Journal of Cleaner Production 231 (2019) 913e927

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Journal of Cleaner Production

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

Review

Challenges and prospects for the anaerobic treatment of

chemical-industrial organic wastewater: A review
Zhe Kong a, Lu Li a, Yi Xue b, Min Yang c, Yu-You Li a, b, *
a
Laboratory of Environmental Protection Engineering, Department of Civil and Environmental Engineering, Graduate School of Engineering, Tohoku
University, 6-6-06 Aza-Aoba, Aramaki, Aoba Ward, Sendai, Miyagi, 980-8579, Japan
b
Graduate School of Environmental Studies, Tohoku University, 6-6-06 Aza-Aoba, Aramaki, Aoba Ward, Sendai, Miyagi, 980-8579, Japan
c
State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, 100085,
China

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

Article history: Anaerobic digestion, an economic and energy-efficient biological process, is extensively applied in the
Received 10 January 2019 treatment of a variety of wastewater streams and organic wastes. However, the ineffective mineralization
Received in revised form of degradation-resistant organic wastes is considered a limiting factor for this promising technology, and
16 May 2019
has prevented it from being widely adopted for the anaerobic treatment of chemical-industrial organic
Accepted 20 May 2019
wastewater. In this work, the advantages and benefits of anaerobic digestion and those conventional
Available online 21 May 2019
physical/chemical/biological methods are compared. This review also suggests the current challenges
and barriers to the application of anaerobic digestion to the treatment of chemical-industrial organic
Keywords:
Anaerobic digestion
wastewater by considering some typical degradation-resistant organic wastes as examples. Design im-
Industrial wastewater provements are required to enhance the degradation from refractory organics to fermentable organics.
Degradation-resistant The applications of the up-flow anaerobic sludge blanket, anaerobic membrane bioreactor and their
Bioenergy recovery derivatives are highly recommended in the anaerobic treatment of chemical-industrial organic waste-
Pre-treatment water. While some state-of-the-art physical/chemical technologies have been widely reported and are
Synergistic process currently applied in anaerobic treatment of chemical-industrial organic wastewater, high energy con-
sumption and low efficiency of these processes is an obstacle to their smooth operation and presents
clear difficulties. Therefore, this work provides some perspectives for future applications and practical
advice for improving and enhancing the hydrolysis step of those degradation-resistant organic wastes.
Synergistic processes, such as the co-culturing method, co-digestion and nitrate-reducing anaerobic
digestion are suggested as a means to achieve the effective anaerobic treatment of chemical-industrial
organic wastewater and sustainable regeneration of cleaner production.
© 2019 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 914
2. Insights into the treatment of chemical-industrial organic wastewater (CIOW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
2.1. Physical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 915
2.2. Chemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916
2.3. Activated sludge process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
2.4. Anaerobic digestion process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
2.5. Applications of AD for the anaerobic treatment of chemical-industrial organic wastewater (CIOW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
2.5.1. Up-flow anaerobic sludge blanket . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
2.5.2. Anaerobic membrane bioreactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 917
3. Obstacles and challenges to the anaerobic treatment of chemical-industrial organic wastewater (CIOW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920

* Corresponding author. Laboratory of Environmental Protection Engineering, Department of Civil and Environmental Engineering, Graduate School of Engineering, Tohoku
University, 6-6-06 Aza-Aoba, Aramaki, Aoba Ward, Sendai, Miyagi, 980-8579, Japan.
E-mail address: gyokuyu.ri.a5@tohoku.ac.jp (Y.-Y. Li).

https://doi.org/10.1016/j.jclepro.2019.05.233
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
914 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927

3.1. General obstacles and difficulties for the AD of CIOW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920

3.2. Difficulties with some specific DROWs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
3.2.1. Aromatic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 920
3.2.2. Azo dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
3.2.3. Antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
3.2.4. Amides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 921
4. Practical implications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
4.1. Current applications and challenges in practical wastewater treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
4.1.1. Physical/chemical pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 922
4.1.2. Two-stage micro-aeration process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
4.2. Future perspectives and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
4.2.1. Co-culture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
4.2.2. Co-digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923
4.2.3. Nitrate-reducing anaerobic digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 924

Abbreviations DROWs Degradation-resistant organic wastes

EGSB Expanded granular sludge bed
AD Anaerobic digestion HC Hydrodynamic cavitation
CIOW Chemical-industrial organic wastewater HRT Hydraulic retention time
AGS Anaerobic granular sludge IC Internal circulation
Anammox Anaerobic ammonia oxidation NMF N-methlyformamide
AnMBR Anaerobic membrane bioreactor NRAD Nitrate-reducing anaerobic digestion
AOPs Advanced oxidation processes OD Oxidation ditch
ASP Activated sludge process OLR Organic loading rate
BOD Biochemical oxygen demands ORP Oxidation-reduction potential
BTEX Benzene, toluene, ethylbenzene and xylene PAHs Polycyclic aromatic hydrocarbons
COD Chemical oxygen demand SRT Sludge retention time
CSTR Continuously stirred tank reactor SS Suspended solids
DMAc N, N-dimethyacetamide UASB Up-flow anaerobic sludge blanket
DMF N, N-dimethlyformamide VFAs Volatile fatty acids
DO Dissolved oxygen

1. Introduction CIOWs tend to be toxic, mutagenic, teratogenic, and/or carcino-

genic, and are much more hazardous and harmful to humans. The
With the rapid development of modern industrialization and specific nature of some typical CIOW organic wastes is listed in
economic globalization, the massive quantity of industrial waste- Table 1. Another feature of CIOWs is that because they are either
water discharged from a variety of chemical industries is becoming extracted from natural substances or artificially synthesized as
a formidable global environmental issue. The clear negative im- chemical compounds, they can also be defined as degradation-
pacts on ecosystems and the potential to endanger the health of the resistant organic wastes (DROWs). In other words, they are char-
general public make it import to address the problem urgently acterized by a low BOD and are resistant to biodegradation. As is
(Kong et al., 2018a; Mun ~ oz Sierra et al., 2018b), especially in also indicated in Table 1, DROWs are typically sourced from the
developing countries. The map of global chemical sales shown in pharmacy, petrochemicals, coal coking, pesticide, herbicide, textile
Fig. 1 indicates that China accounted for the highest sales volume of and polymer synthesis industries. Rather than simply assigning
chemical products in 2016 (Cefic, 2017). As the world's largest DROWs as hazardous wastes with no further potential for use,
producer of industrial chemicals, China was reported to have dis- many of them should be recycled or reused as carbon sources or
charged approximately 18.64 billion tonnes of industrial waste- bio-energy (see Table 1).
water that year (MEE, 2017). Among the state-of-the-art technologies, anaerobic digestion
It should be noted that chemical-industrial organic wastewater (AD) is one of the most reliable and cost-effective techniques for the
(CIOW) is different from the type of wastewaters and organic treatment of wastewater and biomass (Kong et al., 2018a). With a
wastes from common industrial streams, like sewage excessive series of synergistic biological degradation processes performed by
sludge, livestock manure, food waste, agricultural wastes and pulp a microbial consortium in the absence of air, organics are converted
waste (Carvalheira et al., 2018; Li et al., 2019) etc. Whereas these to methane and carbon dioxide in the AD process. The loading rates
common organic contaminants are mostly natural biomass with are much higher than in the aerobic process, the destruction of
high biochemical oxygen demands (BOD) and are considered pathogens is greater, and the method has been shown to be a good
conveniently biodegradable, the organic wastes derived from way to manage waste and reduce greenhouse gas emissions (Harris
 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927 915

Fig. 1. A statistic graph of world chemicals sales in 2016 (Cefic, 2017), unit: billion Euro V. *Rest of Europe covers Switzerland, Norway, Turkey, Russia and Ukraine.**North America
Free Trade Agreement, including U.S., Canada and Mexico. ***Asia excluding China, Japan, South Korea and India.

and McCabe, 2015). In order to take advantage of the low sludge
production, low energy requirement and high energy recovery
offered by the AD process, various industries have embraced the AD
process for the effective treatment of high-strength wastewater
and organic wastes (Fern andez-Rodríguez et al., 2015). However,
the refractory and obstinate characteristics of DROW combined
with poor operational stability have prevented the AD process from
being widely commercialized in the treatment of CIOW streams.
Because of the rapidly increasing demand for AD technology, a
number of review papers have been published in the recent past on
the anaerobic treatment of industrial wastewater streams. How-
ever, the perspectives and investigations on the application of AD to
CIOW have rarely been discussed or overviewed. In this paper, new
directions are provided, and suggestions are made for the
improvement of the anaerobic treatment of CIOW through the
following: 1) The superiorities and merits of AD process are
reviewed and AD is compared to those conventional physical/
chemical/biological processes; 2) The current applications of the
AD process are introduced for the anaerobic treatment of CIOW; 3)
The difficulties and obstacles faced in the AD of some specific
DROWs and the challenges in practical wastewater treatment are
specified; 4) The future prospects of synergistic AD process in the
anaerobic treatment of CIOW are carefully considered.
2. Insights into the treatment of chemical-industrial organic
wastewater (CIOW)
2.1. Physical methods
Among the variety of physical technologies currently available
and in use for the treatment of industrial wastewater are such
processes as distillation, adsorption, extraction and membrane
filtration (Abdel-Shafy et al., 2016; Quist-Jensen et al., 2017). These
processes involve the removal of organic pollutants by physical
methods; that is, they are “transferred” rather than “converted” or
“decomposed”. While acknowledging that this kind of “mass
transfer” is sometimes essential, effective and helpful to recover or
reclaim specific materials or pollutants, physical methods are not
916 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927

Table 1
A list of some common DROWs derived from different types of CIOW, their hazards and concentrations.

DROW categories Representative Chemical formula Molecular Hazards DROW COD CIOW industrial Reference
DROW weight (g mol- concentration concentration sources
1
) (mg L-1) (mg L-1)

Antibiotics Amoxicillin C16H19N3O5S$3H2O 419.46 Bacterial toxicity 70e105 13000 Pharmaceutical (Chen et al.
Toxicity Livestock (2011))
Ampicillin C16H19N3O4S$3H2O 403.14 Irritability 3.5 16240 manure (Zhou et al.,
Aureomycin C22H23ClN2O8 478.88 Resistance 4.6 2300 Brewery 2006)
Berberine C20H18ClNO4 235.32 Fungi infection 1500 3800 Slaughterhouse Qin et al. (2015)
Erythromycin C37H67NO13 733.93 200 17200 Amin et al.
(2006)
Nalidixic acid C12H12N2O3 232.24 38 3400 Sirtori et al.
(2009)
Sulfamethoxazole C10H11N3O3S 253.28 1e45 4400 Cetecioglu et al.
(2015)
Tylosin C46H77NO17H3PO4 1982.31 20e200 7000 Chelliapan et al.
(2006)

Homocyclic Phenol C6H6O 94.11 Toxicity/ 100e500 40000 Textile/ Mun ~ oz Sierra
aromatic corrosivity petroleum et al. (2018a)
compounds Benzene C6H6 78.11 Toxicity 1300 4000 Petroleum Eke and Scholz
Mutagenicity Gasoline/oil (2008)
Toluene C7H8 92.14 Carcinogenicity 5e100 5000 Coking Enright et al.
Pharmaceutical (2007)
Ethylbenzene C8H10 106.16 250e850 2700 Aisien (2013)
Xylene C8H10 106.17 Toxicity 600 1900 da Silva et al.
(2012)

Heterocyclic Pyridine C5H5N 79.1 Toxicity/ 1700 65000 Pharmaceuticals Padoley et al.
aromatic irritability Pesticides (2011)
compounds Carbazole C12H9N 167.2 Genotoxicity 12.5 1700 Coal Shi et al. (2014)
Quinoline C9H7N 129.16 Mutagenicity 28 1400 Coking Bai et al. (2011)
Indole C8H7N 117.15 Carcinogenicity 440 2600 Lu et al. (2010)

Polycyclic aromatic Naphthalene C10H8 128.18 Toxicity/ 285.3 1361 Petroleum Panizza et al.
hydrocarbons Anthracene C14H10 178.22 irritation/ 172.8 Pesticides (2000)
Phenanthrene C14H10 178.23 Mutagenicity 500 30000 Coal/coking Machate et al.
Carcinogenicity (1997)

Azo dyes Reactive Black 5 C26H21N5Na4O19S6 991.82 Toxicity 200 7250 Textile Türgay et al.
Irritation (2011)
Reactive Red 2 C19H10Cl2N6Na2O7S2 615.32 Genotoxicity 300 7200 Balapure et al.
Mutagenicity (2015)
Acid Red 14 C20H12N2Na2O7S2 502.42 Carcinogenicity 20e60 1000 Franca et al.
(2015)
Reactive Orange 16 C20H17N3Na2O11S3 617.54 100e1000 20393 Ma et al. (2014)
Acid Black 10B C22H14N6O9S2Na2 616.49 25e750 3000 Naresh Kumar
et al. (2015)
Remazol Brilliant C20H16N3Na3O15S4 735.58 10e2000 1000 Yurtsever et al.
Violet 5R (2015)

Amides N,N- C3H7NO 73.09 Toxicity 2000 3000 Pharmaceuticals (Kong et al.,
dimethylformamide Irritation Textile 2019c, 2018a)
N,N- C4H9NO 87.12 Genotoxicity 9910 18924 Herbicides Zhuo et al. (2018)
dimethylacetamide Mutagenicity Pesticides
a
Acetochlor C14H20ClNO2 269.77 Carcinogenicity 150 N.A Li et al. (2013)
Propanil C9H9Cl2NO 218.08 48.2 N.A Herrera-
Gonza lez et al.
(2013)
Metolachlor C15H22ClNO2 283.8 40.6e45.3 1662 - 1960 Vilar et al. (2012)
Malathion C10H19O6PS2 330.36 10e11200 14e1220000 Zhang and Pagilla
(2010)
a
Some studies did not provided the exact data of concentrations.

considered the most suitable option for the treatment of high-
strength CIOW: they are mainly applied in the pre-treatment or
subsequent processing combined with the mainstream wastewater
treatment technologies (De Gisi et al., 2016). The use of the
adsorption (physisorption and chemisorption) method, for
example, is widespread in wastewater treatment due to its effec-
tiveness and low cost. Although the majority of DROW may effec-
tively be removed using the absorption method, the regeneration of
the adsorption capacity, the modification of new absorbents, the
disposal of the end-of-life adsorbents, and the post-treatment of
transferred absorbates elevate the cost of this technology.
Therefore, adsorption is considered more suitable to the recovery of
heavy metals from industrial wastewater or the decolorization of
low-strength dye wastewater (Sohni et al., 2018). Due to the high
concentration and the low biodegradability of DROWs, the sole
using physical methods is inadequate in the treatment of high-
strength CIOWs. A better option is to adopt other state-of-the-art
technologies for use with physical methods.
2.2. Chemical methods
The effectiveness and reliability of chemical methods are better
 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927
than that of other methods. The series of enhanced chemical re-
actions allow for the thorough degradation and complete miner-
alization of some refractory and obstinate DROWs. Recently, more
attention has been paid to the techniques of advanced oxidation
processes (AOPs) (Oller et al., 2011) due to their ability to effectively
degrade DROWs. The Fenton oxidation process is one of the most
prevalent and promising oxidative techniques for the removal of
those toxic and refractory DROWs, and has been shown capable of
effectively degrading a variety of DROWs derived from dye, textile,
pesticides and pharmaceutical wastewater (Hayat et al., 2015). The
high removal and degradation ability of this technique can be
explained by the formation of a strong hydroxyl radical ($OH) from
the decomposition of H2O2 with oxidation of ferrous (Fe2þ) to ferric
ions (Fe3þ).
However, the cost of the chemical reagents used in this
advanced technique is prohibitive. In the mass balance of the
chemical reaction, a higher amount of DROW in the wastewater
certainly requires more hydrogen peroxide and ferrous ions (Gar
Alalm et al., 2015): this “equivalent exchange” makes this process
more expensive. This suggests that AOPs are not suitable for use in
the large-scale treatment of millions tonnes of CIOW. Another
problem is that both ferrous and ferric ions serve as coagulants and
precipitate as ferric hydroxide (Fe(OH)3) sludge, and the disposal of
the Fe-sludge is also a troublesome issue (Bokare and Choi, 2014).
While the sole use of chemical methods allows for the effective and
thorough treatment of CIOW, the use of other technologies with
chemical methods would result in a reduction in the cost of
chemical reagents. The hydrodynamic cavitation (HC) process is a
new energy-efficient technology which constitutes a drastic
reduction in the consumption of energy while achieving the
excellent removal and degradation of DROWs contained in indus-
trial wastewater (Rajoriya et al., 2016).
2.3. Activated sludge process
Due to its distinct advantages as a pure biological wastewater
treatment technology derived from natural microbial consortia, the
activated sludge process (ASP) is praised as an effective and eco-
friendly method capable of realizing the thorough degradation
and mineralization of a variety of organic pollutants in large scale
operations. As long as sufficient organic waste is fed to the sludge,
the proliferation of microorganisms make the ASP a repeatable
method for wastewater treatment. Nevertheless, the biodegrada-
tion of organic wastes and the behaviors and activities of those
aerobic microorganisms in ASP are significantly influenced by dis-
solved oxygen (DO), and to ensure a sufficient oxygen supply, a high
flow rate of aeration is required. It has also been reported that the
energy cost for aeration generally accounts for 45e75% of the total
energy expenditure in ASP wastewater treatment plants (Rosso
et al., 2008). The high energy consumption of aeration severely
reduces the feasibility of using ASP to treat CIOW, because the
energy cost of maintaining the DO in the aerobic treatment of high-
strength wastewater increases with increasing DROW concentra-
tion. Another problem is the rapid cell growth rate under the aer-
obic condition: it is reported that 25e50% of the influent chemical
oxygen demand (COD) converts to primary or secondary sludge
during the treatment process (Leite et al., 2016). This results in a
shortened sludge retention time (SRT) and a huge amount of excess
sludge. It should be noted that excess activated sludge is another
form of organic waste, contaminated with pathogens, and must be
stabilized and minimized before disposal in landfill or incineration.
The cost of the further treatment and disposal of excess sludge is
also prohibitive: it accounts for 25e40% of the total cost in a
wastewater treatment plant, and has been reported to represents as
much as 60% (Wu et al., 2014). It is because of these considerable
917
costs that attention has turned to technologies designed to mini-
mize excess activated sludge, such as the HC process, which has
also been recognized as an excellent technology for the minimi-
zation and reduction of waste activated sludge.
2.4. Anaerobic digestion process
To date, CIOWs and some degradation-resistant organic solids
are treated by highly effective physical/chemical methods. How-
ever, the potential of the AD process in the anaerobic treatment of
CIOWs is under-appreciated. Due to its ability to recover bioenergy
from organic wastes, its low biomass (excess sludge) yield and
strong tolerance to high organic loading, AD basically overcomes all
the drawbacks of the conventional ASP, and has become the
mainstream process for the treatment of both high-strength
organic wastewater and organic solid wastes (Chen et al., 2017; Li
et al., 2019). Whereas municipal wastewater has a COD concen-
tration in the range of 300e500 mg L-1, the COD concentrations of
the organic pollutants contained in industrial wastewater streams,
and especially those of CIOW, are high, well in excess of 1000 mg L-
1
, as shown in Table 1. The aerobic treatment of such high strength
of industrial wastewater is therefore not an option. Generalizing
and popularizing AD technology in developing countries is essen-
tial to prevent harmful greenhouse gas emissions and to save
energy.
2.5. Applications of AD for the anaerobic treatment of chemical-
industrial organic wastewater (CIOW)
2.5.1. Up-flow anaerobic sludge blanket
The up-flow anaerobic sludge blanket (UASB), introduced in the
1970s, is still by far the most popular and preferred anaerobic
digester for the anaerobic treatment of various types of wastewater
around the world (Kong et al., 2019c). While there is much diversity
in terms of the shapes and designs, the principal conceptual graph
of a UASB is illustrated in Fig. 2. The degradation of organic matter
relies on the establishment of a dense sludge bed in the bottom of
the reactor, which consists of anaerobic granular sludge (AGS) and
serves as the core component of the UASB reactor. The AGS is a
mixture of aggregated flocs and granules in a system formed by
natural turbulence and the hydrodynamic shear force of the
influent up-flow velocity along with biogas production. Due to its
high removal efficiency, small footprint, flexibility and tolerance of
high organic loading rate (OLR), the UASB has been extensively
adopted in the treatment of various types of industrial wastewater
streams (Jiang et al., 2016; Moussavi and Ghorbanian, 2015). Since
the AGS can tolerate much higher concentrations and organic
loading (as can be seen from Table 2), there is increased interest in
applying the UASB to the anaerobic treatment of CIOW. However,
the UASB is also associated with a number of drawbacks, including
a long start-up duration, low pathogen and nutrient removal, and
suspended solids (SS) contained in the effluent. This has driven the
development of UASB derivatives and upgrades, such as the
expanded granular sludge bed (EGSB) reactor and internal circu-
lation (IC) reactor illustrated in Fig. 2, both of which have already
been adopted to improve the performance of AD (Luo et al., 2016).
2.5.2. Anaerobic membrane bioreactor
It is well known that the conventional AD process requires a
long HRT and long sludge retention time (SRT) in order to ensure
the sufficient metabolism of microorganisms and to provide suffi-
cient reaction time for the degradation of organic matters, espe-
cially when applied to organic solid wastes and DROWs (Huang
et al., 2018). When the HRT is too short, a common problem is
that the biomass can easily be washed out with the effluent due to
918 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927

Fig. 2. A conceptual graph of up-flow anaerobic sludge blanket (UASB) reactor (a) and its derivatives expanded granular sludge bed (EGSB) reactor (b) and internal circulation (IC)
reactor (c).

Table 2
Recent studies applying the UASB to the anaerobic treatment of CIOW.

CIOW sources DROW categories Specific DROW Concentration HRT (h) OLR (g COD L-1 d-1) Removal (%) Reference

Pharmaceuticals Antibiotics Berberine 75e375c 24 0.07e0.38 57.6e99.0 Qiu et al. (2013)

Pesticides/herbicides Aromatics Nitrophenol 0.72e 24 N.Aa 90.9e100 Shen et al. (2014)
Explosives/dyes Aromatics 2, 4-dinitrochlorobenzene 0.5e 48e120 N.A 98.4e99.3 Jiang et al. (2016)
Textiles/dyes Azo dyes Direct Black 22 1045e1143d 12 1.84e2.7 48.0e53.0 Amaral et al. (2014)
Petroleum Aromatics/PAHs Chlorophenols/PAHs 950e2500c 9e24 0.95e2.5 84.2e99.6 Moussavi and Ghorbanian (2015)
Petrochemicals Aromatics Terephthalic acid 10250d 12e24 10.2e20 69.2e76.9 Yen et al. (2016)
Pharmaceuticals Antibiotics Sulfamethoxazole 2012e7165d 24e72 0.5e5.0 36.0e57.0 Y. Chen et al. (2018)
Textiles/pharmaceuticals Amides N, N-dimethylformamide 2000c 6e48 1.63e6.17 47.4e97.9 (Kong et al., 2019c, 2018b)
Pharmaceuticals Antibiotics Sulfamerazine 3000d 19.9 3.6e3.8 80.0e90.0 Sponza and Demirden (2007)
Pharmaceuticals Antibiotics Amoxicillin 19951d 16.8e40.3 12.57e21.02 39.0e85.0 (Chen et al. (2011))
a
Some studies did not provided exact data for OLRs.
c
Unit: mg L-1.
d
Unit: mg COD L-1.
e
Unit: mM L-1.

its poor settling properties, further compromising the degradation
ability in the UASB system. As shown in Fig. 3, in recent years, there
has been growing interest in the studies of both UASB and anaer-
obic membrane bioreactor (AnMBR) for the anaerobic treatment of
CIOW. The AnMBR, especially, has been the focus of much research
attention, with the number of reports growing continuously. The
AnMBR is a combination of anaerobic digester and a series of
advanced membrane modules, which uses a membrane as a
physical barrier to facilitate a short HRT coupled with long SRT
(Kong et al., 2019b). Due to the membrane modules, the sludge can
be completely retained in the reactor under a short HRT: the
biomass proliferates at a relatively low growth rate to ensure a
much longer SRT, stabilizing the organic matter in the AnMBR and
resulting in increased biogas production. The many advantages of
the AnMBR include its higher removal efficiency, higher methane
production, and better effluent quality without SS, and ability to
scale down the reactor volume to approximately 1/5 that of con-
ventional anaerobic digesters.
The currently applied AnMBR configurations can be divided into
two types: the internal submerged membrane module and the
external (or side-stream) submerged membrane module. That is,
the membrane is either immersed directly into the bioreactor or
immersed in a separate chamber, as can be seen in the illustrations
of both modes in Fig. 4. In the AnMBR system, the liquid crossflow
and biogas circulation are used to generate the surface shear to
control membrane fouling, while the permeate flow is driven by the
crossflow generated by pump suction. It has been shown that while
the internal submerged membrane module helps to cut the foot-
print of the reactor, observing and maintaining the membrane is
a challenge (Chen et al., 2017). A good alternative is to use an
external membrane operation which can be coupled with another
anaerobic digester, such as a continuously stirred tank reactor
(CSTR) or an UASB. The flat sheet membrane and hollow fiber
membrane are currently the most commonly used types of mem-
brane modules (Sethunga et al., 2018). While advanced polymer
materials, such as poly-ethersulphone, poly-ethylene, poly-
vinylidene fluoride and poly-tetra-fluoroethylene, are used in the
fabrication of the membrane, non-polymeric materials like ce-
ramics are also used (Skouteris et al., 2012). As the membrane
separation technology significantly facilitates the elimination of SS
in the effluent, AnMBR has been widely used in the AD of organic
solid wastes such as food waste and paper waste (Jeong et al., 2017).
 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927 919

Membrane fouling is the most pressing concern in the appli-

Fig. 3. Statistic numbers of reports searched in the database of (a) Google Scholar and
(b) Science Direct in the year 2008e2018 using the keywords “UASB chemical
wastewater” and “AnMBR chemical wastewater”, respectively. The statistical results
were carried out on Jan 10th, 2019.
cation of AnMBR to wastes and wastewater treatment, and involves
a series of parameters, including sludge concentration, HRT, and
soluble metabolic products and extracellular polymeric substances.
(Kong et al., 2019b, 2019a). Recently, extensive research has been
done to reduce the possibility of membrane fouling and prolong the
service life of a membrane (Chen et al., 2017). It is widely recog-
nized that a higher SS concentration is a heavy burden on mem-
brane filtration and aggravates membrane fouling. Because some of
the DROWs contained in CIOW are inherently liquid or miscible in
water, and therefore do not function as SS, the AnMBR is considered
a suitable option in the anaerobic treatment of CIOW. Compared
with the serious burden on membrane filtration during the AD of
organic solid wastes, the AnMBR is much more likely to manage
and handle higher the OLR of wastewater. It is therefore conceiv-
able that AnMBR could obtain a higher sludge concentration and
much shorter HRT for the effective treatment of CIOW, and would
also help to elevate the treatment capacity. Consequently, as can be
seen in Table 3, the AnMBR is commonly employed in the anaerobic
treatment of high-strength CIOW.

Fig. 4. A conceptual graph of anaerobic membrane bioreactor (AnMBR): (a) Internal submerged AnMBR; (b) external submerged AnMBR.

Table 3
Recent studies applying the AnMBR to the anaerobic treatment of CIOW.

CIOW sources DROW categories Specific DROW Concentration (mg COD L- HRT (h) OLR (g COD L-1 d- Removal Reference
1 1
) ) (%)

Pharmaceuticals Antibiotics Penicillin 15365 10.6 8.7e34.0 36.7e50.8 Ng et al. (2014)

e42.6
Textiles Azo dyes RO16 600e3200a 2.5 2.7 55.0e95.0 Spagni et al. (2012)
Textiles Azo dyes Remazol Yellow Gold RNL 50a 24 0.53e0.59 73.0e94.0 ^ta et al. (2013)
Bae
Pharmaceuticals Antibiotics/ Tetrahydrofuran/ 550e10600 1.7e5 0.6e14.2 44.4e94.0 Svojitka et al. (2017)
amines tripropylamine
Textiles/ Amides/ DMF/m-Cresol/isopropyl 8053e22077 18e48 3.9e12.7 94.7e98.9 Z. Chen et al. (2018)
pharmaceuticals antibiotics alcohol
Pharmaceuticals Antibiotics Tetrahydrofuran 4250e5129 12e48 2.0e10.0 81.0e97.0 Hu et al. (2018)
Coal/coke/pulp-paper Aromatics Phenol 100e500a 223 1.86e4.37 61.3e72.7 Mun~ oz Sierra et al.
(2018b)
Pharmaceuticals Antibiotics b-lactams 4428e5118 23.9 2.37e4.46 87.1e94.0 Huang et al. (2018)
e48.1
Pharmaceuticals Antibiotics Etodolac 2500e10000 56 0.30e0.54 85.0e90.0 Kaya et al. (2017)
Petrochemicals Aromatics 2-chlorophenol 150e300 5.2e13.4 N.Ab 70.8e82.4 Wang et al. (2015)
a
Units of the DROW concentrations were unified as COD concentrations, however, some studies measured the exact concentrations of the DROW.
b
Some studies did not provide exact data for OLRs.
920 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927
3. Obstacles and challenges to the anaerobic treatment of
chemical-industrial organic wastewater (CIOW)
3.1. General obstacles and difficulties for the AD of CIOW
It is well known that the entire metabolic progress of AD is
divided into four phases: hydrolysis, acidogenesis, acetogenesis and
methanogenesis, and each phase is characterized by corresponding
microorganisms. Hydrolysis is considered the most important step
and also the rate-limiting step which plays the role of the depoly-
merization of organic matters. The hydrolysis of the majority of
common biomass or organic wastes in the AD system, such as
polyaccharides, proteins and fats/lipids, occurs due to the function
of the extracellular enzymes of bacteria to monosaccharides, amino
acids and long chain fatty acids. After the acidogenesis phase be-
gins, these monomers further degrade to organic acids, such as
volatile fatty acids (VFAs), which are typically C2 e C6 compounds,
or convert to alcohols. During the acetogenesis phase, VFAs and
alcohols further degrade to acetate and H2/CO2. These then serve as
the “direct substrates” for methane-producing archaea or metha-
nogens in the final methanogenesis phase. Therefore, in most of the
AD systems, the methanogenic types are acetotrophic or hydro-
genotrophic (Franke-Whittle et al., 2014; Ros et al., 2017). Another
unique metabolic pathway is methylotrophic methanogenesis: in
this process, methanogens feed on low-molecular-weight methyl-
compounds such as amines from the rot of proteins (Jiang et al.,
2005). Note that methylotrophic methanogenesis is quite uncom-
mon in the majority of AD cases. Hence, in most cases, in order to
produce methane through either the acetotrophic or hydro-
genotrophic pathways shown in Fig. 5, the established condition
should provide enough direct substrates (acetate and H2/CO2) to
methanogens in the final stage. In other words, no matter how high
the molecular weight is obtained by a complicated polymeric
compound, methanogenesis should be realized until this com-
pound is finally decomposed or depolymerized into acetate and H2/
CO2, both of which are directly fed to methanogens.
Since both the conversions from VFAs to acetate and from VFAs
to hydrogen are convenient and functioned by abundant acetogenic
Fig. 5. Metabolic pathways of anaerobic digestion of biomass (common organic matters) and degradation-resistant organic wastes (DROWs) derived from chemical-industrial
organic wastewater (CIOW) streams.
and H2-producing bacteria in most AD systems, it is also conceiv-
able that the degradation potential to VFAs indicates a high feasi-
bility of AD from a high-molecular-weight DROW to acetate and H2/
CO2 and finally to methane. While hydrolysis is also the rate-
limiting step in the digestion of DROWs, the hydrolysis of DROW
is clearly more complicated than that of common biomass and
organic wastes, such as protein, lipids or hemicellulose. One reason
for this is that hydrolytic enzymes for DROWs are rare and specific:
the corresponding bacteria (or fungi) which excrete such enzymes
are not common in typical AD systems and usually require a long-
term for domestication and acclimation to establish an enriched
microbial consortium (Carballa et al., 2007). Another reason is that
before successfully converting to C2 e C6 monomeric compounds
via hydrolysis, some specific and high-molecular-weight DROWs
require a series of chemical reactions for ring cleavage and the
breakage of chemical bonds: this process is far more complicated
than the enzymatic hydrolysis in common biomass and organic
wastes. This is especially the case for aromatic compounds. Such
difficulties and obstacles significantly hinder the application of AD
process to the treatment of CIOW. However, some state-of-the-art
technologies are demonstrated to greatly help to enhance this
rate-limiting step and accelerate the rate of hydrolysis, and the
combination of conventional AD process with these new technol-
ogies should be specifically concerned.
3.2. Difficulties with some specific DROWs
3.2.1. Aromatic compounds
Aromatic compounds are also known for their toxicity, muta-
genicity and carcinogenicity, and are regarded as hazardous organic
pollutants dangerous to both humans and environment (Ghosal
et al., 2016). Due to the great stability caused by the resonance
energy of CeH and CeC bonds, aromatic compounds are among the
most the prevalent and persistent DROWs contained in CIOW
streams, and the degradation of these organic compounds under
the anaerobic condition is difficult to achieve. In general, aromatic
compounds can be divided into three major categories: monocyclic
aromatics, heterocyclic aromatics and polycyclic aromatic
 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927
hydrocarbons (PAHs).
Monocyclic (or homocyclic) aromatics consist of only one aro-
matic ring connected to at least one substituent group. Typical
examples are benzene, toluene, ethylbenzene and xylene (BTEX),
which are common monocyclic aromatic pollutants derived from
petro-industries. Because it is widely understood that oxygen as-
sists in the degradation of aromatic compounds, the aerobic
degradation of aromatic compounds has been extensively studied
and summarized (Ramos et al., 2016). However, due to the lack of
oxygen and reductive agents with redox potentials required in the
reduction of the aromatic ring, the anaerobic degradation of aro-
matic compounds is considered relatively difficult and slow. A
central intermediate benzoyl-coenzyme A (benzoyl-CoA) has been
reported to play the most important role in the anaerobic degra-
dation of aromatic compounds: benzoyl-CoA is further inserted
with carboxyl groups from carbon dioxide or succinic acids for the
ring cleavage and is degraded to a chain intermediate 3-
hydroxypimelyl-CoA, and finally degraded to acetate or succinate
€ ffler et al., 2011). Therefore, the most important step is to
(Lo
enhance the conversion of aromatics to the central intermediate
benzoyl-CoA. After the ring cleavage, with a mixed anaerobic
consortium containing methanogens, these end intermediates
(VFAs, hydrogen or lactate etc.) serve as the substrates in the pro-
cess of methanogenesis, and promote the thorough methanogenic
degradation of aromatic compounds (Mun ~ oz Sierra et al., 2018b).
Heterocyclic aromatics are cyclic compounds whose carbon
chain contains one or more non-carbon atoms. These substituted
atoms are typically nitrogen, sulfur or oxygen: common examples
are carbazole, quinoline, pyridine, indole, thiophene and furan.
Because their heterocyclic structure makes them more soluble
than their homocyclic analogues, transporting them in aquatic
environments is much easier. These compounds are commonly
occurring in the natural environment, and are also produced in
large quantities of pharmaceuticals, dyes, pesticides and herbi-
cides. It is reported that under anaerobic conditions, the initial
step in the metabolism of heterocyclic aromatics can either be
ring reduction or ring hydroxylation, and the source of atomic
oxygen for hydroxylation reaction can be molecular oxygen or
water (Padoley et al., 2008). To date, investigations on the
fermentation of heterocyclic aromatic compounds have focused
on the most common heterocyclic nitrogenous compounds: pyr-
idine, picoline, lutidine and quinolone. The fermentative path-
ways for N-heterocyclic aromatic compounds are reported to
involve an initial ring hydroxylation step prior to the ring
reduction ring cleavage sequence. Due to the electron-rich
chemical property of these heteroatoms and their relatively
weak bond energies and long bond lengths, the weaker stability of
heterocyclic compounds may make them more easily degradable
under the anaerobic condition to achieve the thorough mineral-
ization of CH4 and CO2 than the more stable homocyclic com-
pounds like benzene and phenol.
PAHs typically consist of at least two aromatic rings with or
without substituent groups. Typical examples include naphthalene,
anthracene, phenanthrene and pyrene. PAHs are relatively stable
and recalcitrant in soils and are more difficult to degrade than many
other organic compounds. The anaerobic degradation of PAHs is
also much more complicated than monocyclic aromatics because it
involves more steps of ring-cleavage reactions by enzymes and
carboxylation. The methanogenic degradation of homocyclic and
heterocyclic aromatics, including alkyl benzenes and phenolic
compounds have been reported (García et al., 2005). However,
perhaps because ring cleavage is both complicated and slow, and
the acclimation of specific microbial consortium is also time-
consuming, few investigations have focused on the methanogenic
degradation of PAHs in the AD system with low concentrations
921
(Moussavi and Ghorbanian, 2015). Because the dominant reaction
in the degradation of aromatic compounds is the ring cleavage,
more effort is required to enhance and accelerate this reaction by
the application of such promising state-of-the-art technologies as
the HC process.
3.2.2. Azo dyes
The effective treatment of textile wastewater containing high-
strength dyes is another concern in developing countries. It is
well known that the majority of dyes are azo compounds
(eNeNe): these are linked by an azo bridge and this is the most
common chromophore of reactive dyes (Balapure et al., 2015).
Because azo dyes are electron deficient, they are less susceptible to
aerobic degradation. However, the decolorization of azo-dyes can
be gratuitously achieved under the anaerobic condition (Yurtsever
et al., 2015). After the successful cleavage of the azo bond, the
compound is separated into two aromatics, which are either
monocyclic or polycyclic aromatic amines. It should be noted that
dyes are not normally cytotoxic, mutagenic or carcinogenic, but
because these aromatic amines derived from the cleavage of azo
bond, they may possess these hazardous characteristics. Because
the degradation of aromatic compounds under the anaerobic
condition is difficult to achieve, the conventional treatment of azo-
dyes involves a cooperation of anaerobic and aerobic processes:
decolorization during the anaerobic stage and mineralization
during the aerobic stage (Franca et al., 2015). Currently, due to the
preference for the further methanogenic degradation of those ar-
omatic amines under the same anaerobic condition as the decol-
orization, interest in applying the AD process to the treatment of
dyes-containing textile wastewater is currently growing
(Yurtsever et al., 2015). Considering the refractory and persistent
poverty of aromatic compounds, it should be also noted, however,
that most of the AD studies on the treatment of azo-dyes has been
focused on limited concentrations and organic loading rates.
Therefore, new approaches and chemical pre-treatment should be
applied in order to enhance the degradation of azo dyes (Rajoriya
et al., 2017).
3.2.3. Antibiotics
Although antibiotics are arguably the most successful family of
drugs ever developed for improving human health, they present an
urgent environmental issue. The introduction of antibiotics into the
environmental through anthropogenic sources, mainly as phar-
maceuticals, constitutes a risk to aquatic and terrestrial organisms,
and may also cause resistance in bacteria, resulting in the feeble or
ineffective treatment of several diseases in the future (R. Chen et al.,
2018). While most of these antibiotics derive from microorganisms,
they may be also semi-synthetic or totally synthetic, characterized
by a large molecular weight and complicated monocyclic or het-
erocyclic structures. While a number of antibiotics have been re-
ported degradable under the anaerobic condition (Pan and Chu,
2016), due to the large molecular weight and low biodegrad-
ability of antibiotics, few studies have focused on the application of
the AD process to the treatment of antibiotics-containing phar-
maceutical wastewater (Ng et al., 2014). It should be noted that
some promising technologies are also helpful to the enhancement
on the degradation of antibiotics, synergistic process combined
with wet oxidation and alkaline hydrolysis is also considered a
good alternative.
3.2.4. Amides
Amides are generally small-molecular-weight DROWs, and can
be defined either as the nitrogenous derivatives of carboxylic acids
(eOH replaced by eNH2 or eNR2) or the derivatives of amines. The
most typical amides are formamide, N-methlyformamide (NMF), N,
922 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927

N-dimethlyformamide (DMF) and N, N-dimethyacetamide (DMAc), 4. Practical implications

which are widely used as organic polar solvents in the textile in-
dustry, the manufacturing of synthetic leather and fiber, polymer
dissolution, and in the manufacturing of pesticides and pharma-
ceuticals (Kong et al., 2018a). DMF is a typical example: it remains
persistent and stable in the natural environment and is also hep-
atotoxic and carcinogenic (Kong et al., 2019c). It has been reported
that the cleavage of the CeN bond could be realized by a specific
enzyme under the anaerobic condition. The formate and dime-
thylamine produced from the hydrolysis of DMF serve as the direct
substrates to methanogens, and a large quantity of methane can be
recovered from DMF (Kong et al., 2018a). However, the number of
studies reported on the anaerobic treatment of high strength DMF-
containing wastewater is limited (Kong et al., 2019c). Because of the
assumed low biodegradability of DMF under the anaerobic condi-
tion, the aerobic treatment of DMF has been investigated
(Rahmaninezhad et al., 2016). While it is conceivable that the ma-
jority of these low-molecular-weight amides share the same CeN
bond cleavage mechanism, few studies have been focused on
their ability to be degraded anaerobically.
4.1. Current applications and challenges in practical wastewater
treatment
4.1.1. Physical/chemical pre-treatment
As mentioned before, on the one hand, although the physical/
chemical methods are capable of effectively treating high-strength
CIOWs, the cost for thorough mineralization is often prohibitive. On
the other hand, the AD process is compromised by the rate-limiting
step of hydrolysis of those refractory DROWs, which significantly
lowered the effectiveness of AD process. Therefore, an appropriate
solution is to make up for deficiencies in the AD process by applying
state-of-the-art physical/chemical processes. As shown in Fig. 6 (a),
the combination of physical/chemical methods and the AD process
is suitable for the effective treatment of CIOWs. Some state-of-the-
art technologies such as wet oxidation (Baroutian et al., 2016),
alkaline hydrolysis (Kim et al., 2016) and hydrodynamic cavitation
process (Ciriminna et al., 2016) have significant benefits and are
therefore promising in the pre-treatment of DROWs into ferment-
able intermediates, while the AD process is able to consume the

Fig. 6. Future prospects and improvements proposed by the authors and their laboratory, including: (a) hybrid process with the combination of physical/chemical methods and AD
process; (b) two-stage micro-aeration process to facilitate and enhance hydrolysis and acidification of DROWs; (c) co-culturing method to establish a mixed microbial consortium;
(d) co-digestion of two (or more) kinds of DROWs or co-digestion of one kind of DROW and other biomass to enhance the anaerobic digestion; (e) nitrate-reducing anaerobic
digestion (NRAD) to enhance the anaerobic digestion under redox conditions.
 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927 923

residual high-strength intermediate organic acids to produce
methane. As shown in Table 4, unlike the conventional single
processes, the synergistic processes combined with promising
physical/chemical pre-treatments and conventional AD regenerate
bioenergy from the methane as a cleaner production, and also
greatly help to cover the energy cost in the pre-treatment progress.
However, in practical wastewater treatment, these physical/
chemical pre-treatments might still consume large quantities of
electricity when treating high-strength CIOW.
4.1.2. Two-stage micro-aeration process
It is well recognized that aeration consumes a large quantity of
energy during the aerobic degradation of organic matters in ASP,
which is also shown in Table 4. Apparently, as mentioned earlier,
aerobic degradation is not suitable for the treatment of high-
strength CIOW. However, some DROWs are indeed much more
susceptible and accessible to be hydrolyzed or acidized under the
aerobic condition with a relatively high DO and oxidation-
reduction potential (ORP). With this in mind, the two-stage mi-
cro-aeration process can also be considered promising for the
effective treatment of CIOW: the concept is provided in Fig. 6 (b). It
should be noted that the majority of this process belongs to
anaerobic technology while only the hydrolysis and acidogenesis
phases are performed under the aerobic condition with the micro-
aeration strategy. Take the degradation of glucose as an example:
Based on the stoichiometric calculation, to degrade 1 mol of
glucose aerobically, at least 6 mol of oxygen is required. However,
in the AD process, by partially acidizing the glucose into acetate by
micro-aeration, the oxygen demand is reduced by two thirds,
which greatly reduces the energy cost for aeration. Benefiting
from the relatively high oxidative environment established by
micro-aeration, DROWs are hydrolyzed into VFAs in the pre-
acidification stage, while VFAs then flow into the post-
methanogenesis stage for methane production. As the digestion
of VFAs or other low-molecular-weight organic acids is consider-
ably more convenient than that of the original DROWs, there is
growing interest in applying the two-stage micro-aeration process
as a pre-treatment strategy to the anaerobic treatment of CIOW,
such as petrochemical wastewater (Wu et al., 2015) and crude oil
wastewater (Firmino et al., 2015). Nevertheless, this technology
has not yet been widely extended to the anaerobic treatment of
CIOW. This is because controlling the extent of aeration is difficult:
low aeration may result in ineffective hydrolysis, and over-
aeration may result in a large proportion of COD being
consumed during the aerobic phase.
4.2. Future perspectives and recommendations
4.2.1. Co-culture
The entire AD process is a synergetic metabolism of different
microorganisms. Therefore, as shown in Fig. 6 (c), it is conceivable
that the artificial co-culture of different bacteria (or fungi) and
archaea could to establish a symbiotic mixed consortium capable of
achieving the corresponding steps of the four phases of AD, and
finally realize the complete degradation of specific organic matters.
The co-culture strategy has been implemented in bio-hydrogen
production from biomass, and there is currently growing interest
in applying this strategy to the anaerobic degradation of DROWs
(Patel et al., 2018; Kong et al., 2019a). Since the cultivation and
enrichment of large quantities of functional microorganisms are
quite convenient in the real wastewater treatment, this strategy is
considered promising and sustainable.
4.2.2. Co-digestion
Co-digestion has been extensively applied in the anaerobic
treatment of solid organic wastes in a variety of AD studies
(Edwards et al., 2017). The main principle of the co-digestion
strategy is to facilitate an appropriate C/N ratio in the AD system
by introducing a type of nitrogen-enriched biomass like food waste
or livestock manure, which contain abundant nitrogenous proteins,
to a nitrogen-deficient one like paper or pulp waste, which consist
largely of cellulose or lignocellulose and lack nitrogen (Li et al.,
2019). However, this promising strategy has not yet been widely
extended to the treatment of CIOW. As shown in Fig. 6 (d), it is
conceivable that the co-digestion of solid organic wastes offers
insight into how improvements can be made to the AD of DROWs.
As some specific hydrolyzing and acidogenic bacteria are probably
unable to feed on just one kind of DROW as the sole substrate, the
introduction of other organic matters is likely to facilitate the
growth of the corresponding bacteria which help to degrade the
DROW, enhancing the entire degradability of this co-system. The
co-digestion strategy could be either the combination of two
different DROWs, or the combination of one DROW with other
common degradable organic matter or biomass. Currently, there is a
growing interest in the co-digestion strategy for the AD of DROW,
such as co-digestion of DMF and antibiotics (Z. Chen et al., 2018) and
the co-digestion of azo dyes and brewery grains (Gonçalves et al.,
2015). It should be noted that wastewater from the pharmaceuti-
cals and textile industries typically contains more than two kinds of
organic matters, therefore, the co-digestion of DROWs is considered
the most appropriate option for the real application of AD.

Table 4
Comparison of energy balance between single processes and the synergistic process.

Single process Energy consumption (MJ kg-1 COD) Energy production (MJ kg-1 COD) Net energy consumption
e (MJ kg-1 COD)
Complete degradation Partial degradation Possibility Electricity from methane

Activated sludgea 2.48 N.A e N.A 2.48

Physical (eg. HC)b 30.46 N.A e N.A 30.46
Chemical (eg. Electro/Fenton)c 29.23 N.A e N.A 29.23
Anaerobic digestion (AD, eg. AnMBR)d 3.48 N.A þ 4.39d 0.91
Synergistic process (this study)
Micro-aeration with AD N.A 0.83 þ 2.93 2.10
Physical (eg. HC) with AD N.A 10.15 þ 2.93 7.23
Chemical (eg. Electro/Fenton) with AD N.A 9.74 þ 2.93 6.82
a
The specific power consumption of a wastewater treatment plant in Japan is reported as 2.07 kWh m-3, while the COD concentration of municipal wastewater is around
300 mg L-1, an energy consumption for degrading 1 kg COD is calculated as 2.48 MJ (Mizuta and Shimada, 2010).
b
The energy efficiency of a HC process is reported to consume 1.1 KWh electricity for a 13% COD removal (Boczkaj et al., 2018).
c
This study reported that the energy consumption in electro/Fenton process is 8.12 KWh kg-1 COD (Wang et al., 2019).
d
The energy consumption of a lab-scale AnMBR including pump, biogas sparging, blender mixing, heating and heat loss, while only 35% of combustion heat from the
generated methane was converted into electricity (combustion heat value of CH4 is 35.8 kJ L-1) (Chen et al., 2019).
e
Partial degradation proposed in this study was assumed as 33.3% since 1/3 of COD is lost during the conversion from glucose to acetate.
924 Z. Kong et al. / Journal of Cleaner Production 231 (2019) 913e927
4.2.3. Nitrate-reducing anaerobic digestion
The removal of nitrate (NO 3 ), one of the most common inor-
ganic contaminants contained in various kinds of wastewater
streams, by a denitrification process is necessary to prevent nitrate
from causing eutrophication in the aquatic environment. Conse-
quently, in the conventional denitrification process, doses of
organic matter are usually the additional carbon sources (Kong
et al., 2016). In contrast, nitrate could be regarded as an excellent
oxidant adapt at oxidizing a majority of organic matters under the
anaerobic condition. The oxidability of nitrate also offers insight
into the enhancement of the anaerobic degradation of DROWs. A
great number of studies have investigated the anaerobic degrada-
tion of different DROWs under the nitrate-reducing condition
(Junghare et al., 2016), and nitrate-reducing degradation is
considered much easier and more accessible than methanogenic
degradation. However, it should be noted that most studies focused
on nitrate-reducing degradation have pursued the thorough
mineralization of DROWs by dosing with excessive nitrate.
Although the results indicated that the DROWs are biologically and
anaerobically completely removed, they are totally converted to
useless CO2. From our perspective, however, it would be preferable
if conversion was to CH4, a bioenergy resource, rather than CO2.
Because of the failure to achieve this, the cost of such large amounts
of nitrate reagents is similar to that involved in “chemical”
methods. As shown in Fig. 6 (e), our strategy requires the nitrate
dosage to be moderate and strictly controlled at a relatively low
level in order to realize the nitrate-reducing anaerobic digestion
(NRAD): excessive nitrate and low C/N ratio in the AD system
significantly inhibits the methanogenesis, and denitrifying bacteria
overwhelmingly outcompete methanogens for organic matter as
the carbon source (Sakthivel et al., 2012), consuming the majority
of COD to reduce nitrate into nitrogen gas instead of producing
methane. It has been reported that the methanogenic activity is
significantly weakened when the C/N ratio is lower than 5:1 due to
the increased dosage of nitrate (Sun et al., 2018). In other words, by
determining the appropriate dosage of nitrate, it is possible to bring
the nitrate-reducing degradation of DROW to the completion of the
hydrolysis and acidogenesis phases, allowing the majority of COD
to be fed by methanogens rather than denitrifying bacteria, and be
converted to methane: the intermediates then directly follow the
metabolisms of methanogenic degradation for the recovery of
methane from the DROW (Kong et al., 2019d).
Although some other redox processes have been comprehen-
sively reported for the biodegradation of DROWs, such as the
sulfate-reducing (SO2 3þ
4 ) process, the ferric-reducing (Fe ) process
or the manganite-reducing (Mn4þ) process (Nzila, 2018), they more
or less generate byproducts which are not environmental-friendly.
NRAD is considered well-suited to the degradation of those N-
containing compounds, such as nitrogenous heterocyclic aromatics,
azo dyes and amides. As one of the end products of these nitrog-
enous compounds after the AD process, ammonium (NHþ 4 ) could be
easily oxidized and nitrified, and then completely reduced to ni-
trogen gas (N2) as a clean product by the anaerobic ammonia
oxidation (anammox) process (Ma et al., 2018). The nitrate origi-
nating from those nitrogenous DROWs can be flowed back into the
AD process. It is also very convenient to realize the back-flow of
nitrate in the real wastewater treatment system. NRAD is consid-
ered a promising strategy which utilizes the recycling of nitrate and
provides literally “thorough” anaerobic degradation of DROWs and
realize the cleaner production from wastewater.
5. Conclusions
Anaerobic digestion is a suitable and promising treatment op-
tion for the effective treatment of chemical-industrial organic
wastewater derived from a variety of industries. This work sys-
tematically reviewed the advantages, obstacles and challenges of
anaerobic digestion in the treatment of chemical-industrial organic
wastewater. The following key conclusions were made with regard
to the feasibility and potential of this technology:
 Compared with conventional physical/chemical/biological pro-
cesses, anaerobic digestion is a sustainable technology with the
potential to recover energy from wastewater. However, this
promising process has not been widely extended to the treat-
ment of chemical-industrial organic wastewater.
 Up-flow anaerobic sludge blanket and anaerobic membrane
reactor are considered appropriate in the treatment of chemical-
industrial organic wastewater due to their high efficiency and
high organic loading tolerance.
 The effective hydrolysis of those degradation-resistant organic
wastes from refractory organics to fermentable organics is the
major obstacle that prevents the anaerobic digestion process
from being generalized to the treatment of chemical-industrial
organic wastewater.
 Future improvements and upgrades to the anaerobic treatment
of chemical-industrial organic wastewater should be focused on
the synergistic process combined with such state-of-the-art
physical/chemical/biological methods and anaerobic digestion
process as co-culture, co-digestion and nitrate-reducing anaer-
obic digestion strategies.
Acknowledgements
This work was supported by Japan Society for the Promotion of
Science (JSPS) KAKENHI Grant No. 17J02720 (the first author) and
No. 18J11397 (the second author). The second author also gratefully
acknowledge the financial support from a Grant in Aid of Tohoku
University Division for Interdisciplinary Advanced Research and
Education.
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