Bioresource Technology xxx (xxxx) xxxx

Contents lists available at ScienceDirect

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

Review

Waste based hydrogen production for circular bioeconomy: Current status

and future directions
⁎
K. Chandrasekhara, Sunil Kumarb, Byung-Don Leec, Sang-Hyoun Kima,
a
School of Civil and Environmental Engineering, Yonsei University, Seoul 03722, Republic of Korea
b
CSIR-National Environmental Engineering Research Institute (NEERI), Nehru Marg, Nagpur 440 020, India
c
Institute of Chemical and Environmental Process, JEONJIN ENTECH,.LTD, Busan 46729, Republic of Korea

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: The present fossil fuel-based energy sector has led to significant industrial growth. On the other hand, the
Integrated approaches dependence on fossil fuels leads to adverse impact on the environment through releases of greenhouse gases. In
Microbial electrolysis cell this scenario, one possible substitute is biohydrogen, an eco-friendly energy carrier as high-energy produces. The
Bioenergy substrates rich in organic compounds like organic waste/wastewater are very useful for improved hydrogen
Biorefinery approach
generation through the dark fermentation. Thus, this review article, initially, the status of biohydrogen pro-
Circular bioeconomy
duction from organic waste and various strategies to enhance the process efficiency are concisely discussed.
Then, the practical confines of biohydrogen processes are thoroughly discussed. Also, alternate routes such as
multiple process integration approach by adopting biorefinery concept to increase overall process efficacy are
considered to address industrial-level applications. To conclude, future perspectives besides with possible ways
of transforming dark fermentation effluent to biofuels and biochemicals, which leads to circular bioeconomy, are
discussed.

1. Introduction can be employed as feedstock and a different product, for example,

ethanol, butanol, methane (CH4), hydrogen (H2), and commercially
In recent years biofuels have arisen as a possible substitute of pet- crucial volatile fatty acids (VFAs) were produced (Venkata Mohan
roleum-derived energy sources where carbon-rich organic wastewater et al., 2016). The biological roots of H2 production are of great interest

⁎
Correspondence author.
E-mail address: sanghkim@yonsei.ac.kr (S.-H. Kim).

https://doi.org/10.1016/j.biortech.2020.122920
Received 30 November 2019; Received in revised form 24 January 2020; Accepted 25 January 2020
0960-8524/ © 2020 Elsevier Ltd. All rights reserved.

Please cite this article as: K. Chandrasekhar, et al., Bioresource Technology, https://doi.org/10.1016/j.biortech.2020.122920
K. Chandrasekhar, et al.
in the current global energy situation because of its environmentally
friendly nature and renewability (Tian et al., 2019). Microorganisms
have a stretchy and varied metabolic mechanism to transform different
substrates into numerous forms of energy (Kumar et al., 2018). Creating
a free association among terminal electron-acceptor-limited microbes
and an electron sink is the crucial root for several types of bioenergy
production methods (Kumar et al., 2018). Presently, comprehensive as
well as in-depth research going on in the direction of bioenergy gen-
eration using renewable capitals across the globe (Budiman et al., 2017;
Keskin and Hallenbeck, 2012; Zahedi et al., 2016). In recent years, H2
gas has been receiving global attention as a versatile, clean-burning,
effective and renewable power currency that can potentially shift the
use of liquid fossil fuels and also reduce the GHGs emission. On com-
bustion, H2 yields only H2O as a by-product and henceforth is as de-
liberated a clean energy source, therefore environmentally benign
(Kumar et al., 2017). It is, therefore deliberated as a renewable source
of substitute power sources in the realm of environmental pollution as
well as depleting global fossil fuel reserves (Chandrasekhar et al., 2015;
Ramprakash and Muthukumar, 2016).
In the frame of energy systems, H2 is the preeminent thought of an
energy carrier, more comparable to electricity than fossil fuels
(Baykara, 2018). Hence, H2 gas emerged as a highly fortunate fuel for
stationary and transport uses. Large-scale H2 gas production occurs
mainly from fossil-fuel based petroleum compounds through the steam
reforming of natural gas or CH4 augmenting slightly from the energy-
intensive, electrolysis of H2O and as a co-product from few industrial
processes (Baykara, 2018) while H2 production from further sources is
negligible (Bakonyi et al., 2014; Chandrasekhar et al., 2015). The H2
making from the fossil-fuel based petroleum compounds is going to-
gether with the release of GHGs, namely, CO2, CH4, etc. into the en-
vironment. Consequently, there is a necessity to investigate a renewable
and eco-friendly way for H2 production. Presently, H2 production using
organic wastewater over fermentation has gained much attention due
to its sustainable nature and less energy consumptive than physico-
chemical methods (Yun et al., 2018; Chandrasekhar et al., 2015).
They contain numerous types of H2 production ways, containing
direct and indirect biophotolysis, photofermentation (PF), and dark
fermentation (DF). Amongst, the DF process is considered the most
appropriate way as it does not necessitate any external energy, and due
to the high production rate of this process over other methods (Saidi
et al., 2018). Furthermore, when coupled with the organic waste
treatment such as food waste, it can produce biohydrogen (bio-H2) with
simultaneous waste treatment. This type of approach will reduce eco-
logical issues and enhance the production of eco-friendly energy at the
same time (Srivastava et al., 2018).
As stated earlier, due to the rapid industrialization and urbanization
in the developed countries, a significant quantity of waste is producing
in each year. This carbon-rich organic waste was occupying a note-
worthy percentage, for example, food waste, dairy waste, vegetable
waste, agricultural residuals, sewage sludge, etc. The organic fraction of
this waste attracting the researcher’s attention to convert this organic
waste into bio-H2. There are several technologies, for instance, fer-
mentation, microbial electrolysis cell (MEC), and gasification technol-
ogies have been established to harvest H2 from a wide variety of organic
waste in the past decades (Nikolaidis and Poullikkas, 2017). Due to its
complex nature, bio-H2 production from wastewater faced several
hurdles in terms of efficiency of the technology to reach theoretical
hydrogen yield. Hence, it is essential to optimize operational para-
meters, reactor configurations and screening of efficient H2 producing
microbes to overcome these technical confines. So far, there are nu-
merous review articles available on diverse aspects of bio-H2 produc-
tion methods. However, most of them dedicated to precise themes of
every individual process. The combined use of biomass and the pro-
duction of biofuels is related to the biorefinery concept, which harvests
numerous biofuels and biochemicals from biomass. This biorefinery
approach can take benefit of the carbon-rich waste biomass and get the
2
Bioresource Technology xxx (xxxx) xxxx
most out of the value resulting from the feedstock. In this direction, an
integrated biorefinery approach will lead to the most efficient use of
waste biomass resources to produce a range of products, such as biofuel,
industrial biochemicals, and biomaterials including commercially im-
portant biopolymers (Moncada et al., 2016). The concepts such as the
“waste biorefinery” make extending goals in the direction of progres-
sively integrated technologies in the form of circular bioeconomy
(Bastidas-Oyanedel et al., 2016). The integration of diverse biohy-
drogen processes in a circular way gives an additional holistic product
through an efficient ‘product versus energy’ explored in the bioec-
onomy (Venkata Mohan et al., 2016). Besides, a few old review articles
exclusively focused on waste-to-hydrogen techniques, for example, DF
of food waste, but they are past reports. Therefore, a comprehensive
review concentrating on the research articles in the last decade cannot
be evaded.
Hence, aiming on the bio-H2 production methods that utilize
carbon-rich organic wastes as substrate, the key goals of present review
article are to (1) present a holistic summary of the state-of-the-art of
numerous waste-to-H2 knowledge; (2) summarize the limitation of
different waste-to- H2 methods; (3) propose integrated approaches to
increase the H2 production efficacy and eco-friendly performance of
different methods by adopting biorefinery approach. Current challenges
of fermentative H2 production need to be investigated for technology
leapfrog or breakthrough.
2. Scientometric evaluation of biohydrogen research
A scientometric study with the data existing in the ISI Web of
Knowledge (since the year 2000) specified that the sum of articles
available on bio-H2 account for 4282 records with a significant amount
of citations (127983), average records for each item (29.89), and H-
index (141). It allied with bio-H2 research showed a sharp increase after
2003, stretched higher records of 277 in 2010, and standard cumulative
trend till 2019 (records, 425) with minimal deviations. Besides, year-
wise average citations showing rapid increment, clearly representing
that rapid and promising research is underway to make the bio-H2
production process technologically viable. Moreover, country/region-
wise distribution of bio-H2 related research community stating that the
bio-H2 production research has engrossed global attention.
3. Biohydrogen production from organic waste
H2 is acting a vital role in several industrial sectors for example in
chemical industries as the building block/feedstock for the manufacture
of several valued compounds and serving as an eco-friendly energy
source in the transportation sector (Han et al., 2016a). Nonetheless,
presently, H2 gas is majorly producing from non-renewable fossil fuels
(Baykara, 2018; Dincer and Acar, 2015). Therefore, an investigation on
exploiting organic waste as a carbon-rich substrate to produce bio-H2
gas has gained much attention in the contemporary years (Han et al.,
2016a). The current extensively developing and deliberated technolo-
gies that produce bio-H2 from organic waste comprise fermentation
(both DF and PF methods), gasification and MEC system (Lin et al.,
2018; Watson et al., 2018; Zhang and Angelidaki, 2014). The bio-H2
production through biological origins mostly depends on the metabolic
action of diverse microbes to breakdown the composite waste materials
with concurrent H2 production.
Organic waste has the potential to transform into a possible feed-
stock due to its carbon-rich in nature. Most of the wastewater comprises
a higher amount of easily biodegradable organic fraction that helps to
overcome the pre-treatment requisite and can directly be used as a
potential substrate in the H2 producing bioreactors (Ghimire et al.,
2018; Han et al., 2016a; Han et al., 2016b; Naresh Kumar and Venkaa
Mohan, 2018). However, organic waste is categorized by means of a
variable elemental composition dependent on its source of origin, and
chiefly consist a combination of carbohydrates, lipids, and proteins or,
K. Chandrasekhar, et al. Bioresource Technology xxx (xxxx) xxxx

Note: WW – wastewater; VS – volatile solids; TOC – total organic content; T- temperature; COD - chemical oxygen demand; OLR – organic loading rate; CH – carbohydrate; RS - reducing sugar; CSTR - Continuous stirred
if produced from oil refinery-industrial sectors, it may comprise a

(Ramprakash and Muthukumar, 2015)

(Ramprakash and Muthukumar, 2014)

(Ramprakash and Muthukumar, 2016)

higher amount of hydrocarbon residues (Sarkar et al., 2018). Industrial

(Al-Mohammedawi et al., 2019)

(Sivagurunathan and Lin, 2016)
wastewater includes readily biodegradable organic fractions, which
leads to net energy production. Organic waste materials are metabo-
lized distinctly by the microorganisms based on their elemental com-

(Eker and Erkul, 2018)

(Pintucci et al., 2013)
position. For example, the waste collected from the food processing

(Eroğlu et al., 2008)

(Eroğlu et al., 2009)

(Salem et al., 2018)

(Patel et al., 2016)
(Silva et al., 2019)
(Lin et al., 2017)
industry consists of carbohydrates abundantly can degrade quickly by
the organisms due to its high biodegradability. Thus, carbohydrate-rich

Reference
organic waste was deliberated to be the ultimate substrate for the
production of bio-H2 (Rajesh Banu et al., 2019). In the last two decades,
researchers are more focused in the direction of exploring waste va-
lorization for definite products such as biogas, biomaterials, value-

6.35 ± 0.2 mol H2/mol lactose

added chemicals, and fuels apart from CH4 production (Ghimire et al.,

2.56 ± 0.62 mol H2/mol CH

320 mL H2/g VS (sucrose)

2018; Zhang et al., 2014). Besides with the manufacture of biobased

1.97 mol H2/mol sugar

1.92 mol H2/mol sugar

products, bio-H2 production is an attractive way for resource recovery

1.05mol/molsubstrate

197.9 mL H2/ g TOC

1.74 mol H2/mol RS
from organic waste, since it deals with numerous compensations

408.33 mL H2/L
counting volume reduction, waste stabilization, and biogas production

31.50 L H2/L
17.60 L H2/L

3.8 L H2/L-d
1.03 L H2/L
(Qin et al., 2019). For bio-H2 production purpose, numerous types of

H2 yield
organic waste (such as food waste, dairy waste, agriculture waste, etc.,)
has been widely using as a potential substrate (Lee and Chung, 2010).
Yang et al. (2019) investigated bio-H2 production potential of fallen

Enterobacter aerogenes (MTCC 2822)

leaves and sewage sludge mixture (20:80 ratio) and observed that H2

Rhodopseudomonas palustris 42OL

Rhodobacter sphaeroides O.U.001
Rhodobacter sphaeroides O.U.001

Sludge from WW treatment plant

yield reached a maximum of 37.8 mL/g volatile solids added, which
was comparatively higher over the mono-fermentation of sludge

Enterobacter aerogens RM08

(10.3 mL/g volatile solids added). Further, they also observed the good

Rhodobacter sphaeroides

Clostridium sp. IODB-O3

Enterobacter aerogenes
amount of volatile solids removal (15.7%), whereas sludge mono-fer-

Fermentation biomass
mentation and leaves mono-fermentation documented a 6.2% and Microbial culture

Granular sludge
12.8% of volatile solids removal respectively. Here co-fermentation

Mixed culture

Mixed culture
process enhanced the volatile solids removal, and carbohydrate utili-
zation might be due to the co-fermentation induced effective metabolic
pathways of H2 producing biocatalyst. Laurinavichene et al. (2018)
Biohydrogen production potential of many types of wastewater as a potential substrate reported in various studies.

investigated distillery wastewater (40 g/L COD) treatment in a con-

pH: 6.3; T: 37 °C; HRT: 1.5 h; substrate concentration: 20 g

pH: 6.5 to 7; T: 33 ± 2 °C; substrate concentration: 10.2 g

pH: 6.8 to 7.2; pretreatment: dry-Azolla and granular active

pH: 6.5 to 7; T: 33 ± 2 °C substrate concentration: 10.2 g

secutive DF and PF processes by employing anaerobic saccharolytic
microorganisms and purple nonsulfur bacteria respectively. A combi-

HRT: 24, 18 and 12 h; substrate concentration: 10 g/L

pH: 8.5; T: 37 °C; biomass production: 4.2 ± 0.3 g/L
nation of these two processes resulted in the highest H2 yield of 17.6 L/
L of distillery waste. At the end of these two stages process, sugars and
T: 24 to 30 °C; OLR: 28.7 ± 8.9 g COD/L-d

acid metabolites were utilized by the microorganisms for their meta-

pH: 6.8; T: 25 °C pretreatment: Zeolite-4A

bolic activities that mean H2 production associated wastewater treat-

ment. Vatsala et al. (2008) assessed the possibility of H2 production
pH: 6.8; T: 35 °C; HRT: 8 h and 4 h

from distillery effluent by mixed culture of Citrobacter freundii, En-

terobacter aerogenes, Rhodopseudomonas palustris. The stated average H2
pH: 6.8; pretreatment: clay;

yield and rate of H2 were 2.76 mol H2 per mol glucose and 0.53 kg H2 pH: 6.8 ± 0.3; T: 37 °C
pH: 7.0; T: 33 ± 2 °C;

per 100 m3 per hour, respectively.

Operating conditions

Leaño et al. (2012) investigated batch bio-H2 production and

T: 30 ℃; pH: 7;

bioelectricity harvest from palm oil mill waste employing sludge as seed
inoculum. The reported higher bio-H2 production is 0.7 mmol H2/g
starch/L

starch/L
COD/L

carbon

COD with 65% of COD removal efficiency. Leaño and Babel (2012)
investigated the H2 production efficiency of palm oil mill wastewater in
batch experiments. The reported H2 yield is 1.88 mol H2/g COD of
Stirred tank reactor digester

pretreated palm oil mill effluent at pH 7. Heat-treated seed culture

enhanced H2 production and suppressed CH4 producers. The results
Fluidized-bed reactor

indicate that palm oil mill effluent can be used as a preferred feedstock
Reactor involved

Batch bioreactor

Batch fermenter
Photobioreactor
Photobioreactor
Photobioreactor

for bio-H2 production. Table 1 represents a detailed note on numerous

Batch reactor

Batch reactor

Batch reactor
Glass reactor

types of organic waste/wastewater used for bio-H2 production reported

in various studies. Lin et al. (2017) investigated continuous biohy-
CSTRs
CSTR

drogen production from coagulation-pretreated textile desizing waste-

water in a stirred tank reactor digester operated at pH–6.8 and tem-
perature of 35 °C. They observed 3.8 L H2/L-d hydrogen yield by using
Brewery WW & banana peels

granular sludge. Silva et al. (2019) investigated the biohydrogen po-

tential of dairy wastewater (organic loading rate of 28.7 ± 8.9 g COD/
Textile desizing WW

Cheese whey waste

L-d) which is one of the carbon-rich wastewater in an anaerobic flui-

Olive mill WW
Olive mill WW
Olive mill WW

dized-bed reactor and achieved 2.56 ± 0.62 mol H2/mol carbohy-

Type of waste

Beverage WW

Rice mill WW

Rice mill WW

Rice mill WW

tank reactor.
Potato WW

drate. Further, Patel et al. (2016) operated batch fermenter with lactose
Sugar beet
Dairy WW

rich cheese whey waste as a potential feedstock for biohydrogen pro-

Table 1

duction and observed 6.35 ± 0.2 mol H2/mol lactose at pH–8.5 and
temperature of 37 °C. From the existing literature reports, it has been

3
K. Chandrasekhar, et al.
determined that organic waste/wastewater is deliberated as preferable
substrates for bio-H2 production to make the overall process econom-
ically viable. Various kinds of organic waste have different modes of
biodegradation based on their source of origin and organic content.
Nonetheless, additionally, further exploration and optimization are
necessary for this emerging field to enhance the overall process effi-
ciency.
Among the biological roots for H2 production, the DF process
mainly involved in the alteration of chemical energy packed in the
organic waste to other forms of energy without any light source (Rajesh
Banu et al., 2019). Besides, the reactor design used in this DF process is
more straightforward and inexpensive related to PF (no need to provide
solar energy). For example, DF can be easily combined with existing
wastewater treatment schemes to harvest H2 with concurrent waste
treatment. Producing H2 from organic waste has the potential to de-
crease overall process economics as wastewater widely available and
inexpensive substrate. However, low substrate conversion efficiency
and low production rates were considered as the significant challenges
of anaerobic digestion (AD). Biophotolysis and PF processes are pho-
tonic-driven (natural or artificial light source) biological H2 production
methods from water/wastewater (Keskin et al., 2011). Hence, re-
searchers classify H2 production via biophotolysis into direct, indirect,
and PF. In biophotolysis, microbes with light-sensitivity (micro-algae)
will play a vital role as a biocatalyst to produce H2 in a designed photo-
bioreactor.
4. Technical challenges in biohydrogen production
In recent years, several researchers are seriously focusing on ad-
dressing the limitation of waste-to-hydrogen production technologies to
reduce the overall process cost (Chandrasekhar et al., 2017). Never-
theless, few significant technical challenges, for example, less feed
transformation efficacy, and leftover acid metabolites (volatile fatty
acids (VFAs) such as formic acid, acetic acid, propionic acid, and bu-
tyric acid, etc.,) in the reactor. Low substrate conversion efficiency was
one of the common problems when the reactor operated with composite
organic waste. Generally, this issue occurs due to the complex nature of
the substrate or due to the lack of specific microbial population, which
can hydrolyze this complex substrate (Chandrasekhar and Venkata
Mohan, 2014a; Chandrasekhar and Venkata Mohan, 2014b; Reddy
et al., 2011). Besides, the accumulation of intermediate acid metabo-
lites is one of the standard limitations usually occurs in almost all the
bio-H2 process (Gonzalez del Campo et al., 2012). During the initial
stage of the bio-H2 process, H2 producing microbial population utilizes
simple substrate and produce VFAs as by-products. These VFAs will
leads to a raise of acidic conditions in the reactor, ultimately show an
adverse effect on metabolic activities of hydrogen-producing microbes
(Venkateswar Reddy et al., 2014). Henceforth, it is essential to over-
whelm this limitation to enhance the overall process efficiency. Besides,
there are several other limitations too which listed in the given table
(Table 2). To make the bio-H2 production process more efficient, it is
necessary to resolve all these limitations listed in the table.
Table 2
5. Strategies to improve the overall process efficiency
In the absence or presence of light, living creatures can utilize
biochemical energy, which is present in organic matter as in the form of
chemical energy. The fundamental limitations to the biological roots for
the H2 production are the less substrate transformation efficacy and
leftover acid metabolites (VFAs). Because of these limitations, overall
bio-H2 production is far too low which makes the process economically
not feasible (Dahiya et al., 2020). Notably, even though the theoretic H2
production could reach 12 mol per mole glucose, H2 production
through the DF process is metabolically restricted to four moles of H2
from one mole of glucose, which has been considered a major technical
4
Bioresource Technology xxx (xxxx) xxxx
impediment to make the total process economically viable (Venkata
Mohan and Pandey, 2019).
Moreover, after the DF process, higher quantities of acid metabolites
accumulate in the reactor effluent (Dahiya et al., 2018). As a result,
further treatments are needed before releasing that effluent into the
environment (Sarkar et al., 2018). In this scenario, the reprocessing of
these acid metabolites for additional energy generation will be con-
sidered as a wise action in view of several ecological and financial is-
sues (Hemalatha et al., 2017). Besides, the design and fabrication of
photobioreactors with larger surface areas to utilize the internal light
supply efficiently considered as one of the significant challenges in PF
(Gadhamshetty et al., 2010; Venkata Mohan et al., 2019). Whereas in
the case of direct and indirect biophotolysis methods for bio-H2 are also
having few limitations such as low product yield and needed custo-
mized photobioreactor with high surface area to intake light energy and
purity of the product. It is necessary to focus on these issues need to find
other alternative ways to overcome these limits to make the process
economically viable.
These technical limitations may be overwhelmed by way of the ef-
ficient design of bioreactors, amendments in the process, choice of
suitable substrate, and with the option of appropriate and effective
hydrogen-producing microorganisms as an inoculum. Usually, the
substrate will go through a series of metabolic reactions that yield H2,
the microbial byproducts formed are a contest for the undistinguishable
reductants as the H2 and this rerouting of the reductants in the direction
of soluble end metabolites drastically reduces the overall H2 yields
(Chandrasekhar et al., 2015). Hence, the actual bio-H2 yield is lesser
than 50% of the theoretical maximum (4 mol H2/mol glucose), and this
is attributed to the thermodynamic limitations, and acetogenic bio-H2
consuming metabolic reactions (Yun et al., 2018). Therefore, many
scientists are trying to reroute the biological reactions to lower the
generation of soluble byproducts. To overcome the stoichiometric
constraint of the DF process, strong and efficient microorganisms must
be investigated that can be metabolically engineered (Yun et al., 2018).
Therefore, the yield of H2 can be increased with an effective reactor
design and with the identification of the perfect process parameters.
Nevertheless, it is a fact that the low molar conversion rates have an
adverse impact on the process economics, and consequently, the in-
vestigation is in progress toward higher bio-H2 yield above 4 mol per
mole glucose. In recent times, scientists are investigating appropriate
hybrid processes, for instance, the two-stage integration approaches
such as the DF, subsequently the PF, to generate bio-H2 (Venkata
Mohan et al., 2019). In this method, the VFAs generated during the DF
(first stage) is utilized as the carbon-rich substrate in the PF process
(second stage). This method can be used to attain the higher theoretic
H2 production limit of 12 mol of bio-H2 per mole glucose (Venkata
Mohan et al., 2019). Likewise, hybrid methods that comprise successive
CH4 production or microbial electrolysis cell can also be performed to
enhance the overall process efficiency. Even though there are few ar-
ticles available regarding this integration method, further investigation
is needed to make the biological H2 generation pathways economically
viable (Hallenbeck and Ghosh, 2009; Venkata Mohan et al., 2013).
Furthermore, the coupling of bio-H2 producing methods using the ex-
isting waste remediation method has quite a few benefits, for instance,
waste treatment with concurrent bio-H2 production in the form of eco-
friendly energy sources. Eventually, organic wastes might be considered
as an appropriate feedstock for bio-H2 output since it is carbon-rich and
their natural abundance (Yun et al., 2018). The utilization of organic
wastewater as cheaper feedstock would enhance the overall bio-H2
production through the biological ways makes the process economically
feasible.
5.1. Integration of approaches
In recent times, researchers were focusing on several integrated
methods to overwhelm the technical confines of numerous individual
K. Chandrasekhar, et al. Bioresource Technology xxx (xxxx) xxxx

Table 2
Type of bioprocess for H2 production and technical limitations.
Bioprocess type Technical limitations

Photofermentation • The obligation of an external light source (required light intensity should be maintained throughout the reactor)
• This bioprocess is limited by day and night cycles when reactor operated with sunlight as the sole light source
• Low H yield due to a very low light transformation efficacy
• Low
2
volumetric H production rates
• Large
2
surface area requirement
Direct biophotolysis • Release/generation of oxygen gas due to the activity of PS II
• This process required customized photobioreactors because this process demands a large surface area.
• Low H yield due to an extremely low light conversion efficacy
• Separation
2
of H from O needs some energy input as these two gas will produce together in this process.
• Lower
2 2
Indirect biophotolysis H yield make happen due to the hydrogenase enzymes
• An
2
external light source is needed to the bioreactor
• Overall light conversion efficacy was very low
Dark fermentation • Low substrate conversion efficiency mainly when reactor operated with higher substrate loading rate
• Low bio-H yield compared to theoretical yield
• Thermodynamic
2
limitations
• Quality of the end product (production of CO2 and CH4 as co-products, which need to separate from the main product, that is H2)
• Accumulation of intermediary metabolites as byproducts
• Presence of methanogens in the H2 bioreactor
• H2 losses due to the presence of hydrogen-utilising methanogens in the reactor
routes to improve the overall process efficiency, especially in DF. The
re-rooting the leftover acid metabolites from the bio-H2 discharges as a
possible substrate for further energy retrieval is a feasible and in-
novative idea, predominantly by coupling DF with other methods in
two-stage energy harvesting approach (Chandrasekhar et al., 2015;
Sivagurunathan et al., 2017). Several secondary methods, such as CH4
production, DF, PF, MEC systems for H2, anoxygenic processes for
biopolymers, algae cultivation for lipid production, and microbial fuel
cell (MFC) to harvest electricity (Chandrasekhar and Ahn, 2017;
Chandrasekhar et al., 2018), were successfully united with the primary
DF process. The main motive behind this approach is to make the entire
process economic and practically applicable to bio-H2 generation from
wastewater (Chandrasekhar et al., 2015).

5.1.1. Integration of photobiological process with dark fermentation

The light-sensitive microorganisms like photosynthetic bacteria
eagerly used up the leftover acid metabolites (Chandra and Venkata
Mohan, 2011; Rai et al., 2012; Rai et al., 2014). The DF metabolic in-
termediates (VFAs) can be efficiently utilized as a carbon-rich substrate
by some purple non-sulfur bacteria. Hence, the coupling of PF with the
DF leads to dual benefits of enhancing H2 production efficiency with
simultaneous waste treatment (Chandra and Venkata Mohan, 2011;
Chandrasekhar et al., 2015; Mohanakrishna and Venkata Mohan, 2013;
Özkan et al., 2012; Rai and Singh, 2016) (Fig. 1). Chandra and Venkata
Mohan (2011) examined the possibilities of producing H2 by feeding
carbon-rich DF reactor effluents to the mixed microalgal population.
The composition and the survivability of light-sensitive microbial po-
pulation during their growth under glucose and VFAs produced from
the DF process has examined. The PF with the acid metabolites of
glucose showed a higher H2 production efficiency of 5.22 mmol than
acid metabolites of DF (1.21 mmol). The Chlorella also utilizes VFAs
from DF for bio-H2 production (Bala Amutha and Murugesan, 2011;
Chandra and Venkata Mohan, 2011). Further, Rai et al. (Rai et al.,
2014) H2 production from sugarcane bagasse by coupling DF and PF
was investigated. The sugarcane bagasse was initially pretreated with
acid and subjected to DF. Reported cumulative H2 production during DF
is 1000 mL/L. The spent media of DF was utilized for PF by Rho-
dopseudomonas and reported a maximum cumulative H2 production of
755 mL/L. Nonetheless, the utilization of acid-rich effluents in PF pro-
cess is more intricate over DF process due to the poor light penetration,
nutritional necessities of the light-sensitive microorganisms, adverse
environmental circumstances, inhibition of substrates, and contamina-
tion hurdles (Bala Amutha and Murugesan, 2011; Özkan et al., 2012;
Ozmihci and Kargi, 2010). To overwhelm the above-mentioned
Fig. 1. Schematic representation of sequential dark- and photo-fermentation.
confines, proper light source provisions to the photobioreactor is es-
sential, and need to supplement the necessary nutrients. Furthermore,
optimal temperatures and feed quantity must be managed throughout
the process. Clean and closed type bioreactors must be designed and
used to avoid contamination issues.
5.1.2. Integration of bioplastic production process with dark fermentation
Polyhydroxyalkanoates (PHAs) and polyhydroxy butyrate (PHBs)
are a group of biopolymers produced in numerous prokaryotic microbes
in response to famine conditions (Dahiya et al., 2018; Ray and Kalia,
2017; Venkateswar Reddy and Venkata Mohan, 2012; Waller et al.,
2012). Different ecological and commercial requirements were de-
manding the progress of eco-friendly and readily biodegradable bio-
polymers (Amulya et al., 2016; Amulya et al., 2015). Recently, these
biopolymers attracting several researchers due to their unique proper-
ties such as biocompatible and thermoplastic assets. Organic wastes like
food waste/canteen waste (Venkateswar Reddy and Venkata Mohan,
2012), spent wash discharges (Amulya et al., 2014), and bakery was-
tewater was widely utilized as a carbon-rich feedstock for biopolymers

5
K. Chandrasekhar, et al.
production. However, an integration of DF with a biopolymer produc-
tion process has also been reported (Amulya et al., 2015). By in-
tegrating DF effluents for the production of biopolymers, a maximum
PHA production of 23.7% was observed (Amulya et al., 2015). Reddy
and Venkatamohan (2012) have investigated food waste effluents as a
carbon-rich substrate and achieved 39.6% of PHA production efficiency
over unfermented food waste (35.6%). Integrating DF process with
biopolymers production will make the process economically more vi-
able.
5.1.3. Integration of microbial electrolysis cell process with dark
fermentation
Microbial electrolysis cells (MEC) are electrochemical devices that
use electrochemical assistance to the microorganisms to transform or-
ganic matter into H2 (Bakonyi et al., 2018; Cheng and Logan, 2007;
Kumar et al., 2018; Rathinam et al., 2019). The MEC system utilizes
typical microorganisms or electrochemically active microbes to perform
electrically assisted H2 production. Hence, an external power supply is
essential as the transformation of a substrate is not a natural process at
normal circumstances (Chandrasekhar et al., 2015). In this MEC re-
actor, H2 production occurs near the cathode through the reduction of
H2 ion by electrons resulting in H2 generation (Hasany et al., 2016). The
MEC systems look a lot like an MFC, for MFC operations, the external
power supply is not needed (Deval et al., 2017; Chandrasekhar, 2019;
Kumar et al., 2012) (Fig. 2). According to the thermodynamics, a po-
tential greater than 110 mV together with the voltage generated by
electrochemically active microbes (−300 mV) will form bio-H2
(Chandrasekhar et al., 2015). Though MEC is capable of reaching 90%
of H2 production efficiency, several factors such as reactor configura-
tion, type of electrodes used and microorganisms will strongly influence
the overall process efficiency (Parameswaran et al., 2011). MEC system
design is a crucial concern disturbing the overall reactor performance.
However, there is no explicit consent has yet arisen on what model is
very much suitable to couple with an existing domestic sewage treat-
ment plant. So, several researchers are working in this direction to in-
vestigate more suitable MEC reactor design which will also enhance the
overall process efficiency, with that these systems can also compete
with conventional biological technologies (Escapa et al., 2012). Higher
Fig. 2. Schematic illustration of single-chambered Microbial electrolysis cell
(MEC).
6
Bioresource Technology xxx (xxxx) xxxx
Fig. 3. Schematic representation of a two-stage process integration approach,
i.e., integration of MEC process with dark fermentative biohydrogen production
process to attain higher hydrogen yield.
H2 yield of these technologies related to other biological processes and
getting used to degrade/treat several types of organic waste has im-
proved academic interests. Thus, in some investigates, MEC reactors
were used as complementary systems to other processes (Commault
et al., 2013).
On the other hand, there are a few limitations in the commerciali-
zation of these MEC systems for bio-H2 production and/or waste
treatment (Escapa et al., 2012). The integration of MECs with other
biological processes has also gained much attention in recent years
(Fig. 3). Lenin Babu et al. (2013) examined the viability of coupling
MEC with DF to reuse VFAs present in the bioreactor effluents for extra
H2 production. For this purpose, the external power supply range from
200 mV to 1000 mV has been applied to the MEC reactor which is op-
erated with 3000 mg VFAs/L. Under optimum conditions (600 mV),
MEC system reached maximum H2 rate pf 0.53 mmol/h with 49.8%
substrate conversion efficiency. Hence, MECs integrated with DF, could
be a feasible choice to enhance the overall substrate conversion effi-
ciency and H2 yield.
5.2. Role of biorefinery approaches and circular bioeconomy in the waste
valorization
The increasing energy demands and GHGs emissions are forcing the
human race to move from fossil fuel-based linear economy in the di-
rection of green and sustainable circular bioeconomy (Kumar et al.,
2013; Lee, 2019). Multidisciplinary research in science and engineering
will help to produce various bioproducts from renewable feedstocks
(Mishra et al., 2019). So far, biomass waste familiar by means of a
potential substrate for bioeconomy, while organic waste can also be
considered as a potential substrate (Meena et al., 2019). Biological
transformation of organic waste into viable platform compounds offers
an innovative resource retrieval substitutions intended for fossil fuel-
based compounds to a certain extent (Mak et al., 2019). In this direc-
tion, exclusion, reduction, and reuse are the crucial strategies that need
to follow to manage the quantity of preventable organic waste to a
certain level. The biorefinery concept deals with the conversion of
biomass into an extensive variety of products, including platform che-
micals, specialty chemicals, and bulk products in an integrated ap-
proach. In the biorefinery process, both preventable and unpreventable
organic waste can be widely utilized by implementing various, biolo-
gical, and physicochemical procedures (for instance, acidogenesis, bio-
K. Chandrasekhar, et al.
Fig. 4. Overview of biorefinery approaches in aid of waste valorization to value added bioproducts production in circular bioeconomy (MEC – microbial electrolysis
cell; PS – power supply; CO2 – carbon dioxide; VFAs – volatile fatty acids; C - cathode).
electrogenesis, etc.) (Xiong et al., 2019). In the last two decades, the
biorefinery model is deliberated as one of the research keystones and as
the greatest choice in the direction of converting various organic waste
into value-added chemicals. These strategic waste valorization ap-
proaches can be functional in a closed-loop, wherein reactor effluent
from one process will act as a potential feedstock in the next process.
This approach provides economic benefits to the waste treatment pro-
cess.
Furthermore, these approaches perform a vital role in the trans-
formation of organic waste into valued bioproducts, for example, bio-
fuels, bioelectricity, biofertilizers and animal feed (Fig. 4). Deployment
of these strategic approaches to carbon-rich organic waste will deliver
an extra advantage in the direction of product recovery and overwhelm
the technical limitations of a single process (Mak et al., 2019). Hence,
these biorefinery approaches in the direction of value-added biopro-
ducts recovery will trigger the development of sustainable organic
waste-based bioeconomy. Consequently, the massive quantity of gen-
erated organic waste can be recycled by means of a potential feedstock
for the production of value-added bioproducts.
The waste biorefinery is a linkage of amenities that integrate waste
conversion methods in a cascade order that can result in the formation
of several bioproducts such as bio-H2, biodiesel, carboxylic acids,
ethanol, bioelectricity, bioplastics, animal feed, etc. with simultaneous
waste remediation (Sadhukhan et al., 2018). Usually, a biorefinery
strategy involves a series of bioprocesses wherein the first step, after
feedstock selection, often includes the feedstock treatment generally
referred to as a pretreatment step. As explained in the Fig. 4, the AD
and/or MEC processes will act as a pretreatment process to simplify the
complex waste biomass. In this first stage, the complex substrate will be
hydrolyzed through a series of microbial metabolic reactions into
simple monomers, which can be readily utilized as a potential feedstock
in further processes. In the next stage, the feedstock subject to a series/
grouping of biological and physicochemical methods. The harvested
products (monomers) from this stage can be used as building blocks for
further processing usages (Liu et al., 2012; Moncada et al., 2016)
(Fig. 4). For instance, the effluents from the AD/MEC are carbon-rich in
nature and can be readily used as a potential substrate to start PF for
bio-H2 production or for the bioplastic production process to produce
biopolymers such as PHAs and PHBs under famine conditions. Further,
the effluents from the AD can also use as a substrate in MEC for bio-H2
production. In these integrated processes, the waste biomass further
degraded and biotransformed into valuable products and chemicals
7
Bioresource Technology xxx (xxxx) xxxx
such as bio-H2 and biopolymers as illustrated in the Fig. 4. Further, the
effluents from the MEC will act as a substrate in different processes such
as MFC for bioelectricity generation, anoxygenic process for biopoly-
mers production and for algal cultivation to produce biodiesel. Finally,
the effluents out from these processes consist of very less organic matter
and can be employed for gardening purposes as illustrated in the Fig. 4.
The primary goal of this approach is to develop the most efficient
consumption of renewable biomass resources by coupling various bio-
logical methods in a cascade order (Moncada et al., 2016). Another
beauty of this approach is that this biorefinery of organic waste can
encourage sustainable methods by minimal ecological impact in the
long run. The integration of different biological and thermochemical
methods (mentioned above) in a precise circular way makes the best
use of the resources for enhanced product recovery from organic waste,
which leads to circular bioeconomy. Hence recently, researchers fo-
cusing on circular bioeconomy to fulfill the rising energy demand and
to regulate the process economics (Venkata Mohan et al., 2016a). To
reach the global climate change mitigation agenda, nations moving
forward with defined sustainable development goals. Hence, to achieve
appreciable socio-economic growth rate and sustainable development
goals, every nation should shift towards bioenergy, biorefinery, and
circular bioeconomy approaches (Sadhukhan et al., 2018). Biorefinery
and bioeconomy play a useful role in achieving sustainable develop-
ment goals by focusing on supporting environmentally friendly energy
generation technologies by adopting sustainable manufacturing and
feeding concept, preserving natural resources for the future generation.
Biomass/organic waste can aid in justifying the impact by substituting
fossil fuels for the reason that entrenched carbon out from biomass
utilization is sequestrated in the course of biomass growth (Sadhukhan
et al., 2018).
Symbiotic flows can interconnect industrial, manufacturing and
agricultural sectors. Such as remains created from the farming industry
might be used as potential feedstock to produce various products in the
industrial and manufacturing sectors to make the process economically
viable. Production of bio-H2 as an environmentally friendly energy
source as a substitute to fissile fuel-based non-ecofriendly energy
sources are promising solutions for a sustainable society (Kumar et al.,
2015; Kumar et al., 2013). The bio-H2 market is emerging rapidly and
shaping towards an integrated prophecy (Dahiya et al., 2018; Mak
et al., 2019). A defined integration of DF with other biological processes
in a circular/cascade approach offers further advantages and appen-
dages for both the environment and industries (Kumar et al., 2016).
K. Chandrasekhar, et al.
Different waste biorefinery approaches in the direction of utilizing or-
ganic waste as potential feedstock have been widely discussed else-
where (Venkata Mohan et al., 2016b). In the direction of circular
bioeconomy, shika dahiya et al. (Dahiya et al., 2018) deliberated nu-
merous integrating closed-loop bioprocesses to enables maximum re-
source recovery from food waste. Several physiological microbial
groups existing in the mixed culture mediate dissimilar metabolic re-
actions, which leads to the advantage of generating different products
rather than producing a bio-H2 or CH4 as a single product. This would
make the overall process economically viable over other well-estab-
lished chemical and electrochemical bio-H2 production methods.
6. Future prospective
Cumulative discharge of GHGs and a limited quantity of petroleum
oil reserves have made bio-H2 a more convincing renewable and eco-
friendly substitute fuel source. In recent years, bio-H2 production re-
search trends are directing towards process enhancement by two-stage
integrating of DF and PF, regulating key operational factors, integrating
the processes in a biorefinery approach with effective fermentation
effluents utilization. Alternatively, utilization of carbon-rich waste-
water such as dairy wastewater, beverage wastewater, food waste and
palm-related biomasses as the potential feedstock for bio-H2 production
purposes. Several researchers have demonstrated that bio-H2 produc-
tion by using carbon-rich industrial effluents is technically possible.
There is no appropriate question of whether bio-H2 production from
organic waste, but made this process economically viable and can
produce at a scale adequate to meet the existing demand for fuel is the
major challenge. The DF has been considered as the rapid biological
root for H2 production. Nonetheless, there are few significant technical
limitations in biological roots for H2, which have to be resolved to at-
tain this goal. Low substrate conversion efficiency and accumulation of
acid metabolites limiting the DF efficiency, thus prevent the commer-
cialization of bio-H2. In the PF process, the specific design of bioreactor
is needed with the high surface area for better light penetration for H2
production, which increases the overall cost of production.
Recent reports revealing the importance of integrated approaches to
making the process economically viable. For instance, the two-stage AD
of producing bio-H2 and CH4 can certainly upsurge energy recovery
from biomass over an only CH4 producing process. In recent years re-
searchers are reporting that bio-H2 has the possible progressively to
turn out to be the main H2-producing technology for the upcoming
progress of the green economy. Furthermore, waste biorefinery ap-
proaches can be considered as viable alternative technologies to pro-
duce various biofuels (bio-H2, CH4, and biohythane, etc.) and bio-
chemical (PHAs and PHBs, etc.) from waste biomass to replace the fossil
fuels. The bio-H2 reactor effluents can be used as a potential feedstock
in the further process to produce biofuels. In this direction, once can
integrate multiple processes (for example DF-PF-MFC; AD-DF-PF; AD-
DF-MEC; DF-MEC-bioplastic production; AD-DF-MFC-gardening, etc.)
in a cascade manner to attain high yield and make the process eco-
nomically more viable.
7. Conclusions
Biological H2 production has numerous benefits compared to other
conventional and fossil-fuel-based technologies as it can effectively
utilizes carbon-rich industrial wastewaters without GHGs emissions.
The specific routes have their intrinsic restrictions, for instance, low the
H2 yield, and VFAs accumulation which makes the process economic-
ally non-viable. Although innovative tactics are expected in the future
to avoid the existing confines, bio-H2 production technology in aid of
waste valorization necessitates a multidisciplinary methodology to
make the overall process environmentally friendly and economically
feasible. Consequently, process integration approaches would imple-
ment a viable waste biorefinery to reach the circular bioeconomy goals.
8
Bioresource Technology xxx (xxxx) xxxx
CRediT authorship contribution statement
K. Chandrasekhar: Conceptualization, Methodology, Writing -
original draft. Sunil Kumar: . Byung-Don Lee: . Sang-Hyoun Kim:
Supervision, Data curation, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by Korea Institute of Energy Technology
Evaluation and Planning (KETEP) grant funded by the Korea govern-
ment (MOTIE) (No. 20188550000540).
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