Anaerobic Sludge Digestion

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Some of the key takeaways are that anaerobic digestion plays an important role in wastewater treatment by reducing operating costs and environmental footprint. It transforms organic matter into biogas which can be used as an energy source. The paper reviews various aspects of anaerobic digestion including principles, process parameters, design methods, biogas utilization and problems/solutions.

The basic principles of anaerobic digestion involve several bacterial groups breaking down organic matter in the absence of oxygen in multiple steps. Hydrolysis is recognized as the rate-limiting step. Modelling concepts are used to understand dominant parameters affecting the process.

The microbiology involved in anaerobic digestion is complex and delicate. Several process parameters like pH, alkalinity, concentration of ammonia, hydrogen, metals, volatile fatty acids can inhibit the bacterial groups if outside their optimum working conditions.

Principles and potential of the anaerobic digestion of waste-activated sludge

Lise Appels
a
, Jan Baeyens
c
, Jan Degre` ve
a
, Raf Dewil
a,b,
a
Department of Chemical Engineering, Katholieke Universiteit Leuven, W. De Croylaan 46, B-3001 Heverlee, Belgium
b
Department of Chemical Engineering, Associated Faculty of Technology and Biosciences, Campus De Nayer, Katholieke Universiteit Leuven, Jan De Nayerlaan 5,
B-2860 Sint-Katelijne-Waver, Belgium
c
Department of Chemical Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT, UK
a r t i c l e i n f o
Article history:
Received 4 February 2008
Accepted 12 June 2008
Available online 8 August 2008
Keywords:
Anaerobic digestion
Modelling
Biogas
Waste-activated sludge
a b s t r a c t
When treating municipal wastewater, the disposal of sludge is a problem of growing importance,
representing up to 50% of the current operating costs of a wastewater treatment plant. Although
different disposal routes are possible, anaerobic digestion plays an important role for its abilities to
further transform organic matter into biogas (6070vol% of methane, CH
4
), as thereby it also reduces
the amount of nal sludge solids for disposal whilst destroying most of the pathogens present in the
sludge and limiting odour problems associated with residual putrescible matter. Anaerobic digestion
thus optimises WWTP costs, its environmental footprint and is considered a major and essential part of
a modern WWTP. The potential of using the biogas as energy source has long been widely recognised
and current techniques are being developed to upgrade quality and to enhance energy use. The present
paper extensively reviews the principles of anaerobic digestion, the process parameters and their
interaction, the design methods, the biogas utilisation, the possible problems and potential pro-active
cures, and the recent developments to reduce the impact of the problems. After having reviewed the
basic principles and techniques of the anaerobic digestion process, modelling concepts will be assessed
to delineate the dominant parameters. Hydrolysis is recognised as rate-limiting step in the complex
digestion process. The microbiology of anaerobic digestion is complex and delicate, involving several
bacterial groups, each of them having their own optimum working conditions. As will be shown, these
groups are sensitive to and possibly inhibited by several process parameters such as pH, alkalinity,
concentration of free ammonia, hydrogen, sodium, potassium, heavy metals, volatile fatty acids and
others. To accelerate the digestion and enhance the production of biogas, various pre-treatments can be
used to improve the rate-limiting hydrolysis. These treatments include mechanical, thermal, chemical
and biological interventions to the feedstock. All pre-treatments result in a lysis or disintegration of
sludge cells, thus releasing and solubilising intracellular material into the water phase and transforming
refractory organic material into biodegradable species. Possible techniques to upgrade the biogas
formed by removing CO
2
, H
2
S and excess moisture will be summarised. Special attention will be paid to
the problems associated with siloxanes (SX) possibly present in the sludge and biogas, together with the
techniques to either reduce their concentration in sludge by preventive actions such as peroxidation, or
eliminate the SX from the biogas by adsorption or other techniques. The reader will nally be guided to
extensive publications concerning the operation, control, maintenance and troubleshooting of anaerobic
digestion plants.
& 2008 Elsevier Ltd. All rights reserved.
ARTICLE IN PRESS
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/pecs
Progress in Energy and Combustion Science
0360-1285/$ - see front matter & 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2008.06.002
Abbreviations: AD, anaerobic digestion; BOD, biochemical oxygen demand (5 days, 201C) (mg O
2
/l); BOD
L
, ultimate BOD of the inuent sludge (see Eq. (5)) (mg O
2
/l);
CHP, combined heat and power; COD, chemical oxygen demand (mg O
2
/l); CSTR, continuously stirred tank reactor; DMDO, dimethyldioxirane; DS, dry solids content of the
sludge (wt%); EU, European Union; HRT, hydraulic retention time (d); IC
50
, concentration of 50% inhibition (mg/l); LCFA, long-chain fatty acids; MDS, mineral dry solids of
the sludge (wt%); ODS, organic dry solids of the sludge (wt%); ORP, oxidation reduction potential (mV); pe, population equivalent; POMS, peroxymonosulphate;
SBR, sulphate reducing bacteria; sCOD, soluble fraction of the chemical oxygen demand (mg O
2
/l); SRT, solids retention time (d); SRT
des
, design value of SRT, including a
safety margin (d); SX, siloxanes; VFA, volatile fatty acids; VSS, volatile suspended solids; WAS, waste-activated sludge; WWTP, wastewater treatment plant.

Corresponding author at: Department of Chemical Engineering, Associated Faculty of Technology and Biosciences, Campus De Nayer, Katholieke Universiteit Leuven, Jan
De Nayerlaan 5, B-2860 Sint-Katelijne-Waver, Belgium. Tel.: +3215316944; fax: +3215317453.
E-mail address: raf.dewil@skynet.be (R. Dewil).
Progress in Energy and Combustion Science 34 (2008) 755781
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 756
2. Basic principles and parameters of AD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
2.1. Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
2.2. Affecting parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
2.2.1. pH, alkalinity and volatile acids/alkalinity ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 758
2.2.2. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
2.2.3. Solids and hydraulic retention time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
2.3. Types of anaerobic digesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
2.3.1. Standard-rate (cold) digestion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 759
2.3.2. High-rate digester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
2.3.3. Two-stage digester. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
2.3.4. Mesophilic and thermophilic digestion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 760
2.4. Design criteria for single-stage, high-rate ADs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
2.4.1. Population basis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
2.4.2. Volumetric solids loading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
2.4.3. Solids retention time (SRT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
2.4.4. Volatile solids reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
2.4.5. Gas production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 761
2.4.6. Tank design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762
2.4.7. Digester mixing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 762
2.4.8. Heating and temperature control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
2.4.9. Digester covers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
3. Modelling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763
3.2. Simple models and principal kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 764
3.3. The IWA AD model No. 1 (ADM1) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 764
3.4. Modelling, monitoring and regulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
4. Inhibition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
4.1. Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 766
4.2. Sulphide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
4.2.1. Competition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 767
4.3. Sodium and potassium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
4.3.1. Sodium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
4.4. Heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
4.5. Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 768
4.6. Volatile fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
4.7. Long-chain fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
5. Pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
5.2. Thermal pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 770
5.3. Mechanical pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
5.4. Chemical pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
5.4.1. Acid and alkaline (thermal) hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
5.4.2. Oxidative sludge pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 771
5.5. Ultrasound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
5.6. Bacterial and enzyme hydrolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
6. Biogas enrichment, compression and storage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
6.1. Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 772
6.2. Biogas utilisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
6.3. Biogas upgrading technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774
6.3.1. Carbon dioxide removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 774
6.3.2. Removal of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
6.3.3. Removal of H
2
S . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
6.3.4. Removal of trace gases. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 775
6.4. Biogas compression and storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776
7. Operation, maintenance and troubleshooting of digesters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
8. Conclusions and recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 777
1. Introduction
When treating municipal wastewater, the disposal of sludge is
a problem of growing importance, representing up to 50% of the
current operating costs of a wastewater treatment plant (WWTP)
[1]. Municipal WWTPs generate sludge as a by-product of the
physical, chemical and biological processes used during treat-
ment. Current daily amounts, expressed as dry solids (DS) range
from 60 to 90g DS per population equivalent (p.e.), i.e. nearly 10
million tons of dry sludge per year for the EU.
This sludge must undergo some treatment in order to reduce
its associated volumes, to improve its character and to reduce the
associated health problems and hindrance. This treatment will
hence (i) rstly reduce the water content of the raw sludge, (ii)
transform the highly putrescible organic matter into a relatively
stable or inert organic and inorganic residue, and (iii) nally
ARTICLE IN PRESS
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 756
condition the residue to meet disposal acceptance regulation.
Since land application is difcult due to stringent regulations
concerning the tolerated composition [24], (co-)incineration is
gaining increasing interest where permits can be obtained [5].
The water purication part of a WWTP commonly comprises a
pre-treatment to remove about 5060% of the suspended solids
and 3040% of the BOD [6,7]. The settled primary sludge contains
mainly water (between 97% and 99%) and separates mostly
organic matter that is highly putrescible.
The pre-treatment is followed by a biological step, where
aerobic micro-organisms remove the remaining (or nearly total)
BOD and suspended solids. Nitrogen (N) and phosphorus (P) are
commonly removed simultaneously, although N is more usually
and easily targeted rst. A secondary clarier produces the
dischargeable efuent as overow and a bottom sludge (9899%
water), partly recycled to the biology to maintain the concentra-
tion of the micro-organisms at the required level, and partly
evacuated to the sludge treatment units of the WWTP. If a pre-
treatment is present, primary and secondary sludge are generally
combined and thickened to undergo further treatment.
This further treatment can be a combination of various steps,
as reviewed in Table 1. Anaerobic digestion (AD) is an important
step in most of the treatment routes.
All routes start with raw sludge (primary and secondary)
produced at 12wt% DS. The mineral part of the DS (MDS) is
between 30wt% and 45wt%.
A rst step is its thickening by gravity, otation or belt
ltration. In doing so, the amount of sludge can be reduced
to as little as a third of its initial volume. The separated water
is recycled to the inuent of the WWTP. Once this has
been accomplished, the sludge is subject to some form
of biochemical stabilisation, with AD playing an important
role for its abilities to further transform organic matter into
biogas (6070vol% of methane, CH
4
), thereby also reducing the
amount of nal sludge solids for disposal is also reduced,
destroying most of the pathogens present in the sludge,
and limiting possible odour problems associated with residual
putrescible matter.
For these reasons, anaerobic sludge digestion optimises WWTP
costs and is considered a major and essential part of a modern
WWTP. The potential of using the biogas as energy source is
widely recognised. Biogas is currently produced mostly by
digestion of sewage treatment sludge, with minor contributions
from fermentation or gasication of solid waste or of lignocellu-
losic material (processes currently being further developed). It is
considered an important future contributor to the energy supply
of Europe, although upgrading is needed.
The annual potential of biogas production in Europe is
estimated in excess of 200 billions m
3
.
AD of sludge uses airtight tanks. Essentially all organic material
can be digested, except for stable woody materials since the
anaerobic micro-organisms are unable to degrade lignin. The biogas
which is formed has a high caloric value and is considered as a
renewable energy source. Clearly, it is benecial to produce as much
biogas as possible. Despite these advantages of AD, some limitations
are inevitable, e.g. (i) only a partial decomposition of the organic
fraction, (ii) the rather slow reaction rate and associated large
volumes and high costs of the digesters, (iii) the vulnerability of the
process to various inhibitors, (iv) the rather poor supernatant
quality produced, (v) the presence of other biogas constituents such
as carbon dioxide (CO
2
), hydrogen sulphide (H
2
S) and excess
moisture, (vi) the possible presence of volatile siloxanes in the
biogas that can cause serious damage in the energy users
(generator, boiler) due to the formation of microcrystalline silica,
and (vii) the increased concentration of heavy metals and various
industrial organics in the residual sludge due to the signicant
reduction of the organic fraction during digestion, leaving the
mineral and non-degradable fraction untouched.
A process owchart of the sludge-processing steps is shown in
Fig. 1.
The present paper will attempt to extensively review the
principles of AD of sewage sludge, the process parameters and
their interaction, the design methods, the biogas utilisation, the
possible problems and potential pro-active measures, and the
recent developments to reduce the impact of the difculties
described above.
Section 2 will review the basic principles and parameters of
the AD process, including the process description, the types of
anaerobic digesters (standard rate, high-rate, two-stage, meso-
philic, thermophilic), the current empirical design methods, the
common operating parameters and the resultant biogas yields.
Modelling and monitoring the AD process are dealt with in
Section 3: models can tentatively be divided into either simple
steady-state models or complex dynamic simulation models.
When required system performance criteria are dened, steady-
state models predict the operating parameters and lead to a
system design with reasonable accuracy. These approximate
design and operating parameters can then be used as input to
the more complex simulation models to investigate the dynamic
behaviour of the system and ne-tune the design and operating
parameters in real-time.
Having studied the dominant parameters, Section 4 will focus
on the operational vulnerability of digestion. The microbiology of
the AD is complex and delicate, involving several bacterial groups,
each of them having their own optimumworking conditions. They
are sensitive to several process parameters such as pH, alkalinity,
concentration of free ammonia, hydrogen, volatile fatty acids
(VFA), etc. These parameters can be inhibiting factors to some or
all bacterial groups, and modern approaches include these
inhibiting effects in modelling, in investigating the behaviour of
the system and in controlling the process.
Section 5 will describe novel methods to accelerate the
digestion through enhancing the rate-limiting hydrolysis. Various
pre-treatments have recently been studied and include mechanical,
thermal, chemical and biological interventions. All pre-treatments
result in a lysis or disintegration of sludge cells, thus releasing
and solubilising intracellular material into the water phase and
transforming refractory organic material into biodegradable spe-
cies, therefore making more material readily available for micro-
organisms. It will be shown that these pre-treatments enhance the
biogas generation. Since the degradation rate is moreover acceler-
ated, the dimensions of the digesters can be reduced for a given
load, thus reducing the capital requirements.
ARTICLE IN PRESS
Table 1
Different sludge disposal routes
Route Outlets Required operations
1 Agriculture (land application) T, R
2 Agriculture T, MD, R
3 Agriculture T, AD, R
4 Agriculture T, AD, MD, R
5 Landll T, MD, R
6 Landll T, AD, MD, R
7 Solid fuel T, MD, ID, R
8 Solid fuel T, AD, MD,ID
9 Ash T, MD, ID, I
10 Ash T, AD, MD, ID, I
T: thickening to 56wt% DS; AD: anaerobic digestion to produce biogas (up to 50%
conversion of ODS); R: road transport; MD: mechanical dewatering to 2535wt%
DS; ID: indirect drying to 8595wt% DS; I: incineration (autonomous in mostly
uidised bed, or co-combustion with solid fuels in power plants, cement kilns,
etc.))
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 757
Section 6 will focus on the possible techniques to upgrade the
biogas formed by removing CO
2
, H
2
S and excess moisture. A
special attention will be paid to the problems associated with
siloxanes (SX), including their origin and behaviour in sludge, and
the techniques to either reduce their concentration in sludge
by preventive actions such as peroxidation, or to eliminate the
SX from the biogas by adsorption or other techniques.
Section 7 will guide the reader to extensive publications
concerning the operation, control, maintenance and troubleshoot-
ing of AD plants.
2. Basic principles and parameters of AD
2.1. Principles
The AD of organic material basically follows; hydrolysis, acid-
ogenesis, acetogenesis and methanogenesis as shown in Fig. 2. The
biological aspects of AD are dealt with in specialised literature [811].
AD is a complex process which requires strict anaerobic
conditions (oxidation reduction potential (ORP)o200mV) to
proceed, and depends on the coordinated activity of a complex
microbial association to transform organic material into mostly
CO
2
and methane (CH
4
). Despite the successive steps, hydrolysis is
generally considered as rate limiting [7,1216].
The hydrolysis step degrades both insoluble organic material
and high molecular weight compounds such as lipids, polysac-
charides, proteins and nucleic acids, into soluble organic sub-
stances (e.g. amino acids and fatty acids). The components formed
during hydrolysis are further split during acidogenesis, the second
step. VFA are produced by acidogenic (or fermentative) bacteria
along with ammonia (NH
3
), CO
2
, H
2
S and other by-products.
The third stage in AD is acetogenesis, where the higher organic
acids and alcohols produced by acidogenesis are further digested
by acetogens to produce mainly acetic acid as well as CO
2
and H
2
.
This conversion is controlled to a large extent by the partial
pressure of H
2
in the mixture.
The nal stage of methanogenesis produces methane by two
groups of methanogenic bacteria: the rst group splits acetate into
methane and carbon dioxide and the second group uses hydrogen as
electron donor and carbon dioxide as acceptor to produce methane.
2.2. Affecting parameters
Within the anaerobic environment, various important para-
meters affect the rates of the different steps of the digestion
process, i.e. pH and alkalinity, temperature, and retention times.
2.2.1. pH, alkalinity and volatile acids/alkalinity ratio
Each group of micro-organisms has a different optimum pH
range. Methanogenic bacteria are extremely sensitive to pH with
ARTICLE IN PRESS
Thickener
Sludge pretreatment
Digester * Biogas Residual sludge
Dewatering
Further drying,
combustion or
land application
Supernatant
To influent of WWTP
Storage vessel
Direct
Use**
Upgrading
and
storage**
Denitrification
Fig. 1. Process owchart of the sludge processing steps: * see Fig. 4, ** see Fig. 8.
Suspended organic matter
Soluble organics
Volatile Fatty Acids
Acetic acid
H
2
, CO
2
CH
4
+ CO
2
Hydrolysis
Acidogenesis
Acetogenesis
Methanogenesis Methanogenesis
Fig. 2. Subsequent steps in the anaerobic digestion process.
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 758
an optimum between 6.5 and 7.2 [17,18]. The fermentative micro-
organisms are somewhat less sensitive and can function in a
wider range of pH between 4.0 and 8.5 [19]: at a low pH the main
products are acetic and butyric acid, while at a pH of 8.0 mainly
acetic and propionic acid are produced [17].
The VFAs produced during AD tend to reduce the pH. This
reduction is normally countered by the activity of the methano-
genic bacteria, which also produce alkalinity in the form of carbon
dioxide, ammonia and bicarbonate [18,20]. The system pH is
controlled by the CO
2
concentration in the gas phase and the
HCO
3
-alkalinity of the liquid phase. If the CO
2
concentration
in the gas phase remains constant, the possible addition of
HCO
3
-alkalinity can increase the digester pH [18]. A buffering
capacity of 70meq CaCO
3
/l or a molar ratio of at least 1.4:1 of
bicarbonate/VFA should be maintained for a stable and well-
buffered digestion process although it has been shown that
especially the stability of the ratio is of prime importance, and not
so much its level [20].
2.2.2. Temperature
The temperature has an important effect on the physicochem-
ical properties of the components found in the digestion
substrate. It also inuences the growth rate and metabolism of
micro-organisms and hence the population dynamics in the
anaerobic reactor. Acetotrophic methanogens are one of the most
sensitive groups to increasing temperatures. The degradation of
propionate and butyrate is also sensitive to temperatures above
701C. The temperature has moreover a signicant effect on the
partial pressure of H
2
in digesters, hence inuencing the kinetics
of the syntrophic metabolism. Thermodynamics show that ender-
gonic reactions (under standard conditions), for instance the
breakdown of propionate into acetate, CO
2
, H
2
, would become
energetically more favourable at higher temperature, while reac-
tions which are exergonic (e.g. hydrogenotrophic methanogenesis)
are less favoured at higher temperatures [21].
An increasing temperature has several benets [17,21] includ-
ing an increasing solubility of the organic compounds, enhanced
biological and chemical reaction rates, and an increasing death
rate of pathogens (thermophilic conditions).
However, the application of high temperatures (thermophilic)
has counteracting effects: there will be an increase of the fraction of
free ammonia, which plays an inhibiting role for the micro-
organisms; but the increasing pK
a
of the VFA will make the process
more susceptible to inhibition [17]. Control is thus a very sensitive
issue for thermophilic as compared to mesophilic digestion.
It is important to maintain a stable operating temperature in
the digester, since sharp and/or frequent uctuations in tempera-
ture affect the bacteria, especially the methanogens. Process
failure can occur at temperature changes in excess of 11C/day;
and changes in temperature of more than 0.61C/day should be
avoided [18].
2.2.3. Solids and hydraulic retention time
The solids retention time (SRT) is the average time the solids
spend in the digester, whereas the hydraulic retention time (HRT)
is the average time the liquid sludge is held in the digester. The
subsequent steps of the digestion process are directly related to
the SRT. A decrease in the SRT decreases the extent of the
reactions and vice versa. Each time sludge is withdrawn, a fraction
of the bacterial population is removed thus implying that the cell
growth must at least compensate the cell removal to ensure
steady state and avoid process failure [18,20].
The inuence of the retention time on the breakdown
efciency is mostly studied on laboratory scale [20] and the
obtained relationship between gas production and retention time
in a (semi-)CSTR indicates that (i) retention times shorter than
5 days are insufcient for a stable digestion: VFA concentrations
are increasing due to a washout of methanogenic bacteria, (ii) VFA
concentrations are still relatively high for SRT of 58 days: there is
an incomplete breakdown of compounds, especially of the lipids,
(iii) stable digestion is obtained after 810 days: low VFA
concentrations, the breakdown of lipids starts, and (iv) the
breakdown curve stabilises at SRT 410 days; all sludge com-
pounds are signicantly reduced. The SRT is a fundamental design
and operating parameter for all anaerobic processes.
A schematic representation of SRT vs. degree of digestion is
added in Fig. 3.
2.3. Types of anaerobic digesters
2.3.1. Standard-rate (cold) digestion
This type of AD is the simplest type using a long digestion
period of 3060 days. A schematic representation of this type of
digester is added in Fig. 4. The sludge content is usually neither
heated nor mixed. Although the biogas generated provides some
form of mixing, stratication occurs in four zones: (i) a scumlayer,
(ii) a liquid layer (or supernatant), (iii) a layer of digesting solids,
and (iv) a layer of digested solids. The supernatant is withdrawn
and recycled to the wastewater treatment plant. The accumulated
digested solids at the bottom of the digester are periodically
ARTICLE IN PRESS
0
0.1
0.2
0.3
0.4
0.5
0.6
100 80 60 40 20 0
Retention Time (days)
S
p
e
c
i
f
i
c

b
i
o
g
a
s

p
r
o
d
u
c
t
i
o
n
(
m
3
/
k
g

O
D
S
)
Steady-state Maximum biogas production Batch
Fig. 3. Biogas production vs. SRT.
Gas
Scum layer
Supernatant
Digesting sludge
Digested sludge
Supernantant
returned to
secondary treatment
Digested sludge to
dewatering
Thickened
sludge
Gas outlet
Fig. 4. Standard-rate digester.
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 759
extracted. Nowadays standard rate units are seldomly built,
except for smaller WWTPs [6,7,18].
2.3.2. High-rate digester
This digester is a major improvement of the standard-rate
digestion. The sludge is heated and completely mixed, the raw
sludge is thickened and the feeding is uniform. All these elements
combined create a uniform environment as a result of which the
tank volume can be reduced and the process stability and
efciency are improved [18]. The sludge is mixed by gas
recirculation, pumping or draft-tube mixers; it is mostly heated
by external heat exchangers because of their exibility and ease of
maintenance. Other ways of heating include internal heat
exchangers and steam injection [6,18]. Uniform feeding is very
important, and the sludge should be fed continuously or at regular
intervals to help maintain steady-state conditions in the digester
and reduce shock loadings, especially important for the sensitive
methanogenic bacteria [6,7,18]. This steady draw and ll mode is
also important to improve pathogen kill. This type of digester is
shown in Fig. 5.
2.3.3. Two-stage digester
In two-stage digestion, a high-rate digester is coupled with a
second tank, sometimes called a secondary digester (see Fig. 6)
although merely used to store the digested solids and decant the
supernatant: it is neither heated nor mixed. The tanks may have
xed roofs or oating covers. If the secondary tank is of the
oating cover type, it can also be used to store digester gas. Very
little solids reduction and gas production take place in the second
tank. Sometimes, primary and secondary tanks are of equal
design, each with heating and mixing capacity to serve as a
standby digester. The supernatant withdrawn from the second
tank may contain high concentrations of suspended solids and
these poor settling phenomena are commonly associated with an
incomplete digestion in the primary digester, leading to small gas
bubbles present in the suspension within the second tank.
Moreover, due to the mixing and natural breakdown of the solids,
ne particles or ocs are produced which do not settle easily
[6,7,18].
Although this type of twin digestion was very popular in the
past, it is rarely used in newer plants.
2.3.4. Mesophilic and thermophilic digestion
Most high-rate digesters are operated in the mesophilic range,
with a temperature between 30 and 381C [7]. AD can also take
place at higher temperatures, in the thermophilic region, where
digestion occurs at temperatures between 50 and 571C suitable
for thermophilic bacteria. Thermophilic digestion is faster than
mesophilic digestion since the biochemical reaction rates increase
with increasing temperature. Other advantages are an increased
solids reduction, improved dewatering, and increased destruction
of pathogenic organisms. The use of thermophilic temperatures
ARTICLE IN PRESS
Gas
Digested sludge to
dewatering
Thickened
sludge
Gas outlet
Heat exchanger
Active mixing
Fig. 5. High-rate digester.
Gas
Thickened
sludge
Mechanical
Gas
Digested sludge to
dewatering
Supernatant
Digested sludge
Gas outlet
Fig. 6. Two-stage digester.
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 760
however has a higher energy requirement, a lower quality
supernatant with large quantities of dissolved solids, a higher
odour potential and much poorer process stability requiring great
care. The latter is due to the fact that thermophilic bacteria are far
more sensitive to temperature uctuations than their mesophilic
colleagues [6,7,18].
2.4. Design criteria for single-stage, high-rate ADs
A number of guideline parameters for the design and operation
of single-stage high-rate ADs have been discussed in the literature
[6,7,18,22], and are summarised hereafter. They can be used for a
preliminary sizing of the AD.
2.4.1. Population basis
Digestion tanks can be designed based on a certain volume
(in m
3
) per capita. Table 2 lists some typical design values. The per
capita loading factors should only be used for the preliminary
digester sizing since it presumes constant values for different
important parameters e.g. solids removal efciency. These para-
meters can vary considerably from one WWTP to another. If
industrial waste loads are part of the wastewater inuent, the
values of Table 2 for capita design criteria should be increased on a
population-equivalent basis [18].
2.4.2. Volumetric solids loading
One of the most common methods in dening the digester
volume is the volatile suspended solids (VSS) loading rate as given
in Table 2. The design criteria are commonly based on continuous
loading conditions, typically on the basis of monthly peak of the
2-week peak solids production. Low solids loadings decrease the
efciency of the digester [6,18].
2.4.3. Solids retention time (SRT)
The digester volume can also be dened on the basis of the
solids retention time since the digestion process is a function of
the time required by the micro-organisms to digest the organic
material and to reproduce. In ADs without recycle or supernatant
withdrawal, the SRT is equal to the hydraulic retention time. The
shortest SRT for a digestion temperature of 351C is 10 days to
prevent washout of the micro-organisms. For SRT values exceed-
ing 1213 days (at 351C), changes in increasing volatile solids
destruction are relatively small. In selecting the design SRT for AD,
the peak hydraulic load must be taken into account. Table 3 gives
the critical SRT values that should be respected when using the
SRT as a design criterion. Since these values were established in
ideal conditions of temperature, mixing and feeding, a safety
margin should be provided when selecting the design SRT and in
practice, a multiplication factor of about minimum 2.5 is
recommended [6,18].
2.4.4. Volatile solids reduction
During the digestion process, volatile solids are degraded to a
certain extent and converted into biogas. The sludge volume is
hereby reduced and the supernatant is returned to the plant. The
degree of stabilisation is often expressed as the percent reduction
in volatile solids, itself associated with either the SRT or the
detention time based on the untreated sludge feed.
The MDS content is assumed to stay constant during the entire
digestion period.
The following empirical equation allows the estimation of the
amount of volatile solids destroyed [6]:
V
d
13:7 lnSRT
des
18:9 (1)
where V
d
is the volatile solids destruction (%) and SRT
des
the time
of digestion (d).
The destruction of volatile solids can also be estimated using
the values of Table 4. This method is frequently used since the
ow rate of the untreated sludge can easily be measured.
2.4.5. Gas production
Digester gas contains about 6570% methane, 3035% carbon
dioxide and trace amounts of nitrogen, hydrogen, hydrogen
sulphide and water vapour. It has a relative density of around
0.86. With an average concentration of 65% methane, the heating
value is approximately 2125MJ/m
3
, about 3040% lower than
the heating value of 37.3MJ/m
3
for natural gas.
The methane generation rate can be estimated from the kinetic
equations developed for the ADs [7]:
P
x

YES
o
1 k
d
y
c
(2)
V 0:35m
3
=kgfES
o
1:42P
x
g (3)
where P
x
is the net mass of cell produced (kg/d) and Y the yield
coefcient (g/g). For municipal sludge: 0.040.1mg VSS/mg BOD
utilised, E the efciency of waste utilisation (0.60.9), S
o
the
ultimate BOD
L
of the inuent sludge (kg/d) and k
d
the endogenous
coefcient (d
1
). For municipal sludge: 0.020.04d
1
, Y
c
the
ARTICLE IN PRESS
Table 2
Typical design criteria for mesophilic digestion [6,7,18]
Parameter Units Value
Standard
rate
High rate
Volume criteria
Primary sludge m
3
/capita 0.060.08 0.030.06
Primary sludge+trickling lter
humus sludge
m
3
/capita 0.060.14 0.070.09
Primary sludge+activated sludge m
3
/capita 0.060.08 0.070.11
Solids loading rate kg VSS/m
3
d 0.641.60 1.64.8
Solids retention time d 3060 1020
Sludge concentration
Primary sludge+biological sludge
feed
% 24 47
Digested sludge draw-off % 46 47
Table 3
Suggested SRT for the design of completely mixed high-rate digesters [6]
Operating temperature
(1C)
Minimum SRT (d) Minimum design
SRT
des
(d)
18 11 28
24 8 20
30 6 14
35 4 10
40 4 10
Table 4
Volatile solids destruction in high-rate fully mixed mesophilic anaerobic digesters
[6]
Digestion time (d) Volatile solids destruction (%)
30 65.5
20 60.0
15 56.0
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 761
mean cell residence time (d), equal to the SRT, V the volume of
methane produced (m
3
/d), 0.35 the theoretical conversion factor
for the amount of methane produced from the conversion of 1kg
BOD and 1.42 the conversion factor for cellular material into BOD.
The specic gas production [6,7] lies in the range of
0.751.12m
3
/kg VS destroyed, or 0.50.75m
3
/kg VS loading, or
0.030.04 m
3
/personday.
2.4.6. Tank design
AD tanks are mostly cylindrical or egg shaped [7]. The
cylindrical tank has a diameter from 6 to 40m, a conical oor
with a slope of about 15%, and a withdrawal of the sludge in the
centre of the tank. The water depth has to be minimum 7.5m to
allow proper mixing and can be as high as 15m. Some digesters
are equipped with a so-called wafe bottom to minimise grit
accumulation and reduce digester cleaning [6,7,18]. The design of
egg-shaped digester tanks has been discussed in literature
[6,7,18].
2.4.7. Digester mixing
Proper mixing of the AD is essential for providing an optimum
performance. Mixing provides intimate contact between the feed
sludge and active biomass, yielding uniformity of temperature, of
substrate concentration, of other chemical, physical and biological
aspects throughout the digester, and preventing both the forma-
tion of surface scum layers and the deposition of sludge on the
bottom of the tank. Due to the rise of gas bubbles and the thermal
convection currents created by the addition of heated sludge,
there is always some degree of natural mixing in the digestion
tank. However, despite being the largest component, this is not
sufcient for an optimum performance; therefore, auxiliary
mixing is needed. Methods of auxiliary mixing are external
pumped recirculation, internal mechanical mixing and internal
gas mixing [7,14,22], as illustrated in Fig. 7.
2.4.7.1. External pumped recirculation. In external pumped re-
circulation a large amount of the digesting sludge withdrawn from
the centre of the digester is pumped through external heat ex-
changers where the digested sludge is blended with the raw
sludge and heated. It is then pumped back in the digestion tank
through nozzles at the base of the digester or at the top to break
the scum [7,23]. The ow rate in the recirculation should, how-
ever, be very large for ensuring a complete mixing of the tank
which limits the sole use of this method of mixing. The minimum
power required is 0.0050.008kW/m
3
of digester volume and
may be higher, if friction losses are excessive. Other disadvantages
of external pumped recirculation are plugging of the pumps by
rags, impeller wear from grit and bearing failures [18,23].
2.4.7.2. Internal mechanical mixing. Mechanical stirring systems
generally use low-speed at-blade turbines. In both systems, the
sludge is transported by the rotating impeller(s), thereby mixing
the content of the digestion tank. The mechanical pumping action
is provided by centrifugal pumps, generally set up in an internal or
external shaft tube to support vertical mixing. Mixing is sup-
ported by the circulation of the sludge. These systems are most
suited for digesters with xed covers [6,7,18].
2.4.7.3. Internal gas mixing. This is a successful method of mixing
the digester content and avoid the build-up of scum. Gas mixing
systems can be conned and unconned. In unconned systems,
the gas is collected at the top of the digestion tank, compressed
and then released through a pattern of diffusers or a series
of radially placed lances suspended from the digester cover.
ARTICLE IN PRESS
Low speed mixer
External draft tubes
Gas
compressor
Bubble generator
Gas pistons
Gas compressor
Gas lifter
Fig. 7. Types of digester mixing (a) external, pumped recirculation, (b) internal, mechanical mixing, and (c) external, gas recirculation.
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 762
The digester content is mixed, releasing gas bubbles that rise and
push the sludge to the surface. Scum has to be specically con-
trolled as it causes roof fracture, gas surging, etc. The lance system
is successful against the build-up of scum; however, due to an
ineffective mixing regime there is a greater risk of solids deposits.
The opposite occurs with the diffuser system: top mixing is not
adequate, resulting in a scum build-up. This system is, however,
effective against solids deposition. On the other hand, there is a
possibility of diffuser plugging, which results in digester drainage
for tank cleaning. The unit gas ow requirement for unconned
systems is 0.00450.005m
3
/m
3
min [18].
There are two different types of conned systems: the gas lifter
and the gas piston. Generally, in conned systems the gas is
collected at the top, compressed and discharged through conned
tubes. The gas lifter system is composed of ooded gas pipes
placed in an eductor tube or gas lifter. The compressed gas is
released from these pipes and gas bubbles rise, creating an air-lift
effect. The gas piston system releases gas bubbles intermittently
at the bottom of the piston, hereby creating piston pumping
action of the bubbles and pushing the sludge to the surface. These
conned systems generally have a low power requirement and a
gas ow rate of 0.0050.007m
3
/m
3
min [6,18].
Table 5 shows some typical design parameters for digester
mixing systems.
2.4.8. Heating and temperature control
It is crucial for a stable and efcient operation to maintain a
constant digestion temperature. Heat is necessary to (i) raise the
incoming sludge to the temperature of the digestion tank and (ii)
compensate for heat loss through walls, oor and roof of the
digester [6].
2.4.8.1. Heating requirements. The amount necessary to heat the
sludge to the temperature of the digester is given by the following
equation:
Q
1
W
f
C
p
T
2
T
1
(4)
where Q
1
is the heat required (J/d), W
f
the feed sludge rate (kg/d),
C
p
the specic heat of the sludge (4200J/kg 1C), T
2
the operating
temperature of digester (1C) and T
1
the temperature of feed
sludge (1C).
The amount of heat required to compensate heat losses is
given by
Q
2
UAT
2
T
a
(5)
where Q
2
is the heat loss (J/s), U the heat transfer coefcient
(W/m
2
1C), A the surface area of digester through which heat
losses occur (m
2
), T
2
the temperature of sludge in digester (1C) and
T
a
the ambient temperature (outside digester) (1C)
Data for heat transfer coefcients are given in literature [24]
for wall, oor and roof constructions, with or without insulation.
2.4.8.2. Heating equipment. The most common method for heating
the sludge is the external heat exchanger, although steam injec-
tion can also be applied [6,7,18].
Steam injection heating requires no heat exchanger, but the
presence of a steam boiler is not common to WWTPs.
External heat exchangers have the benet of enabling to mix
recirculating digester sludge with raw sludge before heating, and
in seeding the raw sludge with anaerobic micro-organisms.
Although there are three types of external heat exchangers
frequently used, i.e. water bath, tubular and spiral exchanger,
both tubular and spiral exchangers are favoured for their counter-
current ow design and heat transfer coefcients in the range of
8501000W/m
2
K. The hot water used in the heat exchangers is
commonly produced in a boiler driven by digester gas. At start-up
and/or under conditions of insufcient biogas production, provi-
sions for burning an alternative fuel source such as natural gas
must be made [7].
2.4.9. Digester covers
Digesters are covered to maintain operating temperature and
anaerobic conditions and of course to collect the digester gas. The
cover can be either xed or oating. When sludge is withdrawn,
no air should be allowed to enter the digestion tank to avoid
explosion danger through mixing of oxygen and digester gas.
Fixed covers are dome shaped or at and are made of reinforced
concrete, steel or breglass-reinforced polyester. Floating covers
are normally used for single-stage digester and for the second
stage of two-stage digesters. A variation of the oating cover is the
oating gas holder, consisting of a oating cover with an extended
skirt, so that gas can be stored during periods when the supply of
digester gas exceeds the demand. A recent development in gas-
holder covers is the membrane cover. It consists of supported,
exible gas and air membranes. When the gas storage volume
decreases or increases in the space between the liquid surface and
the membranes, the space between the membranes is pressurised
or depressurised using an air-blower bleed-valve system [18].
Floating covers directly oat on the liquid and generally have a
maximal vertical ravel of 23m [6,7]. The gas pressure under a
digester cover is typically in the range of 03.7kN/m
2
[7]. In egg-
shaped digesters, there is only limited storage available for gas
and the provision of external gas storage is needed [18].
3. Modelling
3.1. Introduction
The optimisation of the AD and the assessment of its operation
as a function of varying feed or operating conditions are important
objectives and can be pursued by using appropriate digestion
models. These models can be of steady-state mode (i) to estimate
retention time, reactor volume, gas production and composition
for a requested system performance, (ii) to investigate the
sensitivity of the system performance to various parameters,
(iii) to provide cross-checking of simulation results and plant
performance, and (iv) to determine how the digestion process can
affect the design of upstream or downstream WWTP operations.
More complex dynamic models could be integrated in plant-
wide modelling, predicting on a time basis how the system will
react to sudden or progressive changes in operating parameters of
feedstock ow rate and composition, temperature, inhibition, pH,
etc. [2527].
ARTICLE IN PRESS
Table 5
Typical design parameters for anaerobic digester mixing systems [6]
Parameters Type of mixing
system
Typical values Unit
Unit power Mechanical systems 0.0050.008 kW/m
3
of
digester
volume
Unit gas ow Gas mixing
Unconned 0.00450.005 m
3
/m
3
min
Conned 0.0050.007 m
3
/m
3
min
Velocity gradient G All 5080 s
1
Turnover time of
tank contents
Conned gas mixing
and mechanical
systems
2030 min
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 763
It is nally important to note that modelling will also be the
guideline to develop, apply and validate digestion in-line
monitoring.
The number of models presented in literature is extensive, and
often of very specic nature. The most frequently used model,
ADM1 developed by the IWA [11], forms a good basis and is often
used in expanded models, as proposed by, e.g. So temann et al.
[28,29]. Simpler models for digestion have been proposed by, e.g.
Bala [30], Siegrist [31] and others. Due to the complexity of the
models, the present review will be limited to the essential
features, giving the interested reader ample references to
published research.
3.2. Simple models and principal kinetics
Most initial models were based on a single rate-limiting step,
which itself may be dependent on various conditions such as
wastewater characteristics, hydraulic loading and temperature
[32]. Some models considered acetogenic methanogenesis as the
rate-limiting step [33], whereas others considered the conversion
of fatty acids [34], or the hydrolysis of biodegradable suspended
solids [35]. Pavlostathis and Gossett [36] studied, developed and
evaluated a comprehensive kinetic model capable of predicting
digester performance when fed biological sludge. Preliminary
conversion mechanisms such as cell death, lysis, and hydrolysis
responsible for rendering viable biological sludge organisms to
available substrate were studied in depth. The results of this study
indicate that hydrolysis of the dead, particulate biomassprimary
consisting of proteinis the slowest step and therefore kinetically
controls the overall process of AD of biological sludge. This rate
control by hydrolysis was conrmed by several authors, including,
e.g. Hiderani et al. [37], who used anaerobic respirometry to
determine digestion kinetics. Additional data are given in
[12,16,3845].
The developed models are simple but do not very accurately
describe the digester behaviour.
Additional literature deals with the modelling of biolm
reactors. The reader is referred to the literature [4648].
Table 6 reviews the key AD models that have been developed
so far. Some models have assumed various forms of the kinetics,
the bacterial groups, occurring processes, rate-limiting steps and
possible inhibition.
3.3. The IWA AD model No. 1 (ADM1)
The ADM1 model, initially developed by the IWA-ADM Test
Group [56] was presented in book form [11]. This book presents
the outcome of the study undertaking and is the result of 4 years
of collaborative work by a number of international experts from
various elds of anaerobic process technology. The approach
provides a unied basis for AD modelling and promotes the
increased application of modelling and simulation as a tool for
research, design, operation and optimisation of anaerobic pro-
cesses. The ADM1 model was developed on the basis of the
extensive but often disparate work in modelling and simulation of
AD systems over the previous 20 years. In developing the ADM1,
the Task Group tried to establish common nomenclature, units
and model structure, consistent with existing anaerobic modelling
literature and the popular-activated sludge models [62]. Outputs
from the model include common process variables such as gas
owand composition, pH, separate organic acids, and ammonium.
The structure encourages specic extensions or modications
where required, but still maintaining a common platform. The
model structure is presented in a readily applicable matrix format
for implementation in many available differential equation
solvers.
The ADM1 includes biochemical as well as physicochemical
processes. The biochemical part includes all three overall
biological (cellular) steps, i.e. acidogenesis, acetogenesis of both
VFA and LCFAs, and methanogenesis) as well as an extracellular
(partly non-biological) disintegration step and an extracellular
hydrolysis step. The physicochemical equations describe ion
association and dissociation, and gasliquid transfer.
The biochemical part of the model uses the following basis:
All biochemical extracellular steps are assumed of rst order.
Substrate uptake use Monod-type kinetics as the basis for all
intracellular biochemical reactions.
Biomass growth is implicit in substrate uptake.
Death of biomass is represented by rst-order kinetics.
Inhibition by pH, hydrogen and free ammonia is included.
The physicochemical factors taken into account are:
liquidliquid reactions;
gasliquid exchanges.
For the full model equations, the reader is referred to [56]. The
model has been successfully tested on a range of systems from
full-scale waste sludge digestion to laboratory-scale thermophilic
high-rate UASB reactors [6368]. Various modications have been
developed with the ADM1 as a basis. These extended models were
reviewed by Batstone et al. [69] and amongst the most promising
expansions, the reader is referred to So temann et al. [28,29], Zaher
et al. [63] and Blumensaat and Keller [70].
For possible connections with the activated sludge models
ASM1, ASM2, ASM2d and ASM3, the reader is referred to IWA [62]
and Henze et al. [71].
The approach of So temann et al. [28,29] is very comprehensive.
As an alternative to characterising the sewage sludge feed into
carbohydrates, proteins and lipids, as is done in ADM1, it
is characterised in terms of total COD, its particulate non-
biodegradable COD fraction, the short chain fatty acid (SCFA)
COD and the CHON content of the particulate organics, i.e. X, Y, Z
and A in C
X
H
Y
O
Z
N
A
. Having thus characterised the sludge in terms
of measurable parameters, the model allows COD, C and N mass
balances to be set up over the AD system. The interactions
between the biological processes and weak acid/base chemistry
are predicted for stable steady-state operation of ADs. The model
of So temann et al. is a steady-state model, validated only for
conditions of steady ow and load. The model equations can
however be transformed to predict the digestion under dynamic
operating conditions.
All kinetic and stoichiometric constants in the model, except those
for hydrolysis, were obtained from the literature so that model
calibration is reduced to determining the non-biodegradable parti-
culate COD fraction of the sewage sludge, the associated constants of
the hydrolysis kinetics and the sewage sludge CHON composition.
Various formulations for the hydrolysis rate of sewage sludge
particulate biodegradable organics were evaluated and surface-
mediated reaction (Contois) kinetics were selected similar to that
used by Dold et al. [72] and ASM1 [73] for slowly biodegradable
organics in activated sludge systems. Once calibrated against the
Izzett et al. [74] data, this formulation showed the required
sensitivity of gas production and unltered efuent COD con-
centration to variation in retention time, without changing the
constants in the hydrolysis rate equation.
The inuent COD, organic N and VSS measurements of Izzett
et al. [74] determined the stoichiometric formulation of the inuent
ARTICLE IN PRESS
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 764
ARTICLE IN PRESS
Table 6
Overview of anaerobic digestion models
Model Kinetics Bacterial groups Processes Limiting step Included inhibition
Graef and Andrews [49] Andrews Acetoclastic methanogens Methanogenesis Methanogenesis Unionised VFA, toxic
compounds
Kleinstruer and Powegha
[50]
Andrews Acid-forming bacteria Acetogenesis Methanogenesis Unionised acetate, toxic
compounds
Andrews Methane-forming bacteria Methanogenesis Unionised acetate, toxic
compounds
Moletta et al. [51] Andrews Acidogenic bacteria Acetogenesis Methanogenesis Unionised acetate
Methanogenic bacteria Methanogenesis Unionised acetate
Smith et al [52] First order Hydrolysis Methanogenesis
First order Acidogenic bacteria Acidogenesis Total VFA
Andrews Methanogenic bacteria Methanogenesis Unionised VFA
Bryers [53] First order Hydrolysis Acetogenesis
Monod Acid-forming bacteria Acidogenesis
Monod Propionic acid-utilising
bacteria
Acetogenesis
Monod Methanogenic bacteria Methanogenesis
Siegrist et al. [31] First order Hydrolysis Acetogenesis H
2
, acetate
Monod Acidogenic bacteria Fermentation of amino acids
and sugars
H
2
, acetate
Monod Acetogenic bacteria Anaerobic oxidation of
fatty acids
pH
Monod Acetogenic bacteria Anaerobic oxidation
of propionate
Free NH
3
Monod Acetoclastic methanogens Acetate conversion
to methane
pH
Monod Hydrogenotrophic
methanogens
Hydrogen conversion
to methane
pH
Mosey [54] Monod Acid-forming bacteria Acidogenesis H
2
Monod Propionic acid-utilising
bacteria
Acetogenesis Acetogenesis H
2
Monod Butyric acid-utilising bacteria Acetogenesis H
2
Monod Acetoclastic methanogens Methanogenesis
Monod Hydrogenotrophic
methanogens
Methanogenesis
Costello [55] Monod Acid-forming bacteria Acidogenesis H
2
, pH products ??
Monod Lactic acid-utilising bacteria Acidogenesis H
2
, pH products
Monod Propionic acid-utilising
bacteria
Acetogenesis Acetogenesis H
2
, pH products
Monod Butyric acid-utilising bacteria Acetogenesis H
2
, pH products
Monod Acetoclastic methanogens Methanogenesis pH
Monod Hydrogenotrophic
methanogens
Methanogenesis pH
Batstone et al. [56] First order Disintegration pH
First order Hydrolysis Hydrolysis pH
Monod Sugar-degrading acidogens Acidogenesis pH
Monod Amino acid-degrading
acidogens
Acidogenesis pH
Monod Propionate-utilising
acetogens
Acetogenesis pH, H
2
Monod Butyrate and valerate-
utilising acetogens
Acetogenesis pH, H
2
Monod Acetoclastic methanogens Methanogenesis pH, free NH
3
Monod Hydrogenotrophic
methanogens
Methanogenesis pH, free NH
3
Kiely et al. [57] Monod Hydrolysis/acidogenesis NH
3
Monod Aceticlastic methanogenesis
Lokshina and Vavilin [58] Andrews Propionate degradation Propionate degradation
Acetate degradation Acetate degradation
Nopharatana et al. [59] Contois Acid-producing bacteria Hydrolysis Hydrolysis
Mass balance,
stoichiometry
Acidogenic bacteria Acidogenesis
Acetoclastic methanogens Methanogenesis
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 765
sewage sludge as C
3.4
H
7
O
2
N
0.192
. With the sludge biodegradability
and hydrolysis process rate dened, the anaerobic digester perfor-
mance data of Ekama et al. [75] ranging over 720 day retention time
(i.e. efuent COD, TKN, FSA, SCFA, H
2
CO
3
* Alk, pH, gaseous CO
2
and
CH
4
production and partial pressures), could only be matched if the
sewage sludge composition was rened to C
1.5
H
7
O
2
N
0.196
to conform
to the COD, C and N mass balances of the data. This formulation was
conrmed with primary sludge CHON composition tests, the average
of which was C
3.65
H
7
O
1.97
N
0.19
. The model predicts CHON content
and molar masses close to 100%, thereby provides persuasive
validation of the UCTADM1 model.
Validation of the model under steady-state conditions vali-
dates only its stoichiometry and the system rate-limiting process,
which is hydrolysis. However, the model, which includes the
inuence of high hydrogen partial pressure on the acidogenesis
and acetogenesis processes, shows the expected sensitivity to a
digester upset (although commonly unnoticed due to the system
inertia) initiated by temporary inhibition of the acetoclastic
methanogens, which is the usual cause in practise. The model
demonstrates that even a brief inhibition of this organism group
causes an irreversible failure of the digester (pHo6.6).
The successful integration in a kinetic way of the two-phase
mixed weak acid/base chemistry and biological processes of the
AD has provided a sound basis for further model development.
Still to be included are mineral precipitation and the P content
of sewage sludges. This will extend the model to digestion of
biological excess P removal waste-activated sludge and provide a
direct and quantitative link between feed sludge composition and
mineral precipitation problems, e.g. struvites in digesters.
Additional software has been presented by several authors or
institutions, with the DESASS example [76] certainly worth exploring.
3.4. Modelling, monitoring and regulation
The previously mentioned models, and their validation, stress
the importance of monitoring essential parameters during diges-
tion. These essential parameters include pH, alkalinity, VFA and
biogas ow rate and composition. Again literature data are
extensive and the quoted references of Table 7 illustrate the trend
used in the monitoring and control of digestion plants.
4. Inhibition
Inhibiting compounds are either already present in the
digester substrate or are generated during digestion.
4.1. Ammonia
Ammonia is produced during the degradation of nitrogenous
matter, mainly proteins and urea [17,100]. Ammonium (NH
4
+
) and
free ammonia (NH
3
) are the two most predominant forms of
inorganic nitrogen present. It has been indicated that free
ammonia is the most toxic of both, due to the fact that it can
pass through the cell membrane [100,101] and into the cell,
causing proton imbalance and potassium deciency [100]. The
free ammonia concentration mainly depends on three para-
meters: total ammonia concentration, temperature and pH
[102]. An increased temperature has a positive effect on the
microbial growth rate but also results in a higher (free) ammonia
concentration. It is found that thermophilic digestion is more
easily inhibited than mesophilic digestion [101,102]. An increase
in pH would result in a higher toxicity level due to the shift to a
higher ratio of free to ionised ammonia. The resulting instability
of the process often leads to an increase in the amount of VFA,
which again leads to a decrease in pH and consequently to a lower
free ammonia concentration [100]: the process remains stable but
the methane yield is reduced [101,102]. Ammonia concentrations
below 200mg/l are benecial to AD because nitrogen is an
essential nutrient for the micro-organisms [103]. Free ammonia of
560568mg NH
3
-N/l can cause a 50% inhibition of methanogen-
esis at pH 7.6 under thermophilic conditions [101]. The acetogenic
population is more tolerant than the methanogens. When the
ARTICLE IN PRESS
Table 6 (continued)
Model Kinetics Bacterial groups Processes Limiting step Included inhibition
Pontes and Pinto [60] Monod Fermentors Acidogenesis pH, VFA, H
2
Monod Butyric acid-utilising
acetogens
Acetogenesis
Monod Ethanol-utilising acetogens Acetogenesis
Monod Acetoclastic methanogens Methanogenesis
Monod Hydrogenotrophic
methanogens
Methanogenesis
Endogenous residue
Siegrist et al. [61] Mathematical Biogas stripping
First order Hydrolysis pH, free NH
3
, H
2
, acetate
Monod Fermentation pH, free NH
3
, H
2
, acetate
Monod Anaerobic oxidation of LCFA pH, free NH
3
, H
2
, acetate
Monod Anaerobic oxidation of
propionate
pH, free NH
3
, H
2
, acetate
Monod Acetoclastic methanogens Acetotrophic methanogenesis pH, free NH
3
, H
2
, acetate
Monod Hydrogenotrophic
methanogens
Hydrogentrophic
methanogenesis
pH, free NH
3
, H
2
, acetate
So temann et al. [28] First order,
Monod, Contois
Acidogenic bacteria Hydrolysis Hydrolysis
Monod Glucose-utilising acidogens Acidogenesis H
2
Monod Propionate-utilising
acidogens
Acidogenesis H
2
Monod acetogenic bacteria Acetogenesis pH, H
2
Monod Acetoclastic methanogens on
acetic acid
Acetoclastic methanogenesis pH, H
2
Monod Hydrogenotrophic
methanogens on H
2
Hydrogenotrophic
methanogenesis
pH, H
2
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 766
concentration of ammonia was increased to 40515734mg NH
3
/l,
the acidogens were hardly affected whereas the methanogens lost
56.1% of their activity [100]. However, the methanogenic bacteria
can be acclimated to ammonia inhibition as a result of a shift in
the methanogenic population or because of internal changes in
the predominant methanogenic species [100]. Sung and Liu [101]
showed that the acclimated methanogens could tolerate concen-
trations up to 2g-N/l under thermophilic conditions without
inhibition, albeit with total inhibition of the methanogenic
activity when a concentration of 10g-N/l was reached.
4.2. Sulphide
Sulphate is commonly found in many wastewaters and hence
in WAS [104]. Under anaerobic conditions, sulphate is used as an
electron acceptor and hence reduced to sulphide by sulphate
reducing bacteria (SRB) [17,100]. Two groups of SRB are respon-
sible for the reduction, the incomplete and the complete oxidisers.
The rst group oxidises compounds like lactate to acetate and
CO
2
, whereas the second one converts acetate to CO
2
and HCO
3

[100]. In both processes, the reduction half reaction transforms


SO
4
2
into S
2
.
Inhibition occurs at two different levels: the primary inhibition
caused by the competition for substrates from SRB, whereas
secondary inhibition is due to the toxicity of sulphides for the
different groups of micro-organisms [100].
4.2.1. Competition
SRB can metabolise a number of substrates, such as alcohols,
organic acids, aromatic compounds and long-chain fatty acids
(LCFA). They compete with the fermentative, acetogenic or
methanogenic bacteria for acetate, H
2
, propionate and butyrate
in the digester system. Normally, inhibition through competition
does not occur in the rst stage of digestion since the SRB are not
capable of degrading biopolymers. They depend on the fermenta-
tive micro-organisms to degrade these organics so they can
metabolise the degradation products [17,21,100]. Nevertheless the
acetogenic and the methanogenic micro-organisms are affected
by the presence of SRB since they compete for the same
fermentation products. When looking at it from a thermodynamic
and kinetic point of view, the SRB should be able to overgrow
the acetogens for the propionate and butyrate, but there are some
factors like the COD/SO
4
2
ratio, the sulphide toxicity and the
relative population of SRB and the acetogens that inuence
the competition. SRB are utmost important in the degradation of
propionate, it is even believed to be the key degradation pathway.
The acetogens are capable of effectively competing with the SRB
for butyrate and ethanol. Methanogenesis and sulphate reduction
can happen simultaneously, but the hydrogenotrophic methano-
gens are easily undercut by the SRB for H
2
[17,100]. If wastewater
with a high sulphate concentration is fed to a methane reactor, the
population may gradually shift from hydrogenotrophic methano-
gens to hydrogenotrophic sulphate reducers, due to a more
favourable K
s
value for hydrogen of the sulphate reducers
[17,21]. Temperature has an effect on the competition between
SRB and hydrogenotrophic methanogens. It appeared that SRB
were dominant at mesophilic conditions and the methanogens
had the largest population at thermophilic temperatures [100].
Contradictory data were reported in the literature regarding the
competition between the acetoclastics and the SRB, with some
authors nding an effective competition of methanogens, whereas
others concluded that SRB are superior [100].
4.2.1.1. Toxicity. Non-dissociated hydrogen sulphide is toxic for
both methanogens and sulphate reducers. This form is the toxic
form since it can freely diffuse through the cell membrane,
ARTICLE IN PRESS
Table 7
Review of programming, monitoring and control literature
Author Topic of investigation
Bernard et al. [77] Telemac: an integrated system to remote monitoring control anaerobic wastewater treatment plants through the
internet
Programming
Lardon et al. [66] Methodological framework based on evidence theory to manage the fault signals generated by conventional
approaches
Programming
Mailleret and Bernard [78] A simple robust controller to stabilise an anerobic digestion process Programming
Alatiqi et al. [79] A control system including a proportional-integral (PI) controller and variable groups is proposed to analyse
mesophilic and thermophilic processes for process stability and controllability
Monitoring
Alcaraz-Gonzalez et al. [80] A robust asymptotic observer for chemical and biochemical reactions Monitoring
Bernard and Chachuat [81] Design and practical use of probabilistic observers for mass balance-based bioprocess models Monitoring
Bernard and Gouze [82] Multi-observateurs en boucle ferme e pour des mode` les biotechnologiques mal connus Monitoring
Chachuat et al. [83] Design of probabilistic software sensors for anaerobic digestion Monitoring
De Pauw et al. [84] Protocol and optimal experimental design to set up a monitoring and control system at an anaerobic digester Monitoring
Gomez et al. [85] Monitoring anaerobic digestion processes using thermal analysis with mass spectrometry Monitoring
Liu et al. [86] A computer-controlled automated BOD-analyzer with the purpose of on-line monitoring of a process for
conversion of biomass under eld conditions
Monitoring
Steyer et al. [87] Sensor networks and uncertainty management in anaerobic digestion processes Monitoring
Vanrolleghem and Lee [88] On-line monitoring equipment for wastewater treatment processes: state of the art Monitoring
Yamaguchi et al. [89] Enzyme activity for monitoring the stability in a thermophilic anaerobic digestion of wastewater Monitoring
Zaher et al. [90] Titrimetric monitoring of anaerobic digestion: VFA, alkalinities and more Monitoring
Alcaraz-Gonzalez et al. [91] Robust interval-based siso regulation in anaerobic digestion Regulation
Cresson et al. [47] Better control biolm formation in order to reduce the time of colonization during the start-up phase of an
anaerobic high-rate biolm reactor
Regulation
Hess and Bernard [92] Detection of the conditions of destabilisation in anaerobic wastewater treatment processes Regulation
Mailleret et al. [93] Robust regulation of anaerobic digestion processes Regulation
Mailleret et al. [94] Controle asymptotique non-line aire des fermenteurs anae robie Regulation
Mailleret et al. [95] Robust nonlinear adaptive control for bioreactors with unknowm kinetics Regulation
Punal et al. [96] Automatic control of VFA in anaerobic digestion using a fuzzy logic-based approach Regulation
Punal et al. [97] Compared fuzzy logic approaches for automatic control of CH
4
ow rate production and VFA efuent
concentrations in a digestion
Regulation
Ruiz et al. [98] Transient state detection and prediction of organic overload in anaerobic digestion process using statistic tool Regulation
Vanrolleghem et al. [99] Continuity-based interfacing of models for wastewater systems described by Peterson matrices Regulation
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 767
causing denaturation of proteins, interfering with the assimilatory
metabolism of sulphur, etc. [17,100]. Concentrations as low as
0.0030.006mole/l total S or 0.0020.003mole/l H
2
S are reported
to be inhibitory to the micro-organisms [17], other sources
suggest that with a concentration of 150mg/l sulphide stable
methanogenesis can occur [21]. There are authors who claim
that the toxicity should be related to the unionised sulphide
concentration in the pH range of 6.87.2 and to total sulphide
concentration at a pH higher than 7.2 [17,100]. The range of sen-
sitivity of the different anaerobic bacteria follows: fementative-
soSRB acetogensomethanogens.
4.3. Sodium and potassium
Various cationic elements, including Na, K and others, are
found in the digester inuent, where they can be released due to
the degradation of organic material or with compounds added for
pH adjustment [100]. Although they are required for microbial
growth, they can be toxic or inhibitory to the activity of the micro-
organisms when present in high concentrations.
4.3.1. Sodium
The presence of low concentrations of sodium is essential for
the methanogenic bacteria, presumably because it is important
for the formation of ATP or the oxidation of NADH. High
concentrations of sodium, however, inhibit the activity of the
micro-organisms and interfere with their metabolism [100,105].
The level of inhibition depends on the concentration found in the
sludge. Optimal growth conditions of hydrogenotrophic methano-
gens occur at concentrations of 350mg Na
+
/l. Inhibitory effects
start at concentrations between 3500 and 5500mg/l causing a
rather moderate inhibition, whereas a concentration 8800mg/l is
strongly inhibitory to methanogenic bacteria during mesophilic
digestion [100]. If exposed a sufcient period of time, the
anaerobic bacteria can acclimate to the toxic cation and their
activity is not affected signicantly. However, there is a limit for
the micro-organisms to tolerate the high concentrations
[100,106]. The adaptation or acclimation of the methanogenic
bacteria to high concentrations of sodium is apparent when
investigating the optimal sodium concentration in different saline
media. In a medium with a low salt content the optimal
concentration range is in the range 230350mg/l [105]. This fact
is due to the adaptation of the sludge to sodium. VFA-degrading
bacteria have a different resistance to sodium toxicity: it caused
50% inhibition of propionic acid, acetic acid and n-butyric acid
utilising bacteria at concentrations 10,500, 7000, and 19,000mg/l,
respectively [105]. This is in agreement with the results of Liu and
Boone [107], who found that acetate-utilising bacteria are more
susceptible to the toxicity of NaCl than propionate-utilising and
H
2
/CO
2
-utilising micro-organisms.
The simultaneous addition of calcium and potassium in
suitable concentrations was found to be very benecial in
improving the efciency of the anaerobic treatment process by
reducing sodium toxicity to methanogens. For the highest
reduction in sodium toxicity, the cations must be present in or
very close to their optimum concentrations; 326 and 339mg/l of
potassium and calcium, respectively. Potassium and magnesium
were also found to be very effective in reducing the toxicity of
sodium when present in the optimum concentration. However, if
the concentrations of the cations are too far from the optimum,
their effect is irrelevant [100,106,108].
4.3.1.1. Potassium. High concentrations of potassium can lead to
the passive inux of potassium ions, thereby neutralising the
membrane potential [100]. When the concentration of potassium
is below 400mg/l, functioning in both mesophilic and thermo-
philic temperatures ranges are improved. However, higher po-
tassium levels induce an inhibitory effect, especially for the
thermophilic organims [100,109]. It was found that when using
acetate and glucose as substrates together with sludge (in-
oculum), the half maximal inhibitory concentration (IC
50
) for
acetate-utilising bacteria was 0.74mole/l [100]. The bacteria can
exhibit an acclimation effect, which depends on both concentra-
tion of potassium and exposure time. If allowed a sufcient time
of exposure, the anaerobic bacteria can acclimate to the toxic
cation and their activity is not affected signicantly. However,
beyond a certain level of the toxic cation, the bacteria can no
longer tolerate. Sodium, magnesium, ammonium and calcium
were found to be very effective in moderating the toxicity of po-
tassium [109,110]. There are, however, optimal concentrations
that should be respected to accomplish mitigation effects. For
sodium, the optimumwas found to be 564mg/l [111]. Calcium and
sodium should be present at 837 and 379mg/l, respectively [110].
The reader is referred to the literature for more information
about the effects of other cations such as magnesium, calcium
and aluminium [100,109,112], and some overall data are given in
Table 8 below.
4.4. Heavy metals
Industrial contributions are the primary source of heavy
metals in urban wastewater and account for up to 50% of the
total metal content in sewage sludge. Industrial contaminants
include zinc, copper, chromium, nickel, cadmium and lead.
Domestic sources are mainly associated with leaching from
plumbing materials (Cu and Pb), gutters and roofs (Cu and Zn)
and galvanised materials, use of detergents and washing
powders containing Cd, Cu and Zn, and use of body care products
containing Zn. The presence of heavy metals can often
cause difculties in the nitrication/denitrication step of the
wastewater treatment processes due to inhibition [113] and
may hamper the sludge disposal by land application [114].
The behaviour of heavy metals in wastewater and sludge
treatment processes has been widely discussed in literature
[100,109,115120].
Some values of inhibitory concentrations of metals are also
listed in Table 8.
Many enzymes and co-enzymes depend on a minimal amount
of certain traces of metals for their activation and activity. When
present in large amounts, they cause an inhibitory or toxic effect
to micro-organisms. The chemical binding of heavy metals to the
enzymes and subsequent disruption of the enzyme structure and
function are the main cause of this toxic effect [121].
4.5. Hydrogen
Molecular hydrogen is formed during different stages of AD. In
the hydrolysis stage the bacteria produce fatty acids, CO
2
and
hydrogen from carbohydrates. During the acetogenesis, bacteria
(Syntrophobacter wolinii or Syntrophomonas wolfei) produce acet-
ate, CO
2
and hydrogen, or acetate and hydrogen by anaerobic
oxidation of propionate and n-butyrate [21]. In this last stage,
hydrogen can only be formed when it is consumed by methano-
genic bacteria so it does not accumulate (reaction 1). This can also
be achieved by the activity or sulphate reducing bacteria (reaction 2)
via interspecies electron transfer [21]. The hydrogen concentra-
tion can also be decreased in sewage sludge by acetate formation
from CO
2
and H
2
(reaction 3).
Acetogenesis of fatty acids or of other reduced metabolites
may only function if hydrogen does not accumulate but is
ARTICLE IN PRESS
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 768
consumed by methanogens. In sludge digesters, the hydrogen
concentration may be decreased by acetate formation from CO
2
and H
2
.
Several studies determined the effect of hydrogen partial
pressure pH
2
on the production of acetic acid, propionic acid and
butyric acid [122]. Conversions of propionic acid and butyric
acid to acetic acid were found to be thermodynamically possible
only when pH
2
is less than 10
4
for n-butyric acid and 10
5
atm
for propionic acid. They also indicated that when pH
2
is
higher than 10
4
atm, the Gibbs free energy change is larger for
CO
2
reduction than for the acetate cleavage, resulting in a
reduction of CO
2
instead of a acetate cleavage. A decrease in
H
2
concentration allows conversion of acetic acid to methane to
resume [21,122]. The methanogenic and sulphate reducing activity
of the respective micro-organisms is not sufcient to maintain
pH
2
at the required level. However, by reversed electron transport
electrons may be shifted to a lower ORP suitable for proton
reduction [21].
A well-functioning, stable digester has a very low dissolved
hydrogen concentration and converts most of the (organic)
substrate to acetic acid [122].
4.6. Volatile fatty acids
VFA are the most important intermediates in the AD process,
where they are degraded by proton-reducing acetogens in associa-
tion with hydrogen consuming methanogenic bacteria [123].
However, the production of VFA can be toxic to micro-organisms,
especially to methanogens at a concentration of 6.79.0mol/m
3
[124]. These increased concentrations are the result of accumula-
tion due to process imbalances which can be caused by variation in
temperature, organic overloading, toxic compounds, etc. [123]. In
such cases, the methanogens are not able to remove the hydrogen
and volatile organic acids fast enough. As a result the acids
accumulate and the pH decreases to such a low value that the
hydrolysis/acetogenesis can be inhibited [125].
The toxicity is due to an increase in the undissociated form of
the VFA. They can ow freely through the cell membrane where
they dissociate and hence cause a pH reduction and a disruption
of homoeostasis [17].
According to Siegert and Banks [125] the presence of increasing
concentrations of VFA in a batch anaerobic reactor system have a
differential effect on the metabolically distinct phases of hydrolysis,
acidogenesis and biogas production. The tests were conducted on
cellulose and on glucose as primary substrate for digestion.
Independent of the system pH, VFA caused inhibition of the
cellulolytic hydrolysis at concentrations 2g/l, while for glucose a
concentration of more than 4g/l was observed to give the same
effect. The inhibitory effect on the production of biogas was evident
above 6g/l VFA for cellulose and 8g/l for glucose [125].
High concentrations of acetate and propionate inhibit their
own degradation by sludge enrichments. Acetate also non-
competitively inhibits propionate degradation and uncompeti-
tively inhibits benzoate degradation. VFA can enhance the
inhibitory effect of pH on methane production and VFA degrada-
tion in anaerobic digesters [21].
4.7. Long-chain fatty acids
LCFAs are formed during the degradation of fat and lipids and
are further reduced to acetate and hydrogen through b-oxidation
by proton-reducing acetogens [17,126]. LCFAs are known to be
inhibitory at low concentrations, for Gram-positive bacteria, and
not for Gram-negative bacteria [100]. Angelidaki and Ahring [127]
found that 18-C LCFA such as oleic acid and stearic acid are
inhibitory at concentrations 1.0g/l. They also found that the toxic
effect was one of a permanent kind since growth did not reoccur
when the concentrations in the culture were diluted to a non-
inhibitory one.
The mechanism of the LCFA toxicity is caused by adsorption
onto the cell wall or cell membrane, which interferes with the
transport and/or protection functions of the cell [100,126].
Moreover, the sorption of a layer of LCFA to biomass leads to
otation of sludge and sludge washout [100].
Acetoclastic methanogenis bacteria are reported to be more
affected by the LCFA than the hydrogenotrophic methanogens
ARTICLE IN PRESS
Table 8
Critical concentrations for various inhibitors [18,20]
Substance Stimulating concentration (mg/l) Moderately inhibitory concentration (mg/l) Strongly inhibitory concentration (mg/l)
Na
+
35005500 8000
K
+
200400 25004500 12,000
Ca
2+
100200 25004000 8000
Mg
2+
75150 10001500 3000
NH
4
+
15003500 3000
S
2
200 200
Cu
2+
0.5 (soluble)
5070 (total)
Chromium
Cr
6+
3.0 (soluble)
10 200250 (total)
Cr
3+
2.0 (soluble)
180240 (total)
Ni
2+
30 (total)
Zn
2+
1.0 (soluble)
Arseniate and arsenite 40.7
Barium chloride
Cyanide 12 (acclimatisation possible up to 50)
Lead-containing compounds 5
Cadmium-containing compounds
Iron-containing compounds 435
Cupper-containing compounds 1
Potassium chloride 410,000 (acclimatisation possible up to 40,000)
Nickel-containing compounds
Chloride 6000
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 769
[126] and thermophilic bacteria seem to be more sensitive to LCFA
toxicity compared to their mesophilic colleagues. This is possibly
related to the composition of the cell membrane, which is
different for the two species [100].
Angelidaki and Ahring [127] found that LCFAs had a bacter-
icidal effect and that the bacteria showed no sign of adaptation to
the fatty acids toxicity. However, a study performed by Alves et al.
[126] postulated that sludge acclimated with lipids showed a
higher tolerance to oleic acid toxicity (IC
50
137mg/l) compared
with sludge that was fed a non-fat substrate (IC
50
80mg/l). Also,
the biodegradability of oleic acid was improved by this acclima-
tisation with lipids or oleate [126]. Oleic acid (C18:1) is the most
abundant species in LCFA-containing wastewater [128]. Values of
the IC
50
of oleate were obtained from a batch test and ranged from
0.26 to 3.34mM [129]. The authors also found that the oleate
toxicity did not depend upon any of the biological factors (i.e. the
origin of the sludge, the specic acetoclastic methanogenic
activity or the adaptation of sludge to lipids) but it appeared to
be correlated with the specic area of the sludge [129]. This
means that sludge with a high specic area such as suspended
sludge, will be inhibited to a larger extent than granular sludge.
5. Pre-treatment
5.1. Introduction
The AD of biosolids was previously shown to be a valuable
treatment, resulting in reduction of sludge volume, destruction of
pathogenic organisms, a stabilisation of the sludge and production
of an energy-rich biogas. However, the application of AD to bio-
solids were often limited by very long retention times (2030 days)
and a low overall degradation efciency of the organic dry
solids (3050%). Those limiting factors are generally associated
with the hydrolysis stage [14]. During hydrolysis, cell walls
are ruptured and extracellular polymeric substances (EPS) are
degraded resulting in the release of readily available organic
material for the acidogenic micro-organisms. This mechanism is
particularly important in the digestion of sludge, since the major
constituent of its organic fraction are cells, being a relatively
unfavourable substrate for microbial degradation [130]. The cell
envelope of micro-organisms is a semi-rigid structure which
provides sufcient intrinsic strength to protect the cell from
osmotic lysis. Microbial cell walls contain glycan strands cross-
linked by peptide chains, causing resistance to biodegradation.
Several authors, e.g. Refs. [14,130], have indeed identied hydro-
lysis as the rate-limiting step in AD of sewage sludge.
Various sludge disintegration methods have hence been
studied as a pre-treatment: these methods disrupt cell walls
which results in a lysis or disintegration of sludge cells. Slowly
degradable, particulate organic material is converted to low
molecular weight, readily biodegradable compounds, thus by-
passing the rate-limiting hydrolysis stage. Possible pre-treatments
include mechanical, thermal, chemical and biological action, as
reviewed in the present section with their working mechanism
and potential.
The integration of WAS pre-treatment methods in the sludge
cycle has already been shown in Fig. 1.
5.2. Thermal pre-treatment
The heat treatment of waste-activated sludge (WAS) was
shown as early as 1970 [131] to be an effective pre-treatment
method for AD. The sludge is generally subjected to temperature
in the range 1502001C, although lower temperatures have also
been reported. The pressures adjoining these temperatures are in
the range 6002500kPa [132]. Heat applied during thermal
treatment disrupts the chemical bonds of the cell wall and
membrane, thus solubilises the cell components. Various authors
describe the use of thermal pre-treatment for enhancing AD. Their
ndings are reported in Table 9.
All studies report a positive impact of thermal pre-treatment
on AD. The optimum conditions and magnitude of the improve-
ment, however, vary considerably. This is in line with the ndings
of Gavala et al. [143] who concluded that temperature and
duration of the optimum pre-treatment depend on the nature of
the sludge: the greater the proportion of difculty in hydrolysing
biological sludge substances, higher the intensity of pre-treatment
needed. In general, thermal pre-treatment of WAS can consider-
ably increase methane production for mesophilic AD and to a
lesser extent for thermophilic AD, showing that the impact of
preconditioning is more signicant in a low-rate system such as in
a mesophilic digestion. Thermophilic digestion is already more
efcient at VSS reduction and methane production as compared
ARTICLE IN PRESS
Table 9
Overview of thermal pre-treatment studies
Reference Treatment
conditions
Comments
Hiraoka et al.
[133]
601001C Maximum increase in gas production at
601C
Maximum VS reduction at 100 1C (only
510%)
Pinnekamp
[134]
1202201C ODS reduction of 1055% for WAS
ODS reduction from 7% to 34% for primary
sludge
Maximum gas yield for treatment
temperature of 1701C
Positive correlation between gas yield and
treatment temperature
Li and Noike
[135]
621751C Increase of sludge solubilisation ratio by
2545% (optimum at 901C) for WAS
Increase of 30% VSS degradation and of
100% methane production (optimum at
1701C and 60min)
No further improvement for longer
treatment times
Reduction of retention time in digester by
5 days
3060min
Tanaka et al.
[136]
1801C 90% increase of methane production
VSS solubilisation of 30%
60min
Zheng et al.
[137]
2201C 55% VS reduction during digestion
Increase in gas production of 200% during
rst 2 days
Total increase in gas production of 80%
30s
Kim et al. [138] 1211C Increase of VS reduction by 30%
30min
Valo et al.
[139]
1701C 59% increase of TS reduction
92% higher gas production
15min
Ferrer et al.
[140]
701C Studied thermophilic digestion
Positive effect on gas production
Higher temperature (1101341C) did not
have any effect
972h
Climent et al.
[141]
701341C Studied thermophilic digestion
50% increase of biogas production at 701C
(9h)
No effect for high-temperature treatment
90min9h
Bougrier et al.
[142]
1351901C Increased methane production by 25% at
the 1901C treatment
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 770
with mesophilic digestion, and reduced benets of pre-treatment
can be expected.
Some commercial processes were developed based on thermal
pre-treatments. The Norwegian company Cambi developed a
system based on thermal hydrolysis [144]. A solids solubilisation
of approximately 30% was reported (dependant on the type of
sludge being processes) for a 30min treatment at 180 1C. An
associated increase of biogas production by 150% is reported by
the company. A similar thermal treatment is sold as BioThelys
s
by
Kru ger Inc., a subsidiary of Veolia Water.
Evidently, the thermal pre-treatment requires the input of a
considerable amount of heat, since the sludge feedstock needs to
be preheated to the operating temperature (700kJ/m
3
) at the
expense of using some of the biogas produced.
5.3. Mechanical pre-treatment
Mechanical treatment employs several strategies for physically
disintegrating the cells and partly solubilising their content.
The use of a colloid mill (with stationary and rotating disc) for
disrupting microbial cells was rst reported by Harrison [145].
The heating of the suspension by energy dissipation can moreover
enhance the disintegration. The same paper also describes the use
of a high-speed shaker ball mill for sludge disintegration. In the
treatment reactor, moving impellers transfer kinetic energy to
grinding glass beads thereby creating high shear stresses that
break the cell walls. Alternative ball mills using ceramic or steel
beads were also reported. The use on an agitator ball mill was
studied by Kunz et al. [146]. Sludge was pressed through a
cylindrical or conical space by an agitator inducing shear stresses
of sufcient magnitude to break the bacterial cell walls.
One of the most frequently used methods for large-scale
operation is high-pressure homogenisation, compressing the
sludge to 60MPa [145,147]. The compressed suspension is then
depressurised through a valve and projected at high speed against
an impaction ring. The cells are hereby subjected to turbulence,
cavitation and shear stresses, resulting in cell disintegration.
Some studies reporting the effects of these mechanical
methods on AD are summarised in Table 10.
Although less results are available than for the other pre-
treatment methods, it is seen that their efciency of improving AD
of sewage sludge is rather low, compared to the other methods.
Although most techniques consume a lot of power [130], they do
not require the addition of chemicals or heat.
5.4. Chemical pre-treatment
Chemical pre-treatment to enhance the AD treats the sludge to
hydrolyse the cell wall and membrane and thus increase the
solubility of the organic matter contained within the cells. Various
chemical methods have been developed, based on different
operating principles. The major groups are (i) acid and alkaline
(thermal) hydrolysis, (ii) ozonation, and (iii) advanced oxidation
methods. These methods are described hereafter.
5.4.1. Acid and alkaline (thermal) hydrolysis
In (thermo)chemical hydrolysis methods, an acid or base is
added to solubilise the sludge. The addition of acid or base avoids
the necessity of high temperatures and these methods are thus
mostly carried out at ambient or moderate temperatures. An
overview of these methods is presented in Neyens and Baeyens
[153]. Some experimental results are given in Table 11. The
methods are shown to be an effective albeit cumbersome method
for sludge solubilisation since required pH levels are extreme, and
sludge needs subsequently to be re-neutralised. Their use as a pre-
treatment for AD is hence rather limited.
5.4.2. Oxidative sludge pre-treatment
Oxidative waste sludge destruction was rst practised in the
aerobic Zimpro process originally designed as a wet oxidation
method in the USA (1954). This process uses oxygen or air at high
temperatures (2601C) and pressures (10MPa) [159]. An effective
solubilisation of a large part of the sludge was achieved. Problems
ARTICLE IN PRESS
Table 10
Overview of mechanical pre-treatment studies
Reference Method Comments
Rivard and Nagle [148] Shear treatment Increase of TSS degradation by 90%
Choi et al. [149] Mechanical jet (550bar) Increase of soluble protein concentration up to 86% (50 bar)
Increase of VSS removal with 50%
Baier and Schmidheiny [150] Ball mill and cutting mill Increase of 19% in VS degradation
Ball diameter, speed, ball material and sludge concentration are important parameters
Kopp et al. [151] Stirred ball mill, high-pressure
homogenisation, shear gap
homogenisation
Enhancement of biodegradation especially for short times (increase of 100% after 2 days)
Improvement of about 20% after 4 days
Nah et al. [152] Mechanical jet (30bar) Increase of TSS removal efciency by 50%
Table 11
Overview of acid and alkaline thermal hydrolysis pre-treatment studies
Reference Used chemicals Comments
Knezevic et al.
[154]
NaOH No signicant improvement in
VSS reduction
Improved gas production with
increased NaOH dosage
Tanaka et al. [155] NaOH Increase of biogas production
by 20%
Improvement of methane
production of 50%
1301C
Inagaki et al. [156] NaOH Improvement of digestion by
60%
Tanaka and
Kamiyama
[157]
NaOH 60% increase of overall SS
reduction
1301C
Kim et al. [138] NaOH, KOH,
Mg(OH)
2
, Ca(OH)
2
Increase of VS reduction by
30%
Carballa et al.
[158]
CaO No signicant improvement of
anaerobic digestion
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 771
with odour, corrosion and high energy cost however restrict the
practical applications of this process. A modern method using wet
oxidation is the Vertech process, achieving 20% solubilisation and
75% complete oxidation [160].
In the nineties, the Cambi process combined thermal hydro-
lysis with AD to produce a safe, storable and stable product [161].
The most frequent studies oxidative methods are ozonation
and peroxidation, belonging to the advanced oxidation processes
and based on the generation of hydroxyl (OH
d
) radicals which are
extremely powerful oxidants (oxidation potential 2.8V). Due to
the oxidative power, hazardous by-products were not detected
[162].
Ozone (O
3
) is a powerful oxidant which is commonly used for
the disinfection of drinking water and the destruction of
pathogens. The treatment can also be applied to the destruction
of cellular material in WAS. The results of some previous studies
are reported in Table 12.
These radicals are frequently generated using hydrogen
peroxide H
2
O
2
in combination with transition metal salts.
Generally, Fe
2+
-ions are used in combination with H
2
O
2
. This
reaction is referred to as the Fenton peroxidation. A major
drawback of this method is the necessity of bringing the sludge
to a very low pH (optimum at 3). For a complete review of the
chemistry behind this process, the reader is referred to Neyens
and Baeyens [165]. Its application in sludge treatment was studied
by Neyens et al. [166,167]. More recent research uses alternative
peroxidants such as peroxymonosulphate POMS and dimethyl-
dioxirane (DMDO) which do not require stringent reaction
conditions and signicantly increase the biogas production during
the anaerobic treatment of raw secondary sludge [165]. Additional
tests are currently carried out using thickened sludge. Although
oxidative treatments are considered promising, additional research
is needed to avoid extreme reaction conditions in terms of pressures
and temperatures, or pH (Fenton). Advantages, drawbacks and
economics have been described by Neyens et al. [165168].
5.5. Ultrasound
Sonication is no doubt the most powerful method to disrupt
sludge cells. Although cell disintegrations of 100% can be obtained
at high power levels, power consumption then becomes a serious
drawback [130]. The principle of ultrasonic treatment relies on the
induced cavitation process. Through subsequent compression and
expansion of the uid under the effect of the ultrasonic waves,
implosions are generated which give rise to local extreme
conditions (temperatures of several thousands degrees centigrade
and pressures of up to 500bar). The nature of cavitation and the
application of ultrasound in sludge treatment is reviewed by
Dewil et al. [169]. Other references to its use as pre-treatment for
AD are given in Table 13.
Ultrasound treatment units are commercially available in a
wide range of capacities (between 1 and 20kW) and modular lay-
out. Capital costs today are roughly h 20,000/kW, with 1kW
capable of treating sludge from a WWTP of 10,000 p.e. Operation
and maintenance costs are minimal although the ultrasound
probes need replacement every 1.52 years.
The use of ultrasound enhancement has been tested in several
WWTP, ranging from 50,000 to 750,000 p.e. (for a total of nearly
1.5Mp.e.). Improved VS destruction ranged from 40% to 55%,
enhancing the biogas production by about 50%. Improvements
were also found in the dewatering plants, where cake dryness
increased by 5% in spite of using 33% less polymer.
Savings are approximately h1.52/p.e./year. Since the degrada-
tion rate is accelerated, the dimensions of the digesters can
moreover be reduced for a given load, thus reducing the impact of
high capital requirements. A recent paper by Appels et al. [172]
describes the principles, application and tentative economics.
5.6. Bacterial and enzyme hydrolysis
Recently, tests have been conducted on the effect of adding
specic strains of bacteria to the sludge being anaerobically
digested. Although literature is still scarce on the subject, with
major sewage treatment companies not willing to divulge results,
the onset of the research was given by Miah et al. [173] who
measured a 210% enhanced biogas production during thermo-
philic digestion (at 651C) caused by the protease activity of the
Geobacillus sp. strain AT1.
Biological hydrolysis with or without enzyme addition relies
on the enzymatic lysis to crack the cell-wall compounds by an
enzyme catalysed reaction. Analytic processes can be used at
ambient temperatures or external enzyme can be added [174,175].
6. Biogas enrichment, compression and storage
6.1. Perspectives
As produced by digestion, biogas is a clean and environmen-
tally friendly fuel, although it contains only about 5565% of CH
4
.
Other constituents include 3040% of CO
2
, fractions of water
vapour, traces of H
2
S and H
2
, and possibly other contaminants
(e.g. siloxanes).
Without further treatment, it can only be used at the place of
production. There is a great need to increase the energy content of
the biogas, thus making it transportable over larger distances if
economically and energy sensible. Ultimately, the compression
and use of gas cylinders or introduction into the gas network are
targets. This enrichment and enhanced potential of use, can only
be achieved after removing the CO
2
and contaminants. A typical
composition of biogas from sewage sludge AD or landll capture
and natural gas (NG) are shown in Table 14.
The heating value of biogas is determined by the CH
4
content,
with the higher heating value being the energy released when
1Nm
3
of biogas is combusted and the water vapour formed
within combustion is condensed. The lower heating value omits
the vapour condensation.
ARTICLE IN PRESS
Table 12
Overview of ozonation pre-treatment studies
Reference Comments
Weemaes et al. [162] Increase of methane production up to 112%
Increase of COD degradation up to 64%
Battimelli et al. [163] Increase of SS removal by 22%
Goel et al. [164] Increase in TS destruction by 28%
Table 13
Overview of ultrasonic pre-treatment studies
Reference Comments
Shimizu et al. [170] Increased solubilisation ratio up to 80%
Wang et al. [13] Enhancement of digestion by 46% for a 40-min
treatment at 200 W
Neis et al. [171] Enhancement of anaerobic digestion by 42.4% at
intensity of 18W/cm
2
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 772
The methane number describes the gas resistance to knocking
when used in a combustion engine. Methane has per denition a
methane number of 100 and H
2
a methane number of 0. CO
2
increases the methane number because it is a non-combustible
gas with a high knocking resistance. Upgraded biogas, therefore,
has a methane number in excess of 100.
Biogas contains a variety of sulphur compounds, mostly
sulphides, although traces of disulphides and thiols are also
detected. Especially oxidised sulphur (sulphate and sulphite) is
corrosive with the presence of H
2
O. H
2
S itself is reactive with
most metals and the reactivity is enhanced by concentration and
pressure, by the presence of H
2
O and at elevated temperature.
Halogenated compounds are often present in landll gas, but
rarely in biogas from digestion of sewage sludge since, if present,
they would have killed off the digester in the rst place. Siloxanes
are volatile compounds of silicium bound by organic radicals. The
amount of silicium has to be reduced to a minimum, especially in
engine applications.
High concentrations of ammonia are a problem for gas engines,
and normally 100mg/Nm
3
NH
3
can be accepted. The combustion,
however, leads to NO
x
formation.
All biogas plants must be equipped with some kind of lter to
reduce the amount of ne particles in the gas. These lters, with a
25mm mesh size, not only remove particulates, but also reduce
the content of droplets of water or foam.
6.2. Biogas utilisation
Gas is an excellent fuel for a large number of applications and
can ultimately also be used as feedstock for the production of
chemicals. Biogas can more or less be used in all applications that
were developed for natural gas.
There are four basic ways of biogas utilisation, production of
heat and steam, electricity generation/co-generation, use as
vehicle fuel, and (possibly) production of chemicals.
These utilisations are governed by national frameworks like
the tax system, subsidies, green energy certicates and increased
feed-in tariffs for electricity, availability of heat or gas grids.
Worldwide, biogas is mainly used in combined heat and power
(CHP) applications, whereas various EU countries have embarked
on programmes to use a growing portion of the biogas in the
transport sector, especially attractive in view of the steady
increase of the cost of fossil fuels. The various utilisation pathways
are illustrated in Fig. 8.
Conventional gas burners can easily be adjusted to biogas by
changing the air-to-gas ratio. Burning biogas is an established and
reliable technology, with low demands on biogas quality. Pressure
usually has to be between 8 and 25mbar. It is recommended to
reduce the level of H
2
S below 1000ppm to maintain the dew
point at approximately 150 1C.
Biogas is also the ideal fuel for CHP applications. Although gas
turbines could be used (micro-turbines, 25100kW; large turbines,
4100kW) with low emissions, efciencies comparable to spark-
ignition engines and low maintenance, the investments are on the
high side. Mostly internal combustion engines are used in CHP
applications, either as spark-ignition or dual fuel engines. Dual fuel
engines, with, e.g. injection of diesel (X10%) are, although much
less economic, very popular in smaller scales, with good power
efciency (up to 40%). They have high emissions, unless a
treatment of combustion gas is used, but allow easy start-up
by using diesel only (when the biogas production is started).
ARTICLE IN PRESS
Table 14
Composition and parameters from different gas sources [176]
Parameter Unit Landll gas Digestion biogas North Sea NG Dutch NG
Lower heating value MJ/Nm
3
16 23 40 31.6
KWh/Nm
3
4.4 6.5 11 8.8
MJ/kg 12.3 20.2 47 38
Density kg/Nm
3
1.3 1.2 0.84 0.8
Methane number 4130 4135 70
Methane (and variation) vol% 45 (3065) 63 (5370) 87 () 81 ()
Higher hydrocarbons vol% 0 0 12 3.5
Hydrogen vol% 03 0 0
Carbon monoxide vol% 0 0 0 0
Carbon dioxide (and variation) vol% 40 (1550) 47 (3050) 1.2 () 1 ()
Nitrogen (and variation) vol% 15 (540) 0.2 () 0.3 () 14 ()
Oxygen (and variation) vol% 1 (05) 0 () 0 () 0 ()
Hydrogen sulphide (and variation) ppm o100 (0500) o1000 (010
4
) 1.5 (12) ()
Ammonia ppm 5 o100 0
Total chlorine (as Cl

) mg/Nm
3
20200 05 0
Biogas
S-removal S-removal Full Treatment
Reforming
Fuel Cell
Heat
Full Treatment
Power
Boiler
Heat
CHP
Heat Power
Compression
Pressure Tank
Fuel
Fig. 8. Biogas utilisation and required upgrading.
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 773
Spark-ignition engines can be stoichiometric or lean-burn engines,
the latter common for larger sizes and having a higher efciency.
Fuel cells are considered to become the small-scale power plant
of the future, having the potential to reach very high efciencies
(460%) and low emissions. Special interest for biogas is focussed
on hot fuel cells (48001C) where CO
2
does not inhibit the
electrochemical process, but rather serves as a heat carrier. Either
the solid oxide fuel cell, for small applications of a few kW, or the
molten carbonate fuel cells (up to 250kW and more) can be
envisaged.
Gas vehicles can use biogas as fuel [177], provided it is upgraded
to natural gas quality, and application in the same vehicles that use
natural gas (NGVs) becomes possible. At the end of 2005 there
were more than 5 million NGVs in the world. The number of public
transport vehicles driven on gas such as buses and waste trucks is
increasing considerably. Most of the gas driven personal cars are
converted vehicles that have been retro-tted with a gas tank in
the luggage compartment and a gas supply system in addition to
the normal petrol fuel system. Dedicated gas vehicles run at a
better efciency and also allow for more convenient placement of
the gas cylinders without losing luggage space. Gas is stored at
200250bar in pressure vessels made from steel or aluminium
composite materials. Today more than 50 manufacturers world-
wide offer a range of 250 models of commuter, light and heavy
duty vehicles. Gas vehicles have substantial advantages over
vehicles equipped with diesel or petrol engines, since CO
2
emissions are reduced by more than 95%. Emissions of particles
and soot are also drastically reduced. Heavy duty vehicles are
normally converted to run on methane gas only, but in some cases
dual fuel engines can also be used. The dual fuel engine still has the
original diesel injection system and gas is ignited by injection of a
small amount of diesel oil. Dual fuel engines normally require less
engine development and maintain the same driveability as a diesel
vehicle. However, emission values are not as good as for the
corresponding dedicated gas vehicle and the engine technology
remains a compromise between spark ignition and diesel engine.
Beside the close to 100% CO
2
reduction, pure gas engines with
catalytic converters demonstrate far better emission values than
the most modern diesel engines (EURO 4 and 5) tested according to
the European Transient Cycle (ETC) or the Enhanced Environmental
friendly Vehicle (EEV) standard at the EMPA, Switzerland. Stoichio-
metric gas engines with an air-to-fuel ratio of 1 demonstrate a
better emission pattern than lean engines. However, both are far
better than dual fuel engines although at a reduced efciency.
The number of biogas and natural gas lling stations is still
insufcient in Europe and elsewhere in the world, although the
situation is improving enormously with the number of pumping
stations multiplied over the last few years: at the end of 2005
there were 1600 pumping stations in Europe. By the end of 2006
Germany had 1000 stations in operation, Switzerland 100 and
Austria more than 50.
Biogas injection in the gas grid is possible, and various countries
of the EU have proposed standards for injecting upgraded biogas
into the grid to avoid contamination of the grid. These standards
of, e.g. Sweden, Switzerland, Germany and France, x limits for,
e.g. sulphur, oxygen, particles and dew point. Upgrading methods
must allow treated biogas to meet these stringent quality
standards. This upgrading and associated cost outweigh the rising
costs of fossil fuels.
6.3. Biogas upgrading technologies
The major reasons for gas upgrading include the need to full
the requirements of gas appliances (engines, boilers, fuel cells,
vehicles, etc.); to increase the heating value of the biogas; and/or
to standardise the biogas quality. The required quality depends
strongly on the application, as shown in Table 15.
6.3.1. Carbon dioxide removal
Removing CO
2
increases the heating value and leads to a
consistent gas quality, similar to natural gas. When using removal
techniques, it is important to keep methane losses low for
economical and environmental reasons since CH
4
is a greenhouse
gas 21 times stronger than CO
2
[178].
There are different methods of removal, most commonly
performed as absorption or adsorption. Cryogenic separation
would also be possible, albeit expensive. Membrane separation
gains interest [179].
In absorption processes, CO
2
and H
2
S are simultaneously
removed due to the difference in binding forces of the polar CO
2
and H
2
S and the non-polar CH
4
. Water is the most common
solvent for counter-current scrubbing of pre-compressed biogas
(47bar). The design of a water scrubbing system depends on the
solubility of CO
2
, as solubility is governed by pressure, tempera-
ture and pH as given in Table 16: as the pressure increases, the
solubility of CO
2
in water increases; but decreases as the
temperature increases.
After pressure scrubbing, CO
2
and H
2
S are released in a ash
tank, where the pressure is reduced and the temperature possibly
increased. H
2
S, which is released to the air can create an emission
problem. Some of the sulphur accumulates in the water and can
cause problems of fouling or corrosion of piping. It is hence
recommended to separate H
2
S beforehand. Air or vacuum
stripping are seldom used since introducing O
2
in the system.
Results show that 510% of CO
2
remains in the biogas.
Of course, absorption can be nearly complete if Ca(OH)
2
solutions are used to remove both CO
2
and H
2
S, resulting in the
formation of insoluble CaCO
3
and CaS.
Organic solvents such as polyethyleneglycol (Selexol
s
, Geno-
sorb
s
) and alkanol amines (mono-ethanol-amine, or di-ethanol-
amine) can be used to dissolve CO
2
and H
2
S, which are more
soluble than CH
4
in these liquids, and low-pressure operation is
possible. The chemical needs to be regenerated with steam. Only
small amounts of CH
4
are removed. Reductions of CO
2
to
0.51vol% in biogas are possible. The organic solvent removal
units are, however, more expensive than those using water as a
solvent, and suffer from the need to periodically partly discharge,
dispose and replace its solvents.
ARTICLE IN PRESS
Table 15
Required removal of biogas components
Application H
2
S CO
2
H
2
O Traces
Gas heater (boiler) o1000 ppm No No Yes (e.g.
siloxanes)
CHP o1000 ppm No Avoid
condensation
Yes (e.g.
siloxanes)
Vehicle fuel Yes Yes Yes Yes
Gas grid Yes Yes Yes Yes
Table 16
Approximate solubility of CO
2
in water
Pressure
(atmospheric)
Solubility, in kg of CO
2
per kg of water at different temperatures
01C 10 1C 201C 301C
1 0.40 0.25 0.15 0.10
20 3.15 2.15 1.30 0.90
50 7.70 6.95 6.00 4.80
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 774
The removal of CO
2
by pressure swing adsorption on solids such
as activated carbon or molecular sieves is possible. The selectivity
is achieved with different mesh sizes. Various processes are
described in the literature [180182]. Adsorption is generally
accomplished at high temperatures and pressure. It is simple in
design and easy to operate, but is a costly process with high-
pressure drops and high heat requirements. Desorption is
performed by depressurisation or even by using a slight vacuum.
The process needs dry biogas, hence the need to remove the water
vapour as pre-treatment step.
Cryogenic separation can be used since CH
4
has a boiling point
of 1601C at 1atm, whereas CO
2
has a boiling point of 781C.
CO
2
can be removed as liquid by cooling the biogas mixture at
elevated pressure. Until now, this expensive method has only been
tested in pilot plants in Europe and in the USA. More than 97%
pure CH
4
is produced. Investment and operational costs are high
and limit its current application [9].
Membrane separation gains interest [179,183187]. Some
components of the raw gas can be transported through a thin
membrane while others are retained. The transportation of each
component is driven by the difference in partial pressure over the
membrane and is highly dependent on the permeability of the
component in the membrane material [179,188]. For high
methane purity, permeability must be high. Solid membranes
constructed from acetate-cellulose polymer have permeabilities
for CO
2
and H
2
S up to 20 and 60 times the value for CH
4
. However,
high pressures (up to 25bar) are required for the process.
Although the gas ux across the membrane increases proportio-
nately with the pressure difference, thus reduces the size of the
membrane, there is a maximum pressure which the membrane
can withstand. Since some CH
4
passes through the membrane to
the permeate stream, methane losses occur. If the permeate can
be used in a CHP (combined with raw gas), these CH
4
loss can be
recovered.
Additional techniques are under investigation such as the
chemical conversion by e.g. catalytically reacting CO
2
and H
2
to
CH
4
[189]. This process is extremely expensive and the need of H
2
makes the process generally unsuitable. In-situ CH
4
enrichment is
under development [176]. Sludge from the digestion chamber is
counter currently contacted by air. Carbon dioxide that is
dissolved in the sludge is desorbed. The CO
2
-lean sludge is led
back to the digestion chamber where more carbon dioxide can
now dissolve into the sludge, resulting in CH
4
enriched gas in the
chamber. The results from lab scale test in Sweden indicate that it
is technically possible to construct a system that increases the
methane content of the gas to 95% and still keeps the methane
losses below 2% [176].
6.3.2. Removal of water
Biogas is saturated with water vapour when it leaves the
digester. Drying is generally needed or recommended. Refrigera-
tion or sensible pipework design is a common method to
condense the water. In order to reach higher dew points, the gas
can be compressed before cooling.
Adsorption on silica gel or Al
2
O
3
is applied when very low dew
points need to be achieved. An alternative method of drying
biogas can be the absorption in glycol or hygroscopic salts, which
can be recovered at elevated temperatures.
6.3.3. Removal of H
2
S
It should be remembered that appropriate conditioning of
the sludge can limit the H
2
S content present in the biogas [190].
The addition of Fe
3+
-salts to the sludge can indeed produce
insoluble sulphides and reduce the free H
2
S in the biogas to less
than 150ppm (depending on the amount of Fe
3+
added).
An excess of Fe
3+
salts added can however inhibit the biogas
formation.
H
2
S can also be adsorbed on activated carbon [191]. Activated
carbon acts as a catalyst to convert H
2
S into elemental S.
Impregnation with KI is needed. Impregnated-activated carbon
is a common method of removal of H
2
S before upgrading with
PSA.
Micro-organisms, belonging to the Thiobacillus family, can
be used to reduce the level of sulphides in biogas, by oxidising it
mainly to elementary sulphur and some sulphates. These
bacteria are commonly present in the digestion material and thus
do not have to be inoculated. Furthermore, most of them are
autotrophic, which means that they use carbon dioxide from
the biogas as carbon source. Oxygen needs to be added to the
biogas for biological desulphurisation and the level needed
depends on the concentration of hydrogen sulphide, usually
around 26vol% air in biogas. The simplest method for desul-
phurisation is to add oxygen or air directly into the digestion
chamber. With this method, H
2
S level can be reduced by up
to 95% to levels less than 50 ppm, however function of
temperature, place and amount of air added and reaction time.
When adding air into the biogas, safety measures need to be taken
into consideration to avoid overdosing of air in case of a pump
failure. Methane is explosive in the range 515% in air. Biological
desulphurisation can also take place in a separate bio-lter lled
with plastic bodies on which desulphurising micro-organisms are
attached. In the unit up-owing biogas meets a counter ow of
liquid consisting of gas condensate and liquid from efuent slurry
separation or a solution of minerals. Before the biogas enters the
unit, 510vol% air is added. The H
2
S level can be reduced from
30005000ppm to 50100ppm. Ammonia is separated at the
same time [192].
H
2
S can also be reduced by NaOH scrubbing to form Na
2
S of
NaHS, both unsoluble salts.
6.3.4. Removal of trace gases
It was already mentioned that siloxanes can be present in the
biogas. The reduction of their concentration and/or abatement
processes were described in detail by Dewil et al. [193].
The presence of siloxanes in biogas gives rise to some problems
regarding its thermal valorisation [193]. These silicon-containing
compounds are widely used in various industrial processes (e.g.
for replacing organic solvents) and are frequently added to
consumer products (e.g. detergents, personal care products,
etc.). Moreover they are released as a residue in the production
of silicon-containing chemicals. The consumption of siloxanes is
growing steadily, e.g. wet wipes, disposable nappies, etc. A
signicant amount of siloxanes reaches the wastewater and are
not decomposed in a conventional-activated sludge wastewater
treatment plant. Although a large part is volatilised to the
atmosphere during the treatment, a signicant amount is
adsorbed to the sludge ocs.
During the AD of the sludge, siloxanes are released from the
sludge and volatilise due to the breakdown of the organic material
and the elevated temperature in the digester. Therefore the biogas
is enriched with siloxanes. The siloxane concentrations typically
found in biogas are between 30 and 50mg/m
3
with peaks up to
400mg/m
3
in some WWTPs [193]. Only volatile siloxanes are
detected in the biogas. Schweigkoer and Niessner [194] reported
that a only two cyclic siloxanes, i.e. octamethylcyclotetrasiloxane
(D4) and decamethylcyclopentasiloxane (D5), are detected in
signicant amounts.
During the combustion of the biogas, these siloxanes are
converted into a hard and abrasive microcrystalline silica which
ARTICLE IN PRESS
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 775
gradually coats the gas beneciation equipment. The coating leads
to serious motor damage by abrasion of gas motor surfaces, the
overheating of sensitive motor parts (thermal insulator) and by
depressing the function of spark plugs. Moreover, the catalytic gas
exhaust treatment is affected [195]. The crystalline sand moreover
accumulates in lubricant oil and coats turbine surfaces. For the
biogas of Trecatti (UK), the presence of up to 400mg/m
3
of volatile
siloxanes led to a major engine failure within 200h of operation
[196]. The problem is moreover enhanced by the use of efcient
spark-ignition engines which are fast running, operate at high
temperature and use biogas only. Previous dual fuel engines (slow,
low temperature, with fuel oil to aid ignition) were less prone to
silica deposits. Illustration of the silica fouling on the pistons of an
engine is shown in Fig. 9.
Although it is difcult to measure the concentration of
siloxanes in sludge and biogas, a recent testing of analytical
methods revealed that extraction followed by GCMS was an
adequate method [197].
All the currently used treatment techniques are end-of-pipe
and remove siloxanes from the biogas. The most frequently
used method for removing siloxanes is the adsorption on
activated carbon. Since biogas contains a broad range of
compounds (H
2
S, siloxanes, organics) with concentrations cover-
ing several orders of magnitude, a competitive adsorption of
siloxanes and a variety of trace compounds must be considered
leading to large adsorption capacities needed for the target silicon
compounds when using adsorbent materials in biogas pre-
treatment [194]. Active sites of the adsorbent will retain water
vapour and other pollutants, thus decreasing adsorbent life [198].
Moreover the adsorbent beds have to be replaced regularly
because siloxanes are difcult to desorb from the material. At
Trecatti (UK) for example, a weekly change of activated carbon is
necessary, with a 1-day downtime at the adsorber and a cost of
nearly h 2000 per change.
Other possible adsorbents are molecular sieves and polymer
pellets. Schweigkoer and Niessner [194] made a comparative
study of adsorption materials using polymer beads, silica gel and
activated carbon, which all exhibited large adsorption capacities
for the siloxane D5. Especially silica gel seemed to be promising
and a highly cost-effective candidate, since this can be used
simultaneously for biogas drying.
Absorption in non-volatile organic solvents has also been
reported in both spray and packed columns (e.g. with Raschig
rings). A major drawback of this gas pre-treatment method is the
fact that complete siloxane elimination is difcult to obtain since
the highly volatile siloxanes are easily stripped from the solvent at
elevated gas ow rates. This problem does not arise if the
siloxanes are chemically absorbed, i.e. they are converted to
compounds of low volatility [194].
The cryogenic condensation of the siloxanes from the gas is a
feasible, but an expensive alternative. When the temperature of the
biogas is decreased, a condensate is formed which contains part of
the siloxanes that are present. Schweigkoer and Niessner [194]
studied the removal efciency when the biogas was cooled to 51C.
Over 88% of the initial siloxane concentrations were still present in
both landll and digester gas. Hagmann et al. [195] reported a
cleanup efciency for a range of volatile siloxanes of 25.9% when
cooling to 251C, and of 99.3% when freezing to 701C.
A nal reported method for removing siloxanes from biogas is
chemical abatement. The caustic- or acidic-catalysed hydrolysis of
the siliconoxygen bond seems to be useful. The high stability of
these compounds, however, requires high or lowpH-values and/or
high temperatures [199]. Sulphuric, nitric and phosphoric acid
were reported [194] as well as sodium hydroxide [199]. The
removal efciencies of these methods are, however, rather low.
Recently, Appels et al. [200] reported the potential of partly
removing siloxanes from the sludge phase by using a peroxidative
treatment.
6.4. Biogas compression and storage
Compressing the biogas reduces the storage requirements,
concentrates the energy content and increases the pressure to a
level overcoming pressure drops in subsequent techniques or
pipelines. Although various studies have been published [201204],
there is still no large-scale application. In general, the biogas
storage options, summarised in Table 17, are presented [205].
ARTICLE IN PRESS
Fig. 9. Fouling of engine pistons by silica.
L. Appels et al. / Progress in Energy and Combustion Science 34 (2008) 755781 776
7. Operation, maintenance and troubleshooting of digesters
ADs operate in a stable way if solids levels and the alkalinity/
acid ratio are controlled. They have large inertia, even at 12 days.
The routine operation needs adequate maintenance and
repairs, cleaning and start-up/shutdown procedures.
A very detailed account for operations, troubleshooting and
control has been published by EPA [206] and summarised by
Qasim [7]. The reader is referred to this extensive summary, which
deals with: (i) digester start-up, involving the start-up sequence
and actions needed to achieve stable digestion condition,
(ii) common operational problems and troubleshooting in the
event of occurring instabilities such as increases in CO
2
or pH,
poor supernatant quality and foam, faulty temperature or mixing,
consistency of the digester sludge, occurrence of a scum blanket,
etc., (iii) routine operation and maintenance with a monitoring
programme, a routine maintenance and operator checklist, and
(iv) some specications and descriptions of the main components
such as digester cover, mixing and heaters.
8. Conclusions and recommendations
AD is a complex process which requires strict anaerobic
conditions to proceed, and depends on the coordinated activity
of a complex microbial association to transform organic material
into mostly carbon dioxide (CO
2
) and methane (CH
4
). Despite the
occurrence of successive steps, hydrolysis is generally considered
as rate-limiting. Within the anaerobic environment, various
important parameters affect the rates of the different steps of
the digestion process, i.e. pH and alkalinity, temperature, and
retention times. These parameters are assessed in Section 2 of the
paper, together with the various types of anaerobic digesters used.
The design is commonly based upon a population basis, using a
volumetric solids loading or solids retention time, or on the basis
of a required volatile solids reduction. Empirical design data are
included. The methane generation rate can be estimated from
kinetic equations.
An appropriate tank design (size, shape, covering), mixing and
heating are needed to optimise the operation.
The optimisation of the AD and the assessment of its operation
in function of varying feed or operating conditions are important
objectives and can be pursued by using appropriate digestion
models, reviewed in Section 3. These models are generally of the
steady-state type and allow (i) to estimate retention time, reactor
volume, gas production and composition for a requested system
performance, (ii) to investigate the sensitivity of the system
performance to various parameters, (iii) to provide cross-checking
of simulation results and plant performance, and (iv) to determine
how the digestion process can affect the design of upstream or
downstream WWTP operations.
The number of models presented in literature is extensive, and
often of very specic nature. The most frequently used model,
ADM1, developed by the IWA forms a good basis and is often used
in expanded models, as proposed by, e.g. So temann et al.
The previously mentioned models, and their validation, stress
the importance of monitoring essential parameters during diges-
tion. These essential parameters include pH, alkalinity, VFA and
biogas ow rate and composition. Again literature data are
extensive and the quoted references illustrate the trend used in
the monitoring and controling digestion plants.
Inhibiting compounds are either already present in the
digester substrate or are generated during digestion. Section 4
reviewed the most commonly encountered inhibitors including
ammonia, sulphide, sodium and potassium, heavy metals, hydro-
gen, VFA and LCFA.
Limiting factors in AD are generally associated with the
hydrolysis stage. During hydrolysis, cell walls are ruptured and
extracellular polymeric substances (EPS) are degraded resulting in
the release of readily available organic material for the acidogenic
micro-organisms. Various sludge disintegration methods have
been studied as a pre-treatment and are discussed in Section 5.
These methods include mechanical, thermal, chemical and
biological action, as reviewed with their working mechanism
and potential.
Biogas enrichment, compression and storage was dealt with in
Section 6, which also deals with one of the emerging problems
related to the energetic valorisation of the biogas, i.e. the presence
of siloxanes. Only volatile siloxanes are posing a problem. All the
currently used treatment techniques are end of pipe and remove
siloxanes from the biogas. The most frequently used method for
removing siloxanes is the adsorption on activated carbon.
As produced by digestion, biogas is a clean and environmen-
tally friendly fuel, although it contains only about 5565% of CH
4
.
Other constituents include 3040% of CO
2
, fractions of water
vapour, traces of H
2
S and H
2
, and possibly other contaminants
(e.g. siloxanes).
Without further treatment, it can only be used at the place of
production. There is a great need to increase the energy content of
the biogas, thus making it transportable over larger distances.
Ultimately, compression and use of gas cylinders or introduction
into the gas network are targets. This enrichment and enhanced
potential of use can only be achieved after removing the CO
2
and
contaminants. The basic ways of biogas utilisation in the
production of heat and steam, the electricity generation/co-
generation, and as vehicle fuel were included in the discussion,
each with required upgrading needs and applicable techniques.
The routine operation of digesters needs adequate mainte-
nance and repairs, cleaning and start-up/shutdown procedures. A
very detailed account for operations, troubleshooting and control
has been previously published. Section 7 referred the reader to
these extensive summaries.
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ARTICLE IN PRESS
Table 17
Most commonly used biogas storage options [205]
Pressure Storage device Material
Low (0.140.41bar) Water sealed gas holder Steel
Low Gas bag Rubber, plastic, vinyl
Medium (1.051.97bar) Propane or butane tank Steel
High (200bar) Commercial gas cylinders Alloy
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