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PERSPECTIVE

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Algae as a source of renewable chemicals: opportunities and challenges

Patrick M. Foley, Evan S. Beach* and Julie B. Zimmerman

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Published on 04 April 2011 on http://pubs.rsc.org | doi:10.1039/C1GC00015B

Received 4th January 2011, Accepted 1st March 2011

DOI: 10.1039/c1gc00015b
Algae are being explored as a sustainable energy feedstock, having potential to reduce dependence
on petrofuels and offset greenhouse gas emissions. Economic considerations and principles of
green design suggest that if algae-to-fuel technology is to be successful, biofuels must be produced
simultaneously with value-added co-products. At present, the algae industry is centered around a
limited number of products, such as low-volume/high-value speciality nutrients. New products for
medium- and high-volume markets will be needed as biomass production increases in scale. This
Perspective highlights non-fuel applications of algal biomass that have received relatively little
attention to date but are promising for future development. It is our goal to draw attention to
some of the unique opportunities that algae present with respect to biochemical composition as
compared to lignocellulosic energy crops.

Introduction
Global demand for energy has been projected to increase
49% by 2035.1 This demand, coupled with a nite oil supply
is expected to dramatically increase oil prices, and challenge
economic and institutional security worldwide.24 Adding to
these nancial and geopolitical concerns is the probability that
a continued reliance on petroleum-based feedstocks will lead to
an unacceptable amount of greenhouse gas emissions, harming
vital ecosystems.5 As a result, researchers and policy-makers are
exploring alternative energy feedstocks in the hope of averting
some of the most unfortunate scenarios. Much of this attention
has been directed at liquid biofuels from plant and, more
recently, algal feedstocks. Microalgae, in particular, have been
proposed as an appropriate source for hydrocarbons due to their
potentially high yield of lipid- and carbohydrate-rich biomass
per acre.67
While algal biofuels may prove to be a renewable and
sustainable alternative to petroleum energy, they have yet to be
viably produced on a commercial scale. However, the incentives
to make these technologies successful are signicant and have
thus resulted in considerable investment. This is evidenced, not
only by the number of dollars invested in algae,8 but also by the
markedly increased number of scholarly articles and intellectual
property lings on this topic in recent years (Fig. 1). This level
of activity has generated both optimism and scepticism among

Center for Green Chemistry and Green Engineering at Yale, 225 Prospect
Street, New Haven, CT 06511. E-mail: evan.beach@yale.edu; Fax: +1
203-436-8574; Tel: +1 203-432-5215
This paper was published as part of the themed issue of contributions
from the Green Solvents Alternative Fluids in Science and Application
conference held in Berchtesgaden, October 2010.

This journal is The Royal Society of Chemistry 2011

Fig. 1 The number algae-related patents and publications per year

using algae as a search term for patents, and algae and fuel as
search terms for publications in Chemical Abstracts.

interested parties. Arguments from the sceptical viewpoint

suggest challenges with energy balance, scale-up logistics and
economic viability.910 The biorenery concept, in which both
fuels and multiple value-added co-products are pursued in
parallel,11 has been proposed as a way to assuage many of
these concerns.12 This point of view is promoted by the United
States Department of Energy (DOE) National Algal Biofuels
Technology Roadmap, which cites the potential for valuable
co-products as one of the key reasons for exploring algae as
a source of biofuels.13 In our view, the biorenery approach is
both compelling and necessary. In the same way that petroleum
reneries maximize prots and material efciency through value
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Fig. 2 General schematic for algal biomass fractionation and co-product generation. References are provided in italics.

optimization of every chemical fraction, so too must algal

bioreneries if they are to be a viable and competitive alternative.
In addition to economic considerations, the biorenery concept
is in accordance with the principles of green engineering: systems
must include integration and interconnectivity with available
energy and materials ows.14
While species selection, cultivation and harvesting technology
will be deterministic factors in the economic viability of any
algae biorenery,1516 equally important will be the nature of
the chemical co-products recovered from the algal biomass.17
Accordingly, in addition to biofuels such as biodiesel and biogas,
the opportunity to make value-added chemicals from algal
biomass must not be overlooked1819 nor taken for granted.20
Commercial interest in the co-production of chemicals is
evidenced by several high prole collaborations in the private
sector, including the SolixBASF and SolazymeUnilever joint
ventures, both announced in 2010.2122 These efforts aim to
take advantage of the scale on which algae will be produced
and harvested for biofuels and chemicals, which is expected
to rapidly outstrip that of previous algal culturing efforts. The
United States Energy Independence and Security Act of 2007
mandates that transportation fuel contain 36 billion gallons
(136 billion liters) of renewable fuels by 2022.13 If algal biofuels
are to account for even 10% of that amount in the US alone,
production must be on the scale of tens of billions of liters.
As a result, chemicals generated as value-added co-products
must have broad applications to avoid immediately saturating
1400 | Green Chem., 2011, 13, 13991405

their respective markets. It will be important to align the target

chemical co-products with known commodity markets and
applications. Specically, high-value, low-volume markets that
are currently associated with the algae industry, such as pigments
and food supplements, must be augmented with moderatevolume, moderate-value markets (e.g., polymers, surfactants and
building block chemicals) and high-volume, low-value markets
(e.g., animal feed and fertilizer). The importance of portfolio
diversication in the algae industry is further underscored by
the fact that lignocellulosic fuels have projected production at a
similar scale. For algal biofuels to be competitive, overlapping
co-product markets such as dried distillers grain solids (DDGS)
for animal feed must be coordinated.23
The unique chemical composition of algal biomass will
differentiate the algae biofuel renery from lignocelluloseoriented bioreneries. As a rst approximation, the composition
of algal biomass is similar to that of conventional plant
biomass, with both containing primarily lipids, carbohydrates
and protein. Therefore, it might seem that many of the chemical
technologies associated with plant crops would be directly
transferrable to algae crops. However, unlike conventional plant
crops, algae lack the structural component lignin. This can be
viewed as advantageous in that the separation of more-valuable
carbohydrates from less-valuable lignin is often complicated and
resource intensive. Also, algae are commonly cultured under
dilute conditions, and while this results in the need for extensive
de-watering, it also allows for growth conditions to be tweaked
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to meet market demands in real time. This consideration, as well

as subtle differences in both lipid and carbohydrate composition
compared to plant crops, will inuence the resulting chemical
processes pursued, and will be the topic of the rest of this
discussion.

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The algae biorenery

A general schematic for the fractionation of algal biomass is
shown in Fig. 2. Algal biomass is primarily made up of lipids,
carbohydrates and protein, with the precise constitution varying
widely according to species and growth conditions. An example
breakdown for the lipid-rich green alga Neochloris oleoabundans
is shown in Fig. 3. Following will be a discussion of the potential
use of each fraction of algal biomass given its respective make-up
and a comparison to conventional plant resources.

Fig. 4 Lipid compositions of selected algae and plant crops; the circle
size corresponds to the average degree of unsaturation per lipid tail.

Table 1 Comparison of fatty acid composition between the green alga

C. vulgaris and soybean (as percentage of total fatty acids)

Fig. 3 Biomass composition of Neochloris oleoabundans, an oftenstudied candidate species for biofuels production. Data are taken from
Arredondo-Vega et al.24

Algal lipids. Vegetable and animal oils have long served as

important raw materials for a number of applications, including
surfactants, lubricants, polymers and foodstuffs.25 The primary
precursors for these products are mono-, di- and poly-functional
linear alkyl alcohols, aldehydes and acids are derived from
the oxidative or reductive functionalization of acyl lipids and
fatty acids.2628 These modications generally occur at either
the carboxyl or olenic moieties on the lipid, and the resulting
products thus depend on both the tail length and the degree
of unsaturation of the lipid precursor. Algal lipids are very
similar to many plant lipids, with the notable exception that
algal lipids are more likely to contain fatty acid components
having higher degrees of unsaturation.16,29 Fig. 4 aggregates
reported values of both tail length and unsaturation for several
representative algae and plant crops.25,2932 As can be seen,
many plant and algal crops have an average tail length in the
17/18 carbon range, with algal crops having only a slightly
higher average degree of unsaturation (see also Table 1). Not
captured by the gure is the importance of lipid distribution.
It has been observed for algae that highly unsaturated lipids
occur more frequently in polar lipid fractions, specically
phospholipids.33 Depending on species and growth conditions,
phospholipids can compose anywhere from 847% of the total
fraction of algal oil.34 In contrast, soy oil contains only 23%
phospholipid.35 Owing to the presence of the phosphate moiety,
these lipids complicate many transesterication, reduction and
combustion processes,3637 and are therefore not desirable for
biodiesel production without pre-treatment. Before use, these
This journal is The Royal Society of Chemistry 2011

Fatty acid

C. vulgaris

Soybean

C16:0
C16:1w7
C16:2w7
C16:3
C18:0
C18:1w9
C18:2w6
C18:3w3

18
5
12
2.1

9.2
43
10

210

26
2332
4852
212

phospholipids would have to be hydrolyzed or treated with

phospholipase enzymes to remove the phosphate moiety and
then be partially hydrogenated to comply with standards for the
maximum allowable polyunsaturated fatty acid (PUFA) content
in biodiesel.16,38
Alternatively, part or all of the phospholipid fraction could
be utilized for value-added chemicals. PUFAs present in this
fraction are well known for their nutritional value to humans
and other animals, and the potential of PUFAs as an algal
product have been extensively reviewed.12,18,28,3945 Although
these are currently valuable in terms of dollars per ton, the
potential market has been estimated at 100000 tons-equivalent
of dry biomass, far less than what would be necessary for
large-scale biofuel production.10 Similarly, phospholipids are
known to be surface active and are used as emulsiers in
food, cosmetic and pharmaceutical applications, but the existing
market for lecithins from soy and other conventional sources is
also limited.35 New opportunities may arise from the fact that
phospholipids will be amenable to many of the chemical transformations currently used in oleochemistry, such as epoxidation
and ozonolysis (Fig. 5).2628,46 These transformations can be used
to generate building block chemicals for large-scale commodities
such as polymers,4748 surfactants27 and lubricants.49
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Fig. 5 Phospholipids, which often make up a signicant portion of algal

lipid fractions, are amenable to chemical transformations that could lead
to novel and useful industrial products.

It is important to note that the higher degree of unsaturation

in these phospholipids will shift the prole of lipid oxidation
products towards greater functionality, and thus new products
and processes must be developed to accommodate this output.
For example, residual phosphorylated glycerides will be generated by ozonolysis chemistry,50 which will result in products
that have yet to be dened and utilized, as this chemistry
has previously been detailed only for fatty acid methyl esters
(FAME) and fatty acids, as shown in Fig. 6.5152 This represents
one of many opportunities that warrants further investigation
for next-generation algal bioreneries.

Fig. 6 The ozonolysis of oleic acid to yield commodity chemicals.

Beyond phospholipids, pigments like astaxanthin and uorescent phycobiliproteins may be recovered and used in small
niche markets estimated at hundreds or thousands of tons
per year in total.10,42 The recovery of pigments from algae has
been extensively reviewed.12,18,28,3941,45 The balance of the lipid
fraction will largely resemble traditional plant oils. The bulk
of this fraction will most likely be directed towards biodiesel
production, and will thus generate FAME and glycerol.29,5354
The glycerol co-product has been of great interest since the
inception of biodiesel production and has been proposed as a
platform chemical for a number of valuable products, including
solvents, building block chemicals and fuels.5558 As will be the
case with phospholipid derivatives, glycerol products must be
numerous and diverse in order to optimize the use of this byproduct on a very large scale.
Algal carbohydrates. Similar to lipids, algae and plant crops
differ signicantly in their carbohydrate fraction composition.
The diversity of algal species corresponds to diversity in the
polysaccharides they produce. Red algae are well known as
a source of gelling polysaccharides not found in plants such
1402 | Green Chem., 2011, 13, 13991405

as agar, furcellaran or carrageenan; these are predominantly

composed of D-galactose, 3,6-anhydro-L-galactose and sulfated
versions of the same. Several species of brown algae are
a source of alginates based on D-mannuronic acid and Lguluronic acid.39,59 Among the green algae, glycans are more
prevalent; galactose and mannose are also common components
of polysaccharides, and arabinose, fucose, rhamnose, ribose and
xylose can be found in small percentages.60 The algae growth
conditions and light regime affect polysaccharide make-up,61 as
do the culture medium and temperature,60 and the proportions
may change as the culture ages.62 These offer more potential
design variables for an algae biorenery compared to plant feedstocks. Also, many algae excrete extracellular polysaccharides
that are exotic in their composition and linkages. The green alga
Ankistrodesmus desmus, for example, produces a hydrophobic
polymer consisting mainly of fucose and 3-O-methylgalactose,
as well as a mannan with 12 and 14 linkages. Another
green alga, Dunaliella salina, which has no cell wall, excretes
sulfated polysaccharides. These are linked to nucleic acids and
concentrate in the growth medium up to levels of 1 g L-1 ,
increasing with salt concentration.6364 Among this wide variety
of biopolymers, so far, only red and brown algae extracts have
been exploited to any signicant extentagar, carrageenan and
alginates are well known as food additives and are used in niche
applications, but production levels are relatively low (tens of
thousands of metric tons per year).35 Cereplast has reportedly
used leftover biomass from lipid extraction to prepare plastic
materials, which could provide one additional outlet for algal
starches.65
There have been some efforts to study the fermentation of algal
biomass to produce bioethanol,66 but otherwise applications
of algal carbohydrates have scarcely mirrored the US DOE
Top 10 or Top 10 + 4 lists of value-added chemicals from
biomass.6768 Among the DOE principles for bio-based products
with greatest commercial importance are the ability of a chemical to be adapted to production of diverse structures, analogous
to petroleum reneries where a small number of building block
chemicals are the initial platform for both commodity and ne
chemicals.68 Intact algal polysaccharides would not meet these
criteria, but depolymerization to recover C5 and C6 sugars could
lead to several of the DOE Top 10 chemicals and possibly
new opportunities based on the more exotic components that
are more readily obtained from algae than land plants. The
unique potential of algal polysaccharides as a source of valuable
building block chemicals was highlighted in a recent report by
Kim et al.,69 who found that agar sourced from a species of red
macroalgae can be chemically transformed to yield much higher
amounts of 5-hydroxymethyl-2-furfural, a well known biomass
platform chemical, than would be expected from the amount
of galactose present in the biopolymer. This was ascribed to
the presence of 3,6-anhydrogalactose and the 13 linkages in
the polymer backbone (as opposed to 14 commonly found in
amylose and cellulose). They also found that agar could be used
to produce levulinic acid derivatives (Fig. 7).69 Besides chemical
methods for biomass conversions, biological transformations
may also benet from the presence of relatively exotic C5
and C6 monomers in algae. For example, the fermentation of
fucose and rhamnose can lead to a higher production of 1,2propanediol compared to starting from glucose.70 Therefore,
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mercial products.77 If algal biofuel production increases to the

billion-liter scale, natural products recovered from harvested
biomass or growth medium will assume a greater importance, and methods for their isolation and purication will be
needed.

Conclusions

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Fig. 7 The transformation of agar into biomass platform chemicals.

Conditions: (i) Dowex 50WX8 (50 wt%), DMSO solvent, 110 C, 5 h;
(ii) Dowex 50WX8 (50 wt%), [EMIM]Cl (50 wt%), CrCl2 (5 wt%), EtOH
solvent, 90 C, 15 h.69

algal polysaccharides rich in those particular sugars could be

more easily exploited for commodity chemical production.
In the context of FAME production, the processing method
will be critical to the success of any carbohydrate utilization
scheme. There have been some reports of simultaneous lipid
recovery and polysaccharide hydrolysis by chemical and enzymatic methods.71 Given the diversity of algal species and
their biochemical compositions, as well as varying cultivation
conditions, it will be important for carbohydrate processing and
recovery methods to be robust. A recent report describes a mild
cellulose hydrolysis technique that is effective in concentrated
sea water, which might prove to be useful in the treatment of
biomass from marine algae.72
Protein and residual fractions. As is the case for lipid and
carbohydrate fractions, the protein content of algae can vary
widely among species; for example, one survey of 40 species
representing a range of classes found protein levels ranging from
652%.60 Growth conditions are also important; in nutrientdepleted algae, the proportion of protein can drop by half.73
In some algae, as much as 40% of the total amino acids may
be found in the free form within the cell, with varying degrees
of enrichment in particular components. Many species are also
a source of non-standard amino acids like ornithine.61 Most
commonly, the protein fraction of algae strongly inuences nutrient recycling, including biofertilizers, and these applications
have been reviewed previously.41 The protein content of algae
has also been successfully exploited in integrated biorenery
systems, for example, the simultaneous production of biogas,
fertilizer and seed coatings has been reported for a full-scale
research plant primarily geared toward waste water treatment.74
Aquaow Bionomic is developing an integrated system for the
simultaneous production of biofuels, biochar and activated carbon with concomitant water remediation. The protein portion
of the algae can be converted to nitrogen heterocycles, including
pyrazines, pyridines and pyrrolidinones.75
Medicinal uses of algae are said to date back to ancient
China, and a variety of antibiotic, antifungal and antiviral effects
have been discovered.39 Many algae, particularly dinoagellates,
are associated with highly toxic natural products.76 Bioactive
and pharmaceutical chemicals from algae have been previously
reviewed in the literature, and it has often been noted that there
have been few commercial successes; however, this may stem
from the relatively limited efforts made in the eld.40,59 Some
whole or partial algae extracts, including protein-rich fractions,
have been used by cosmetics manufacturers to formulate comThis journal is The Royal Society of Chemistry 2011

Among biofuel feedstocks, algae hold the promise to offset much

or all of our fossil fuel use. However, many challenges in the
large scale production of algae have yet to be addressed and
the ultimate economic viability of algae-to-fuel technology is
not yet proven. While many of the outstanding challenges are
daunting, there are many reasons to be optimistic. Investment
in research and development has been steadily increasing, and
new multi-stakeholder collaborations bode well for innovation.
The further development of co-products for algal fuels will
help increase the likelihood of success. The criteria for which
chemicals are most promising as value-added algal biorenery
co-products will be scalability, demand and, most importantly,
raw materials. The algal biomass that will serve as the feedstocks
for chemical co-products is likely to have a unique and somewhat
tunable chemical composition in comparison to traditional plant
crops. The absence of lignin, the presence of phospholipids
and the unique carbohydrate fractions of algae, as well as the
variability between and within algal species, will require new
product platforms and technological adaptations beyond those
currently realized in conventional bioreneries. However, these
challenges can easily be viewed as opportunities. The biorenery
is an ideal setting for innovation, and the creativity of the green
chemistry and green engineering community with respect to
biomass transformations will be critical in improving the future
prospects for our energy and material economy.

Acknowledgements
We thank Erik Fyfe for bringing a number of interesting
references to our attention.

Notes and references

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