major chemical constituents that might be included in an algal life-cycle
analysis (LCA).
TABLE B-1 Formulations for Algae Growth Media from the Literature (grams per liter)
Substance
NH4Cl
NaNO3
KNO3
Ca(NO3)24H2O
(NH2)2CO
(NH4)2HPO4
K2HPO43H2O
K2HPO4
KH2PO4
K2SO4

Substance

BG 11a

1.5

Modified
Allensa

1.5

Bolds
Basala

Sorokin/
Kraussa

0.25

Zarroucka

Ben-Amotz &
Avrona

Chu
13b

2.5
1.25

0.505

0.2

0.014

0.04

0.02

0.04

0.039

0.075
0.175

0.5
1.25
1

Kratz & Myers,


Cc,d

Modified
Hughesc

Kesslerc

Sueokac

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

GPMd

NRELe

2
0.049
0.028
0.2

72

B.2 NUTRIENT LIFE CYCLE


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

B.2.2 Ammonium Chloride (NH4Cl)


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

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

73

B.2.3 Sodium Chloride (NaCl)


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

B.2.5 Nitric Acid (HNO3)


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

74

B.2.7 Potassium Chloride (KCl)


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

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

B.2.11 Potassium Phosphates (K2HPO4, K2HPO43 H2O, KH2PO4)


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

75

H3PO4 + KOH KH2PO4 + H2O.


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

B.2.12 Potassium Hydroxide (KOH)


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

76

B.2.15 Potassium Sulfate (K2SO4)


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

B.2.16 Langbeinite (K2SO42 MgSO4)


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

77

B.2.18 Sulfuric Acid (H2SO4)


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

B.2.20 Assumptions for Energy Inputs


Before calculating the energy inputs for each of the nutrient components, we must specify
some assumptions regarding the feedstock and intermediate components:

The split of reactants energy inputs between the reaction products is an important issue
for several components. We can distinguish several cases:

When there is a single reaction product, it receives the total energy inputs of the
reactants.

When some of the products escape from the process or are clear subproducts (gases or
water in solid reactions, etc.), the main product receives the total energy inputs of the
reactants.

Other cases (such as the NH4Cl manufacturing reaction above) are more complicated.
As a first approximation, we have assigned the energy inputs of the reactants by mass
allocation on the basis of the molecular weight of the products.

78

In terms of weighting the mining versus manufacturing energy inputs from the existing
energy inputs in GREET for agricultural components, we understand that, in most cases,
mining energy requirements dominate the result, except in cases where a particularly
energy-intensive manufacturing process is needed, such as high pressure (e.g., ammonia,
urea) or electrolysis (KOH below).

GREET already contains two feedstock types of materials from mining: KO2 and CaCO3.
GREET assumes the energy inputs for both of them to be identical, with the values in the
CaCO3 column in Table B-3 (appears later).

There are four more mining components needed as inputs to algae nutrient
manufacturing. We assume the energy required for each of these to be equal to the values
already in GREET for mining of K2O and CaCO3:

KCl is often mined together with K2O. This practice further supports the assumption
of using the same energy inputs for both of these components.

NaCl and KCl are very similar components, both in mining and usage. Therefore, the
energy inputs for these components should be similar.

NaNO3 is mined almost exclusively in Chile. Therefore, one can argue for using
higher values for its energy inputs to account for transportation uses.

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

B.2.21 Nutrients from Feedstock and Intermediates


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

79
TABLE B-2 Inputs per Mass Unit of Nutrient Product (Data are from GREET and manufacturing
reactions.)
Product
Input
NH3
NH4Cl
NaNO3
KNO3
Ca(NO3)2
Ca(NO3)24H2O
(NH2)2CO
K2HPO4
K2HPO43H2O
KH2PO4
(NH4)2HPO4
K2SO4
Ca(H2PO4)2 + 2 CaSO4
Ca(H2PO4)2
Ca(H2PO4)2H2O

NH3
(GREET)

HNO3
(GREET)

(NH2)2CO
(GREET)

H3PO4
(GREET)

CaCO3
(GREET)

H2SO4
(GREET)

Ca3(PO4)2
(GREET)

0.387

0.613
0.442
0.410

1.000
0.318
0.623
0.768
0.534

0.610
0.424
1.000
0.815
0.622
1.043
1.075

0.258

0.809
0.751

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

NaCl
(Mining)

KCl
(Mining)

KOH
(From KCl)

NaNO3
(Mining)

K2SO42MgSO4
(Mining)

1.093
1.000
0.737

0.653
0.856
0.548
0.570

0.794

80

B.3 ENERGY INPUTS OF NUTRIENTS


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

NH3

HNO3

(NH2)2CO

H3PO4

CaCO3

H2SO4

Ca3(PO4)2

27.490
26.370
1.120

0.532
0.526
0.006

2.269
2.140
0.129

4.637
4.173
0.464

3.900
1.053
1.638

0.108
0.045
0.064

0.245
0.000
0.245

1.209
0.405

0.567
2.674
3.525

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

TABLE B-4 Additional Energy Inputs for Remaining Feedstock and Intermediate Components
(mmBtu/ton product)
Intermediate Component

Total energy input


Natural gas
Electricity
Residual oil
Diesel fuel
Coal
Ammonia (ton)
Nitric acid (ton)
Sulfuric acid (ton)
Phosphoric rock (ton)

NaCl

KCl

KOH

NaNO3

K2SO42MgSO4

3.900
1.053
1.638

3.900
1.053
1.638

12.400
1.053
10.138

3.900
1.053
1.638

3.900
1.053
1.638

1.209

1.209

1.209

1.209

1.209

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

NH3

HNO3

Total energy input


Natural gas
Electricity
Residual oil
Diesel fuel
Coal

27.490
26.370
1.120

11.665
11.206
0.460

(NH2)2CO

H3PO4

CaCO3

H2SO4

Ca3(PO4)2

17.856
17.092
0.764

5.789
4.292
1.497

3.900
1.053
1.638

0.108
0.045
0.064

0.245
0.000
0.245

1.209

Chemical Intermediate
Energy Input

NaCl

KCl

KOH

NaNO3

K2SO42MgSO4

Total energy input


Natural gas
Electricity
Residual oil
Diesel fuel
Coal

3.900
1.053
1.638

3.900
1.053
1.638

12.400
1.053
10.138

3.900
1.053
1.638

3.900
1.053
1.638

1.209

1.209

1.209

1.209

1.209

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

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

Natural
Gas

Electricity

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

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

Residual
Oil

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

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

Coal

82
TABLE B-7 Energy Inputs for All Considered Algae Nutrients without Loss of Nitrogen in HNO3
Conversion (mmBtu/ton product)
Energy Input

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

Total
Energy
Input

Natural
Gas

Electricity

27.490
13.014
3.900
7.831
8.485
5.895
17.856
12.818
14.214
12.832
13.312
5.321
0.192
4.790
4.448

26.370
9.546
1.053
5.539
6.511
4.524
17.092
4.185
3.570
5.054
11.414
1.437
0.017
3.471
3.223

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

Residual
Oil

Diesel
Fuel

Coal

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

B.4 LCA RESULTS ON A MOLAR BASIS


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

83
TABLE B-8 Energy for All Considered Algae Nutrients on a Molar Basis
Energy Content
Substance
NH3
NH4Cl
NaNO3
KNO3
Ca(NO3)24 H2O
(NH2)2CO
(NH4)2HPO4
K2HPO4
K2HPO43 H2O
KH2PO4
K2SO4
Ca(H2PO4)2 + 2 CaSO4
Ca(H2PO4)2
Ca(H2PO4)2H2O

g/mol

mmBtu/ton

Wh/g

Wh/mol-N

17.03
53.49
84.99
101.1
236.15
60.06
132.06
228.22
174.18
136.09
174.26
506.33
234.05
252.07

27.49
13.014
3.9
10.146
7.878
17.856
13.312
14.214
12.818
12.832
5.321
0.192
4.79
4.448

8.88
4.20
1.26
3.28
2.54
5.77
4.30
4.59
4.14
4.14
1.72
0.06
1.55
1.44

151.2
224.8
107.1
331.3
300.5
173.2

Wh/mol-P

1,047.8
721.1
564.1
15.7
181.1
181.1

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

84
TABLE B-9 Energy Allocations Expressed as Fractions of Total
Energy (Derived from Table B-6)
Nutrient
NH3
NH4Cl
NaNO3
KNO3
Ca(NO3)2
Ca(NO3)2.4 H2O
(NH2)2CO
K2HPO4
K2HPO4.3H2O
KH2PO4
(NH4)2HPO4
K2SO4
Ca(H2PO4)2 + 2 CaSO4
Ca(H2PO4)2
Ca(H2PO4)2.H2O

Natural Gas

Electricity

Diesel Fuel

0.959
0.734
0.270
0.765
0.816
0.816
0.957
0.326
0.251
0.394
0.857
0.270
0.089
0.725
0.725

0.041
0.165
0.420
0.147
0.119
0.119
0.043
0.612
0.676
0.555
0.143
0.420
0.911
0.275
0.275

0.000
0.102
0.310
0.088
0.065
0.065
0.000
0.062
0.073
0.052
0.000
0.310
0.000
0.000
0.000

TABLE B-10 Energy Allocations on a Molar Basis for


Nitrogen and Phosphorus
Wh/mol
Element

Natural Gas

Electricity

Diesel

N
P

200
198

24
198

12
16

85

B.5 REFERENCES FOR APPENDIX B


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of Hydrocarbons and Exopolysaccharides in Various Media, Biomass and Bioenergy 31(1):87
93.
Freilich, M., and R. Petersen, 2005, Potassium Compounds, pp. 142 in Kirk-Othmer
Encyclopedia of Chemical Technology, Vol. 20, Wiley.
Gard, D., 2005, Phosphoric Acids and Phosphates, pp. 155 in Kirk-Othmer Encyclopedia of
Chemical Technology, Wiley.
Kratz, W., and J. Myers, 1955, Nutrition and Growth of Several Blue-Green Algae, American
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Muller, T., 2006, Sulfuric Acid and Sulfur Trioxide, pp. 152 in Kirk-Othmer Encyclopedia of
Chemical Technology, Vol. 23, Wiley.
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Starr, R., 1971, Algal CulturesSources and Methods of Cultivation, pp. 2953 in Methods in
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Weston, C., et al., 2003, Ammonium Compounds, pp. 711762 in Kirk-Othmer Encyclopedia
of Chemical Technology, Vol. 2, Wiley.
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Lawrence Berkeley National Laboratory, Berkeley, Calif.

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