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Bioresource Technology 331 (2021) 125024

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

Preface

Renewable hydrogen production from biomass and wastes (ReBioH2-2020)

A R T I C L E I N F O A B S T R A C T

Keywords Growing consumption of fossil reserves to meet the rising demand of energy has led to climate deterioration and
Renewable biohydrogen simultaneous waste generation, urging modern society to find sustainable energy resource that can meet the
Dark fermentation growing energy demands and reduce greenhouse gas emissions and carbon footprints. In this aspect, hydrogen
Microbial electrolysis cell
(H2) is one of the most promising sustainable clean fuels that has gained significant interest in recent years. This
Bioresources
article highlights the major research progress on biohydrogen production from renewable bioresources such as
Industrial waste
Gasification organic wastes, lignocellulosic biomass, algal biomass, and industrial wastewaters. It summarizes the research
highlights of manuscripts published in the special issue (VSI: ReBioH2-2020), which contains twenty-two arti­
cles, including seven critical reviews and fifteen research articles, focusing on biotechnological and thermo­
chemical routes for biohydrogen production from renewable feedstocks. The major findings of the research
works in this special issue can be used as a road–map for sustainable renewable hydrogen production from
bioresources.

1. Introduction growing drastically in recent years. It shows immense potential in


transforming the global energy production strategies towards a more
Urbanization and economic developments aimed at sustaining the sustainable and greener future by contributing to 8% of global energy
growing population have resulted in significant increases in energy de­ demand by 2050, through cost-effective production of 2.50 USD/kg
mand and consumption with the simultaneous generation of a huge (Hydrogen Council 2050) (https://hydrogencouncil.com/ko/). Consid­
amount of organic waste. According to the International Energy Asso­ ering the limitations and impact of fossil fuel consumption, most
ciation, total world energy production driven by fossil fuels, including countries proclaimed ambitious project plans for a sustainable H2-based
natural gas, coal, and oil. Of the 14,421 million tonnes of oil equivalent economy for transport and industrial sectors. According to the Hydrogen
(Mtoe) produced in 2018, 81% was derived from fossil fuels Council (2020), the global share of hydrogen will increase to 15–18% by
(https://www.iea.org/). Consumption of finite fossil fuel reserves has 2030 with a further reduction of delivery cost to 1.80 USD/kg. Addi­
resulted in critical environmental and climate damage; a sustainable tionally, the demand for hydrogen has increased every year with its
green future requires concerted efforts to find alternative energy re­ application in NH3 production (51%), oil refining (31%), CH3OH pro­
sources. In addition to technological development, policies for major duction (10%), etc. Recently, the appeal of H2 as a sulfur-free fuel for
transformation towards renewable energy production are needed to transportation and for electricity production, has increased H2 demand.
ensure that the global temperatures do not rise to >2 ◦ C above pre- Currently, most hydrogen (~96%) is obtained from petroleum-based
industrial levels (Liu et al., 2020). Aims should be to limit the increase non-renewable feedstock such as natural gas through a steam methane
in global temperature to 1.5 ◦ C above pre-industrial levels (Liu et al., reforming process, electrolysis, and liquid reforming, but these pro­
2020). In view of this, renewable energy resources such as hydro, wind, cesses are costly and not environmentally-friendly for continuous pro­
solar, nuclear, and organic waste have been considered to produce duction. The excessive exploitation of fossil-based resources has
alternative carbon-free energy resources in recent years. Currently, increased greenhouse emissions causing environmental concerns. Bio­
varying renewable energy policies by developing countries requires the logical processes can aid in the shift towards development of alternative
implementation of advanced bioenergy technologies with annual routes to achieve sustainable hydrogen-based bioeconomy. Through
growth rate of 3.1% until to 2030. Modern advanced bioenergy naturally occurring processes, hydrogen is captured and chemically
contributed to 5.1% of total energy demand excluding traditional use of transformed in the form of water, and lignocellulosic biomass, microbial
biomass. biomass, organic wastes; etc can be used as renewable, low-cost sub­
Hydrogen (H2) - a versatile carbon-free clean fuel - produces only strates in various biohydrogen production strategies. Renewable
water as a by-product. Hydrogen is has high energy density ranging from hydrogen strategies seek to decarbonize the current fuel scenario,
120 to 142 MJ/kg and is capable of tackling critical energy demands improve energy security with clean energy transformation, promote and
driven by fossils fuel consumptions. Hydrogen production has been strengthen environmental protection and pave the way forward for

https://doi.org/10.1016/j.biortech.2021.125024

Available online 17 March 2021


0960-8524/© 2021 Elsevier Ltd. All rights reserved.
Preface Bioresource Technology 331 (2021) 125024

international economic development. challenge nowadays with a growing economy. In recent years, dark
Towards these ends, this special issue published new logical research fermentation of organic-rich waste streams demonstrated an economical
articles to accomplish a renewable hydrogen energy society in the near and environmentally friendly way for bioremediation of organic wastes,
future. The objective of this special issue is to extend knowledge and simultaneously producing biohydrogen. However, the complex struc­
recent progress in renewable biohydrogen production. Biohydrogen ture of organic waste and low hydrogen yield are major obstacles for
production from waste organic materials could meet the desired criteria large-scale activities. Recent reports showed that the coupling of
for a decarbonized economy. However, biohydrogen is still facing fermentation with biological anaerobic pretreatment could effectively
challenges of process optimization and scale-up. Additionally, this issue improve hydrogen production. For example, Paillet and co-workers
emphasized the various biotechnological, and thermochemical routes investigated the effect of three heat shock pretreatment conditions on
such as dark fermentation, biohythane production, utilization of recycled organic-rich efficacy, including initial heat shock (90 ◦ C, 30
microalgae, lignocellulosic biomass and organic-rich waste streams for min), systematic heat treatment and without any heat treatment.
biohydrogen production. Moreover, this review also emphasize inte­ Optimal conditions achieved with systematic heat treatment, yielded a
grated biorefinery development and technoeconomic, socioeconomic maximum of 17.2 ± 3.8 mLH2/gVS with a 331% increase in stable
studies for biohydrogen production for commercial viability. productivity of 1.51 ± 0.29 mLH2/gVS/h after the 8th recycling cycle
(Paillet et al., 2021).
2. Recent advances in biohydrogen production: Approaches and Renaudie et al. (2021) investigated dark fermentation activities and
challenges developed a hollow fiber continuous liquid/ gas (L/G) fermenting
membrane bioreactor for continuous long-term hydrogen production
2.1. Dark fermentative hydrogen production without seeding. They evaluated the membrane’s role in retaining
hydrogen-producing bacteria using waste industrial sludge, which
Hydrogen and gaseous fuels from renewable feedstocks have opened reduced in-between seeding. A steady-state reactor operating for 551
up future possibilities to substitute fossil energy resources to combat days without seeding produced 1.1 ± 0.2 mol H2/mol sugar (added
global warming and energy needs. Renewable biohydrogen from an initially), and maximum productivity of 135 ± 22 mL H2/L/h was
integrated biorefinery is critical for developing a low carbon fuel achieved using acetate and butyrate metabolites. They noted that an L/G
economy with biowaste remediation in an environmentally–friendly membrane served as an interface for in situ hydrogen extraction and
way. In this special issue, the authors review the potential challenges; preserved the Clostridium beijerinckii, Clostridium pasteurianum, and
environmental, economic, and social aspects that need to be tackled for Enterobacter sp. In another article in VSI ReBioH2-2020, Sarkar and his
commercial-scale production (Dahiya et al., 2021). colleague showed the optimized and scale-up activity in uncontrolled
Dark fermentative biohydrogen production involves the anaerobic pH conditions for H2 and volatile fatty acids (VFAs) production using
digestion of various renewable resources such as crop residues, agri­ brewery spent grains (BSG) (Sarkar et al., 2021). Additionally, they
cultural biomasses, organic waste, the organic fraction of municipal evaluated the impact of varying pH (4–10) on acidogenic fermentation
solid waste, and organic-rich wastewater into carbon dioxide-free of BSG at different scales (2, 5 and 10 L). The two-stage study showed
hydrogen. It is a highly efficient process with high hydrogen produc­ that the first stage stabilized the pH, whereas the second stage optimized
tivity and could develop long term energy projects using renewable hydrogen production. Moreover, the initial alkaline condition could
energy resources. Theoretically, 4 mol H2/mol hexose can be produced serve as a pretreatment agent to hydrolyze soluble carbohydrates, which
through the acetate (1), or butyrate (2) pathway. Comparatively, the could further increase the enzymatic yield and simultaneous bio­
butyrate pathway produced a low hydrogen yield (2 mol H2/mol hex­ hydrogen production by 15–90% with a maximum volume of 834 mL
ose). The investigation by Dauptain and co-workers revealed that and 10–50% higher volatile fatty acid (8936 mg/L). Extension of
hydrogen production could be significantly affected by inoculum, stor­ fermentation time could significantly favor short-chain fatty acids
age condition, and the microbial community. They showed that long- (SCFs) to medium-chain fatty acids (MCFs). This approach could be
term freeze-drying could improve hydrogen production in dark adopted and coupled to pretreatment with the simultaneous conversion
fermentation (Dauptain et al., 2021). of native biomass to biohydrogen and VFAs.
Rambau and co-workers highlighted the enrichment in biohydrogen
C6 H12 O6 + 2H2 → 2CH3 COOH + 2CO2 + 4H2 acetate pathway (1)
production using nano-metal oxides-based dark fermentation reactions
(Rambabu et al., 2021). They reported that the rice mill wastewater
C6 H12 O6 → 2CH3 CH2 CH2 COOH + 2CO2 + 2H2 butyrate pathway (2)
stream could be enriched in organics, which can be employed for
hydrogen production. Inclusion of NiO and CoO nanoparticles in the
2.1.1. State-of-art technologies for continuous hydrogen production
fermentation broth of wastewater received from Rice mill industries
aIn the past, several reports have been presented to the scientific
using Clostridium beijerinckii DSM 791 could further improved bio­
domain for dark fermentative hydrogen production focusing on carbon
hydrogen production by 2.09- and 1.9-fold using 1.5 mg/L of NiO (~26
feedstock, reactor design, operational condition, and the nature of the
nm) and CoO (~50 nm) nanoparticles through acetate and butyrate
inoculum at a laboratory scale. However, further assessment of various
pathways. The results showed that fermentation could effectively reduce
controls for high production rate is needed to commercialize dark
77.6 and 69.5% of chemical oxygen demand (COD) using NiO and CoO
fermentation technology. Therefore, Park et al. (2021) reviewed the
metal oxides as quantified by the Gompertz kinetic model. François et al.
various operational methods, reactor configurations, and microbial
(2021) showed that endogenous dark fermentation of wine byproducts
communities for high rate hydrogen production. They concluded that
(grape must residues), could produce 35 L H2/L biomass and yield of 1.6
assembly improvement, bioreactor regulations, operational strategies,
mol/mol hexose respectively. They showed that endogenous microflora
and reactor configurations could impact the hydrogen fermentation
enriched in Clostridium spp. (butyricum, beijerinckii, diolis, and roseum)
technologies. They reported that a continuous high hydrogen produc­
phylotypes could efficiently degrade sugars to hydrogen molecules
tion rate could be achieved by maintaining symbiosis between
without any addition of nutrient medium or heat treatment.
hydrogen-producing bacteria and biofilm-producing bacteria to avoid
washout. Use of mixed culture, maintaining production parameters such
2.2. Microbial electrolysis cell (Bioelectrical systems)
as hydraulic retention time (HRT), organic loading rate (OLR), pH,
substrate concentration, operating temperature, and microbial com­
Bioelectrical systems (BES) are novel, highly promising bio­
munity coupled to statistical analysis could lead to higher productivity.
electrochemical approaches nowadays for transforming organic mate­
Disposal of the organic municipal solid waste fraction is a major
rials into valuable chemicals, fuels, electricity, or biohydrogen for

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Preface Bioresource Technology 331 (2021) 125024

circular economy and clean energy production. Typically, microbial for development of sustainable technology that employs co-digestion of
electrolysis cells (MEC) are considered a promising BES system for animal waste and lignocellulosic biomass for biohydrogen production in
renewable biohydrogen production from organic resources that utilize a cost-effective way with higher efficacy compared to the mono diges­
anodic bio-catalytic oxidation and cathodic reduction processes (Yang tion process.
et al., 2021). Self-sustainable MEC bioelectrochemical tools can trans­
form organic carbon and waste organic water into hydrogen with low 2.4. Microalgal biomass for biohydrogen generation
energy requirements, i.e., >0.14 V compared to water electrolysis, i.e.,
>1.2 V. They showed that using a high catalytic, cost-effective cathode The photosynthetic microorganisms, cyanobacteria microalgae can
catalyst may promote commercial applicability of MEC process toward produce biological renewable hydrogen through microbial photolysis
self-sustainable high yield hydrogen production. Industrial wastewater and fermentation. In the photosynthetic process, microorganisms utilize
treatment strategies, energy recovery from waste and value-added sunlight to split H2O to produce in-situ hydrogen in the surrounding
products can be coupled by metabolic diversity. They showed that atmosphere. Microalgae are considered third-generation biomass, which
coupling of microbial electrolysis cell systems with other carbon-free have immense potential for biohydrogen and value-added chemical
biotechnologies such as pretreatment, pyrolysis, and fermentation production. Microalgal biohydrogen has gained global interest owing to
could collectively improve the enhanced rate of biohydrogen to 4.3 L its carbon–neutral source for sustainable energy. Salakkam et al. (2021)
H2/L-day and 50.4% yield. Moreover, chemical pretreatment of organic provided a detailed review focused on valorization of microalgal
wastewater stream can significantly convert organic wastes into simpler biomass for biohydrogen production and elaborated the various aspects
molecules that can be digested by exoelectrogens in MECs systems. The such as algal strains, cultivational practices, and harvesting. They have
study revealed that an enhanced rate of biohydrogen (0.59 m3 H2/m3/d) also provided the factors and characteristics that affect the overall
was reached using lignocellulosic biomass employing direct fermenta­ fermentation performance such as biomass pretreatment methods, dark
tion before MEC, wherein VFA produced in fermentation served as fermentation, photo fermentation efficacy, co-digestion with organic
feedstock to subsequent MEC utilization. To achieve high hydrogen materials, technoeconomic study, and application of advanced molec­
yield, two-chamber microbial electrolysis cells separated with a biode­ ular biology for enhanced biohydrogen production.
gradable membrane showed significant improvement in hydrogen pro­ In this special issue, El-Dalatony et al. (2020) review the different
duction. Nafion (DuPont) has a widearray of membranes for hydrogen- metabolic pathways for microalgal biohydrogen production from the
producing microbial fuel cells, however, the high cost of membranes last five years while focusing on operational cost and economic viability
limits commercial applicability. Therefore, González and co-workers of microalgal hydrogen. In this in-depth review, they highlighted the
demonstrated a new cost-effective, eco-friendly membrane comprised major factors such as light, cell density, nutrition composition, and
of polyvinyl alcohol/ chitosan (PVA/ CS) for hydrogen production. A microalgae availability. Moreover, they summarized the different pre­
long term operational study revealed that their PVA/CS membrane treatment approaches for high conversion efficiency. With that, they
could retain its stability for a month, yielding 974 ± 116 mL H2/g ac­ emphasize a new approach, i.e., microbial electrolysis cells for micro­
etate at a production rate of 1277 ± 46 mL H2/Lcathode/d (González- algae biohydrogen production. In this review, they summarized various
Pabón et al., 2021). Biocompatible PVA/CS showed great potential for tools such as genetic, metabolic engineering and synthetic biology for
future hydrogen production with social, environmental and economic further improvement in microbial biohydrogen production via inhibi­
importance. tion of competing pathways and oxygen tolerant hydrogenase.
In another study published in VSI, Li et al. (2021) demonstrated a Goswami and co-workers critically reviewed the different pathways
novel approach for biohydrogen production using Rhodobacter sphaer­ and enzyme involvement for economical production of hydrogen in
oides using a microbial electrosynthesis cell. When they used CO2 as a microalgae and discussed integrated bioprocess engineering strategies
carbon source and applied − 0.9 V vs. Ag/AgCl potential to the cathode, for improved hydrogen production. In their published article in this VSI,
they found R. sphaeroides produced 328 mL H2/L/day on a carbon Goswami et al. (2021) showed that the hydrogen production tendency of
electrode in an MES cell under optimized condition (Li et al., 2021). In microalgae is highly dependent upon strain selection, environmental
another report published in VSI ReBioH2-2020, the PROMETHEE II parameters, enzymes types, metabolic pathways, etc. Microalgae are
method has been displaced with two cation exchange membranes single-cell, photosynthetic aquatic microorganisms that mainly consist
(PSEBS SU22 and CF22 R14) and one bipolar membrane for high of carbohydrates, lipids, and protein. They can produce hydrogen via
hydrogen performance in MEC cells (Cardeña et al., 2021). They docu­ oxygenic pathways following direct photolysis and/ or indirect photol­
mented membrane materials for this technology and filed a patent, ysis mechanistic pathways. They concluded that microalgae can be
where they developed a novel PSEBS SU22 for superior hydrogen efficient in wastewater treatment with cost-effective hydrogen produc­
production. tion. Implementation of advancement strategies such as bioprocess en­
gineering, selection of suitable pretreatment methods, use of
2.3. Biohythane production photosystem inhibitors, O2, scavengers, supplementations, co-culturing,
and genetic modification of strains could improve the direct production
Biohythane is notable and promising gaseous fuel consisting of bio­ of hydrogen (~56%) with reduction of overall production cost.
hydrogen (10%) and biomethane (30%) produced via two-stage anaer­
obic fermentation of organic materials such as agricultural residues and 2.5. Bioconversion of agro-industrial residues to hydrogen
animal wastes through co-digestion with reduced nutrient demand.
Animal waste such as pig manure is categorized by the presence of high Lignocellulosic biomass is the most abundant, available and cheap
moisture with a significantly low carbon-to- nitrogen (C/N) ratio bioresource on Earth. For the most part, lignocellulosic biomass is
compared to lignocellulosic biomass such as rice straw. Thus, a study available in the form of agricultural and forest residues, aquatic plants,
published by Chen et al. (2021) showed the co-digestion of lignocellu­ and crops wastes, which have huge potential for commodity chemicals
losic biomass (e.g., rice straw) and animal waste (e.g., pig manure) to and fuels generation through thermochemical or biotechnological ap­
attain nutrient balance using mesophilic-thermophilic (M1-T1) AcD and proaches. Agricultural residues such as rice straw, bagasse, wheat straw,
thermophilic-mesophilic (T2-M2) AcD system for biohythane produc­ cotton stalk, and rice husk could be used for energy conversion pro­
tion. They found that a maximum ratio of 8.44% v/v (hydrogen: cesses. For example, Sivaramakrishnan et al. (2021) used biologically-
methane) was obtained from rice straw and pig manure. Additionally, pretreated rice bran for anaerobic hydrogen production using Rhizopus
T2–M2 produced pronounced hydrogen (16.68 ± 1.88 mL/gVS) and oligosporus MTCC 556 strain. They documented that biological pre­
methane (197.73 ± 11.77 mL/gVS). This approach could be beneficial treatment using Rhizopus could effectively reduce the 38% lignin

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Preface Bioresource Technology 331 (2021) 125024

content of rice bran in five days. Furthermore, fermentation of nutrient- Table 1


free pretreated rice bran in the presence of yeast and vitamins effectively Hydrogen production cost from different strategies.
enhanced the hydrogen yield by 1.7-fold to 5.4 mmol H2/g. Hydrogen production platforms Production cost

Photobiolysis 1.84–2.27 USD/kg H2


2.6. Thermochemical conversion of biomass Dark fermentation 1.02–2.70 USD/kg H2
Gasification 0.93–2.83 USD/kg H2
Gasification is another most promising technology for converting the Pyrolysis 1.47–2.57 USD/kg H2
organic waste stream into valuable chemicals and gaseous products at Steam reforming 1.25–3.50 USD/kg H2
Waster electrolysis 3.01–4.51 USD/kg H2
high temperature (700–900 ◦ C). For example, syngas can be easily
produced during pyrolysis and gasification mainly consisting of varying
concentration of hydrogen, methane, carbon dioxide, and carbon mon­ costs of different hydrogen production strategies. They showed that
oxide depending upon the feedstock used, reaction temperature, time, natural gas steam reforming is highly favored due to high hydrogen
catalyst concentration, atmosphere, etc. Food waste is in rich in the efficiency (70–85%) with reduced operational cost, feedstock (0.3 USD/
organic fraction and could serve for biohydrogen production following kg H2), and production cost (1.25–3.50 USD/kg H2) as summarized in
either biotechnological or catalytic approaches. Valizadeh et al. (2021) Table 1.
firstly studied the catalytic route of biohydrogen production from waste
food via steam and air gasification. Although various transition metals 3. Conclusions
such as Pt, Ru, Rh have been demonstrated for catalytic transformation,
they prepared less expensive Nickel–alumina-based catalyst (5% Ni/ Renewable biohydrogen is a carbon-free energy carrier that can
Al2O3) over cheap eggshell and Ni/Homo Alumina and performed steam facilitate decarbonization of certain carbon-emitting activities as an
and air-assisted gasification of food waste for biohydrogen production. alternative to fossils fuels. There has been highly interesting de­
Nickel–alumina-based catalyst retains its mechanical and thermal sta­ velopments in various domains of R&D, leading to technological
bility and possess a high active surface area for reaction. Interestingly, advancement on biohydrogen production, which have been nicely
steam gasification produced higher hydrogen (59.48 vol% H2) covered in this special issue. The insights of these articles will illuminate
compared to air gasification. They found that the nickel eggshell catalyst the various approaches considered for economic and sustainable bio­
showed high selectivity and stability during high hydrogen production hydrogen production from readily available cheap bioresources such as
with reduced C2-C4 products compared to non-catalyzed steam lignocellulosic biomass, microalgae, industrial effluents, wastewater,
gasification. food wastes, and the organic fraction of municipal solid waste, which is
Foong et al. (2021) reviewed different thermal conversion pathways expected to make a massive impact in the field.
such as pyrolysis, gasification, and reforming for hydrogen and gaseous
fuel production. The authors have provided an overview of recent
advancement in pyrolysis technology, CO2 pyrolysis, steam reforming, Acknowledgements
and process parameters, emphasizing reaction kinetics for further
improvement in the commercial production of waste-based hydrogen We warmly thank all the authors and co-authors who submitted their
and gaseous fuels. CO2 pyrolysis is a new concept to unlock new op­ manuscripts to this special issue (SI) of Bioresource Technology (BITE).
portunities for young researchers to further enhance pyrolysis perfor­ The accepted manuscripts describe many interesting signs of progress in
mance and efficiency for CO2 to fuel establishment. the production of renewable biohydrogen from organic-rich waste ma­
terials. We are very grateful to all distinguished scientists/reviewers for
their valuable contribution in reviewing the manuscripts in this special
2.7. Integrated biorefinery concept
issue, which assured the high technical quality of the manuscripts.
Finally, we sincerely acknowledge the full support of Prof. Ashok Pan­
Acidogenic fermentation of effluents is highly promising for bio­
dey, Editor-in-Chief, Bioresource Technology for his valuable guidance,
hydrogen, and short-chain fatty acid productions under two stages such
encouragement, and assistance to the guest editors in review process and
as bioelectrochemical system or via photofermentative process. Rajesh
in assembling this Special Issue. Furthermore, we greatly acknowledge
Banu et al. (2021) showed that nearly 60% of fermentative effluents
the full support of the Publishing Editor, Dr. Adam Fraser, Journal
might be utilized directly or indirectly to generate 1,3–propanediol and
Manager, Leonard Daniel, SI Content Developer, Ms Hannah Zhnag and
organic acids. They reviewed and showed that an integrated biorefinery
the production team of Elsevier to publish this special issue.
approach could significantly address the emergence of integrated dark
fermentation, microbial fuels cells and anaerobic digestion process for
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oxides assisted dark fermentation. Bioresour. Technol. 319, 124243 https://doi.org/ Department of Aeronautics and Astronautics, National Cheng Kung
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Technol. 322, 124533 https://doi.org/10.1016/j.biortech.2020.124533. Engineering, College of Engineering, 50 Yonsei Ro, Seodaemun Gu,
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controlled pH on acidogenic fermentation of brewery spent grains to biohydrogen
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E-mail address: sanghkim@yonsei.ac.kr (S.-H. Kim).
319, 124233. https://doi.org/10.1016/j.biortech.2020.124233.

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