Algal Biofuels:

The Process
Eric P. Knoshaug The production of algal biofuels involves
Al Darzins*
National Renewable algae cultivation, biomass harvesting and dewatering,
Energy Laboratory (NREL) lipid extraction, and conversion to fuel.

T
he idea of converting oils derived from microalgae volatility in the petroleum oil market, with crude oil prices
into high-energy-density transportation fuels is not hitting $145/bbl and a corresponding rise in gasoline and
new. In fact, from 1979 to 1996, the U.S. Dept. of diesel prices at the pump. Although prices have fallen back
Energy (DOE) sponsored the Aquatic Species Program to some degree since, they are projected to rise again as
(ASP), which thoroughly explored many facets of algal worldwide energy demand begins to increase. Second, as
biofuel production — from basic biology involving strain the concentration of CO2 in the atmosphere continues to
selection, growth, and lipid productivity to process-rele- rise due to the combustion of fossil fuels, concerns over
vant, large-scale cultivation. greenhouse gas (GHG) emissions and their environmental
Ultimately, however, the program was shut down for effects have spurred worldwide interest in reducing CO2
several reasons, including the conclusion at the time that emissions.
the estimated $40–60/bbl cost of producing algal oil would Finally, there is significant concern in the U.S. about
not be competitive national energy security, since more than half of the
with petroleum at country’s petroleum is imported from foreign sources.
$20/bbl for the fore- With an increased focus on establishing a domestic supply
seeable future (1). of energy, particularly liquid transportation fuels, many
Although that reason- organizations have expressed interest in developing an
ing may have been algae-to-biofuels process, including government agencies
sound then, much has (DOE, the Dept. of Defense (DOD), and Dept. of Agricul-
changed since 1996. ture (USDA)), small and large research and development
First, the world companies, major oil refiners, venture capitalists, utilities,
has experienced a airlines, and engine manufacturers.
period of extreme Another major advancement since 1996 has been
the explosion in biotechnological methodologies, mak-
t An NREL researcher ing it possible to dissect the inner workings of complex
examines a culture tube biological systems and manipulate those systems through
used for storing micro­­ metabolic engineering and systems biology approaches.
algae. More than 10,000
of these tubes are frozen Although genetic engineering of a diatom was attempted
and preserved in a cryo­ during the ASP, it was ultimately unsuccessful at increas-
preservation tank. Photo ing lipid productivities. However, with the abundance of
by Patrick Corkery, NREL new technologies developed in the past 14 years, the time
contract photographer.
may be ripe for achieving this goal using state-of-the-art
* Al Darzins is now with DuPont. biological engineering methods.

CEP  March 2011  www.aiche.org/cep  37

 SBE Supplement: Algal Biofuels
The potential of algae
Several of the attributes for which microalgae have
been long reviled, such as producing swimming pool scum
and clogging waterways, also make algae particularly
attractive as a biofuel feedstock. For example, algae have
greater biomass and oil productivity on a per-acre basis
than most terrestrial plants. Microalgae grow significantly
faster than terrestrial plants, frequently doubling their
biomass two times in one day, and can have an oil content
as high as 50% of the cell on a dry-weight basis. This rapid
growth and high oil content allow microalgae to yield
vastly more oil than traditional terrestrial plant crops. Even
assuming a relatively low areal productivity of 10 g of
dry algal biomass per m2 per day (g/m2-d) and a 15% oil
content, 633 gal per acre (gal/ac) can be produced, whereas
soybeans and corn typically produce only 48 gal/ac and 18
gal/ac, respectively (2).
In addition, algal biomass can be produced on non­
arable land and can be cultivated using a range of water
sources. Land and water use in an algae-to-biofuels process
may have less of an impact than other feedstock sources
and, in fact, may even be beneficial. Shallow, unlined
ponds can be built almost anywhere on any type of other-
wise unusable, nonagricultural, flat land. Algae can also
be found in almost any aquatic environment, from fresh to
brackish to salt water and even in nutrient-laden waste-
waters. This could be especially attractive near otherwise-
unusable saline water sources or produced water from oil
fields, providing the added benefit of cleaning up the water
source while producing raw materials for conversion to
fuels and other valuable products (3, 4).
In addition to the high-energy-density fuels derived
from the intracellular oils, algal residues could be
employed to produce other fuels from biomass after oil
extraction. Anaerobic digestion, which has long been used
to produce methane from various feedstocks, has the poten-
tial for recycling vital nutrients such as ammonia, phospho-
rus, and potassium back into the pond for algal cultivation
— a possible solution to the large fertilizer requirement for
robust, sustained, algal growth (5). Residual carbohydrates
present in the cell walls or as intracellular storage vesicles
could be fermented to produce ethanol or other alcohols.
Fermentation and anaerobic digestion of extracted algal
biomass have not been studied extensively, but they are
areas of ongoing research with potential to reduce the over-
all costs of biofuels production.
Recycling of phosphorus is particularly interesting
because of increasing controversy regarding the world’s
supply of this nutrient, which is essential to growing crops
and feeding the world’s increasing population. Accessible
phosphorus supplies are decreasing worldwide and are
expected to peak by 2030 (4). As supplies peak and begin
38  www.aiche.org/cep  March 2011  CEP
p Lee Elliott, a researcher at DOE’s National Renewable Energy Laboratory,
prospects for algae in saline water bodies throughout the western U.S.
A collaboration between NREL and the Colorado School of Mines, funded
by the Colorado Center for Biorefining and Biofuels, seeks to establish
a collection of up to 500 unique strains of microalgae. Photo by Dennis
Schroeder, NREL staff photographer.
to decline, the price of phosphorus can be expected to rise
rapidly as it becomes harder to mine. In addition, since the
majority of known reserves are controlled by China and
Morocco, there are political and economic consequences
associated with peak phosphorus (4, 6).
Few efforts are currently being made to capture and
recycle phosphorus. An algae-to-biofuels process has enor-
mous potential to address this situation, especially a pro-
cess developed around wastewater or agricultural runoff.
The final benefit — and perhaps the one that makes algae
a very attractive alternative for the production of biofuels
— is its potential to reduce GHG emissions by consuming
the CO2 before it exits the exhaust stacks of point sources
such as power and cement plants. Over 2 billion tons of
CO2 could be captured by growing algae on the space
equivalent to the entire U.S. soybean crop of 63.3 million
acres (based on a conservative algal areal productivity of
10 g/m2-d) (2). This capture of CO2 is actually a step in the
reuse of the carbon, as it will ultimately be released into
the atmosphere when the fuels are burned and the residual
biomass used. Nevertheless, capturing carbon through the
algae-to-biofuels process will ultimately lead to an overall
reduction in GHGs, because it uses CO2 that would have
otherwise been released to the atmosphere and will addi-
tionally reduce or eliminate new CO2 release by displacing
fossil fuel hydrocarbons from being burned.
The process
The production of lipid-based algal biofuels (Figure
1) starts with the cultivation of algae in a water resource
that cannot be easily used for agriculture (i.e., saline, sea,
or wastewater). Following algal growth and allowing for
the accumulation of oil, the algal biomass is harvested and
dewatered, and the lipids are extracted, leaving a residual
algal biomass comprised principally of proteins and car-
bohydrates. The lipids can be processed into high-energy-
density biofuels, either biodiesel (through transesterifica-
tion) or “green” diesel and jet fuel (through hydrotreating
at existing refinery facilities).
Algal growth facilities
A wide range of algal growth systems are currently
being tested. A major design decision is the choice between
open ponds or enclosed photobioreactors (PBRs), both of
which have merits (7).
Open ponds have a few simple designs, mainly a basic
square or round pond with gas sparging for mixing, or a
raceway style pond with paddlewheel mixing. Open ponds
are shallow, typically 10–30 cm deep, and can be unlined
(e.g., made of compacted clay) or lined with plastic or
concrete. The main advantage of open ponds is that they
are generally less expensive to build than PBRs.
However, open ponds have several disadvantages,
including high water consumption rates due to uncon-
trolled evaporation, and uncontrolled diurnal and seasonal
temperature fluctuations. An open pond is also exposed
to environmental variability from rain, wind, and fauna.
Although rare, rain events in the desert southwest can be
severe, and a sudden deluge of water into an open pond can
change the water chemistry and allow algae to escape due
to pond overfilling. Algae escape is of particular concern
when working with algal species that are not native to the
surrounding area or that have been genetically modified.
The choice of algal species can prevent escape. For
Recycle
O2 Water
Cultivation Harvesting
CO2
Water
Nitrogen
CO2
Phosphorus
Electricity
Electricity
Recycle as N, CO2, and Sugars
p Figure 1. An integrated algal biofuels process might capture CO2 from a power plant or industrial facility, obtain nutrients from wastewater or another
nonpotable source, and incorporate significant recycling.
example, a species that requires saline water would not be
able to proliferate in freshwater environments, and fresh-
water species would probably not survive if released into
saline or marine environments. It is likely that a saline spe-
cies will be required in land-based open ponds, which are
subject to constant evaporation that will drive the salinity
of the pond upward to an equilibrium point.
Wind and fauna also present challenges as vectors
of biological transport both into and out of the pond.
The resident algal species cultured in an open pond will
continuously be subjected to invasion and displacement
by bacteria, fungi, plants, and other algal species. A robust
and competitive species of algae is thus essential for an
open pond design. The use of a dense starter culture may
temper the threat of takeover and loss of the algal species
of interest.
Photobioreactors have a wide range of designs (8).
Panel and tube reactors typically consist of flat, horizon-
tal, or vertical panels, or vertical or inclined tubes, built
on support structures and using pumping or air-lift (i.e.,
the action of rising bubbles) for mixing. PBRs can also be
constructed of plastic bags hung from racks, suspended in
ponds or the ocean, or floating on the surface of the ocean.
PBRs have numerous advantages. Because they are
enclosed systems, they do not require as much makeup
water to replace evaporative losses. As a result, it is much
easier to maintain control of salinity, allowing the use of a
broader selection of algal species. PBRs may also be easier
to control in terms of their biological inputs. Without the
High-Energy-Density
Biofuels
Transesterification
or Hydrotreating
Lipids
Dewatering Processing
Protein
Dry Biomass
Residue
Carbohydrates
Waste
Heat
Industrial Facility or Power Plant
Methane
CEP  March 2011  www.aiche.org/cep  39
 SBE Supplement: Algal Biofuels
constant influx of other organisms and because the water
can be sterilized or sanitized, the algae species to be cul-
tured need not be as robust as those for use in an open pond
system.
PBRs do, however, have their own set of disadvantages.
The largest is the cost of materials needed to construct hun-
dreds or thousands of acres of PBRs. The energy required
to operate PBRs can also be large. Some species of algae
are sensitive to oxygen and the buildup and removal of
photosynthetically produced oxygen within the photobio-
reactor could be critical. Without the benefit of evapora-
tive cooling, temperature control will be required to avoid
extremely high daytime temperatures. Mixing is typically
achieved by pumping the algae through the PBR. Although
PBRs typically achieve higher rates of areal productiv-
ity, the energy-intensive nature of their operation calls
into question the overall energy balance and will be an
important determinant in the development of an economic
process.
Hybrid systems that combine features of both open
raceway ponds and PBRs are also being investigated (9).
One type of hybrid system consists of a stepped-
cascade of shallow troughs or an inclined planar surface
(which may be either baffled or unbaffled) (10). A thin
layer of culture is passed over the surface, making use of
gravity and turbulent flow for mixing, and is then pumped
back to the top for another pass. The culture is open and
exposed to the environment, yet a large infrastructure
of materials is required to create the stepped-cascade or
inclined surface. Ideally, such a system would be built on
p NREL is studying algae growth in a raceway-style open pond (left) and a closed photobioreactor (right). dissolved air floatation, and sedimenta-
Left photo by Eric Knoshaug, right photo by Patrick Corkery, NREL contract photographer.
40  www.aiche.org/cep  March 2011  CEP
sloped land to avoid the costs associated with building
a large support structure. The stepped-cascade style will
require additional energy input to pump the culture to the
top of the cascade.
Another hybrid system design uses a smaller PBR to
generate a seed culture, which is then used to inoculate a
large open pond. This dense, contaminant-free, inoculum
has a sufficiently high density to minimize competition
from other organisms during the period of growth and oil
accumulation. Generating it in a smaller-scale PBR elimi-
nates the need to deploy equipment over hundreds of acres.
In this way, costs can be kept to reasonable levels and the
benefits of both systems can be realized.
In all of the growth systems discussed so far, a consid-
eration that will have direct consequences on algal growth
and productivity is the amount of light energy the algae are
able to access. The light energy the culture is able to absorb
and use on an individual cell basis is critical to maintain-
ing high growth and lipid productivity rates. This is largely
influenced by the depth of the culture, and as the culture
grows, by its density. Open ponds are typically 10–30
cm deep, whereas depths in the hybrid inclined systems
studied ranged from 3 cm down to 6 mm for the unbaffled
planar surface design.
In studies, productivity increased as depth decreased
— from 17.2 g/m2-d (dry weight) in a typical open pond to
24.8 g/m2-d in an inclined baffled cascade 3 cm deep, to 32
g/m2-d in an 6-mm-deep, 50 m2, unbaffled, inclined planar-
surface pilot system (10).
The algal cell’s exposure to useful light should be
maximized during daylight hours. In
this regard, PBRs have an advantage
in that they can be made thinner for
better light penetration, whereas it
will be almost impossible to construct
an extremely shallow yet functional
open pond.
Harvesting, dewatering,
and extraction
The harvesting, dewatering,
and extraction steps of an algae-to-
biofuels process are often the most
energy-intensive steps. Typically,
microalgal cells are very small
(1–20 mm dia.) and are present at
only 1–2 g/L (dry weight) in a culture
ready for harvesting.
Existing technologies such as
centrifugation, filtration, flocculation,
tion are well suited to harvesting small
particles from bulk liquid. However, these processes are
either too energy- or chemical-intensive, or require too much
time, to be practical for harvesting lipid-rich microalgae.
The harvesting, dewatering, and extraction steps are
closely linked, in that the extraction process conditions will
dictate to what extent water must first be removed in the
dewatering process. Current solvent-based extraction tech-
nologies that use chloroform/methanol or hexane require
dry algal biomass, although several new solvent systems
are being evaluated.
Post-extraction biomass options
Technoeconomic modeling suggests that the residual
algal biomass remaining after oil extraction must be used
to make a saleable co-product or be recycled back into the
process to offset other costs for the entire process to be
economical. Few options exist for producing co-products
or recyclable nutrients from the protein and carbohydrate
fractions.
If the algal-to-biofuels process is carried out on a scale
that addresses the quantity needed for the fuel markets
(tens of billions of gal/yr), there will likely be an extreme
overabundance of algal proteins that could be used for
animal and fish feed, thereby saturating those markets and
consequently driving the price down. The remaining dry
biomass, composed primarily of carbohydrates, could be
pumped back into the cultivation step as growth-enhancing
sugars to prevent biomass losses at night.
Alternatively, a process step could be eliminated by
sending both fractions to an anaerobic digester. The meth-
ane produced by anaerobic digestion could be burned to
produce electricity, while the ammonia and sludge could be
recycled back through the growth process.
Economic and lifecycle issues
Although substantial investments have been made in
the development of algal biofuels, a variety of technical
barriers need to be overcome before commercialization of
algal biofuels can become a reality. It will be critical that
the industry develop cost-effective and efficient harvest-
ing and extraction methods that can be integrated into a
successful process. In addition, the recycling of nutrients
through anaerobic digestion and/or fermentation needs
much more study. Other critical elements will be the
resource requirements (e.g., land area, water source, yearly
available solar radiation, a nearby CO2 source), easy access
to nearby processing facilities, and the availability of a
suitable algal species.
After a very large land area for testing and development
is identified, the type of water found there will determine
which algae can be cultivated. It is then important to ensure
that the chosen species is robust enough to resist invasion
from other organisms, yet is unable to spread outside of
its designated environment. Furthermore, the local area
selected for cultivation must have readily available nutri-
ents necessary for the growth of the species. The area also
needs to have a large quantity of available CO2, and/or an
inexpensive method of transporting CO2 to the ponds. Algal
growth and processing facilities will likely be paired with
industrial facilities that produce significant quantities of
CO2. The harvesting, dewatering, and lipid extraction steps
should ideally be performed near the cultivation facility
in order to reduce the fuel used to transport the harvested
algal slurry.
A nontechnical issue related to algal biofuels develop-
ment is the misinformation that, at times, has been dissemi-
nated in the marketing of new technologies. Huge overesti-
mations of the realistic volume of algal-based biofuels that
can be produced per acre have appeared in the media. For
example, it has been reported that algae have the poten-
tial to produce 100,000 gal/ac-yr. Based on the amount
of energy that reaches the earth’s surface, the theoretical
maximum amount of oil that can be produced by algae
grown at the equator is 38,000 gal/ac-yr. After accounting
for the inherent inefficiencies in the transmission of light,
photosynthesis, heating of the earth, cellular energy use,
and the production of non-oil biomass, a more-reasonable
estimate is 5,000 gal/ac-yr in the best case scenario (11).
A related area of controversy is the debate on achievable
productivities in open ponds versus PBRs, and the lack of
accessible, reliable, real-world data at the pilot or produc-
tion scale (2). Thus, as investments in the alternative and
sustainable energy fields increase, scientists and the media
need to have realistic expectations for this new technology.
Finally, a thorough investigation of the sustainabil-
ity and lifecycle analysis (LCA) of algal biofuels should
include a detailed look at the net energy produced in the
final algal fuel compared to the energy inputs required
to produce the fuel — that is, energy returned on energy
invested (EROEI), and what portion of those inputs, if any,
are derived from fossil fuels. As algal biofuels are still in
their infancy, much controversy exists with regard to the
overall energy balance. One study suggests that unless
the algal oil content is 40%, anaerobic digestion without
a lipid separation step is the only process that would yield
a positive energy balance using current technology (5).
Similarly, the biochemical route to algal-based biofuels is
only one option — the energetics of gasification, pyrolysis,
and liquefaction of algal biomass directly or in combina-
tion with an initial lipid-extraction step suggest these may
be appropriate technologies as well (7). Only proper LCA
and technoeconomic analysis will reveal whether a given
algae-to-biofuels process can be operated economically
and sustainably.
Article continues on pg. 47
CEP  March 2011  www.aiche.org/cep  41
“Algal Biofuels: The Process” continues from p. 41

Closing thoughts
The technical elements required to produce lipid-based
fuels from algae have been demonstrated: from growth in
large-scale outdoor cultures, to harvesting, to lipid extrac-
tion, and finally the conversion of the oil to biodiesel
or other transportation fuels. Clearly, the production of
biofuels from microalgae is indeed possible. Although
much progress has been made in the laboratory, the large-
scale infrastructure for an algal biofuels industry does not
currently exist, and the economics of the technology at a
sufficiently large enough scale still need to be proven.
A greater understanding of the underlying principles
in algae production is necessary before a commercial
operation is feasible. It remains to be seen whether the
promising lab results can be achieved at scale, outdoors,
under real-world lighting and climate conditions, over
meaningful periods of time, and at a cost that ultimately
will compete with the cost of fuels derived from dwindling
petroleum supplies. CEP

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CEP  March 2011  www.aiche.org/cep  47