Académique Documents
Professionnel Documents
Culture Documents
CONTENTS
ACKNOWLEDGMENTS ........................................................................................................ viii
NOTATION ..............................................................................................................................
ix
ABSTRACT ..............................................................................................................................
INTRODUCTION ..............................................................................................................
1.1
1.2
1.3
1.4
3
3
5
5
METHOD ...........................................................................................................................
2.1
8
9
10
11
13
16
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
iii
16
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
40
40
40
41
44
46
48
49
49
50
50
50
54
REFERENCES ...................................................................................................................
58
63
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 ........
10
11
12
12
14
iv
FIGURES (Cont.)
8
17
17
20
11 Water Movement during Growth and First Dewatering per Gram of Harvested Algae .....
20
30
13 Mass Flows Used to Compute Nitrogen and Phosphorus Flows through the System ........
31
43
43
44
45
45
46
47
47
48
51
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
15
21
22
22
Literature Survey of Energy Inputs for Algae Oil Extraction Using Hexane as
Solvent, per Kilogram of Extracted Oil ...........................................................................
24
24
26
29
31
10
35
11
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
41
6
7
vi
TABLES (Cont.)
15
42
B-1 Formulations for Algae Growth Media from the Literature ............................................
71
79
80
B-4 Additional Energy Inputs for Remaining Feedstock and Intermediate Components ......
80
81
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
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
EPA
gCO2-e
GHG
GPM
GREET
HRSG
H2S
ICE
inWG
IPCC
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
wt%
WTP
WTW
WWT
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
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.
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
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
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
(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.
Exploration and
Recovery
Transportation of
Crude
Petroleum Refining
Co-products
Fuel Transport
and Distribution
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
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
17
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
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
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
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
Power
(W/ha)
Speed
(cm/s)
22
Value
0.11
512
1
1
1.0 10-3
Value
0.54
1022
8
1
8.0 10-3
23
from the decanter centrifuge (i.e., 168 kWh/dry ton for homogenization); however, discussions
with GEA Niro Soavi indicate that it is unusual to work above 20% solids because of pumping
difficulties and homogenizing efficiency. In EPA (2006), pressure homogenization energy
consumption was 750 kWh/dry-ton for 4 to 7 wt% solids, and it was 200 kWh/dry-ton with 90%
disruption efficiency in Davis (2010).
This analysis uses 183 kWh per dry metric ton and 90% efficiency, corresponding to
20 wt% input and some reduction in efficiency for the higher solids content. This treatment
assumes that undisrupted cells flow to recovery, downstream, for digestion. The reasoning is that
although no separation is done, the undisrupted algae will flow through lipid extraction and be
present in the LEA cake that is sent to recovery.
3.4.2 Hexane Extraction of Algal Lipids
Algal lipid extraction with solvents has not been demonstrated at scale or for a broad
range of species. The Aquatic Species Program close-out report included an experimental study
conducted by Nagle and colleagues (Sheehan 1998). Those researchers studied solvent extraction
of algal lipids with n-butanol, ethanol, and hexane/2-propanol and found the highest extraction
efficiencies occurred with n-butanol (90%), followed by hexane/2-propanol and ethanol. The
experiments used slurries with 15% solids, 90-minute reactions, 1,200 g of solvent, and 400 g of
wet biomass, giving a 3:1 solvent to biomass ratio. For comparison, soybean oil extraction mixes
volumes of solvent and soybean meal that are approximately equal. The soybean meal typically
contains 18.5 wt% oil.
A few papers describe models of algal oil extraction with hexane; they are summarized in
Table 5. Stephenson et al. (2010), on the basis of preliminary data (Stephenson et al. cites a
private communication), assumed that a 1:2 solvent-to-biomass volumetric ratio would recover
99% of the algal triacylglycerides. The authors then simulated solvent recovery with the HYSYS
process simulation software. The low solvent-to-slurry ratio is reflected in the low thermal
demand in Table 5 for Stephenson et al. (2010). Note that in the simplest approximation, the
thermal demand derives from the need to vaporize hexane, so the process heat demand should be
related to the total hexane in the process.
Lardon et al. (2009) assumed that the energy demand for a wet process would scale with
the reaction volume to estimate energy from established soybean oil extraction. The authors
appear to have assumed that the energy demand per process volume would be independent of the
lipid concentration, and they then scaled the result by the lipid fraction to prepare two scenarios,
one with 17.5 wt% lipids, and the other with 38.5 wt% lipids. The latter is listed as low N in
the table.
Lundquist et al. (2010) considered extraction from algae flakes produced by solar drying.
The authors thus used data for hexane extraction of soybean oil from dry meal. They considered
a regional extraction facility that would operate at larger scale in order to increase efficiency and
allocate costs over the algal growth facilities served.
24
TABLE 5 Literature Survey of Energy Inputs for Algae Oil Extraction Using Hexane as Solvent,
per Kilogram of Extracted Oil
Lardon et al.
(2009)
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
25
26
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
Ehimen
et al.
2011
Chlorella
25%65%
of VS
0.946
0.00.30
00.32
515
a
b
c
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
0.25
None
<3%, 610%a
Water
Scrubbing
<0.25
None
<12
Organic
Physical
Scrubbing
0.240.33
5580
24
Chemical
Scrubbing
<0.15
160
<0.1
30
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
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
Value
55
15
15
67
10
0.2805
0.2078
0.2009
0.4081
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
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
LHV (MJ/kg)
LHV (Btu/ton)
15.5
13
38.3
13,356,312
11,202,068
33,003,016
39
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
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
Remaining dewatering
Lipid extraction
Anaerobic digester
Biogas cleanup
Process Inputs
Thermal
Electrical
CO2 Demand
(kg CO2/kg lipid)
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
8,301
2,075
632
250
Biogas cleanup
1,310
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
BTU / mmBTU-BD
1200000
1000000
800000
1,000,000
0
600000
400000
548,329
200000
215,388
0
Conventional LS Diesel
Algae BD
44
PTW
WTP
BTU / mmBTU-BD
1000000
800000
600000
1,000,000
400000
200000
0
79,681
73,469
Conventional LS Diesel
Algae BD
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
80000
60000
60000
40000
40000
20000
20000
gCO2-e/mmBTU-BD
-20000
-20000
-40000
-40000
-60000
-60000
-80000
-80000
-100000
-100000
46
gCO2-e/mmBTU-BD
50000
40000
35,313
30000
20000
7,562
10000
12,566
0
Algae BD,
WTW
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
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
BTU / mmBTU-BD
3000000
2500000
2000000
1500000
2,589,441
1000000
1,000,000
500000
0
219,183
Conventional LS Diesel
Algae BD
PTW
WTP
48
Low
High
Alternative Scenario
-20000
-10000
10000
20000
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:
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 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:
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.
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.
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
52
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
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
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
6 REFERENCES
Air Liquide, 2008, Biogas Recovery System, http://www.airliquideadvancedtechnologies.
com/file/otherelement/pj/plaquette-biogaz57164.pdf. Accessed Sept. 2009.
Benemann, J.R., et al., 1982, Microalgae as a Source of Liquid Fuels, Final Technical Report,
U.S. Department of Energy, Washington, D.C.
Benemann, J.R., and W.J. Oswald, 1996, Systems and Economic Analysis of Microalgae Ponds
for Conversion of CO2 to Biomass, Final Report, Pittsburgh Energy Technology Center.
Borjesson, P., and M. Berglund, 2006, Environmental Systems Analysis of Biogas Systems,
Part I: Fuel-Cycle Emissions, Biomass and Bioenergy 30(5):469485.
Brown, S., et al., 2010, Calculator Tool for Determining Greenhouse Gas Emissions for
Biosolids Processing and End Use, Environmental Science and Technology 44(24):95099515.
Bruun, S., et al., 2006, Application of Processed Organic Municipal Solid Waste on Agricultural LandA Scenario Analysis, Environmental Modeling and Assessment 11(3):251265.
Campbell, P.K., et al., 2009, Greenhouse Gas Sequestration by AlgaeEnergy and Greenhouse
Gas Life-Cycle Studies.
Chambers, A., et al., 2006, DIAL Measurement of Fugitive Emissions from Natural Gas Plants
and the Comparison with Emission Factor Estimates, U.S. Environmental Protection Agency.
Chisti, Y., 2007, Biodiesel from Microalgae, Biotechnology Advances 25(3):294306.
Clarens, A.F., et al., 2010, Environmental Life-Cycle Comparison of Algae to Other Bioenergy
Feedstocks, Environmental Science and Technology 44(5):18131819.
Collet, P., et al., 2011, Life-Cycle Assessment of Microalgae Culture Coupled to Biogas
Production, Bioresource Technology 102(1):207214.
Cook, W., et al., 2005, Production of Liquid CH4 Truck Fuel from Landfill Gas, Final Report.
Brookhaven National Laboratory, Upton, N.Y.
Davis, R., 2010, Techno-Economic Analysis of Microalgae-Derived Biofuel Production, Report
EPA-HQ-OAR-2005-0161-2642, U.S. Environmental Protection Agency.
Davis, R., 2011, Techno-Economic Analysis of Autotrophic Microalgae for Fuel Production,
Applied Energy 88(10):35243531.
Eaton, A.D., and M.A.H. Franson, 2005, Standard Methods for the Examination of Water and
Wastewater, American Public Health Association.
59
Ehimen, E.A., et al., 2011, Anaerobic Digestion of Microalgae Residues Resulting from the
Biodiesel Production Process, Applied Energy 88(10):34543463.
Elliott, D.C., and L.J. Sealock, Jr., 1996, Chemical Processing in High-Pressure Aqueous
Environments: Low-Temperature Catalytic Gasification, Chemical Engineering Research and
Design 74a:563566.
Elliott, D.C., et al., 1993, Chemical Processing in High-Pressure Aqueous Environments, 2:
Development of Catalysts for Gasification, Industrial & Engineering Chemistry
Research 32(8):15421548.
EPA (U.S. Environmental Protection Agency), 1979, Process Design Manual for Sludge
Treatment and Disposal.
EPA, 2006, Emerging Technologies for Biosolids Management, Washington, D.C.
EPA, 2008, Catalog of CHP Technologies.
Flesch, T.K., et al., 2011, Fugitive CH4 Emissions from an Agricultural Biodigester, Biomass
and Bioenergy, in press, corrected proof.
Frank, E.D., et al., 2011, User Manual for Algae Life-Cycle Analysis with GREET: Version 0.0,
Draft, Argonne National Laboratory, Argonne, Ill.
Genifuel Corporation, 2011, Genifuel Corporation, http://www.genifuel.com/. Accessed
July 2011.
Grima, E.M., et al., 2007, Downstream Processing of Cell-Mass and Products, Blackwell
Publishing Ltd.
Guyer, J.P., 2011, Introduction to Sludge Handling, Treatment and Disposal, training course,
Continuing Education and Development, Inc., Stony Point, N.Y.
Harris, R.W., et al., 1982, Process Design and Cost Estimating Algorithms for the Computer
Assisted Procedure for Design and Evaluation of Wastewater Treatment Systems (CAPDET),
U.S. Environmental Protection Agency.
Huo, H., et al., 2008, Life-Cycle Assessment of Energy Use and Greenhouse Gas Emissions of
Soybean-Derived Biodiesel and Renewable Fuels, Environmental Science and Technology
43(3):750756.
IPCC (Intergovernmental Panel on Climate Change), 2006, N2O Emissions from Managed
Soils, and CO2 Emissions from Lime and Urea Application, in 2006 IPCC Guidelines for
National Greenhouse Gas Inventories, Vol. 4, Chapter 11.
60
IPCC, 2010, IPCC Expert Meeting on HWP, Wetlands and Soil N2O, http://www.ipccnggip.iges.or.jp/meeting/pdfiles/1010_GenevaMeetingReport_FINAL.pdf. Accessed
August 14, 2011.
Kadam, K.L., 2001, Microalgae Production from Power Plant Flue Gas: Environmental
Implications on a Life-Cycle Basis, National Renewable Energy Laboratory.
Lardon, L., et al., 2009, Life-Cycle Asessment of Biodiesel Production from Microalgae,
Environmental Science and Technology 43(17):64756481.
Liebetrau, J., et al., 2010, CH4 Emissions from Biogas-Producing Facilities within the
Agricultural Sector, Engineering in Life Sciences 10(6):595599.
Lundquist, T.J., et al., 2010, Realistic Technology and Engineering Assessment of Algae Biofuel
Production, Energy Biosciences Institute, Berkeley, Calif.
McPherson, M.J., 1993, Subsurface Ventilation Engineering, MVS Engineering.
Mintz, M., et al., 2010, Well-to-Wheels Analysis of Landfill Gas-Based Pathways and Their
Addition to the GREET Model, Argonne National Laboratory, Argonne, Ill.
Mohn, F.H., 1980, Experiences and Strategies in the Recovery of Biomass from Mass Cultures
of Microalgae, pp. 547571 in Algae Biomass, Elsevier/North-Holland Biomedical Press.
Moller, J., et al., 2009, Anaerobic Digestion and Digestate Use: Accounting of Greenhouse
Gases and Global Warming Contribution, Waste Management and Research 27(8):813824.
Murphy, C.F., and D.T. Allen, 2011, Energy-Water Nexus for Mass Cultivation of Algae,
Environmental Science & Technology 45(13):58615868.
Palou-Rivera, I., et al., 2011, Update to Petroleum Refining and Upstream Emissions, Argonne
National Laboratory, Argonne, Ill., in preparation.
Petersson, A., and A. Wellinger, 2009, Biogas Upgrading TechnologiesDevelopments and
Innovations, IEA Bioenergy.
Pomerantz, M., and L. Turcote, 2004, Production of Pipeline Gas from Landfill Gas in
Canada, presented at Wastecon 2004, Phoenix, Ariz., Sept. 2123.
Ras, M., et al., 2011, Experimental Study on a Coupled Process of Production and Anaerobic
Digestion of Chlorella vulgaris, Bioresource Technology 102(1):200206.
Redfield, A.C., 1958, The Biological Control of Chemical Factors in the Environment,
American Scientist 46:205211.
61
Samson, R., and A. Leduy, 1982, Biogas Production from Anaerobic Digestion of Spirulina
maxima Algal Biomass, Biotechnology and Bioengineering 24(8):19191924.
Sheehan, J., 1998, A Look Back at the U.S. Department of Energys Aquatic Species Program:
Biodiesel from Algae, National Renewable Energy Laboratory, Golden, Colo.
Sialve, B., et al., 2009, Anaerobic Digestion of Microalgae as a Necessary Step to Make
Microalgal Biodiesel Sustainable, Biotechnology Advances 27(4):409416.
Sim, T. S., et al., 1988, Comparison of Centrifugation, Dissolved Air Flotation and Drum
Filtration Techniques for Harvesting Sewage-Grown Algae, Biomass 16(1):5162.
Sperling Hansen Associates, 2007, Highland Valley Center for Sustainable Waste Management Landfill Gas Utilization Options, SHAPRJ06014, http://a100.gov.bc.ca/appsdata/epic/html/
deploy/epic_project_doc_index_263.html. Accessed July 2009.
Stephenson, A. L., et al., 2010, Life-Cycle Assessment of Potential Algal Biodiesel Production
in the United Kingdom: A Comparison of Raceways and Air-Lift Tubular Bioreactors,. Energy
and Fuels 24(7):40624077.
Tchobanoglous, G., et al., 2003, Wastewater Engineering: Treatment and Reuse, McGraw-Hill,
Boston, Mass.
Uduman, N., et al., 2010, Dewatering of Microalgal Cultures: A Major Bottleneck to AlgaeBased Fuels, Journal of Renewable and Sustainable Energy 2(1):012701-1 through -15.
Wang, M.Q., 1999a, The Greenhouse Gases, Regulated Emissions, and Energy Use in
Transportation (GREET) Model Version 1.5, Argonne National Laboratory, Argonne, Ill., Aug.
Wang, M.Q., 1999b, GREET 1.5Transportation Fuel-Cycle Model, Volume 1: Methodology,
Development, Use, and Results, ANL/ESD-39, Vol. 1, Argonne National Laboratory, Argonne,
Ill., Aug.
Wang, M.Q., 2001, Development and Use of GREET 1.6 Fuel-Cycle Model for Transportation
Fuels and Vehicle Technologies, Argonne National Laboratory, Argonne, Ill.
Wang, M.Q., et al., 2011a, Energy and Greenhouse Gas Emission Effects of Corn and
Cellulosic Ethanol with Technology Improvements and Land Use Changes, Biomass and
Bioenergy 35(5):18851896.
Wang, M., et al., 2011b, Methods of Dealing with Co-Products of Biofuels in Life-Cycle
Analysis and Consequent Results within the U.S. Context, Energy Policy, in press, corrected
proof.
62
Weissman, J.C., and R.P. Goebel, 1987, Design and Analysis of Microalgal Open Pond Systems
for the Purpose of Producing Fuels: A Subcontract Report, SERI/STR-231-2840, Solar Energy
Research Institute, Golden, Colo., prepared for U.S. Department of Energy.
Weissman, J.C., et al., 1988, Photobioreactor Design: Mixing, Carbon Utilization, and Oxygen
Accumulation, Biotechnology and Bioengineering 31(4):336344.
63
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.).
67
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
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
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
This point is especially important for mining products, as explained in the assumptions section.
73
74
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.
75
76
77
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).
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
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
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
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
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
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
Natural Gas
Electricity
Diesel
N
P
200
198
24
198
12
16
85
86