Bioresource Technology 215 (2016) 2–12

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

Waste biorefinery models towards sustainable circular bioeconomy:

Critical review and future perspectives
S. Venkata Mohan ⇑, G.N. Nikhil, P. Chiranjeevi, C. Nagendranatha Reddy, M.V. Rohit, A. Naresh Kumar,
Omprakash Sarkar
Bioengineering and Environmental Sciences (BEES), CSIR-Indian Institute of Chemical Technology (CSIR-IICT), Hyderabad 500 007, India, Academy of Scientific and Innovative
Research (AcSIR), India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Resource recovery of bioenergy and Conceptualizing waste biorefinery for recovery of value added products.
platform chemicals from waste.
 Biorefinery as a sustainable approach
for waste mining.
 Exploitation of waste would enhance
biorefinery competitiveness & social
acceptance.

a r t i c l e i n f o a b s t r a c t

Article history: Increased urbanization worldwide has resulted in a substantial increase in energy and material consump-
Received 6 February 2016 tion as well as anthropogenic waste generation. The main source for our current needs is petroleum refin-
Received in revised form 23 March 2016 ery, which have grave impact over energy-environment nexus. Therefore, production of bioenergy and
Accepted 24 March 2016
biomaterials have significant potential to contribute and need to meet the ever increasing demand. In this
Available online 29 March 2016
perspective, a biorefinery concept visualizes negative-valued waste as a potential renewable feedstock.
This review illustrates different bioprocess based technological models that will pave sustainable ave-
Keywords:
nues for the development of biobased society. The proposed models hypothesize closed loop approach
Biofuels
Biobased products
wherein waste is valorised through a cascade of various biotechnological processes addressing circular
Eco-footprints economy. Biorefinery offers a sustainable green option to utilize waste and to produce a gamut of mar-
Low carbon technology ketable bioproducts and bioenergy on par to petro-chemical refinery.
Circular Bioeconomy Ó 2016 Elsevier Ltd. All rights reserved.
Life cycle assessment (LCA)

Contents

1. Current scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Bioprocess based technological models in nexus with biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Acidogenic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

⇑ Corresponding author.
E-mail address: vmohan_s@yahoo.com (S. Venkata Mohan).

http://dx.doi.org/10.1016/j.biortech.2016.03.130
0960-8524/Ó 2016 Elsevier Ltd. All rights reserved.
 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12 3

2.1.1. Biohydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Biohythane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.3. Carboxylate platform . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Carbon-dioxide model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.1. Algae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2.2. Cyanobacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.3. Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Photosynthetic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.1. Microalgal based biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3.2. Synthetic ecology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4. Bioelectrogenic model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.5. Nutrient recovery model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Holistic biorefinery circular bioeconomy approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4. Futuristic biorefinery vision. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Current scenario 2. Bioprocess based technological models in nexus with

The world is undergoing a new wave of urbanization, espe-
cially in the emerging developing countries leading to multiple
impacts over natural resources and the environment. Metropoli-
tan infrastructure, as the interface between the human consump-
tion and natural resources/environment, poses various challenges
and opportunities for sustainable resource management at urban
scale (Clark and Deswarte, 2008). Concerns over dependence on
fossil fuels alongside increasing levels of carbon dioxide (CO2)
in the atmosphere have led to a global drive for renewable and
eco-friendly technologies. In this context, biorefinery has emerged
as a potential alternative of petroleum based refinery where bio-
mass of non-edible feedstock/biogenic waste is used as raw mate-
rials and a range of products, such as biofuel, industrial
biochemicals and biomaterials including commercially important
biopolymers are produced (Clark and Deswarte, 2015; Venkata
Mohan, 2014a).
Concepts such as the ‘biorefinery’ create stretching aspira-
tions towards increasingly integrated technologies (Aresta
et al., 2012). Municipal Solid Waste (MSW) is the one amongst
the most abundant organically bound carbon produced each
year that could be useful resource for biobased technologies.
In India, MSW is >150 million tonnes with more than 50%
bio-waste; on top of that, it covers 60 thousand ha of landfills
emitting landfill gas (GHGs). Sewage is mounting 40 billion
liter/day resulting in >10 million ton of extra sludge and
>20 million ton CO2-emissions upon incineration (http://www.
sahyog-europa-india.eu/inventories). From this standpoint,
humankind has not exploited biogenic waste to even a fraction
of its potential. Waste as a prime target substance in the biore-
finery, shows up in a wide range of opportunities for mercantile
interests rather than utilitarian reasons. On the other hand, cre-
ating a categorical scheme for describing the technologies for
valorising waste is immensely difficult (Tuck et al., 2012;
Zondervan et al., 2011).
This review comprehensively describes the biorefinery
models that are being explored for the utilization of biogenic
wastes as a resource in the framework of circular economy.
The most popular microbial and photosynthetic processes
are widely deployed for many different technological solu-
tions. Integrating different models involving unit operations
and bioprocesses gives a much more holistic outcome
through an updated ‘product versus energy’ explored in the
bioeconomy.
biorefinery
2.1. Acidogenic model
2.1.1. Biohydrogen
Acidogenesis is the biologically mediated process where organic
compounds are converted mainly into various bio-based products
viz., hydrogen (H2), volatile fatty acids (VFA) and other trace by-
products (Sarkar et al., 2016). Oxidation of organic substrates
results in generation of short chain VFA as by-products. Pyruvate,
the end product in glycolysis, is oxidized to acetyl CoA and then
to acetate via acetyl phosphate resulting in ATP generation. The
reduced ferredoxin during pyruvate oxidation to acetyl-CoA is oxi-
dized by the enzyme hydrogenase, which generates ferredoxin and
releases electrons that bind with protons to form molecular H2
(Fig. 1). Hydrogen has highest energy content per unit weight of
any known fuel (143 GJ tonne 1) and is the only fuel that is not
bound to any carbon. An appropriate inoculum selection signifi-
cantly influences the acidogenic process efficiency and substrate
degradation towards value addition (Kapdan and Kargi, 2006).
Mixed consortia as biocatalyst is generally preferred because of
its low cost, non-sterile conditions requirement, operational stabil-
ity and flexibility, effective on diverse substrates, diverse biochem-
ical functions, ease of process control and up-scaling (Nikhil et al.,
2014; Li and Fang, 2007). Selective enrichment of biocatalyst by
pre-treatment of mixed inoculum enhances the overall H2 evolu-
tion rate (Venkata Mohan et al., 2008a). Various physiological
microbial groups present in the mixed consortia, lead to diverse
metabolic functions, having the advantage of producing a mixture
of bio-based products rather than that are not only specific to sin-
gle product (Amulya et al., 2014; Venkata Mohan, 2009). This
would make the process cost-effective when compared with the
well-established chemical and electrolytic H2 production process
(Azwar et al., 2014).
2.1.2. Biohythane
During acidogenesis, H2 along with methane (CH4) is produced
in low quantities because of fluctuations occurred in bioprocess
conditions. H2 and CH4 produced through a separate two-stage pro-
cess leads to a potential high-value solution for the valorization of
waste biomass (Venkata Mohan et al., 2008c). Mixture of CH4 and
H2 is referred as biohythane, which can have a composition of
46–57% H2, 43–54% CH4 and 0.4% CO2. A proper blend of both H2
and CH4, can have impact on the transition of fossil
4 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
Fig. 1. Schematic model of acidogenesis for bioenergy and carboxylate platform for bioproducts applications (1° primary; 2° secondary).
fuel-dependent society (Pasupuleti and Venkata Mohan, 2015). This
technology is believed to bridge the gap between existing to
achieve sustainability in the future. Nevertheless, these mixture
of gases produced during the anaerobic process does not cope up
with complete biorefinery as the liquid waste obtained cannot be
discarded because of other biobased products present in it that
have high commercial value in the market (Rittmann and Herwig,
2012).
2.1.3. Carboxylate platform
There is an opportunity to intervene conventional anaerobic
digestion resulting in valuable intermediates/by-products, thus
proposing the concept of carboxylate platform (Fig. 1). Acidogenic
bacteria upon fermentation produces short chain VFA like acetic
acid (C2), propionic acid (C3), butyric acid (C4) and valeric acid
(C5), etc. (Dahiya et al., 2015). Acetic acid can also be produced by
homoacetogens utilizing H2 and CO2. These short chain carboxylic
acids can be utilized further as they are substrates for various
organic compounds including alcohols, biohydrogen, bioplastics,
microalgal lipids, bioelectricity, etc. Further, addition of VFA assists
in the biological removal of nitrogen and phosphorus from wastew-
ater through aerobic nitrification followed by anoxic denitrification.
All these applications show the potential of VFA to bring about a
revolution in the field of bioenergy. VFA production can be consid-
ered an effective strategy to bridge the gap between waste remedi-
ation and product recovery (Poggi-Varaldo et al., 2014).
2.2. Carbon-dioxide model
2.2.1. Algae
Algae subsist in many forms including macro (sea weeds) and
microalgae (algae, diatoms, red algae, yellow-green algae, etc.,),
which convert the inorganic carbon (CO2) into complex organic
compounds through the Calvin–Benson–Bassham (CBB) cycle.
Ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO) is
the key enzyme to catalyze the carboxylation of ribulose
1,5-bisphosphate to form two molecules of 3-phosphoglycerate
(3PG) in CBB cycle, where one molecule is channeled into central
metabolic pathway whereas other is involved in the continuation
of the cycle (Venkata Mohan et al., 2016). Uptake of inorganic
carbon through diffusion across the membrane (CO2) or mem-
brane pumps (HCO3 ) increases the cytosolic inorganic carbon
pool and enters the pyrenoids. With fast reacting carbonic anhy-
drases, bicarbonate is converted to CO2 for consequent utilization
by RuBisCO (Cannon et al., 2010). High CO2 concentration within
pyrenoids and rigid packing of RuBisCO increases the catalytic
efficiency for carboxylation reaction by suppressing the other
competing reactions resulting in high biomass productivity.
Ultimately, the biomass increases the productivity of secondary
products like lipids, Poly-Unsaturated Fatty Acids (PUFA),
Nutraceuticals, Omega 3 fatty acids, cosmetics, antibiotics, etc.
(Chiranjeevi and Venkata Mohan, 2016; Zhao and Su, 2014).
Optimizing the culture conditions, such as light, temperature
and pH, also increases the yield of lipid to maximize the benefit
of algal CO2 utilization. Genetic engineering strategies like algal
transgenics can be applied to down-regulate light-harvesting
antenna complexes enabling cultivation under elevated light
condition for higher biomass productivity (Cheng et al., 2013).
As depicted in Fig. 2, the oiled/deoiled biomass can be further
utilized by integrated different technological process such as
acidogenic processes (VFAs, H2, CH4 and CO2), thermochemical
liquefaction (bio-oils, biochar and biogas) and Biofertilizer (as
nitrogen sours) for additional products in a closed loop algal
CO2 capture and utilization in a biorefinery.
 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
Fig. 2. Carbon-dioxide sequestration model for biofuels and value-added products using different biological routes.
2.2.2. Cyanobacteria
Cyanobacteria are prokaryotic, with photosynthetic pigments
present in the cytoplasm rather than specialized organelles as in
eukaryotes (plants and algae). Among all photosynthetic organ-
isms, cyanobacteria accounts 20–30% of Earth’s primary photosyn-
thetic activity (Pisciotta et al., 2010). These organisms are able to
fix inorganic carbon and nitrogen from the atmosphere through
nitrogenase. Cyanobacteria have carboxysomes to achieve carbon
dioxide concentrating mechanisms unlike pyrenoids in algae,
which are proteinaceous micro-compartments encapsulating
RuBisCO (Yeates et al., 2010). Cyanobacterial RuBisCO’s character-
istically exhibit low affinity for CO2, but they are able to show high
growth at low CO2 concentration by the action of carbonic anhy-
drase hence it is more efficient at the carbon fixation from the
atmosphere than algae due to its simple structure (Oliver et al.,
2014). Cyanobacteria possess a simpler genetic make-up that can
easily be engineered for improving RuBisCO’s CO2 affinity and
increase biomass yield for production of useful chemicals from
inorganic carbon fixation (Rabinovitch-Deere et al., 2013). Meta-
bolic engineering of cyanobacteria, including production of etha-
nol, isobutanol, isoprene and number of potential products that
can be produced from CO2 has significantly expanded (Quintana
et al., 2011).
2.2.3. Bacteria
CO2 assimilation is not only constrained to photosynthetic
organisms (e.g., plants, algae, cyanobacteria) but also unbolt to bac-
teria (Fig. 2). Bacteria have specific carbon fixation pathways for
assimilation in biological carbon capture and utilization (BCCU).
Among the different classes of bacteria, b-Proteobacteria have
different modes of nutrition (autotrophic, heterotrophic and
5
mixotrophic) depending on the types of carbon source available
(Subhash et al., 2013). In the absence of organic substances, b-
Proteobacteria uptake hydrogen (H2) as sole energy source to fix
CO2 via the CBB cycle. Carbonic anhydrase is main enzyme for
CO2 assimilation in autotrophic metabolism. These bacteria also
have capability to store carbon in the form of polyhydroxyalka-
noates (PHAs), or more generally known as bio-plastics. PHA gran-
ules usually consist of chains of poly (3-hydroxybutyrate) (PHB)
and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). These
bacteria show high tolerance to industrial exhaust gases like car-
bon monoxide (CO) and H2 which can be used as feed for fermen-
tation with industrial exhaust gases. In Wood–Ljungdahl (WL)
pathway, two molecules of CO2 are reduced to produce one mole-
cule of acetyl-CoA with CO or H2 being used to generate reducing
equivalents. Clostridia, particularly display many enviable charac-
ters for biotechnological applications like exploiting a broad spec-
trum of carbon substrates (simple and complex carbohydrates,
CO2/H2 and CO), involves various pathways for production of useful
metabolites/industrial products like ethanol, acetate, acetone, lac-
tate, butanol, 2,3-butanediol, valeroate, caproate, carpylate and
Closthioamide finally resistant to toxic metabolites and substrates
(Tracy et al., 2012). Thermophiles and hyperthermophiles, psy-
chrophiles, acidophiles, halophiles and methanogens comes under
Archaea and are capable of methane production (CH4) using H2 as
energy source and CO2 as carbon source (Rittmann et al., 2015).
This intriguing group of microorganisms presents us with an
opportunity of alternative energy production. Further, strains of
several haloarchaea have been found to accumulate PHA (Garay
et al., 2014). Autotrophic archaea, such as Metallosphaera, Sul-
folobus, Archaeoglobus, and Cenarchaeum species, capture CO2 via
the 3-hydroxypropionate-4-hydroxybutyrate (3HP-4HB) cycle
6 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
Fig. 3. Photosynthetic model for micro-algae cultivation for simultaneous CO2 fixation and wastewater treatment; thereafter, deoiled biomass for diverse applications.
utilizing inorganic carbon in the form of HCO3 where a single
acetyl-CoA molecule and two HCO3 molecules are used to form a
succinyl-CoA, which in turn is converted via 4-HB into two
acetyl-CoA molecules. Many of the archaea are extremophiles,
which are excellent thermostable carbonic anhydrase enzymes
suitable for CO2 capture and can be used for industrial gas fermen-
tation (Henstra et al., 2007).
2.3. Photosynthetic model
2.3.1. Microalgal based biorefinery
Photosynthetic microorganisms are fostering humanity and
sustaining life in multiple dimensions of biofuels and renewable
energy sector. Microalgae are known to exploit natural mechanism
of photosynthesis for transformation of solar energy into high
value bio-based products (Leu and Boussiba, 2014; Venkata
Mohan et al., 2015). The photosynthetically active components
present in the biological inert matrices of microalgal cell structures
store high energy molecules and are a treasure box of biotechno-
logical applications. These microalgae act as bio-solar machines
which incorporate light capture and carbon sequestration mecha-
nisms and convert these inputs into high value biomolecules/
metabolites into the biomass. Microalgae can grow in various
nutritional modes like autotrophic, mixotrophic and heterotrophic
systems (Chandra et al., 2014; Devi et al., 2013). Biofuel production
from photosynthetic microalgae establishes an extensive network
of highly integrated upstream and downstream processes.
Although, there is significant development in microalgae based
biofuels production, there are some major limitations in down-
stream processes like dewatering and harvesting of biomass which
are both energy and cost intensive processes. Due to significantly
low biomass productivities of autotrophic cultivation methods,
algal bioprocesses have shifted focus towards mixotrophic and het-
erotrophic approaches by implementing multiple-product strate-
gies in a biorefinery approach (Rohit and Venkata Mohan, 2016;
Yen et al., 2013).
Microalgal biorefinery concept, can be defined as a methodical
approach which exploits integrative upstream and downstream
processes for the production and conversion of microalgal biomass
(Fig. 3). Integrating biorefinery concept with wastewater treatment
will provide efficient utilization of algae biomass, reduces overall
residual waste component and favors sustainable economics. The
residual biomass (deoiled cake) can be subjected to a range of bio-
chemical processes like fermentation and anaerobic digestion for
recovery of methane and biohydrogen (Subhash and Venkata
Mohan, 2014). Thermo-chemical conversion of algae biomass can
also be performed for synthesis of bio-oil and biochar (Agarwal
et al., 2015; Sarkar et al., 2015). Microalgae that contain glucose
based carbohydrates are the most feasible feedstock for bioethanol
production. The high value co-products can be preferred for eco-
nomic support of main process (Venkata Mohan et al., 2015).
Nonetheless, in order to preserve the micro-algal products along
the several extraction steps, the technologies selected for the pro-
cessing of the algal biomass must be mild so that the integrity and
value of each subsequent product extracted are preserved (Gerardo
et al., 2014).
2.3.2. Synthetic ecology
Microalgae cultivations in large scale are now exploiting princi-
ples of synthetic ecology to transform the existing conventional
 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
systems to advanced biorefineries. These biorefineries will help to
capitalize the enormous potential of microalgae, recover more
products and enhance their production by using an ecological engi-
neering approach (Cho et al., 2015). Ecological engineering or syn-
thetic ecology is an artificial biomimetic systems which uses multi-
organism approach for present day solutions (Ramanan et al.,
2016). Algal biorefinery system would benefit from the beneficial
effects of bacteria for algal growth promotion and harvesting.
The role of algae and photosynthetic bacteria for biohydrogen pro-
duction is being studied, but large-scale application has severe lim-
itations (Chandra et al., 2012). Two stage production of value
added chemicals using microalgae and methane oxidizing bacteria
was developed for simultaneous production of biodiesel and bio-
plastics (van der Ha et al., 2012). During large scale cultivations,
bacteria play a key role in providing phytohormones or macro
and micronutrients to algae which result in enhanced growth rate
and productivity of algae in large scale cultivations. The elimina-
tion of phycosphere bacterial communities, especially Plant
Growth Promoting Bacteria (PGPB) resulted in diminished algal
growth rate under phototrophic condition. Co-cultivation of algae
with growth enhancing bacteria resulted in enriched algal growth
rate between 10% and 70% (Nagendranatha Reddy et al., 2015b;
Cho et al., 2015).
An interesting application of algal–bacterial interactions is the
role of bacteria in microalgal harvesting. Presence of bacteria
enhances microalgae flocculation and can assist in harvesting bio-
mass but the actual reason for flocculation range from quorum
sensing and secretory proteins to genetic apparatus and EPS forma-
tion (Lee et al., 2013). In recent development, algicidal bacteria
have been shown to help in the lipid extraction process from
microalgae, because of their role in algal cell lysis. This process
could be used along with the bio-flocculation technique to enhance
lipid productivity (Lenneman et al., 2014). The pilot-scale biore-
fineries can integrate these novel harvesting technologies with dif-
ferent biomass valorization pathways during microalgae
cultivation. Microalgae based biorefinery technologies with inte-
grated closed loop approach will be phenomenal in future genera-
tion of bio-based products.
2.4. Bioelectrogenic model
Bioelectrogenesis is the process of effective electron capturing
by solid electron acceptors (electrodes) that are generated during
Fig. 4. Bioelectrogenic model depicting various microbial electrochemical systems for multi-faceted applications.
7
microbial metabolism under anaerobic conditions (Venkata
Mohan et al., 2008b). At its core, this transforms chemical energy
into electricity through cascade of redox reactions. Microbial fuel
cell (MFC), a bio-electrochemical set-up that converts the energy
present in the chemical bonds of organic compounds into electrical
energy through catalytic activity of respiring microorganisms
under anaerobic conditions. Generally, a typical MFC consists of
anode and cathode chambers separated by specific membranes.
The bacteria (biocatalyst) present at anode oxidize the organic fuel
generating reducing equivalents, which can be used for various
applications depending on the requirement based on biocatalyst,
bio-based end products formed, treatment, etc. (Logan and
Regan, 2006). Based on the compartment number and type of oper-
ation, MFCs can be categorized into single and double chambered,
up-flow mode, stacked MFC, etc. (Du et al., 2007; Venkata Mohan
et al., 2014a,b). A single chambered MFC is easy to design and scale
up, cost effective due to their simpler designs, operate either in
batch or continuous and eliminates the need for the cathodic
chamber by exposing it directly to the air making the cathode air
exposed. Up-flow mode MFC system that works in continuous flow
mode is best suitable for wastewater treatment because of their
easy relativity to scale up. In stacked MFC, several MFCs are con-
nected in series and in parallel to enhance voltage or current out-
put and substrate removal (Sleutels et al., 2012).
Apart from power generation, MFCs with minimal modifica-
tions, can be broadly classified into bioelectrochemical treatment
system (BET), bioelectrochemical system (BES), microbial electrol-
ysis cell (MEC) and Microbial desalination cell (MDC) based on
their functional utility (Fig. 4). The nutrients (nitrates, sulfates,
phosphates, struvite, etc.) formed through breakdown process of
complex molecules can be used for gardening as biofertilizer
(Kelly and He, 2014; Venkata Mohan et al., 2014b). MEC, through
electrohydrogenesis process, is used for biogas (biomethane or bio-
hydrogen) production from a wide range of wastewaters and other
renewable resources (fermented effluents viz., VFAs) by applying
external potential. Integrating dark fermentation (source of car-
bon) and MFC (for application of external potential) with MEC
wil aid in achieving higher biogas recovery along with complete
treatment of wastes (Lee and Rittmann, 2009). In MDC, saline
water and other effluents with total dissolved solids (TDS) can be
treated simultaneously. The specific ion exchange membranes sep-
arate ions to form into different chemicals in anode and cathode
chambers. This strategy will help in recovering chemicals and
8 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
Fig. 5. Nutrient model flow diagram for harnessing nutrients and other value-products for domestic/industrial applications.
reuse water for drinking purposes or for industrial uses. This way
of integrating various wastewaters and bioproducts obtained,
favors sustainability and will aid in zero liquid discharge towards
closed loop approach (Cao et al., 2009). In BES, the biocatalyst (che-
molithotrophic and/or lithoautotrophic bacteria) play crucial role
in electrode driven biochemical reactions inducing microbial elec-
trosynthesis by utilizing a variety of available and renewable feed-
stock such as waste (atmospheric CO2 and VFAs rich acidogenic
effluent) that engender energy in the form of bioelectricity and var-
ious biobased products which are platform chemicals (ethanol,
acetate, propionate, butanol, polyhydroxyalkanoates (PHA) etc.).
Thus, diverse products are synthesized based on the electron
accepting conditions and redox conditions of the system (Amulya
et al., 2014; Modestra et al., 2015).
These bioelectrochemical systems are capable of producing
electrical power and fermented by-products through bioelectro-
chemical redox reactions. These systems can can be used to power
biosensors and serve as distributed power systems for local uses in
underdeveloped regions of the world as in case of eco-villages
where renewable power sources can be used. The electricity pro-
duced can be also used for applying potential (in situ or ex situ)
to other BES systems and in large scale the power can be utilized
by industries to lower the overall manufacturing/production costs
(Nikhil et al., 2015a,b). Whereas the VFAs produced, have high
market value and hence can be commercialized or can be used as
substrates in other bioprocess applications like MEC and BES pro-
cesses to generate higher value addition (Nagendranatha Reddy
et al., 2015a). This way of integrating various wastewaters and bio-
products favours sustainability and will aid in zero discharge
towards closed loop approach addressing the new area of research
at the nexus of electrochemistry and microbiology. MFCs have doc-
umented various applications addressing the contemporary focus
and hence, the topic bielectrogenesis is intensively studied in both
basic and applied area of research to find a possible solution of sus-
tainable bioenergy production with simultaneous value addition
and bioremediation in near future.
2.5. Nutrient recovery model
Wastewater treatment plants (WWTPs) are the most basic
infrastructures for public health and environmental protection,
but they are well known for their intensive energy consumption
and large chemical dosing (Cai et al., 2013). The development of
novel technologies could transform energy and chemical consum-
ing WWTPs into factories for net energy output and resource
recovery from wastewater (Amulya et al., 2016). Nutrients found
in waste streams are mostly compounds of carbon, nitrogen, and
phosphorus (C, N, P), which are important for sustenance of various
life forms (Nagendranatha Reddy et al., 2015b). Nitrogen and phos-
phorus play critical roles in plant growth and food supply chains
(Fig. 5) (Sengupta et al., 2015). These both will be originate from
point sources like municipal landfill leachates, anaerobic digested
sewage sludge, human urine, swine wastewater, run-off from
waste disposal sites and infiltration from animal feedlots and
mines, etc. (Kumar and Pal, 2015). Point sources of nutrient rich
wastewater are usually continuous and can be monitored and con-
trolled by adopting an effective treatment technology at the
source, while non-point sources are usually intermittent and diffi-
cult to control (Cai et al., 2013). However, controlling the point
sources requires gradual shifts in the conventional treatment
methods (Aerobic Oxidation/Anaerobic digestion). This could be
recouped by extracting the nutrients from waste stream.
Nutrient recovery from wastewater reduces environmental pol-
lution, burden on reactive nitrogen and phosphorus production
thus in turn will ensure less reactive nitrogen and phosphorus
entry into the environment (Ma et al., 2016; Nancharaiah et al.,
 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
2015). This would lead to efficient use of nutrient and cause less
adverse effect on the environment with simultaneous sustainable
wastewater remediation (Le Corre et al., 2009). Three types of
extraction/recovery of nutrients that could be evaluated are –
chemical, physical and biological. In the chemical methods, nutri-
ents that are present in the wastewater will be treated with chem-
icals, causing it to ‘‘fall out” of the solution for easier removal.
Crystallization of nitrogen and phosphorus were extracting in the
form of struvite (MgNH4PO4
6H2O) (Wang et al., 2009). In case of
physical methods, ion exchange, adsorption-based methods, air
stripping methods and membrane-based recovery schemes are
being widely used for the recovery of nutrients from wastewater.
Biological mineralization is the process of conversion of organic
matter into simple inorganic compounds mainly by microbial
degradation (Venkata Mohan et al., 2014a). The use of constructed
wetlands (CWs) for biological assimilation of excess nutrients pre-
sent in wastewater offers significant advantages than conventional
methods (physical/chemical) (Kadlec and Wallace, 2008). Depend-
ing on location and the wastewater being treated, CWs can be cat-
egorized by their water level (free water surface or subsurface
flow), the types of plants used (free-floating, floating-leaved, sub-
merged, or emergent), and the flow direction. Additionally, biolog-
ical assimilation through plant and algae uptake is one of the
reliable and long-term methods for phosphorus removal in most
CWs. Taking the advantage of photosynthesis mechanism, high
rate algal biomass growth in nutrient rich wastewater could be
achieved, this will enrich the nutrient rich biomass and with simul-
taneous wastewater remediation. Additionally, growing aquatic
ferns and plants will also results protein rich biomass. Enrichment
of photosynthetic nutrient rich biomass will result in the removal
of nitrogen and phosphorus from wastewater and simultaneous
production of biofuels, biofertilizer and animal feed. This practice
is in alignment with a paradigm shift where the waste stream is
not just to be looked upon as a cost item but as a carrier of extrac-
table resources. In this direction, future research needs to combine
fundamental understanding with adaptation of technology for par-
ticular site/wastewater (Venkata Mohan, 2014b).
3. Holistic biorefinery circular bioeconomy approach
An expression of interest in modern energy and material recov-
ery technologies using waste feedstock often attempt to integrate
processes along with remediation (Venkata Mohan, 2014a,b). A
biorefinery is a facility analogous to the petroleum refinery, which
integrates biomass conversion processes and technologies to pro-
duce fuels, power and chemicals (Soetaert, 2009). The specific con-
figuration will be shaped by the nature of the following four
features: input feedstock; process technologies; platforms (inter-
mediate substances like platform chemicals); and the output prod-
ucts that are required (Luguel, 2011). However, human utilization
of biogenic materials or biomass as feedstock is not new; but now
there is a renewed interest in effective exploitation of unavoidable
organic wastes, sparked by the aim to reduce eco-footprint and
achieve a more secure supply of renewable resources.
Aspiration to valorise wastes through treatment moves up the
waste hierarchy that is likely to nurture the bioeconomy. For
example, during biohydrogen production by dark fermentation,
60–70% of the substrate is channeled to different by-products.
Ethanol, 1,3 propanediol (PD) and butyric acid are such by-
products which have immense commercial importance. If simulta-
neous H2 production and ethanol recovery are considered, for each
mol of glucose 1.58 mol H2 and additionally, 0.90 mol ethanol
could be recovered. This ethanol yield is equivalent to 0.23 g etha-
nol/g glucose that is almost half of 0.41 g ethanol/g glucose pro-
duced by conventional bioethanol production process.
9
Considering the fact, that H2 is the main product and ethanol
recovered from acidogenic waste has no direct production cost;
the yield is significant. In another aspect, according to an estima-
tion bioconversion of 1 kg of crude glycerol, a waste generated dur-
ing biodiesel production, can produce 48.14 L of H2 and 307.06 g of
PD. Considering present market value of H2 ($7.75–$11.50/m3) and
PD ($2.43/kg–$288/L), the amount of PD that could be recovered
has industrial importance. By bioconversion of 1 kg of glucose, a
part from producing 326.44 L of hydrogen, 299.37 L of butyrate
with a bulk price as high as $50/kg–$74.6/L, can be recovered as
a by-product (Poggi-Varaldo et al., 2014; Sarma et al., 2015).
Alternatively, these by-products can be the precursors for pro-
duction of various other products that have commercial interest
such as polyhydroxyalkanoates (commonly referred as bio-
plastics), lipids, biohythane (mixture of hydrogen and methane)
and bioelectricity. Also these can be a substitute to phosphate sol-
ubilizing bio-fertilizers; ultimately achieving near to zero liquid
discharge (ZLD). Sarma et al. (2015) reported that the acidogenic
effluent can fetch as a ‘platform’ or ‘building block’ for many other
chemical and material products that are currently sourced from
the petrochemical industry. Lastly, it is to be noted that platform
chemicals and bioproducts are not in themselves technologies,
but they are the most important areas for technological explo-
ration in the bioeconomy perspective. Such numerous technologies
may be brought together to valorise a biorefinery process/supply
chain (Schieb et al., 2015a; Scoma et al., 2016). On the other hand,
to substantiate environmental claims, the impacts of bio-based
materials should be typically quantified by applying life cycle
assessment (LCA) commonly referred as cradle-to-grave analysis
i.e. from resource extraction to waste management via manufac-
turing, transport, use and maintenance of the product or service.
LCA is a method to evaluate the potential environmental impact
of products and services (Guide, 2006). LCA is being increasingly
used for environmental evaluation of processes and products in
research, and also for policy applications. Hence, method develop-
ment and evaluation of LCA are important. Other environmental
systems analysis tools include Environmental Impact Assessment
(EIA), Ecological Risk Assessment (ERA) and Material Flow Analysis
(MFA). In general, environmental systems analysis tools examine
social, technical and natural systems and the links between these
systems (Baumann and Tillman, 2004).
4. Futuristic biorefinery vision
It is clear that change from a linear economy towards a circular
economy is obligatory therefore; the futuristic biorefinery platform
should have an ambitious vision to promote a switch from the con-
sumption of fossil reserves to renewable or ‘‘green” resources
(Venkata Mohan et al., 2016). This will contribute in mitigation
of GHG emissions and its impact on climate change (Stahel,
2016). Also, it will lead to incredible employment opportunities
in industries and academia especially in the sectors of agri, food,
chemical and healthcare, pharma and logistics (Amulya et al.,
2016; Clark and Deswarte, 2015). The upcoming state of art
research should focus on the outlined hybrid holistic model to
advance understanding and to provide critical solutions to foster
the sustainability of resource management (Fig. 6). A long-term
inspirational picture is of a connected biorefinery ‘superstructure’
with widening the scope of integration. The sustainable biorefinery
is viewed as a way to move fuels and other valorised co-products
onto much greener footprints, with life cycle analysis providing
the rigor needed to make the best decisions on feedstock utiliza-
tion, up scaling process technology and value chain conformation
(Liu and Shonnard, 2014).
10 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
Fig. 6. Holistic biorefinery approach with hybrid-integrated strategies for multi-purpose applications.
During these exciting developments, it is important not to lose
sight of the GHGs related impacts, concern for which underpins
much of the rationale behind biorefinery and bioeconomy accom-
plishments so far (Bardhan et al., 2015). Perhaps, the greatest chal-
lenge is to learn how to integrate technologies, not only within the
boundaries of biorefinery, but to expand the horizons to integrate
the biological systems and bioprocesses to expand the loops such
as the process chains operating across the waste management sys-
tems (Schieb et al., 2015b). If such systems can become foci for
some serious thinking where innovators are able to bring together
technologies in the right partnerships and with favorable eco-
nomics, new sustainable industrial structures may emerge that
are co-designed and work better. Understanding all these different
technologies fit in (or not) will take considerable effort. Alongside
that will be a need for an appropriate understanding of the flow of
materials (and their value) across waste management/resource
systems. The innovation and industrial sectors should be consider-
ing exactly this kind of integrated understanding and knowledge in
these areas of low-carbon technologies will underpin the sustain-
ability and closed-loop business objectives that will have to drive
modern bioeconomy aspirations. This approach is still in its
infancy, with the large majority of studies being conducted at lab-
oratory scale and few at pilot scale (Poggi-Varaldo et al., 2014; Van
Dael et al., 2014; Rama Mohan, 2016).
In our vision, bio-refineries are highly energy-efficient and
make use of mostly zero-waste production processes, and they
allow industries to manufacture environmental friendly products
with small carbon and water footprints. Therefore, a bio-refinery
should be able to produce a gamut of marketable products and
energy in a sustainable fashion (Gravitis, 1998, 2008). The design
of a bio-refinery should be sustainable by taking into account pos-
sible unintended consequences such as the competition with bio-
mass and other raw material resources, water usage, quality of
the products, usage of land, emission of GHGs and impact on bio-
diversity(Van Dael et al., 2014; Zondervan et al., 2011).
5. Conclusions
The present review explored recent advances in environmental
biotechnology with respect to the possibility of using waste as
renewable feedstock in the framework of biorefinery. Exploitation
of waste organic residues would enhance biorefinery competitive-
ness and social acceptance. Anaerobic fermentation is the widely
investigated strategy for H2 production and other value added
products that has successfully integrated with photosynthetic
processes towards diverse high value bio-based products. Overall,
different stochastic models proposed worked out in tandem
focuses a holistic biorefinery approach that carries tremendous
industrial potential. Hence, the entire process should be evaluated
as an integrated strategy and a proper cost benefit analysis of the
approach is required.
Acknowledgements
The authors wish to thank the Director, CSIR-IICT for the kind
encouragement in carrying out this work. Financial support from
 S. Venkata Mohan et al. / Bioresource Technology 215 (2016) 2–12
Indian funding agencies – Department of Biotechnology (DBT),
Department of Science and Technology (DST), Ministry of New
and Renewable Energy (MNRE) and Council for Scientific and
Industrial Research (CSIR) in the form of research grants as
National Bioscience Award (BT/HRD/NBA/34/01/2012(vi)), New
INDIGO project (DST/IMRCO/New INDIGO/Bio-e-MAT/2014/(G/
ii)), SERI/WTI (DST/TM/WTI/2K1535(G), MNRE Project No.
103/131/2008-NT, XII five year network project (SETCA (CSC-
0113), BioEn (CSC-0116), respectively. G.N.N., P.C., C.N.R. and O.S.
duly acknowledge CSIR providing research fellowship. M.V.R. duly
acknowledge UGC providing research fellowship A.N.K. duly
acknowledge MNRE for providing research fellowship.
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