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Biorenewable chemicals: Feedstocks, technologies and the conflict with food

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 Renewable and Sustainable Energy Reviews 51 (2015) 506–520

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Biorenewable chemicals: Feedstocks, technologies and the conflict

with food production
Soubhik K. Bardhan a, Shelaka Gupta b, M.E. Gorman c, M. Ali Haider b,n
a
Department of Chemical Engineering, National Institute of Technology, Surathkal, Mangalore 575025, Karnataka, India
b
Department of Chemical Engineering, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
c
Department of Science, Technology and Society, University of Virginia, Charlottesville, VA 22903, USA

art ic l e i nf o a b s t r a c t

Article history: Volatile petroleum product prices along with depleting resources of oil and increasing environmental
Received 27 December 2014 concerns had prompted several government agencies to promote and subsidize the production of biofuels
Received in revised form from edible crops. The alarming rate at which edible crops were being deviated to produce biofuels caused
4 May 2015
the price of food crops like corn to shoot by a margin of over 100% in the initial three years (2005–2007). The
Accepted 1 June 2015
twenty-first century has so far witnessed an enormous growth in production of biorenewable chemicals. The
Available online 2 July 2015
economically more lucrative business of biorenewable chemicals is currently projected to grow at a
Keywords: compounded annual growth rate of 22.4% and account for 45% of the chemicals produced in the US by 2025.
Platform molecules This calls for a thoughtful regulation of the parameters, which should be considered for the production of
Edible and non-edible biomass
biorenewable chemicals, in order to avoid any direct conflict with food production. This study addresses the
Fermentation
possible edible and non-edible feedstock sources, conversion technologies used, conflict with food
Chemical conversions
production accessed in terms of market scenario, environmental concerns and availability of land area for
the effective conversion of the individual generation of feedstocks to biorenewable chemicals.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
2. Challenges faced in feedstock choices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
2.1. First generation feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
2.2. Second generation feedstock. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
2.3. Third generation feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508
2.4. Current market scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
2.5. Environmental concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 509
2.6. Estimated biorenewable chemical market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 510
3. Biomass conversion technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
3.1. Biological technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511
3.2. Chemical technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
3.2.1. Physical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
3.2.2. Thermochemical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
3.2.3. Chemical conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
3.3. Integration of biological and chemical technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 516
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517

n
Corresponding author.

http://dx.doi.org/10.1016/j.rser.2015.06.013
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520
1. Introduction
Fossil fuels currently account for over 80% of the primary energy
consumed in the world [1]. Rising concerns over diminishing fossil
fuel reserves coupled with global warming effects caused due to
alarming levels of CO2 in atmosphere has driven the society towards
the search for new renewable sources of energy, which have the
potential of replacing petroleum for the production of valuable fuels
and chemicals. In the recent years, biomass has shown promises as
an alternative feedstock, which can serve the needs of the energy
sector while keeping the CO2 emissions under control [2]. Mean-
while, the production of numerous value added chemicals using
multiple biological and chemical techniques on renewable biomass
has also gained enormous momentum [3]. This trend of increasing
demand of biomass calls for thoughtful regulations so as to
eliminate the chances of any direct conflict with food or environ-
ment in the production of such biorenewable chemicals. A proposed
biorefinery is suggested to have a variety of high value chemicals in
its portfolio leading to greater profits, which further raises concerns
over the use of edible biomass [4]. Inflation of corn prices in USA
post 2005 has been reported to be partly due to the deviation of
corn for biofuel production (Fig. 1a). Initial reports published by
World Bank suggested that there was a serious need to reconsider
all biofuel policies which subsidize its production in light of their
impact on food prices [5]. The production of biofuel alone resulted
in an estimated increase in corn prices by more than 100% in a span
of just three years 2005–2007 (Fig. 1a) [6]. The rapidly growing
production of biorenewable chemicals can further escalate prices of
corn and other edible feedstock. The growing market for biorenew-
able chemicals (Fig. 1b), along with the potential for generating
higher amounts of revenue compared with biofuels alone, has seen
many companies like Blue Marble Energy (Seattle, Washington,
USA) pivoting from producing biofuels to producing biorenewable
chemicals [7]. The potential of biorenewable chemicals to generate
higher revenue has been reaffirmed by reports generated by the US
Department of Energy [8]. According to the reports published by the
Iowa Energy Center, the revenue generated by deviating 70.6% of oil
to fuel amounts to a gross total of $385 bn compared to a revenue of
$375 bn generated by deviating only 3.4% of oil to petrochemicals
[8]. The US department of agriculture (USDA) forecasts that by 2025
at least a 45% share of chemicals will be accounted by biorenewable
chemicals. The biorenewable chemical market is likely to grow at a
rate almost double to that of biofuel [9,10].
The growing market for biorenewable chemicals requires greater
vigilance in order to ensure that the techniques used for their
Fig. 1. (a) Corn price and share of corn used for fuel (2000–2008) [6,126] and (b) estimated renewable chemical market [127].
507
production do not increase food prices. Numerous research reports
have been published in a short span of time regarding the produc-
tion of biofuels using varying feedstocks along with its respective
possible implications on food prices [11–14]. While several studies
have stressed upon the importance of avoiding any conflict with
food crops in biofuel production, to our knowledge no study has yet
concentrated on the impact of biorenewable chemical production
from edible biomass sources or non-edible biomass source grown
on an arable land. In our current work, we address the challenges
faced in dealing with issues related to feedstock selection for
biomass conversion along with the energy efficiency, economic
evaluation and environmental effects of technologies related to
biorenewable chemical production.
2. Challenges faced in feedstock choices
Biofuels have earlier been classified broadly into three genera-
tions based on the kind of feedstock which is being used for its
production (Fig. 2) [14]. The first generation of biofuels and
biochemicals is produced from edible feedstock whereas the second
and the third generations are produced from non-edible feedstock.
All potential feedstocks which can be used for biomass conversion
will be discussed in this study.
2.1. First generation feedstock
Biomass composed of primarily starch (including sugar) and edible
triglycerides comprises this generation of feedstock. Triglyceride feed-
stock derived from plant or animal sources generally consists of fatty
acids and glycerol. On the other hand, starchy feedstock composes of
glucose polysaccharides. The easy production of sugar monomers by
hydrolyzing glucose polysaccharides made starchy feedstock like corn
[15] and sugarcane [16] as one of the most preferred choice. However,
the use of edible food crops for the production of biofuels and
biochemical raises concerns about food prices and quantity, leading
to the search for alternative non-edible feedstocks [17].
2.2. Second generation feedstock
Lignocellulosic biomass qualifies to be an effective alternative to
the previous generation of food crops primarily owing to its non-
edible nature coupled with its abundant availability at a low price
[18]. The main hurdle faced by researchers though is the cost
involved in the conversion of lignocelluloses into simpler sugar
508 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520

Feedstock

First Second Third

Generation Generation Generation

Edible Seeds Lignocellulose

Starchy
(Triglycerides) Algae

Virgin Forestry Agricultural Energy

Wood Residues Residues Crops

Perennial Non-edible Woody

Forage Seeds Forage
Cereals & Beans & Nuts Starchy
Grains Lentils Vegetables

Fig. 2. Classification of biomass feedstock in three generations.

Table 1
Companies using first generation feedstock.

Company Feed Chemicals Market products

ADM Hamburg AG, Germany Rapeseed and grains Citric acid, lactic acid, citrate, ethyl Food ingredients like beverages, dairy and meat
lactate, polyols, ethanol products and biofuel
Diester Industrie, France Oil seeds Glycerol, fatty acids, esters, glycerin Food, pharmaceuticals, cosmetics, solvents,
detergents, paints, lubricants and biofuel
Jilin Fuel Ethanol, China Corn Ethyl acetate, ethanol Biofuel
LS9, Inc., United States Sugar cane, molasses, corn , sweet Esters, fatty acid (C8-C18), alcohols (C1- Diesel, kerosene, jet fuel
sorghum molasses, C14), amides and amines
Henan Tianguan Alcohol Chemical Corn, heat, molasses, and cassava 1,4 Butanediol, ethanol and ethylene Biodegradable plastics, gluten powder, biogas, and
Group Co., Ltd., China biodiesel
National Fuel Alcohol Program Sugarcane Ethanol Biofuel
(Proalcool), Brazil
Ultra Green Energy Services, Grains Ethanol Biodiesel and green home heating oil
United States
Renewable Energy Group (REG), Natural fats and oils Fatty acids, glycerin Biodiesel, naptha, fuel Oil.
United States
Butamax Advanced Biofuels LLC, Corn and sugarcane Bio-butanol Biofuel
United States

monomers [19]. Lignocelluloses comprise of cellulose, hemicellulose
and lignin. Celluloses are long-chain linear polysaccharides consisting
of 6-carbon glucose monomers. On the contrary, hemicelluloses are
short-chain branched polymers having an amorphous structure and
comprise of 5-carbon monomers such as xylose. Cellulose and
hemicellulose are interlaced to form a network of fibers where lignin
fills in to provide mechanical strength to the plant cell wall. Lignin is
a complex polymer comprises of aromatic alcohols and contains no
sugar. Lignin encloses cellulose and hemicellulose making them
difficult to hydrolyze and inaccessible by any operation before
pretreatment. This arises the need for the chemical or physical
pretreatment of lignocellulosic biomass [20]. Pretreatment proce-
dures are aimed at the depolymerization of lignin and the extraction
of celluloses and hemicelluloses. The isolated lignin can be used for
the production of heat and electricity along with the production of
high value chemicals [21]. The hemicellulose fraction can be used for
production of numerous chemicals including few organic acids [22].
The major portion of sugars derived from lignocellulosic biomass
though lies from the cellulosic section, which needs to be selectively
converted into fuels and chemicals.
2.3. Third generation feedstock
Since long, algae has been lumped in with the second generation
feedstocks [11]. Though the higher yield of lipids coupled with its
ability to grow on non-arable land has prompted researchers to
include algal feedstocks under a completely different generation of
feedstock, algae are capable of surviving on a diverse range of carbon
sources. It has the capacity to photosynthetically convert CO2 into
biofuel and valuable chemicals [24,25]. This serves the dual purpose
of both producing biofuels as well as biorenewable chemicals, while
reducing global emissions of CO2 and thus counteracting global
 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520
Table 2
Companies using second generation feedstock.
Company Feed Chemicals
Blue Marble Energy, United Cellulosic Oils, thioesters, esters, thiol/mercaptan(organic sulfur products)
States biomass
DuPont Danisco, United States Cellulosic Phytosterols, lactitol.
biomass
Fujian Zhongde Energy Co., Ltd., Waste oil Fatty acid methyl ester, monomer and trimer acid, dimer acid
China
Gushan Environmental Energy, Waste oil Asphalt, glycerol, and erucic acid
China
SG Biofuels, United States Jatropha oil – Biofuel including jet fuel
seeds
Gevo Inc., United States Cellulosic Isobutanol
biomass
Novozymes, Denmark Cellulosic Enzymes for conversion of biomass to ethanol, polypropylene
biomass and acrylic acid
Jatro BioJet Fuel, Germany Jatropha – Biofuel (mainly jet fuel)
warming. Currently the cost of conversion of algal feedstock is
comparatively higher and thus efforts are concentrated on improving
the existing technologies and building newer ones that can compete
with the present price of petroleum products in the market.
2.4. Current market scenario
The production of fuels and chemicals using an array of first
generation crops like corn and sugarcane via fermentation has gained
considerable momentum since the last decade. Over 45% of the
world's bio-chemicals were being produced by fermentation during
the year 2006, according to a survey conducted by SRI Consulting
[26]. The absence of an inexpensive mechanism for the complete
utilization of algal and lignocellulosic biomass has prompted many
companies to continue with the production of high value chemicals
and fuels through the same decade-old traditional techniques, inspite
of its possible implications for food markets and global hunger.
It is therefore essential to switch as much production as possible
from edible feedstock to non-edible feedstock. The US biofuel industry
has the challenging task of accomplishing high goals set by the newly
signed Renewable Fuels Standard (RFS) [27,28] where an estimate of
36 billion gallons of biofuel is projected to be required by 2022. This
should also include 16 billion gallons of cellulose-derived biofuel. The
simultaneous production of several high value chemicals as by-
products will be certain, thus paving way for the possible substitution
of various petroleum-based chemicals by their bio-based counterparts.
Thus, recently many companies and research institutions have pro-
posed various economical methods of producing biorenewable che-
micals or biofuels using the second generation of crops. Companies
like Novozymes (Bagsværd, Denmark), which have been using first
generation feedstock, have recently shown an inclination to search for
alternative non-edible feedstock. Novozymes, a biotech based com-
pany with an annual revenue of DKK 10.510 billion (2011) [29], plays a
major role in the production of food, pharmaceutical, biofuel and
biorenewable chemicals (polypropylene and acrylic acid). Along with
the production of several grades of biofuels, Novozymes has invested
in multiple research and development activities [30]. Since 2001,
Novozymes has been working alongside Department of Energy's
(DOE) National Renewable Energy Laboratory (NREL) for the efficient
and economic conversion of lignocellulosic biomass, with the help of
blending of various pretreatment strategies along with usage of new
enzymes. DuPont Danisco (Itasca, IL; USA), a joint venture of DuPont
and Genecor, like Novozymes had initially concentrated their focus on
biomass conversion from sugarcane bagasse and corn stover. As
concerns were raised regarding the biomass conversion of edible
feedstock, non-edible feedstock options like lignocelluloses were
explored and consecutively implemented for biofuel and biorenewable
509
Market Products
Cosmetic ingredients and fuel
Biofuel, synthetic rubber, fiber, food enzymes,
sweetners.
Diesel oil, hot melt adhesive, polyamide resin
Biodiesel
Plastics, fibers, rubber and other polymers,
hydrocarbon fuels
–
chemical production. A list of renowned companies using or have
proposed to use first generation feedstock (Table 1) and second
generation feedstock (Table 2) for the production of various end
products have been listed below.
2.5. Environmental concerns
The energy sector has consistently been one of the top con-
tributors to the production of greenhouse gases, including carbon
dioxide. The production of a renewable energy which has the
potential to provide energy security while reducing adverse climatic
effects is essential in the light of rapidly increasing greenhouse
emissions in the environment. This calls for the implementation of
carbon neutral or carbon positive CO2 reduction technologies. In
order to reach this landmark by 2050, the Nordic Energy Technol-
ogy Perspectives (NETP) has laid out a series of required steps,
which includes the steep increase of energy derived from biomass
along with the decrease in energy derived from oil products [31].
Biomass conversion has always been credited for the lower carbon
dioxide emissions in comparison to fossil fuels [32,33].
However, most of these studies failed to account the emissions due
to land use changes, as pointed out by Searchinger et al. [34]. Technically
for a process to be either carbon neutral or positive, the carbon uptake
credit (carbon absorbed by the plant from the atmosphere) should
either exceed or be the same as the net carbon discharge during
biomass conversion [34]. The net carbon discharge should also consider
the carbon storage or sequestration sacrificed during land use changes
due to either deforestation of forests or plowing of land in order to grow
the desired biomass. First generation crops converted to fuel may
therefore not reduce greenhouse gases by a significant amount, whereas
the careful usage of second generation crops might reduce overall
greenhouse gas emissions by as much as 27% [32]. Third generation
feedstocks in this case can be extremely effective. Not only can algae be
grown on a wide range of carbon feedstocks including pollutant carbon
dioxide, it also has the potential to grow on waste non-arable land, thus
not requiring any major land use changes. This ability of microalgae to
be grown on a diverse range of substrates has attracted many research
institutions and industries [35].
Blue Marble Energy (Seattle, Washington, USA) aims at repla-
cing petroleum products with biorenewable carbon neutral alter-
natives. They have played a pivotal role in production of several
biorenewable chemicals from cellulosic biomass. Recently, follow-
ing the emergence of third generation feedstock, Blue Marble
Energy has taken the initiative of producing biorenewable chemi-
cals from algal feedstock by announcing its partnership with algae
producer Bionavitas (Redmond, USA). Solazyme (South San Fran-
cisco, California, USA) is one of the other numerous startups
510 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520

Table 3
Start-ups using algae organisms for biochemical/biofuel production.

Company Feed Chemicals Market Products

Algenol, United States
PetroSun, United States
Sapphire Energy, United
States
Solazyme, United States
Solix Biofuels, United States
Joule Unlimited, United
States
Saltwater, CO2 and sugar Ethanol as by-product Energy in various forms
Organic matter(CO2 is the main required Ethanol, hydrogen Biodiesel
feed)
CO2, nutrients and sunlight Gasoline Biofuels including jet fuel
Sugar Alguronic acid Biofuel and cosmetic products
Sunlight and CO2 Lipids, proteins and Biofuel, bioplastic, jet fuel. cosmetics, food and
polysaccharides nutrition.
Waste water and CO2 Ethanol (requires freshwater) Biodiesel

Table 4
List of intermediates which can be produced from DOE top 12 platform chemicals [20,35,41,129,130].

DOE top 12 platform chemicals Intermediates

Succinic, fumaric and malic acids Tetrahydrofuran, γ-butyrolactone (GBL), pyrrolidones, esters, diamines,
4,4-bionelle, hydroxybutyric acid, derivatives of succinic acd and GBL
2,5 Furan dicarboxylic acid Adipic acid, terephthalic acid, bisphenol A, polyamides
3 Hydroxy propionic acid Malonic acid, acrylic acid, polymers, 3-hydroxy-methyl propionate, 3-hydroxypropionaldehyde.
Aspartic acid Precursor to amino acids,
Glucaric acid Dilactones, monolactones, other products
Glutamic acid Amino diols, glutaric acid,substituted pyrrolidones, 3-cyanopropanoic acid, glutamic acid-5-methyl ester.
Itaconic acid Poly(methyl methacrylate), unsaturated esters, polyitaconic acid, 3-methyl-THF
Levulinic acid Methyltetrahydrofuran, delta-aminolevulinic acid, diphenolic acid, THF, BDO
3-Hydroxybutyrolactone Hydroxybutyrates, epoxy-γ-butyrolactone, butenoic acid
Glycerol 1,3-Propanediol, glycidol, propanol, branched polyesters and nylons, di-glyceraldehydes, glycerol carbonate, glyceric acid
Sorbitol Glycols, glycerol, lactate, isosorbide
Xylitol/arabinitol Glycols, glycerol, lactate, hydroxy furans, sugar acids

OH O

HO
OH OH

O Malic acid
HN NC OH
NH CN H3C
Propylene glycol
Succinonitrile
1,4-Diaminobutane
O
O
O
HO
OH HO O O
HO
OH
H2C
OH
O H3C OH H3C H
O
Tetrahydrofuran O Succinic acid Acrylic Acid Lactic Acid Acet aldehyde
(THF) Fumaric acid

H
O
OH O
O N
OH
HO
H3C CH3
HO
OH
O
1,4-butanediol
2,3-Pentanedione
O OH 2-Pyrrolidone
Tartaric acid

Fig. 3. Common useful products derived from (a) succinic acid and (b) lactic acid.

(Table 3) which are currently operational or have been proposed
for the specific utilization of algal feedstock in the production of
value added products. Solazyme is known to grow algae in dark
and feed them sugar. Such start-ups which have resorted to use
sugar as substrate to grow algae need to ensure that these sugar
monomers are derived from non-edible feedstock, in order to
avoid competition with food.
2.6. Estimated biorenewable chemical market
Most of the commercial processes are focused on the production
of high yield biofuels via the synthesis of platform molecules. The
same process can be adapted for the production of innumerable end
products [4]. In fact in many cases the production of biorenewable
chemicals might turn out to be economically more lucrative than
the production of just biofuels. This might tempt many companies
to either spend considerable energy biorenewable chemicals pro-
duction in the form of by products while producing biofuels or shift
their focus completely towards the production of biorenewable
chemicals from easily accessible biomass. This will indeed set the
platform for a direct conflict of food vs biorenewable chemicals in
case edible feedstock is diverted for the production of these
chemicals. The 12 value added chemicals identified as potential
building blocks by the US Department of Energy have multiple
 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520
applications in the field of textile, medical, transportation and
housing [36]. The major chemical intermediates which can be
produced using various platform chemicals are shown in Table 4.
The microbial production of platform chemicals using first gen-
eration feedstock has been the most predominant biomass conver-
sion technique since the last few decades. Song et al. have thoroughly
reviewed the production of a few value added chemicals like succinic
acid derived from fermentation of agricultural carbohydrates [37].
Recently, the widespread applications of succinic acid in fields
ranging from chemical solvents to plasticizers and pigments have
made it one of the most attractive and sought after platform
chemical. The bacterial species of Actinobacillus, Anaerobiospirillum,
Mannheimia and recombinant Escherichia coli were found to be the
most promising set of succinic acid producing microorganisms [37–
39]. Actinobacillus succinogenes has the potential of producing
succinic acid at yields as high as 110 g/l [40]. Succinic acid derived
from biological sources is thus known to be one of the most
emerging biorenewable chemicals, which accounts for 3% of the
current succinic acid market. Along with its use as an end product in
several industries, succinic acid is also used for the production of a
broad spectrum of chemical intermediates (Fig. 3a). The market value
of succinic acid is expected to surge from approximately $63 million
in 2011 to $539 million by the end of 2020 [41]. Currently, majority of
the available succinic acid is derived from petroleum industries with
a major contribution from Mitsubishi Chemical (Chiyoda, Tokyo,
Japan), Kawasaki Kasel Chemical (Kawasaki, Japan) and Nippon
Shokubai (Osaka, Japan). On the other hand, BioAmber (Plymouth,
USA), Myriant (Quincy, USA), Succinity (Düsseldorf, Germany) and
Reverdia (Urmonderbaan, Netherlands) are playing a major role in
the production of bio-succinic acid. Though the current bio-succinic
acid is more expensive than fossil fuel based succinic acid, the mass
scale production of bio-based succinic acid along with the expected
shortage of petroleum resources in future might results in reduction
in the price of bio-succinic acid.
Lactic acid is another versatile chemical with immense applica-
tions in pharmaceutical, cosmetic, food and chemical industry. Lactic
acid produced by bacterial fermentation amounts to around 90% of
the total worldwide lactic acid production [42]. The usage of both
first and second generation feedstock as substrate for bacterial
fermentation and additional pretreatment strategies of lignocellulo-
sic feedstock for increasing the yield of lactic acid has been studied
thoroughly [42]. According to the review conducted by Hofvendahl et
al., the most common lactic acid bacterial species used for lactic acid
fermentation includes Carnobacterium, Enterococcus, Lactobacillus,
Lactococcus, Leuconostoc, Oenococcus, Pediococcus, Streptococcus, Tet-
ragenococcus, Vagococcus, and Weissella [42]. Lactic acid can be used
for the production of various other chemicals (Fig. 3b) along with the
commercial production of poly-lactic acid (PLA), which is utilized as a
bioplastic. The bioplastic produced from lactic acid monomer has the
potential to be recycled by means of thermal depolymerization or
hydrolysis and degraded by specific enzymes like proteinase K and
bacterial species like Amycolatopsis [43]. Globally around 300,000
metric tons (MT) of bioplastics are manufactured every year which
includes around 150,000 MT of bioplastics produced solely by Nature
Works LLC (Blair, NE, USA) [44]. Although this accounts for less than
1% of the total synthetic plastic produced in the world, one can
expect bioplastics to play a major role in the future, owing to its high
annual market growth of 20–30% and growing environmental
concerns of synthetic plastic.
Lactic acid along with glycerin contributes to more than 75% of
the total market share of platform chemicals. The net market worth
of biorenewable chemicals is expected to reach the height of US$
6.8 billion by 2015 [45]. Biofuels on the other hand recorded a market
worth of US$ 82.7 billion and is expected to grow at an annual rate of
12.406% [46]. Even though the current market of biorenewable
chemicals is much lesser as compared to biofuels, studies indicate
511
that the biorenewable chemical market is expected to grow at least
at a rate of 22.8% by 2015 [45], which is nearly double the market
growth rate of biofuels. This highlights the growing importance of
biorenewable chemicals and the need to be cautious in order to avoid
any direct competition in the production of biorenewable chemicals
with food which can lead to a similar dilemma as food vs fuel [47].
The use of non-edible biomass for biorenewable chemical
production so far has faced multiple challenges. The implementa-
tion of available processes and techniques, which are capable of
converting such non-edible biomass, requires a thorough investi-
gation and up-gradation in order to compete with the edible
biomass conversion technologies.
3. Biomass conversion technologies
The conversion and energy efficiencies of various biomass conver-
sion techniques play a major role in the selection of the category of
feedstock to be used. In order to make an informed decision to decide
on an efficient and ethically correct biomass usage policy, it is therefore
important to access all the available technology options including
chemical, biological and an integration of both chemical and biological
techniques for the production of biorenewable chemicals (Fig. 4).
3.1. Biological technologies
Microbial production of chemicals has been recognized as one of
the greenest technologies [48,49]. In light of recent increasing
concerns of the environment, climate changes and limited natural
resources, the effort to explore more pathways for the microbial
production of chemicals has strengthened [47,50]. A diverse range of
chemicals have been produced by using numerous organisms posses-
sing the capacity to convert sugar or starch into useful end products
by means of fermentation (Fig. 5) [51]. Cellulose and starch are
polymers, which cannot be directly fermented to the required end
product. It generally requires to be broken down into glucose
monomers. The production of simple glucose monomers requires
extensive pretreatment operations of second generation biomass
(lignocellulose biomass) unlike the first generation biomass (dis-
cussed in Section 2.1). The pretreatment operations may vary
according to the feedstock used. Glucose monomers are directly used
as a feedstock for microbial fermentation, though in many cases
multiple first generation feedstocks like corn [52], wheat [53] and
potatoes [54] have been successfully used as feedstock for biofuel or
biochemical production. The easy accessibility of sugar molecules
makes them favorable carbon sources for the growth of microbes.
Fermentation of both first and second generation feedstock is gen-
erally followed by a string of purification processes like centrifugation
and distillation, which are aimed at increasing the concentration of
the required product.
The commercialization of these chemicals produced via fermen-
tation is yet to occur on a large scale in most cases, though multiple
techniques for producing these chemicals on lab scale have been
proposed (Table 5). In order to achieve DOE's target of producing
25% of industrial organic chemicals from biomass by 2025, there is
an urgent need for research institutions to work together for the
installation of plants capable of producing these platform chemicals
on a large scale and that too in an economical manner.
Along with the above platform chemicals, glycerol is one such
chemical which is not only widely used as a building block [55], but
also as a substrate for microbial growth [56]. Considerable amount of
research has been done on the production of glycerol from third
generation feedstock. Species of unicellular algae Dunaliella and
Asteromonas have been found to be capable of producing glycerol by
photosynthesis [57,58]. The production of biodiesel from microalgae
has gained momentum in recent years owing to the production of
512 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520

Butanol, Ethanol, Acetone, Glutamic acid,

Fermentation
Edible Biomass 3-Hydroxypropanoic acid, Malic acid, Acetate.
(Sugarcane, Corn) Hydrolysis Chemical Catalysis Sorbitol, Diesel, HMF
GVL, Furfural
Biodiesel

Oil Seeds Extraction Glycerol

and other chemicals

Penta,1-3diene, Furylglycolic acid

Integrated fermentation
pyruvic acid
Lignocellulosic and catalysis
Biomass
Hydrogenation 1,2 Propanediol, Methane

Acids, Alcohols, Esters,

Acid dehydration Pyrolysis Bio-oil, Charcoal Aldehydes and Ketones
Hemicellulose
Liquefaction Bio-oil

Thermochemical Transportation
Syngas Fuel
Microalgae Biochemical Hydrogen,
Biomass Methane
Direct
Power Generation
Combustion

Fig. 4. Routes of conversion of biomass to biorenewable chemicals. Arrows in green, red and blue shows chemicals obtained from 1st , 2nd and 3rd generation feedstock. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Biomass

Physical and Chemical Pretreatment procedure

Glucose
OH OH O

O CH2 OH OH OH
Fermentation Products OH
OH HO
HO
(a) O O (k) O
O
HO
OH H2N NH2

O
(b) OH (j)
HO OH

NH2 HO OH
(c) H2N
O (g) H3C (i) O
(e)
OH O OH OH OH
HO HO
OH
HO (h)
(d) O
OH OH O
(f)
Fig. 5. Renewable platform chemicals derived from biomass via microbial fermentation of glucose.

larger quantity of oil per unit of land. The production of biorenewable
chemicals from third generation feedstock by means of a variety of
techniques on the other hand has not yet been investigated as
thoroughly as the previous two generations [23]. Fig. 6 shows the
major chemicals, which have been produced on a lab scale from algal
biomass. The usage of algal biomass as a substrate for the growth of
other microbes can also be promoted on a large scale as this eliminates
the need of any external source of carbon supply [59].
The initial step of any commercial process involving the usage of
algae feedstock will include the production of large amount of algal
biomass. The process of production of algal biomass from micro-
algae varies according to the biomass type and downstream
 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520 513

Table 5
Microbial production of building block chemicals from glucose monomers and its current net annual production in market. Serial numbers (a) to (k) correspond to the
molecular structure shown in Fig. 5.

Serial no. Corresponding chemical Commercial annual production (metric tons) Microbial production

Organism Yield (g/g) Titer (g/L) Productivity (g/L/h) Reference

(a) Itaconic acid 80,000 [131] Aspergillus Terreus 0.51 82.3 0.57 [132]
Escherichia coli 0.5 4.16 0.057 [133]
Candida sp. 0.35 – – [134]
Ustilagomaydis 0.85 68.36 0.57 [135]
(b) Malic acid 200,000 [136] Escherichia coli 0.56 9.25 0.74 [137]
Saccharomyces cerevisiae 0.31 59 1.23 [138]
Aspergillus flavus 0.94 113 0.59 [139]
(c) Isoprene 800,000 [140,141] Escherichia coli 0.11 60 2 [142]
(d) Succinic acid 30,000 [143] Escherichia coli 1 71.6 0.75 [144]
Corynebacterium glutamicum 0.90 146 3.20 [145]
Anaerobiosprillum 0.88 83 10.4 [146]
succiniciproducens
(e) Putrescine 10,000 [147] Escherichia coli 0.168 24.2 0.75 [147]
(f) Glucaric acid 42,000 [148] Escherichia coli 0.153 1.13 0.016 [149]
(g) 1,3-PDO 45,000 [150] Klebsiella pneumoniae – – – [151]
Clostridium butyricum – – – [152]
(h) 1,4-BDO 1,380,000 [153] Escherichia coli – 18 – [154]
(i) Lactic acid 450,000 [136,155] Lactobacillus casei 0.44 44 1.69 [156]
Rhizopus oryzae 0.88 83 2.58 [157]
(j) Cadaverine 1,600,000 [158] Escherichia coli 0.131 9.61 0.32 [158]
(k) Fumaric acid 90,000 [159] Rhizopus oryzae 0.53 37.2 1.03 [160]
Rhizopus oryzae 0.82 92 4.25 [161]
Rhizopus arrhizus 0.33 38 0.46 [162]
Rhizopus oryzae 0.75 75.5 3.78 [163]

O OH OH

HO
HO OH
OH OH O
OH Mannuronic acid
Glycerol Isoprene

O
O
H2N OH O
Algal Biomass
HO
O
5-Aminolevulinic acid 5-(Hydroxymethyl)-2-furaldehyd e
O
CH2
O OH OH
HO HO OH
OH
O H
Propanediol
Levulinic acid OH OH O
L-guluronic acid
Fig. 6. Major chemicals produced from algal biomass.

processing requirement. The harvesting of biomass generally com-
prises of using a combination of harvesting and dewatering opera-
tions like: sedimentation in gravity, centrifugation, flotation and
filtration. Biomass harvestation is followed by drying. The major
steps involved in the drying of harvested biomass include spray
drying, drum drying, freeze drying and sun drying. The presence of
high quantity of water in algal biomass makes sun drying hugely
inefficient and spray drying remains unfavorable at times due to its
high cost [60]. The fractionation of the biomass generally generates
the desired product along with a host of by-products at times.
A major role in making the biological production of renewable
chemicals feasible has been played by several emerging bio-
catalysis tools [61]. Case studies published by OECD show how
the cost of processes has been decreased by a margin of 9–90% by
the mere implementation of various biocatalytic and enzyme
technologies [62]. Recombinant DNA is one of the most popular
technologies, which aids the production of the desired enzymes in
a high quantity. Enzymes required for the conversion of a parti-
cular feed can either be produced extracellular or intracellular by a
suitable genetically modified organism. The cake residue produced
514 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520
Fig. 7. Classification of chemical technologies [13].
after the extraction of oil from oil seeds has been a popular
platform for the production of these enzymes. Though oil seeds
like palm, sunflower, rapeseed and canola have mostly been used
for the production of biofuels, several value added chemicals and
enzymes can also be produced from the cake residue [63–65].
3.2. Chemical technologies
Chemical technologies for biomass conversion mainly comprise
of physical, thermochemical and chemical conversion processes as
shown in Fig. 7. Most of the chemical and thermochemical
conversion techniques have been used for the pretreatment and
processing of lignocelluloses [13], though at times the first gen-
eration feedstock like corn, sugarcane and edible oil seeds have
taken the aid of almost all the available chemical technologies for
their respective efficient conversion to valuable end products.
3.2.1. Physical conversion
Mechanical extraction plays a major role in the recovery of crude
oil from oil seeds. A screw press is often used for either pre-pressing or
full pressing the oil seeds. Pre-pressing results in the partial recovery
of oil compared to full pressing where the aim is to extract maximum
amount of oil possible [13]. Transesterification of the extracted oils
(triglycerides) using either heterogeneous or homogenous catalysis
has been the most effective method for the production of biofuels and
biorenewable chemicals from oil seeds. Extracted oils are generally
made to react chemically with alcohols (normally methanol and
ethanol) in the presence of acid [66] or base catalyst [67,68] yielding
a mixture of methyl esters and value added products like glycerol.
The technology for conversion of edible oil seeds (sunflower,
rapeseed, palm and soybean) is well established, whereas the
conversion of non-edible and waste oils has faced multiple road-
blocks. The high fatty acid concentration in these oils has rendered
the conventional transesterification process involving alkaline
catalysts not feasible. Two-step transesterification processes with
efficient conversion rates of up to 90% have been concluded to be
the best possible method for the conversion of non-edible and
waste oils [69]. The free fatty acid content of oil is first reduced by
an acid-catalyzed esterification process followed by the use of an
alkaline catalyst for the conversion of oil and methanol to
the desired products. Main disadvantage of this process lies in
the higher production cost of end products as compared to the
conventional single step transesterification process. The cake
 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520 515

residue left after the pressing of oil seeds can be converted to thermochemical conversions. Initial processing of feedstock involves
several valuable biorenewable chemicals using a string of thermo- the selective transformation into sugar monomers, a step that is
chemical and chemical conversion processes. complicated and expensive for lignocelluloses. Though the isolated
sugar monomers can be treated at relatively mild conditions by a
variety of other chemical conversion methods, size reduction pre-
3.2.2. Thermochemical conversion
treatment procedures make hydrolysis more effective by increasing
Thermochemical techniques mostly involve the processing of
the extent and rate of reaction [13]. For this reason hydrolysis is
lignocellulosic biomass at high temperature and/or pressure. The
considered suitable only for the processing of lignocelluloses where
thermal degradation of the biomass yields intermediates which
higher selectivity may be achieved [81]. Acid hydrolysis is often
can be further upgraded into value added products with the help
preferred over base hydrolysis as it reduces the number of side
of numerous other techniques like pyrolysis or gasification. Overall
reactions and thus gives higher yield of the required products [82].
thermochemical conversion mainly comprises of combustion,
Dehydration of carbohydrates and carbohydrate derived mole-
gasification, pyrolysis and liquefaction.
cules can be used for the production of numerous platform furan
Direct combustion simply involves the burning of the concerned
compounds [83] using a variety of solvents and catalysts, which in
biomass in the presence of air resulting in the conversion of
turn can be used for the production of valuable end products such
chemical energy to different forms of useful energy. Direct combus-
as biopolymers and industrial solvents [84].The dehydration of
tion of biomass is generally considered feasible only if it contains
glycerol resulting in the production of valuable biorenewable
less than 50% of moisture. Even though the sulfate emissions are
chemicals was initially reported as early as 1987 by Ramayya
less, direct combustion is not favored because of the requirement of
et al. [85] Since then, the production of acrolein and acetol by
several pretreatment procedures like drying, chopping which in
glycerol dehydration using a string of acidic catalysts has been
turn results in greater financial expenditures [70]. Gasification, on
studied at length [86,87]. Dumesic and co-workers have worked
the contrary, involves the partial combustion of the biomass in air,
extensively on the production of liquid alkanes ranging from C7 to
oxygen or steam to produce mixtures of syngas and/or producer gas
C15 with the aid of dehydration of carbohydrate feedstock [88,89].
depending on the relative concentration of the products. While
It was observed to be difficult to get the desired selectivity of a
producer gas can be used only as a fuel, syngas has the potential to
product via dehydration. In addition, cost effective production of
be upgraded to multiple biorenewable chemicals using Fisher–
several of these biorenewable chemicals remains major obstacle in
Tropsch synthesis [71]. Gasification has the ability to treat a variety
the commercialization of these chemicals via dehydration [13].
of biomass including a wide range of lignocelluloses, though the
Isomerization of carbohydrates in the presence of acidic or basic
downstream processing might have to be modified taking into
catalysts leading to transformation of aldohexoses to ketohexoses via
consideration the amount of water and impurities present in the
enolate intermediates is generally carried out at mild temperatures
gaseous product. The three major types of gasifiers include the
ranging from 310 K to 350 K [90,91]. Glucose isomerization rates are
traditional fixed and fluidized bed along with the more recent
governed by the amount of glucose present in the open chain form.
entrained suspension gasifier [72]. Fixed bed gasifiers are generally
The reaction temperature and solvent used play a major role in
operated at a temperature of 1000 1C. The fluidized bed gasifiers
determining the percentage of glucose present in open chain form.
can be operated at a uniform temperature distribution throughout
Aprotic solvents like DMSO and temperatures as high as 350 K have
the gasification zone. The entrained suspension gasifiers have the
been effective in maintaining a high isomerization rate [92–94].
advantage of being effective in the processing of a wide range of
Solvent extraction involves the selective elimination of the
feedstock, though pretreatment requires effective size reduction
desired species by allowing it to dissolve in the solvent used and
techniques of the selected feedstock [72].
successively recovering the dissolved substance from the solvent.
Thermal decomposition of the organic biomass in the absence
Similar to isomerization reactions, an important parameter governing
of air/oxygen at a temperature ranging from 623 to 1073 1C
solvent extraction techniques is the process temperature [95–97].
resulting in the production of an array of solid, liquid oil and
Supercritical fluid extraction involves the usage of fluids at tempera-
gaseous products is termed as pyrolysis [70]. Conventional slow
ture and pressure above its vapor liquid critical point. Even though
irreversible pyrolysis produces solid coke or charcoal. Catalytic fast
supercritical fluid extraction is mostly performed at higher pressures
pyrolysis of especially high cellulose containing feedstock on the
as compared to just solvent extraction, it has been used alongside
other hand can lead to the production of a mixture of aromatic and
solvent extraction for the production of several natural products [98]
aliphatic compounds in the form of a bio-oil [73,74]. Several
such as acids [112], lipids [99] and polymers [100]. The production of
varieties of both first and second generation biomasses have been
numerous biorenewable chemicals derived from biomass with
subjected to pyrolysis including agricultural residues [75], switch
enhanced supercritical fluid extraction efficiency and speed has been
grass [76], corn stalks [77], rape seed [78] and sugarcane bagasse
reported by Demirbas [101]. Water has also been found to be an
[79]. Overall, pyrolysis is an effective inexpensive option which
efficient supercritical fluid medium with the potential of breaking
aids in the total utilization of the biomass due to the absence of
down lignocelluloses into sugar monomers which aids in the
requirement of any extensive pretreatment procedure.
production of biorenewable chemicals from biomass [102,103].
Hydrogenation reactions are carried out at moderate temperature
3.2.3. Chemical conversion and pressure of 370–420 K and 10–30 bar respectively. It is used to
Most of the chemical conversions are carried out at milder generally saturate CQC bond in the presence of metal catalysts such
temperature and pressure conditions as compared to the thermo- as Pd, Pt or Ni [104]. The solvent and catalyst used along with the
chemical conversions. The primary chemical conversion processes are partial pressure of hydrogen play a decisive role in selectivity of
hydrolysis, dehydration, isomerization, solvent extraction, supercriti- hydrogenation. Few studies have focused particularly on selective
cal fluid extraction, hydrogenation, hydrogenolysis and oxidiation as hydrogenation for the production of multiple value-added chemicals.
shown in Fig. 7 [80]. Hydrolysis comprises of the cleaving of glycosidic Perhaps, one of the most complete studies is that by Blaser et al.
bonds in polysaccharides at a temperature range of 370–570 K in the [105] In this work, the authors have studied multiple topics including
presence of an acid or base catalyst to form simpler sugar monomers chemo-, diasterio- and enantioselective hydrogenation. Hydrogeno-
such as glucose, fructose, xylose and at times partially hydrolyzed lysis has also been studied extensively and has been shortlisted
dimers, trimers and several other oligomers. Generally hydrolysis of to be one of the key concepts to be applied in upcoming biorefineries
biomass is more complicated and costly as compared to [106,107]. Hydrogenolysis generally involves the cleaving of
516 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520

carbon–carbon bond or carbon–heteroatom (usually oxygen in this
case) by the action of hydrogen at a temperature and pressure range
of 400–500 K and 14–300 bar in the presence of metal catalysts
under basic conditions [108,109]. Hydrogenolysis has been most
popularly used for the production of propylene glycol [110], 1 2-
propanediol [126], 1 3-propanediol [111,112] from glycerol.
Compared to hydrogenolysis, selective oxidation reactions are
generally carried out at a lower range of temperature (330–420 K)
and oxygen pressure (2–10 bar). The possibility of forming a wide
range of chemicals with specific functionality by oxidizing the initial
reactant using a string of metal, metal oxide or metal derivate
catalysts poses the challenge of optimizing the reaction conditions
(maintaining specific temperature and pH along with the usage of a
definite solvent and catalyst) in a way that only the preferred
reaction pathway is followed while minimizing the undesired by-
products [113,114]. The production of a string of biorenewable
chemicals including formic, lactic and oxalic acid has been sug-
gested by selective oxidation from glycerol [115]. Glycerol is a major
platform chemical which has been produced to the tune of over
1995.5 kilotons (2011) and is expected to attain market revenue of
$2.1bn by 2018 at a compounded annual growth rate of 7.7% [116].
This huge demand of glycerol is mainly because of its versatile
nature, which aids in the production of numerous chemicals, thus
acting as an ideal platform molecule and catering to the needs of
pharmaceutical, personal care, food and beverage industries.
3.3. Integration of biological and chemical technologies
The integration of biological and chemical catalysis for producing
biorenewable chemicals has become a popular trend in recent days
as it overcomes many shortfalls of either a purely chemical or a
purely biological approach. Catalytic conversion of biomass by means
of dehydration has been the most predominant chemical technique
for the production of value added chemicals. Generally the basic idea
followed for the production of several value added chemicals from
biomass is to selectively reduce the oxygen content from highly
functionalized substrates and to produce variable carbon number
molecules while selectively retaining the desired product function-
ality. Unlike dehydration processes, bio-catalysis makes the produc-
tion of variable carbon number molecules with the desired high
selectively. Chemical catalysis is further used for upgrading such
biological derived platform chemicals into valuable products like
alkanes [117,118], organic acids [119,120] and liquid alkenes [121].
Sucinnic acid has been a popular platform biorenewable chemical,
which has successfully been produced using an integration of
biological and chemical techniques. 2-Pyrones such as triacetic acid
lactone (TAL) are other such potential platform molecules, which can
be obtained from polyketide biosynthetic routes and have been
recently shown to produce useful chemicals and fuels via catalytic
upgrading [122]. Due to their unique structural features such as the
degree of unsaturation, position of the double bond, keto-ester
functionality and the nature of substituents on the ring, a variety of
catalytic transformations can be performed to obtain a desired
product with high yield and selectivity [122].
Myriant (Quincy, USA) and Bioamber (Plymouth, USA) are two such
companies which are involved in the production of biosuccinic acid and
several other commercially important chemicals derived from succinic
acid which has widespread applications in the field of detergents,
cosmetics and lubricants (Table 6). Because such integrated processes
are still at an initial stage of development compared to the chemical or
biological process, numerous challenges remain as obstacles.
Few studies have focused on the challenges faced by catalytic
conversion of biologically derived chemicals. Fermentation of bio-
mass or derived aqueous sugars produces biogenic impurities such
as protein (cell mass) fragments, residual nutrients from fermenta-
tion, and byproducts, which tend to interfere in catalytic processing,
leading to catalyst deactivation and reduced stability. Therefore, it is
essential to develop an efficient method for product purification,
which may lead to better catalytic processing. Attempts in the past
have been made to separate the acid molecule, which are produced
from fermentation media such as lactic acid by electrodialysis. One
such process has been successfully implemented at the industrial
scale by Eurodia Industrie (Rue Saint Martin, Pertuis, France).
Dumesic and co-workers have reviewed the major dual challenge
of maintaining catalyst stability and impact of impurities present in
feedstock in a comprehensive manner [3]. Impurities in the feed-
stock may either be present due to various biogenic molecules
present in the biomass by default or may also be produced during
fermentation (Table 7). The loss in catalyst activity due to the
presence of various impurities specially amino acids and proteins
was reported by Miller et al. [123] Similar to the process of either
decreasing the amount of impurities or reducing the effect of
impurities on chemical catalysis, the challenge of producing stable
and regenerable catalysts has not been studied in an extensive

Table 6
Companies, which have used an integration of biological and chemical techniques to produce biorenewable chemicals.

Company Strategy used End products

Amyris, Conversion of sugar feedstock into hydrocarbon fuels and chemicals using Cosmetics-squalane, flavors and fragrances—firmenich, IFF and givaudan,
California, genetically modified yeast and further upgrading by catalytic processing polymers and plastic additives—isoprene, home and personal care,
USA lubricants, fuels.
Gevo, Colorado, Production of isobutanol by using an integrated strategey. Utilizes cellulosic Isobutanol and butenes.
USA feedstocks, which include dedicated energy crops and residues from
forestry and agriculture. Biomass is converted into sugar by genetically
engineered yeast.
Myriant, Engineered microorganisms combined with catalytic upgrading to produce Biosuccinic acid and its derivatives, polyester polyols, detergents,
Massachu- a variety of chemicals such as organic acids, vitamins, amino acids and cosmetics, renewable fuels and chemicals such as bio-succinic acid and
setts, USA enzymes etc. chemicals. other commodity chemicals.
Zeachem, Integrated biochemical and thermochemical processing of biomass. Acetic Ethanol and acetic acids. The derivatives include acetic acid, ethyl acetate,
Colorado, acid is produced via the acetogenic fermentation process, which on ethylene, ethylene glycol, propionic acid, lactic acid, butanol, hexanol and
USA subsequent reduction in presence of hydrogen produces ethanol. Hydrogen hexane.
is obtained from the gasification of lignin residue.
Croda, East Vegetable oils and fats obtained from natural based raw material are Adhesives, coatings, paints, plastics, elastomers, foams composites,
Yorkshire, UK converted into fatty acids and glycerol which are further upgraded by graphic arts and inks.
catalytic processing.
Bioamber, Bio-based succinic acid is produced by fermenting sugars using genetically Succinic acid, adipic acid, succinate salts, succinic esters as lubricants and
Montreal, engineered yeast. A catalyst technology is emoloyed that can converts bio- plastisizers, polybutylene succinate, polyurethanes etc.
Canada based succinic acid into other commodity chemicals. Bio-based adipic acid is
also produced from the fermentation by genetically engineered yeast.
 S.K. Bardhan et al. / Renewable and Sustainable Energy Reviews 51 (2015) 506–520 517

Table 7
Challenges faced by the chemical conversion of biological molecules derived from biomass.

Challenges faced Adverse impact on the process Possible remedy

Impurities present in biomass
feedstock
Impurities produced during
fermentation
Stability and regenerability of the
catalyst under high temperature
liquid reaction conditions
Design of highly selective active sites
Various aromatic compounds formed during
pretreatment like phenols have adverse effects on
microbial systems [164].
Presence of biogenic compounds produced during
fermentation adversely effects catalyst activity
[123,165].
Enhanced chances of sintering and leaching.
Inefficient conversion of biologically derived
platform molecules.
Identification and minimization of production of such compounds which
have inhibitory affects along with the development of genetically
modified impurities tolerant microbes [164].
Yet to be studied in detail.
High loading of active metal, co-precipitation methods [166], inducing
metal support interactions [167,168], addition of stabilizing agents [169],
coating the support or catalyst [170,171], silica sol-gel and encapsulation
techniques [172].
Atomic level control of the catalyst structure can be achieved using
techniques like ALD [173], selection of solvent [124].

manner till date. In a bid to avoid deactivation of catalysts, the Acknowledgment

active sites responsible for leaching or sintering can be protected by
atomic layer deposition (ALD). ALD has been instrumental in the
manipulation of the catalyst structure. The manipulation of the
catalyst structure along with the choice of solvent used may play a
pivotal role in the efficient conversion of biologically derived
molecules [124].
The chemical, biological or integrated processing methods have
distinct advantages for the processing of lignocellulosic biomass.
However these technologies, once developed, can very well be
adapted for first generation feedstock to produce biorenewable
chemicals. As per the estimates of the Food and Agricultural Organiza-
tion (FAO) of the United Nations, out of the total available land area,
11.7% is arable land in 2010. Similarly, about 9.7% of the total land area
is severely degraded, which can potentially be cultivated by afforesta-
tion and planting second or third generation energy crops [125]. The
arable land area can be protected only for food production and it is
expected to increase to 12.5% by 2050. However, simultaneously, a
two-fold increase in the food production is required to meet the
demand by 2050 [125]. This can be met, either by improving the
efficiency of food production, or by converting the degraded area into
the arable land. This is where a direct conflict can be perceived which
needs to be avoided by adopting a suitable policy.
4. Conclusion
Based on the challenges presented in this work, it is evident
that the even though the production of biorenewable chemicals
from edible feedstock should be completely replaced with non-
edible feedstock in order to avoid any conflict with food produc-
tion, numerous challenges remain in the commercialization of
technologies concerned with the conversion of non-edible feed-
stock. It is extremely important for government policy making
agencies to work along with research organizations to overcome
these obstacles and promote biorenewable chemical production
with the help of second and third generation feedstocks, while
gradually scaling down the operations concerned with biorenew-
able chemical production from first generation feedstock.
Meanwhile, it is also important to address the environmental
concerns raised as a result of increasing greenhouse gases in the
atmosphere [128]. This further requires policy makers to stress on
greener technologies like algae fermentation, which can either offer
a carbon neutral or carbon positive CO2 reduction technology. Thus
if biorenewable chemicals are to make a sustainable contribution
towards reducing the climate change and safeguarding food secur-
ity, it is extremely important to continuously evaluate the existing
and newer biomass conversion techniques introduced on the basis
of the generation of feedstock used, market potential and its impact
on the environment.
Authors acknowledge IIT Delhi (Grant number MI01060) for the
financial support as a startup grant.
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