Bioresource Technology 215 (2016) 304–313

Contents lists available at ScienceDirect

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

Review

Anaerobic biorefinery: Current status, challenges, and opportunities

Chayanon Sawatdeenarunat a, Duc Nguyen a, K.C. Surendra a, Shilva Shrestha a,b, Karthik Rajendran a,
Hans Oechsner c, Li Xie d, Samir Kumar Khanal a,⇑
a
Department of Molecular Biosciences and Bioengineering (MBBE), University of Hawai’i at Mānoa, 1955 East-West Road, Agricultural Science Building 218, Honolulu, HI 96822, USA
b
Department of Civil and Environmental Engineering (CEE), University of Michigan Ann Arbor, 1351 Beal Ave., 107 EWRE Bldg, Ann Arbor, MI 48109-2125, USA
c
State Institute of Agricultural Engineering and Bioenergy, University of Hohenheim, Garbenstrasse 9, Stuttgart 70599, Germany
d
Department of Environmental Engineering, Tongji University, Shanghai 200092, PR China

h i g h l i g h t s

 Anaerobic biorefineries are a new approach for producing biobased products.

 Most organic substrates can be used as feedstocks for anaerobic biorefineries.
 Large-scale biorefineries have the potential to maximize economic benefit.
 Small-scale anaerobic biorefineries improves living quality in developing countries.

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

Article history: Anaerobic digestion (AD) has been in use for many decades. To date, it has been primarily aimed at treat-
Received 3 February 2016 ing organic wastes, mainly manures and wastewater sludge, and industrial wastewaters. However, with
Received in revised form 11 March 2016 the current advancements, a more open mind is required to look beyond these somewhat restricted orig-
Accepted 12 March 2016
inal applications of AD. Biorefineries are such concepts, where multiple products including chemicals,
Available online 15 March 2016
fuels, polymers etc. are produced from organic feedstocks. The anaerobic biorefinery concept is now gain-
ing increased attention, utilizing AD as the final disposal step. This review aims at evaluating the poten-
Keywords:
tial significance of anaerobic biorefineries, including types of feedstocks, uses for the produced energy, as
Anaerobic digestion
Biorefinery
well as sustainable applications of the generated residual digestate. A comprehensive analysis of various
Bioenergy types of anaerobic biorefineries has been developed, including both large-scale and household level
Value-added products applications. Finally, future directives are highlighted showing how anaerobic biorefinery concept could
Organic feedstocks impact the bioeconomy in the near future.
Ó 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
2. Potential feedstocks for an anaerobic biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
2.1. Lignocellulosic biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
2.2. Municipal solid waste (MSW). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
2.3. Animal manure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
2.4. Food wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
3. Large-scale anaerobic biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
3.1. Biogas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.2. Digestate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.2.1. Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
3.2.2. Lignin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3.2.3. Solid residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310
3.3. Liquid effluent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310

⇑ Corresponding author.
E-mail address: khanal@hawaii.edu (S.K. Khanal).

http://dx.doi.org/10.1016/j.biortech.2016.03.074
0960-8524/Ó 2016 Elsevier Ltd. All rights reserved.
 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313 305

4. Small-scale anaerobic biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311

5. Challenges and prospectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312

1. Introduction an organic fertilizer for crop production and as a fish feed for aqua-
culture application (Surendra et al., 2014). There have been several
The global total primary energy consumption was reported successful examples of implementation of biodigester technologies
around 524 Quadrillion Btu (QBtu) in 2010 (Energy Information in developing countries in Asia including Nepal, Vietnam, Bangla-
Administration (EIA), 2013). The energy consumption is expected desh, Cambodia, and Laos among others. Using biogas for CHP gen-
to increase by nearly 50% by 2050 due to growing demand from eration or transportation fuels is a well-established process in
emerging nations such as India, China, and Brazil among others. developed countries. However, producing biogas alone might not
Currently, fossil-based fuels supply over 85% of world energy be economically competitive, especially due to the volatility of
demands. The excessive use of fossil fuels has also been linked to market and price indexes of fossil fuels (Surendra et al., 2015).
several environmental issues, especially greenhouse gas (GHG) One approach to circumvent this problem is to identify and explore
emissions and local and regional air quality degradation. The CO2 alternative products/chemicals apart from bioenergy production
emissions from the combustion of fossil fuels alone contributes by adopting the biorefinery approach. The biorefinery concept is
to more than 90% of energy-related GHG emissions (International analogous to a traditional petrochemical refinery in which multiple
Energy Agency (IEA), 2015). Moreover, energy security is also a products are produced from crude petroleum. According to the
major concern for countries that rely on imports of fossil energy National Renewable Energy Laboratory (NREL), a biorefinery is a
resources. In the recent years, renewable energy technologies facility that integrates biomass conversion processes and equip-
(e.g., wind, solar, hydro, and biomass) have been promoted to ment to produce fuels, power, and chemicals from biomass. Thus,
address environmental issues such as climate change and local such approach aims at maximizing the profit by producing low vol-
air quality degradation, as well as energy insecurity. The ume high-value products while meeting the energy needs by pro-
renewable-based power generation in 2014 increased to 128 GW ducing low-value high volume fuels. The anaerobic biorefinery is
which is over 40% higher than renewable power generation in one of the biorefinery concepts, in which AD serves as a center-
2010 (IEA, 2015). Among the various renewable energy sources, piece to produce high-value, but low volume products (i.e., chem-
biomass has so far been the largest single source currently being icals and drop-in biofuels to enhance economic viability of the
used, especially in developing countries where biomass (e.g., fire- system) and high-volume but low value products (i.e., heat, elec-
wood, crop residues, and cattle dung) is used as a primary energy tricity, and conventional transportation biofuels) to achieve energy
source for heating and cooking. security. Recently many studies have discussed the biorefinery
Anaerobic digestion (AD) is one of the most promising biotech- concept in general, but there exists only limited studies primarily
nologies for converting diverse organic substrates, ranging from focusing on the anaerobic biorefinery (Maclellan et al., 2013;
high solid feedstocks (i.e., animal manure, food wastes, municipal Surendra et al., 2015). This review provides an overview of the
solid waste, and lignocellulosic biomass), as well as municipal anaerobic biorefinery concept and critically examines the recent
and industrial wastewaters, to energy-rich biogas (Khanal, 2008). advancements in anaerobic biorefineries. Moreover, this review
Although AD technology had primarily been developed and also highlights the challenges and opportunities associated with
adopted for waste stabilization, in recent years, AD process has both commercial and small-scale anaerobic biorefineries, and out-
been widely adopted for bioenergy production. Over 14,000 com- lines directions for future research and development.
mercial AD plants are already in operation in Europe, while Ger-
many alone has more than 8000 plants (EBA, 2014). The
produced biogas is used for combined heat and power (CHP) gen- 2. Potential feedstocks for an anaerobic biorefinery
eration, and/or upgraded to biomethane to be used as transporta-
tion fuels, or injected into natural gas grid. 2.1. Lignocellulosic biomass
In developing nations, AD processes are becoming immensely
popular for conversion of organic wastes (e.g., animal manures, Lignocellulosic biomass (e.g., agricultural and forest residues,
food wastes, agri-residues, etc.) into biogas. The biogas serves as energy crops, and paper wastes among others) is one of the most
a clean energy for cooking and lighting in rural households. The promising feedstocks for producing bioenergy (e.g., biomethane,
residuals after digestion, commonly known as bioslurry, serve as biohydrogen, bioethanol, and biobutanol) and a plethora of

Table 1
The composition of selected lignocellulosic biomass.

Biomass Cellulose (%) Hemicellulose (%) Lignin (%) References

Corn stover 39.7 29.9 8.9 Teater et al. (2011)
Wheat straw 37.9 21.8 22.1 Cui et al. (2011)
Switch grass 37.1 29.9 17.6 Teater et al. (2011)
Rice straw 35.0 26.7 13.3 Ye et al. (2013)
Napier grass 45.7 33.7 20.6 Reddy et al. (2012)
Barley straw 37.5 25.3 26.1 Monlau et al. (2012)
Miscanthus 38.0 18.5 20.9 Vasco-Correa et al. (2016)
Coffee pulp 35.0 46.3 18.8 Karthikeyan and Visvanathan (2012)
Paper waste 11.9 1.0 33.0 Elliston et al. (2013)
306 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313

Table 2
The quantity and composition of municipal solid waste (MSW) in selected countries.

Location Waste generation rate Composition of MSW (%) References

(kg/capita/day) Organic waste Paper Plastic Glass Metal Textile fiber Wood
Malaysia
Kuala Lumpur 1.2 74 1 21 NA NA NA 1 Budhiarta et al. (2012)
China
Beijing 0.98 63.4 11.1 12.7 1.8 0.3 2.5 1.8 Zhang et al. (2010)
Shanghai 66.7 4.5 20 2.7 0.3 1.8 1.2
Shenzhen 40 17 13 5 3 5 NA
United States 2 14.5 27.4 12.7 4.6 8.9 8.7 6.3 EPA (2013)
Palestine
Nablus district 0.82 65.1 9.1 7.6 2.9 2.8 3.1 NA Al-Khatib et al. (2010)
Thailand 1.15a 35.9 20.7 15.9 9.9 3.8 2.5 NA Challcharoenwattana and Pharino (2016),
Chaya and Gheewala (2007)
a
Based on the municipality that has the population between 10,000 and 50,000 people.

bio-based products/chemicals (e.g., organic acids, bioplastic, suc-
cinic acid, citric acid, lactic acid etc.). The lignocellulosic biomass
has a potential to significantly contribute to global demand of
renewable energy and biobased products (Kumar et al., 2008). It
has been reported that globally more than 200 billion dry metric
ton of biomass can be produced per year while 1.4 billion dry tons
of such biomass can be produced in the U.S. alone (Khanal, 2008).
Lignocellulosic biomass is primarily composed of polymers in plant
cell walls including cellulose, hemicellulose, pectin, and lignin
along with small amounts of other organic compounds such as pro-
teins and lipids, and minerals (Frigon and Guiot, 2010). Cellulose is
a long linear chain of homopolysaccharides of b-D-glucopyranose,
which link to each other by b-(1-4)-glycosidic bonds (Kumar
et al., 2008). Cellulose has two different structural forms, the crys-
talline and amorphous. The crystalline structure has a high packing
density resulting from hydrogen bonding. The complexity of this
form creates a resistance to biological degradation and signifi-
cantly reduce its accessibility to cellulose degrading enzymes
(Brown, 2003). Hemicellulose is another form of heteropolysaccha-
rides present in plant cell walls. The monomers of this compound
include hexose, pentose, deoxyhexose, and some acidic sugars. A
lower degree of polymerization and amorphous structure makes
hemicellulose more vulnerable to chemical, thermal, and biological
degradation than cellulose (Cherubini, 2010). Lignin is a non-
polysaccharide component in a lignocellulose structure, which fills
up the space between cellulose and hemicellulose, and acts as a
binder. The monomer of lignin is a phenylpropane-based com-
pounds consisting of aromatic alcohols namely; coniferyl, sinapyl,
and coumaryl alcohol. Typically, lignin provides rigidity to plant
cell wall and is more resistant to biological degradation than to cel-
lulose and hemicellulose. In AD of lignocellulosic feedstocks, lignin
usually remains undigested. Lignin can be used to produce energy
(i.e., heat and electricity) via thermochemical processes and vari-
ous bio-based products (i.e., biopolymer and vanillin among
others) via chemical processes (Surendra et al., 2015). The compo-
sition of a selected lignocellulosic biomass is presented in the
Table 1.
2.2. Municipal solid waste (MSW)
MSW is the refuse generated during daily activities from resi-
dential and business areas. The characteristics of MSW depend
on many factors, including but not limited to, the source, location,
season, the economic and population growth status, urbanization,
and life style of people (Cheng and Hu, 2010). Karthikeyan and
Visvanathan (2012) estimated that the global MSW generation
could be as high as 9.2 million metric tons wet weight/day. The
quantity and composition of MSW generation in some selected
countries are shown in Table 2.
Landfilling, a simple and low-cost technology, has been the
most common practice in disposing the MSW. However, this con-
ventional waste disposal practice has been associated with several
environmental issues including surface and ground water contam-
ination (Cheng and Hu, 2010), GHGs (CH4, N2O and CO2) emissions,
and competition for valuable land around urban and suburban
areas. Additional technologies such as incineration, composting,
and AD have been adopted for the management of MSW and recov-
ery of resources.
Incineration is a combustion process for recovery of energy
from MSW while reducing the volume of the waste. Incineration
reduces approximately 90% and 70% of volume and mass of
MSW, respectively, (Zhang et al., 2010) thereby significantly reduc-
ing required landfill volumes and the associated logistic costs.
Additionally, the clean and stable solid residue following incinera-
tion can also be used as construction materials (Cheng and Hu,
2010; Zhang et al., 2010). The incineration of MSW for power gen-
eration, however, is only economically feasible for MSW with net
caloric value of over 6 MJ/kg (Zhang et al., 2010). Furthermore,
the high cost (i.e., capital, operational, and maintenance cost) and
need for trained professionals to operate incineration plants are
additional limitations on MSW incineration. Also, incineration
plants requires special off-gas treatment systems, which is often
very costly (Zhang et al., 2010).
Composting has been used primarily for waste stabilization
with a more limited reduction in the volume of MSW. During
composting, the organic fraction of MSW (OFMSW) is biologically
converted into a more stable products known as compost (Bernal
et al., 2009). However, the compost is a relatively low-value
product.
AD technology has been applied to stabilize OFMSW and to
recover energy-rich biogas. The AD of OFMSW can be classified into
two main groups, wet AD (W-AD) and dry AD (D-AD) with total
solids (TS) content of the initial substrates being less than 10%
for W-AD, and more than 20% for D-AD (Karthikeyan and
Visvanathan, 2012). The operating organic loading rate (OLR) of
W-AD and D-AD are 2–5 and 5–12 kg volatile solids (VS)/m3/d,
respectively. It is estimated that the AD of the OFMSW produced
globally could generate enough biogas to contribute around 2% of
the total global energy consumption (Rajendran et al., 2014).
Although, AD has a potential to recover energy resources from
MSW, especially the OFMSW, conventional AD only generates sin-
gle low-value product, biogas.
 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313 307

Table 3
The characteristics and energy potential of animal manure.

Animal Total Organic Total Ammonia Methane Energy References

solids (%) carbon (%) nitrogen (%) nitrogen (%) potential (mL/gVS) value (kJ/kgTS)
Cattle 14–30 6.5–12.6 0.4–0.8 0.0–0.2 139.8 NA Bernal et al. (2009), Ro et al. (2007), Qiao et al. (2011)
Dairy NA NA NA 242.7 15,863 Bernal et al. (2009), Ro et al. (2007), Labatut et al. (2011)
Swine 15–33 4.2–13.2 0.4–1.1 0.1–0.6 253.8 19,156 Bernal et al. (2009), Ro et al. (2007), Qiao et al. (2011)
Poultry 22–70 10.3–59.7 1.0–5.8 0.2–1.8 291.0 13,832 Bernal et al. (2009), Ro et al. (2007), Li et al. (2013)

Table 4
The amounts of animal manure annually generated in selected countries.

Location Year Annual amount Unit References

United States 2005 31.8 Million dry metric tons Perlack et al. (2005)
England and Wales 2000 112.0 Million wet metric tons Chambers et al. (2000)
China 2010 2816.0 Million wet metric tons Chadwick et al. (2015)
Japan 2011 84.0 Million wet metric tons Komiyama et al. (2014)
Thailand 1997 3.9a Million dry metric tons Sajjakulnukit et al. (2005)
a
From cattle, swine, and chicken, and assuming that manure is generated 365 days/year.

The anaerobic biorefinery concept aims at maximizing the
recovery of more diverse resources from MSW in addition to the
biogas, while simultaneously remediating the waste.
2.3. Animal manure
Animal manure normally consists of feces, urine, and sometime
animal beddings and is one of the important potential feedstocks
for anaerobic biorefineries. The characteristics of animal manure
strongly depend on animal species, growth stage, and the charac-
teristics of the feed. The characteristics and energy potential of
selected animal manures are presented in Table 3. Animal manure
is usually applied to agricultural land as a source of nutrients.
However, the excessive land application of animal manure can
result several environmental problems, including water pollution,
excessive GHG emissions, phytotoxicity, and presence of the hor-
mones and pharmaceutically active compounds used in treating
the animals (Ro et al., 2007). Composting and gasification (for
renewable fuel generation) are some of the alternative technolo-
gies for managing animal manure. During composting, animal
manure is aerobically treated to stabilize the organic matters and
destroy the pathogens. However, the need for the costly unit
upstream processes such as dewatering and a long retention time
(Ro et al., 2007) makes the economic viability of the animal man-
ure composting questionable. Gasification of animal manure has
merits, including compactness of the system, effective destruction
of pathogens, hormones and antibiotics, and reduced wastewater
generation. However, gasification is still a costly technology and
requires a highly efficient heat recovery system to maximize the
economic gain from animal manure gasification (Ro et al., 2007).
Due to its inherent properties such as relatively small size, high
organic content (i.e., VS), inherent presence of suitable microbes,
and good buffering capacity, animal manures have been widely
used in AD, both for producing bioenergy and for managing waste.
The amounts of animal manure annually collected in selected
countries are shown in Table 4. The effluent from an AD plant
treating animal manure is rich in nutrients such as nitrogen and
phosphorus and needs further treatment prior to disposal to envi-
ronment. This nutrient-rich effluent could be land applied
commonly known as ferti-irrigation. Alternatively, the effluent
could be used as nutrient source for algal cell production
(Sawatdeenarunat et al., 2015). Algae farming using this effluent
not only offers nutrient recovery but also provides an algal biomass
for further diverse end applications such as producing biofuel (e.g.,
biodiesel and biomethane), animal feed, and high-value phyto-
chemicals among others. Phosphorus in the form of struvite can
be recovered from anaerobically digested animal manure and has
potential to serve as marketable organic fertilizer (Le Corre et al.,
2009). Such practice of recycling nutrients not only improves nutri-
ent removal from wastewater but also benefits agricultural prac-
tices by reducing the requirements of costly chemical fertilizer.
Song et al. (2011) developed a struvite crystalization process which
eliminated the need for external chemical addition which could
significantly reduce the operating cost of the struvite production
system.
2.4. Food wastes
Food waste generation occurs throughout the supply chain from
initial agricultural production to final household consumption. In
2011, a study by the FAO estimated that approximately one-third
of all food produced for human consumption worldwide is dis-
carded as waste; representing about 1.3 billion metric tons waste
per year (Gustavsson et al., 2011). This is equivalent to direct eco-
nomic loss of nearly $750 billion annually. In Europe and North
America, an average of 95–115 kg of food waste is generated per
person per year. There are several reasons for such a large genera-
tion of food wastes. For example, at the production level, farmer–
buyer sales agreements result in farm crops being wasted due to
quality standards lacking perfect shape or appearance. At the con-
sumer level, insufficient purchase planning, residual, uneaten, food
components; and last but not least, the careless attitude of the con-
sumers. The general characteristics of the selected food wastes are
summarized in the Table 5. Currently employed methods for food
wastes management include animal feeding, direct disposal into
landfills, incineration, gasification, composting and AD.
Landfilling of food wastes poses several concerns such as high
land cost, GHGs emissions, and leachate generation among others.
Incineration has high capital and operation costs, and there is also
a serious concern of fugitive gas emissions (Arancon et al., 2013).
Gasification has the advantage of being able to handle a wide vari-
ety of feedstocks, but much drier feedstocks are required, and bio-
mass variability may yield inconsistent output with low
thermodynamic efficiency. Composting is a low-cost method of
converting food wastes into biofertilizer. However, compost is a
very low-value product with significant emissions of GHG espe-
cially N2O and CO2 released during the composting process.
The high organic content and moisture levels make food waste an
ideal substrate for AD. Except for the waste from meat processing
plants, food waste in general are low in nitrogen content and the
308 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313

Table 5
The general characteristics of the selected food wastes.

Source Country TS (%) VS (% TS) Soluble Total Total Total TKN References
CODa (g/L) carbohydrate (% TS) protein (% TS) fat (% TS) (gN/L)
Dining hall S. Korea 67.8 94.0 NA 37.6 NA NA NA Shin et al. (2004)
Biowaste digestion plant UK 24.8 92.9 98.2 NA NA NA 7.4 Tampio et al. (2014)
Fruit and vegetable markets, India 15.0 88.5 NA NA 6.87 8.5 1.1 Rao and Singh (2004)
household, and juices centers
University canteen China 19.7 17.0 NA NA 17.3 29.9 NA Qiao et al. (2011)
a
COD: chemical oxygen demand.

co-digestion of such food waste with nitrogen-rich substrates such
as sewage sludge and animal manure can significantly improve
the AD efficiency of food wastes (Zhou et al., 2013). Although AD is
currently the best available technology for food waste-to-
bioenergy production (Khanal, 2008), conventional AD generates a
single relatively low-value output (biogas). The anaerobic biorefin-
ery approach provides significant merits to generate more diverse
value-added products from food wastes in addition to biogas.
3. Large-scale anaerobic biorefinery
The anaerobic biorefinery is a promising concept, in which the
anaerobic reactor/digester acts as a centerpiece for bioconversion
of feedstocks (substrates) into diverse high-value products and
intermediates. AD technology has several inherent merits such as
remediation of highly putrescible organic wastes at a smaller envi-
ronmental footprint, capturing GHGs, and at the same time valoriz-
ing organic wastes into high-value products/chemicals and
intermediates. Diverse organic materials ranging from industrial
wastewaters to municipal and farm wastes could be used as feed-
stocks in an anaerobic biorefinery to produce biogas with concomi-
tant generation of digestate (i.e., solid residue and liquid effluent).
The digestate could be further processed to plethora of biobased
products and chemicals. The anaerobic biorefinery concept is illus-
trated in Fig. 1. Bozell and Petersen presented a revised list of top
ten building block chemicals which can be derived from lignocellu-
losic biomass, including ethanol, furans, glycerol and derivatives,
hydrocarbons, lactic acid, succinic acid, hydroxypropionic acid/
aldehyde, levulinic acid, sorbitol, and xylotol (Bozell and
Petersen, 2010). Details of derivatives from these platform chemi-
cals and their production pathways are found elsewhere (Choi
et al., 2015). Combinations of biochemical and thermochemical
technologies have been adopted for the conversion of biomass to
building block chemicals, biofuels, biomaterials, animal feed, and
fertilizer.
The potential resource recovery through AD from three output
sources (i.e., biogas, digestate, and liquid effluent) is discussed in
following section.

Fig. 1. Schematic of large-scale anaerobic biorefinery for producing biofuels and biobased products.
 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313
3.1. Biogas
Biogas is the prime product of AD. On one hand, AD helps
reduce the volume of organic wastes with a small environmental
footprint and energy consumption; and on the other hand, GHGs,
especially CH4 are effectively captured and utilized.
Individual or combinations of various types of organic wastes
could be used as a feedstock for AD. Besides energy crops, wastes
that need to be managed (e.g., waste activated sludge, MSW, food
waste, agricultural and food processing wastes/wastewater, animal
manure etc.), residues from biofuel processing industries also have
high potential as an AD feedstock. For instance, residues of
bioethanol distillation from sugarcane and corn, known as stillage
and vinasse, respectively, have high potential to be used as AD
feedstocks. However, stillage and vinasse are rich in carbon con-
tent, requiring the addition of nutrients to optimize the carbon to
nitrogen (C/N) ratio. In practice, co-digestion with nutrient-rich
feedstocks like cattle manure to adjust C/N ratio to 20–30:1 have
been widely applied (Khanal, 2008). Other operational parameters
such as pH, total volatiles fatty acids to total alkalinity (VFA/ALK)
ratio, ammonia, etc., should also be maintained within the recom-
mended range for efficient digestion. The potential methane yields
from various organic feedstocks can be found in Table 3 and
Sawatdeenarunat et al. (2015). Utilization of the produced biogas
has been commercialized in a wide range of applications. The most
common industrial-scaled application is heat and electricity gener-
ation using a combined heat and power (CHP) unit. Electrical and
thermal conversion efficiencies of CHP unit are around 40% and
50%, respectively (Pöschl et al., 2010). In case of anaerobic digester
fed with sulfur-rich substrate, the presence of hydrogen sulfide
(H2S) in the biogas at a concentration higher than 250 ppm could
be detrimental to the CHP unit. Thus, the H2S in biogas has to be
removed to a value below 250 ppm prior to feeding to the CHP
engine. Various methods for H2S removal, such as pressure swing
adsorption (PSA), water pressure absorption, ferric oxide adsorp-
tion, alkaline absorption, biological filtration, and micro-aeration
have been studied and commercialized. Besides H2S, biogas impu-
rities such as CO2, ammonia, moisture, and particulates can be
removed to obtain CH4 content greater than 95% in a process called
biogas cleaning and upgrading. PSA, absorption by scrubbing,
membranes, and cryogenic separation have been applied for biogas
upgrading process at commercial-scale plants. Upgraded bio-
methane could be used as transportation fuel in the form of com-
pressed natural gas (CNG) or liquid natural gas (LNG) or injected
into a natural gas grid. More details on biogas production and uti-
lization can be found in Budzianowski (2016).
Apart from using biogas as a renewable energy resource for heat
and electricity generation as discussed above, biogas could be con-
verted to methanol, which is a building block of many high-value
industrial chemicals including anhydride, ethylene, polyols and
other aromatic compounds (Räuchle et al., 2016). This concept of
‘‘low-volume, high-value” conversion pathway for biogas or syngas
(H2 + CO) to liquid fuels and chemicals through chemical and bio-
logical conversions has gained significant interest in recent years
(Munasinghe and Khanal, 2011). Overall, biogas production from
organic wastes is an intrinsic merit of AD technology. However,
adapting biorefinery concepts into the utilization of biogas could
open up ideas for research and development in conversion path-
ways for a variety of higher-value biogas derivatives.
3.2. Digestate
The effluent (digestate) from an anaerobic digester can be sep-
arated into liquid and solid streams. The solid stream primarily
consists of suspended solids and undigested residues. Depending
on substrate type and operating condition of the digester, the com-
309
position of solid residue varies. This solid residue could serve as a
substrate for producing a wide variety of high-value biobased
products via biorefinery concept. In the following sections,
resource recovery from different components of AD residue (e.g.,
carbohydrates, lignin, fat, and protein) is discussed.
3.2.1. Carbohydrates
Feedstock rich in carbohydrates include lignocellulosic biomass
such as energy crops, maize and grass sillages and agri-residues.
Depending on sources, lignocellulosic biomass consists of 30–56%
cellulose and 10–27% hemicellulose (collectively known as holo-
cellulose), and 3–30% lignin (dry wt. basis); the biomass also con-
tains small amount of extractives, and ash (Cheng et al., 2011). AD
can effectively breakdown hemicellulose due to its amorphous
structure. The removal of hemicellulose during AD opens-up ligno-
cellulosic matrix structure that enhances the further breakdown of
the cellulose component of biomass (Mathews et al., 2015). Such
findings have stimulated the idea of using AD as a biological pre-
treatment of lignocellulosic biomass, allowing more efficient
downstream enzymatic saccharification of carbohydrates into sug-
ars. Sugars released from enzyme hydrolysis in the form of glucose,
mannose, galactose, xylose, and arabinose are ideal substrates for
producing different alcohols, organic acids, and a wide range of
biochemicals and biobased products (Surendra et al., 2015).
Bioethanol fermentation by yeast or Zymomonas and biobutanol
production by Clostridium spp. has been extensively studied. Yeast,
Saccharomyces cerevisiae has been widely employed for bioethanol
production with the ethanol yield of 0.4 g/g glucose and 0.3 g/g lig-
nocellulosic biomass (Nanda et al., 2014). Recently, research efforts
have been shifted towards optimization of butanol production due
to its higher value as a fuel and chemical. Clostridium species have
been reported to produce 0.23 g butanol/g glucose and 0.25 g buta-
nol/g xylose (Bramono et al., 2011). Other genetically engineered
microorganisms, such as Escherichia coli have also been reported
to effectively produce a variety of alcohols. Recently, diol (i.e., a
chemical with two AOH functional groups) production from ligno-
cellulosic biomass has gained great interest compared to conven-
tional alcohol due to their higher market value. Propanediols and
butanediols are platform chemicals for producing many industrial
products including solvents, adhesives, resins, and detergents
(Zeng and Sabra, 2011). Sugars could also be converted to short-
chain volatile fatty acids (i.e., acetic, propionic, butyric, and valeric
acids) through the carboxylic acid pathway by using fermentative
microorganisms. These carboxylic acids are precursors for various
valuable derivative chemicals such as diols, esters, and anhydrides.
The microbial fermentation of diacids (i.e., succinic, fumaric, and
malic acids), which are listed among the top ten platform chemi-
cals by U.S. DOE, has been studied extensively (Bozell and
Petersen, 2010). The co-production of bioethanol and succinic acid
from hemp (Cannabis sativa L.), a second-generation energy crop,
has been reported to yield 149 kg and 115 kg per dry metric ton
of biomass, respectively (Kuglarz et al., 2016). Succinic acid, with
a global market demand of up to 50,000 metric ton/year, could be
used as platform chemical to produce high-value products such
as 1,4-butanediol, tetrahydrofuran, and biopolymers (Jansen and
van Gulik, 2014). In addition, lactic acid is also considered a build-
ing block chemical for poly-lactic acid, acrylic acids, and propane-
diol through polymerization, dehydration, and hydrogenation,
respectively (Bozell and Petersen, 2010). Details of biomass-
derived selected platform chemicals with their derivatives and
applications are summarized in Table 6.
Besides alcohol or acid fermentation pathways, dehydration of
sugars to produce furans has been studied as an alternative conver-
sion route. Dehydration of C5 and C6 sugars has been applied to
produce biomass-derived furfural and hydroxymethylfurfural
(HMF), respectively. Furans are platform chemicals to produce a
310 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313

Table 6
Bio-based platform chemicals and derivatives (adopted from Choi et al. (2015)).

Platform bio-based chemical Market demand Conversion pathway Derivatives Applications

(million metric tons/year)
Ethanol 86.0 – – Fuels
Polymerization Polyethylene (PE) Plastic industries
Polypropylene (PP)
Polyethylene terephthalate (PET)
Oxidation Ethylene glycol Plastic industries
Textile fibers
Antifreezes, coolant, solvents
Furans (furfural, 0.3 Polymerization Biopolymers Plastic industries
hydroxymethylfurfural (HMF)) Oxidation Fumaric acid Chemical industries
Furoic acid
Furandicarboxylic acid
Hydrogenation Furfuryl alcohol Chemical industries
Glycerol 2.0 Hydrogenolysis Diols (ethylene/propylene glycols) Chemical industries
Oxidative dehydration Acrylic acid Plastic industries
Coating
Biohydrocarbon NA – – Fuels (jet fuel, diesel, gasoline)
Lactic acid 0.4 Polymerization Polylactic acid Plastic industries
Succinic acid 0.05 Dehydration Acrylic acid Plastic industries
Coating
Hydrogenation Diol (propanediol, butanediol) Chemical and plastic industries
Butylolactone
Hydroxypropionic acid NA Oxidation Maleic acid Chemical industries
Fumaric acid
Polymerization Polyester polyols Adhesives
Coating
Dehydration Acrylic acid Plastic industries
Coating
Levunic acid NA Hydrogenation y-Valerolactone Fuel additives
Sorbitol 1.7 Oxidation Succinic acid Chemical industries
Acetyl acrylic acid
Hydrogenolysis Diols (ethylene/propylene glycols) Chemical industries
Xylitol 0.1 Hydrogenolysis Diols (ethylene/propylene glycols) Chemical industries

wide-range of chemicals, such as levulinic acids, furfural alcohol,
and biopolymers (Bozell and Petersen, 2010).
Instead of going through enzymatic saccharification, an alterna-
tive pathway for utilizing the cellulose present in digestate fiber is
to purify the cellulose by a delignification process. There is a wide
range of derivatives from cellulose, such as polypropylene–micro
crystalline cellulose composite, cellulose esters, and cellulose
ethers, which have many industrial applications. For example, cel-
lulose esters like cellulose acetate and cellulose nitrate have been
widely commercialized in producing membrane filters for water
treatment, food production, and medical supplies (Klemm et al.,
2005).
3.2.2. Lignin
The lignin content of lignocellulosic biomass varies from 10–
35% of dry weight, depending on the plant species (Mathews
et al., 2015). Lignin, a major component of digested fiber following
AD and saccharification processes, has a high potential for biorefin-
ery applications. However, technological challenges have hindered
lignin biorefinery applications due to the intrinsic recalcitrant
structure of this phenolic macromolecule. Lignin has potential
applications in producing heat and electricity, syngas, fuels (e.g.,
methanol, dimethyl ether, and Fischer–Tropsch fuels), vanillin,
and dimethyl sulfoxide. Thermochemical processes such as com-
bustion, gasification, and pyrolysis are commonly used for lignin
conversion (Bozell et al., 2007). Besides the thermochemical path-
way, a potential future technology for utilizing waste lignin uses an
opposite approach, which aims to keep the polymerized structure
of lignin intact instead of breaking it down to its monomers. Tech-
nological advancements to purify lignin for carbon fibers and
biopolymers (e.g., bioplastic, resins and adhesives) pose a poten-
tially very interesting opportunity for a lignin biorefinery.
Bozell et al. (2007) reported a technology for lignin utilization
which produces aromatic compounds, including phenols,
benzene–toluene–xylene (BTX) and lignin monomers through
catalysis and selective oxidation processes. Although the demands
for such products are high, lack of technical experience and high
energy costs have hindered the commercialization of lignin-
based high-value chemicals production.
3.2.3. Solid residues
Besides the lignin utilization via thermo-chemical processes,
the whole solid fibers after the solid–liquid separation of the diges-
tate could be used for the production of bio-oil and biochar via
pyrolysis. Bio-oil can also be produced by hydrous pyrolysis in
which thermal decomposition takes place in the presence of water
known as hydrothermal treatment. Biochar is mainly used as a soil
conditioner, which has been found to be effective in carbon seques-
tration thereby reducing net carbon dioxide emissions. There is an
economic tradeoff between bio-oil and biochar production which
depends on the market price for the product and the type of pyrol-
ysis method used (Pandey et al., 2015).
3.3. Liquid effluent
Ammonium and phosphates are the major nutrients present in
the liquid effluent from AD process. As mentioned earlier, the tra-
ditional practice of applying the liquid effluents as ferti-irrigation
has environmental issues when applied in excess, and thus land
application of the liquid effluent must be carefully regulated.
 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313
Recently, algae farming using such nutrient-rich effluents has
gained significant interest as an efficient approach for nutrient
recovery (Van Den Hende et al., 2015). An algae farm using such
a nutrient source not only offers nutrient recovery from the efflu-
ent, but also provides algal biomass for diverse applications such as
biofuel production (e.g., biodiesel, biomethane, and biohydrogen),
animal feed, nutraceuticals, and high-value phytochemicals among
others. Microalgae (Chlorella spp.) are being widely adopted for this
process due to their high nutrient (nitrogen and phosphorus)
removal efficiencies (Yan and Zheng, 2013). Algal biomass usually
is rich in lipid and protein contents with values as high as 75% and
60% of TS, respectively (Spolaore et al., 2006). Lipid from algal bio-
mass could be extracted and used for producing biodiesel and glyc-
erol as by-products. The protein-rich solid residue after lipid
extraction could be used in animal feed application or as a co-
substrate for AD (Park and Li, 2012). The effluent following algal
biomass separation could be recycled back as process water in
AD plants or used for irrigation with less risk of ground and surface
water contamination. Furthermore, nutrient-rich effluent from AD
process could potentially be used to produce struvite (MgNH4PO4),
an orthophosphate crystalline material with potential application
as a slow release biofertilizer. Struvite formation takes place when
the ratio of Mg:NH4:PO4 is greater than 1:1:1 on a molar basis and
pH is high (Jaffer et al., 2002; Le Corre et al., 2009). Uysal et al.
(2010) determined the fertilizer quality of struvite produced using
effluent from anaerobic digester treating sewage sludge. The
authors reported that the precipitated struvite at Mg:N:P molar
ratio of 1.5:1:1 met the regulations for heavy metal limits for fer-
tilizers. Several studies (Shu et al., 2006; Jaffer et al., 2002)
reported the technical and economic feasibility of recovering nutri-
ents via struvite precipitation from wastewater treatment plants.
Effluents from the AD plants treating nutrient-rich waste streams
such as swine and poultry manure could be an ideal substrate for
recovering nutrients via struvite precipitation.
4. Small-scale anaerobic biorefinery
There is a huge potential for smaller household digesters in
developing countries to utilize the locally available bioresources
such as animal manures and crop-residues for biogas production.
The rural areas in such countries largely depend on traditional bio-
mass such as firewood, crop residues, and animal dung for cooking.
Biogas technology has been introduced primarily to provide a clean
energy for cooking and lighting to rural households and to curtail
deforestation. The residuals after digestion, commonly known as
bioslurry, serve as a fertilizer for crop production and a fish feed
for aquaculture application. China has by far the largest number
of household biodigester with over 30 million operational plants
as of 2012, and is expected to reach 80 million by 2020
(Rajendran et al., 2012). India has approximately 4.75 million bio-
gas plants (Ministry of New and Renewable Energy, 2014) and
Vietnam installed more than 115,000 units between 2003 and
2011 through the combined effort of Ministry of Agriculture and
Rural Development, SNV and the Dutch Government (SNV Nether-
lands Development Organization Vietnam, 2012). Other develop-
ing countries such as Cambodia, Laos, and Indonesia are
gradually extending their biogas programs. For example, the Royal
Cambodian Government has implemented a nation-wide initiative
to deploy biodigester technology and has built over
23,304 household/farm-scale digesters as of July 2015 in 15 pro-
vinces. The government plans to expand to more than 1.0 million
biodigesters in all 24 provinces. Similarly, Nepal has over
250,000 household biogas plants distributed nationwide
(Surendra et al., 2014). Anaerobic biorefinery concepts have been
well received by rural households who have biogas digesters. Bio-
311
gas technology produces two valuable products – biogas as source
of cooking gas and digestate (or bioslurry) as a source of fish feed
and organic fertilizer. Ali et al. (2008) concluded that manure
slurry from biodigesters can be safely used as a fish feed and
reported an increase in fish production by 20–30%. Nguyen and
Fricke (2015) showed that the digester effluent from co-digestion
of pig manure and spent mushroom substrate in Vietnam was suit-
able for application as feed for Tilapia in addition to vegetable gar-
dening. The fish growth rate in the treatments supplied with 50%
digester effluent and 50% commercial feed (CF) was not signifi-
cantly different from the growth rate of fish provided with 100%
CF. Similar research findings have also been reported in China, Ban-
gladesh, and Thailand. In Cambodia, farmers are using bioslurry for
aquaculture applications. Suthar (2010) showed that the dried
slurry from manure-based biodigester could also be used as ver-
mibeds, which is finally used to make vermicompost. Moreover,
the use of bioslurry as a organic fertilizer for rice and horticulture
crop production is being widely promoted in Cambodia. Several
studies reported the use of bioslurry as a fertilizer in upland
(Alburquerque et al., 2012; Smith et al., 2014, 2015) and flooded
(Nishikawa et al., 2012) rice systems. These practices help reduce
the agrarian costs of local farmers and mitigate environmental
impacts at the same time. The local community in the developing
countries should be made aware of and encouraged to explore dif-
ferent avenues in which the AD effluent can be utilized. Proper
awareness and knowledge concerning the operation and mainte-
nance of digesters, the usefulness of local bioresources for biogas
production, increases in financial subsidies for the installation of
biogas plants, and improved designs which deliver lower cost,
improved robustness and functionality, ease of construction, oper-
ation, and maintenance would aid the development of small-scale
anaerobic biorefinery in developing countries.
5. Challenges and prospectives
The biorefinery concept has taken its shape in the last decade,
but has many miles to go before an established system can prosper.
Some of the future directions for anaerobic biorefineries could be
the integration of different biorefinery platforms where the wastes
from these platforms are to be used for the producing biogas. The
produced biogas can be used for on-site energy requirements or
fed to the grid, if in excess. The problem with current AD systems
is that they are perceived only as a method of reducing organic
waste and producing energy. However, with the current fluctua-
tion in energy prices, other sources of revenue, generated from
the residual bioslurry should be exploited. Currently, greater focus
is required to maintain the more consistent nutrient levels. Certifi-
cations programs for the bioslurry could also encourage the cus-
tomer to buy the product as a fertilizer. Other targets include
insuring that the valuable chemicals, amino acids, etc. are recov-
ered in the biorefinery before the feedstock is sent to the AD pro-
cess. Nutrients and potentially valuable chemicals can be
recovered from food production and processing industries, before
final treatment of the food processing waste through AD technol-
ogy (Pandey et al., 2015). There is also a need to conduct a compre-
hensive techno-economic analysis of anaerobic biorefinery by
considering the local conditions.
6. Conclusion
This paper describes the anaerobic biorefinery possibilities. So
far, the default product of AD is mainly biogas. However, the anaer-
obic biorefinery approach to produce high-value products could
enhance the economic viability of biofuels and biobased products.
The anaerobic biorefinery concepts in large-scale and small-scale
312 C. Sawatdeenarunat et al. / Bioresource Technology 215 (2016) 304–313

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