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Reviews in Environmental Science and Bio/Technology (2006) 5:93114  Springer 2006

DOI 10.1007/s11157-005-2754-6

Treatment of biogas produced in anaerobic reactors for domestic


wastewater: odor control and energy/resource recovery

Adalberto Noyola1,*, Juan Manuel Morgan-Sagastume1 & Jorge E. Lopez-Hernandez2


1
Instituto de Ingeniera, UNAM, Circuito Escolar, Ciudad Universitaria, Coyoacan, 04510, Mexico D.F.,
Mexico; 2IBTech, Av. Aztecas 479, Col. Ajusco, Coyoacan, 04300, Mexico D.F., Mexico; (*author for
correspondence: e-mail: noyola@pumas.iingen.unam.mx; phone: +52-55-56233662; fax: +52-55-56162798)

Key words: anaerobic sewage treatment, biogas, biogas utilization, denitrication, hydrogen sulde, Kyoto
protocol, methane, odor control

Abstract
Anaerobic municipal wastewater treatment in developing countries has important potential applications
considering their huge lack of sanitation infrastructure and their advantageous climatic conditions. At
present, among the obstacles that this technology encounters, odor control and biogas utilization or
disposal should be properly addressed. In fact, in most of small and medium size anaerobic municipal
treatment plants, biogas is just vented, transferring pollution from water to the atmosphere, contributing
to the greenhouse gas inventory. Anaerobic municipal sewage treatment should not be considered as an
energy producer, unless a signicant wastewater ow is treated. In these cases, more than half of the
methane produced is dissolved and lost in the euent so yield values will be between 0.08 and 0.18 N m3
CH4/kg COD removed. Diverse technologies for odor control and biogas cleaning are currently avail-
able. High pollutant concentrations may be treated with physical-chemical methods, while biological
processes are used mainly for odor control to prevent negative impacts on the treatment facilities or
nearby areas. In general terms, biogas treatment is accomplished by physico-chemical methods, scrubbing
being extensively used for H2S and CO2 removal. However, dilution (venting) has been an extensive
disposal method in some small- and medium-size anaerobic plants treating municipal wastewaters. Simple
technologies, such as biolters, should be developed in order to avoid this practice, matching with the
simplicity of anaerobic wastewater treatment processes. In any case, design and specication of biogas
handling system should consider safety standards. Resource recovery can be added to anaerobic sewage
treatment if methane is used as electron donor for denitrication and nitrogen control purposes. This
would result in a reduction of operational cost and in an additional advantage for the application of
anaerobic sewage treatment. In developing countries, biogas conversion to energy may apply for the
clean development mechanism (CDM) of the Kyoto Protocol. This would increase the economic feasi-
bility of the project through the marketing of certied emission reductions (CERs).

1. Introduction of its main drawbacks bad odor has not been


properly controlled in many anaerobic digestion
Among the well-known advantages of anaerobic facilities. This general diagnostic is particularly
digestion low energy requirements, limited pro- accurate in the case of the anaerobic treatment
duction of sludge and biogas generation the of domestic wastewater. Additionally, in most of
latter is far from being exploited. Moreover, one the small anaerobic municipal treatment plants
94

biogas is just vented, transferring pollution from Practical aspects for biogas handling and utiliza-
water to the atmosphere and contributing to the tion are also briey presented.
greenhouse gas inventory.
At present, modern anaerobic technologies
are widely applied for industrial wastewater 2. Biogas in anaerobic municipal wastewater
treatment; however, their applications for treatment
domestic and municipal sewage treatment are
still very limited. Developing countries, many in Biogas is a mixture of gases produced during the
warm climate regions, have an enormous lack anaerobic digestion of organic matter. It is gener-
of sanitation facilities, so there is a huge poten- ally composed of 6065% methane (CH4) and
tial application of anaerobic sewage treatment, 3540% carbon dioxide (CO2). Minor constitu-
considering its low-operational and maintenance ents are hydrogen sulde (H2S), nitrogen (N2),
costs and its matching with sustainability crite- hydrogen (H2) and traces of oxygen (O2), carbon
ria (Noyola 2004). In order to favor a wider monoxide (CO), ammonia (NH3), argon (Ar2)
adoption of anaerobic processes and to get this and other volatile organic compounds (VOC)
potentiality into the real world, odor control (Constant et al. 1989). The composition of
and biogas utilization should be properly biogas will depend on the type and concentration
addressed. of organic matter to be digested, on the physico-
Domestic wastewaters are not well suited for chemical conditions in the digester (pH, alkalin-
conventional anaerobic treatment. The low ity, temperature) and on the presence of other
organic matter concentration and ambient anions such as sulfates and nitrates.
temperature must be handled with modern Some important properties of biogas as a fuel
technologies, such as the upow anaerobic sludge (considering a 60% CH4 content) are (Constant
blanket reactor (UASB) and anaerobic xed lm et al. 1989): minimal caloric value of 21.5 MJ/
reactors. However, typical COD content in m3, stoechiometric air to fuel ratio of 5.71, ame
sewage will still produce a low amount of biogas velocity of 25 cm/s, minimum auto-ignite temper-
and water temperatures below 20C will seriously ature of 600C, ammable biogas to air mixture
limit the application of the process. On the other between 8.3 and 20% (512% CH4 in air
hand, odors will be there, due to some end mixture); biogas will not burn if more than 75%
products of the anaerobic digestion, such as of CO2 is present. Methane is lighter than air
suldes. In some places, where water supply is (gas density of methane is 0.55 relative to air),
rich in sulfates, the entire sewage system will be a so in case of leaks, it will not remain on the
source of odors. ground and will migrate to upper spaces. Table 1
In this paper, treatment methods for biogas presents an energy comparison of methane,
conditioning and odor control are reviewed. biogas and other common fuels.

Table 1. Minimum caloric values of biogas and other fuels and equivalence to methane (after Constant et al. 1989)

Fuel MJ/kg MJ/N m3 MBTU/Nm3 Volumetric equivalence to CH4

Methane 50.0 35.9 0.0340 1


Puried biogas (90%) 45.0 32.3 0.0306 0.9
Biogas (60%) 30.0 21.5 0.0203 0.6
Butane 45.7 118.5 0.1123 3.3
Propane 46.4 90.9 0.08617 2.5
Methanol 19.9 15.9  103 15.0732 442.9
Ethanol 26.9 21.4  103 20.2872 596.1
Gasoline 45.0 33.3  103 31.5684 927.6
Diesel 42.1 34.5  103 32.7060 961.0

Nm3: volume at normal temperature and pressure: 273K and 1 atm.


MBTU: Mega British Thermal Unities.
95

This general biogas composition changes Volatile compounds responsible for unpleas-
when a diluted wastewater, such as domestic ant or aggressive odors in sewage works and
sewage, is treated. Anaerobic digestion of domes- treatment facilities are produced mainly by
tic wastewater will produce a mixture of methane microbial mediated organic matter decay.
(7080%), nitrogen (1025%) and carbon Many of the malodorous compounds are per-
dioxide (510%) greatly inuenced by the ceived at very low concentrations, of the order
operational temperature (Noyola et al. 1988). of parts per trillion. Carlson & Leiser (1966)
The high nitrogen fraction in biogas produced classied bad odors according to the following
from domestic wastewaters is due to the N2 categories:
dissolved in the sewage; once in the anaerobic (a) inorganic gases such as hydrogen sulde
reactor, it is stripped to the gaseous phase. (H2S) and ammonia (NH3),
Moreover, low substrate means low methane (b) organic acidic compounds such as acetic,
production. In fact, as previously mentioned, propionic, butyric and lactic acids,
anaerobic municipal sewage treatment should not (c) highly toxic compounds such as skatole, phe-
be considered as an energy producer, unless a nols and mercaptans,
signicant wastewater ow is treated. Actual (d) amines such as cadaverine and putrescine.
methane yields are well below the theoretical va- Hydrogen sulde is produced in an anaero-
lue (0.35 N m3/kg COD removed; Nm3 means bic environment mainly by sulfate reduction.
volume at normal temperature and pressure: Sulfates may be present in municipal sewage
273K and 1 atm); more than half of the methane due to collection of industrial wastes rich in this
produced is dissolved and lost in the euent and anion (usually added as sulfuric acid in the pro-
a fraction of COD, depending on the raw waste duction process) or to natural content in water
sulfate concentration, would be used by the sul- supply.
fate reducing bacteria. The expected methane Odorous organic compounds that has been
yield will thus depend on COD and sulfate con- found in wastewater treatment plants are carbon
centrations in the sewage, as well as on water tem- oxysulde (COS), carbon disulde (CS2),
perature; at higher temperature, less methane will mercaptanes of low molecular weight (R-SH),
be dissolved, as stated by Henrys law constants. thiophenes (C4H4S), dimethylsulde ((CH3)2S),
As a result, methane yields values for anaerobic dimethyldisulde ((CH3)2S2) and dimethyltrisul-
sewage treatment will be between 0.08 and de ((CH3)2S3) (Allen & Phatak 1993). Other
0.18 Nm3/kg COD removed (Noyola et al. 1988). odorous molecules include mercaptans, ammonia,
inorganic and organic amines, organic acids,
aldehydes and ketones. In this environment, H2S
3. Odor and hydrogen sulde generation possesses such characteristic odor that it generally
in anaerobic wastewater treatment masks the scent of other organic sulde
compounds (Bhatia 1978; Smet & Van Langenho-
Odor can be dened as a stimulus of olfactory ve 1998). For this reason, H2S is the most charac-
cells in the presence of specic compounds teristic bad odor constituent in biogas and in the
including volatile organic compounds (VOCs) environment of anaerobic digesters and wastewa-
and volatile inorganic compounds (VICs). In ter treatment facilities in general (Carlson &
general, the most common odor problems are Leiser 1966; Cho et al. 1992; Allen & Phatak
caused by mixtures of low concentrations of 1993; Fernandez-Polanco et al. 1996; Martnez &
highly volatile compounds with very low Zamorano 1996; Metcalf & Eddy 2003). In fact,
threshold detection limits in air. Many industry many research works on odor control consider
branches produce gases which contain odorous H2S as the reference compound.
VOCs or VICs. Those gases can be generated in Hydrogen sulde is also an important hazard-
process industries as synthetic avoring, paint ous compound with the following characteristics:
and dye, paper mills, pharmaceuticals, reneries, Inammable and poisonous gas, perceived in air
slaughterhouses, yeast and alcohol factories, at concentrations of 0.020.13 ppmv. It is a high-
sewage treatment works, solid waste composting ly toxic gas and it can be lethal. Exposure of
works etc (Mukhopadhyay & Moretti 1993). human beings to low H2S concentrations can
96

cause headaches, nausea and irritation of eyes 4. Available treatment options for biogas
and throat as well as rhinitis, Keratoconjuntivitis, treatment and odor control
photophobia, intense cough and bronchopneumo-
nia. High concentrations can cause paralysis of A general classication of common technologies
the breathing system, loss of knowledge and applied for VOC, H2S and odor control is
death. Exposition of few minutes to H2S concen- presented in Figure 1. Some of them are also used
trations exceeding 0.2% (2000 ppmv) can be le- for CO2 removal as its separation may be accom-
thal to human beings. H2S is a corrosive plished together with H2S (absorption, adsorption
compound and attacks dierent materials (iron, and membrane technologies). This classication is
copper, cement etc.) as well as harmful to vegeta- based on the nature of each control technology,
tion in general (Merck 1996). that is, physical, chemical or biological. Generally,
The concentrations of H2S found in treat- physical processes are mostly applied for gas
ment plants can vary considerably depending streams where the ow and pollutant concentra-
on the type of processes involved and on the tion are high. Important parameters for a proper
characteristics of the wastewater. In this sense, application of a biological treatment are the solu-
Rands et al. (1981) found H2S concentrations bility and the biodegradability of the compounds
in municipal treatment works between 45 and to be removed. The most important advantage of
537 ppmv and up to 1000 ppmv in the biogas biological treatment methods over physical and
from anaerobic sludge digesters. On the other chemical technologies is the fact that biological
hand, Pomeroy (1982), Lang & Jager (1992) processes can be operated at local temperature and
and Webster et al. (1996) reported concentra- pressure. Biological purication facilities are inex-
tions of H2S between 0.1 and 10 ppmv. Other pensive compared with most of the physical-chem-
compounds associated with odors in wastewater ical treatments and also are ecologically cleaner.
facilities are dimethylsulde and methyl mercap- However, to make a good selection of a treatment
tan. Cho et al. (1992) and Allen & Phatak method, ow rate, type of pollutant and its con-
(1993) found these VOCs at concentrations centration must be considered. Other important
between 5 and 40 ppmv. factors that determine the selection are tempera-
Hydrogen sulde is a highly soluble gas ture, oxygen content of the waste gas, stream com-
(Henrys constant: 2582 mLgas/(Lwater atm) at position, solubility, production time pattern, and
20 C) that dissociates in water according to the investment and maintenance requirements. The
following equilibrium reactions: occurrence of secondary environmental impacts
and pollution transfer must be evaluated too.
H2 S(gas) " !H2 S(liq.) 1 Some technologies mentioned in Figure 1 may
be useful for biogas treatment; others are suitable
H2 S(liq.) !HS H Ka 1 1  107 pKa 7:0 for odor control. Figure 2 shows the common
application of each type of technology based on
2 pollutant concentration and air or gas ow. As
can be observed, for high pollutant concentra-
HS !S2 H Ka2 1:3  1013 pKa 12:9 tions physical-chemical processes are preferred
instead of biological ones. In general terms,
3 biogas treatment is accomplished by physico-
chemical methods, while biological processes are
Odor problems associated with H2S are thus used basically for odor control as a mitigation
highly dependent on the wastewater pH. When technology to prevent negative impacts on the
the pH is under 5, practically all suldes are as treatment facilities or nearby areas. Biological
H2S and in physical equilibrium with the gas methods are usually used when the concentration
phase; at pH 10, suldes are dissolved as HS). of odorous compounds are low and susceptible
At pH around 7, the common operational value to be treated aerobically.
in anaerobic wastewater treatment, H2S and HS) An economic comparison between several
will be present in solution close to an equal ratio options for control of gaseous emissions is
(50% for each). presented in Table 2.
97

Figure 1. Classication of common technologies for VOC and odor control (after Revah & Morgan-Sagastume 2005).

Figure 2. Applicability of various gaseous pollution control technologies based on gas ow rates and concentrations to be treated
(adapted from van Groenestijn & Hesselink 1993).
98

Table 2. Cost comparison for some common gaseous treat- 4.1.3. Membranes
ment for odor control (Revah & Noyola 1996) VOCs may be removed from gas streams by
Treatment option Cost USD/m3 semi-permeable membranes (Kennes et al. 2001;
Mukhopadhya & Moretti 1993). This barrier is
Biolter 0.13.0 made of synthetic polymers wrapped around a
Bioscrubber 1.53.0 perforated central collection pipe. The driving
Chemical scrubber 0.612 force for the gas ow is the pressure gradient
Combustion 1.515 across the membrane using a vacuum pump. In
Catalytic treatment 1.512
odor control applications, membrane is perme-
able to VOCs but not air, therefore, the polluting
compounds pass through the membrane while
4.1. Physical-chemical methods the puried air stream is released to the atmo-
sphere. Membranes made of acetate and cellulose
4.1.1. Dilution have been used for biogas cleaning, as they may
Dilution can occur by the addition of sucient separate both CO2 and H2S from methane, but
fresh air to reduce the odor concentration below pressures higher than 25 bars should be applied.
the threshold level (Corbitt 1990). This is useful
in certain applications to reduce explosion risk. 4.1.4. UV oxidation
Tall stacks and heated gas streams have been Ultraviolet (UV) radiation is a process that is
successfully used by the industry for dilution of based on the transfer of electromagnetic energy
large volumes of gases by plume dispersion. The from a source (lamp) to the organic matter
stack systems may be used for low concentra- (Kennes et al. 2001; Mukhopadhya & Moretti
tions of odor and can be a second-stage system 1993; Qasim 1999). This is an emerging technol-
following another control method. Dilution ogy for the control of VOCs that uses oxygen
cannot be considered as a treatment method, based oxidants like ozone, peroxide, OH), and
since pollution remains without treatment. O2) radicals to convert VOCs into CO2 and H2O
However, dilution has been an extensive method in the presence of ultraviolet light, enhancing the
in anaerobic plants treating municipal wastewa- activity of oxygen-based oxidants. The primary
ters and where the size of the plant and its source of UV energy is the low pressure mercury
economical situation do not allow a proper lamp. It is almost universally accepted as the
treatment method for biogas treatment. Simple most ecient and eective source of UV radia-
technologies should be developed in order to tion. The lamps are tubes, typically 0.751.5 m in
avoid this practice. length and 1.52.0 m in diameter. Approximately
3540% of the energy is converted to light, and
4.1.2. Condensation approximately 85% of light has a wavelength of
Condensation can occur by lowering the gas 253.7 nm.
stream temperature at constant pressure or
increasing the gas stream pressure at constant 4.1.5. Plasma
temperature (Planker 1998; Waldrop 1998; Plasma is a mixture of free moving electrons and
Kennes et al. 2001; Bell, 1988). It is generally positively charged ions (Van Groenestijn 2001b).
applied to treat euent streams consisting of a Non-thermal plasmas are an excellent source of
condensable pollutant vapor and a noncondens- gas phase free radicals (O2), OH) and H+) and
able gas. There are basically two types of other active species useful for destroying pollu-
condensers: surface and direct contact. Surface tants. Reactive species in non-thermal plasma
condensers are generally shell and tube heat such as OH) radicals, O3 molecules, and O and N
exchangers where coolant ows inside the tubes atoms can react with odorous and toxic gases and
and the gas stream with VOCs ows outside the convert them into non-odorous and non-toxic
tubes. Contact condensers operate by spraying a molecules. Plasma can be generated in a medium
cool liquid directly into a gas stream to cool and between two electrodes where a high voltage AC
condense the VOCs. (1030 kV) is applied for a very short time
99

(110 ms). The plasmas can be generated by


dielectric barrier discharge or an electron beam.
Dielectric barrier discharge, also called corona
discharge, utilizes a dielectric material between
the discharge gap and one of the two discharge
electrodes used. On the other hand, the electron
beam technology is based on an electron gun that
shoots high energetic electrons to a target object.
The use of non-thermal plasmas for gas pollution
treatment has high-potential application, but is
still in its early stages of research and develop-
ment. Plasma technology can be classied as an
electro-chemical process.

4.1.6. Adsorption
Adsorption refers to the process where gaseous
VOC molecules contact the surface of a solid
adsorbent and bond via weak intermolecular Figure 3. Schematic view of a general scrubber system.
forces (Kennes et al. 2001; Mukhopadhya &
Moretti 1993; Smet & Van Langenhove 1998).
Activated carbon is the most common adsorbent 4.1.7.1. Caustic scrubbing. Absorption is favored
in use today for VOC treatment. Others include by highly alkaline conditions (Manseld et al.
silica gel, alumina and zeolite. They are 1992). A gas stream containing the pollutant is
activated by heat under controlled conditions at fed to an absorption tower with high alkalinity
high temperatures to remove volatile non-carbon (i.e., NaOH 50% by weight, pH >12). The
constituents and increase the surface area. absorbent is not regenerated in this process
Several types of carbon adsorption units are which requires high reagent consumption and a
commercially available, but the most common is proper nal disposal of the spent solution.
the xed regenerative bed. It has two or more
beds (columns) of activated carbon working in 4.1.7.2. Regenerative gas scrubbing. As an exam-
parallel. Continuous system operation is possible ple of this process, H2S removal may be accom-
by the concurrent adsorption by at least one bed plished according to the following reaction (Smet
and desorption by the other beds. Adsorbent & Van Langenhove 1998; West 1983):
regeneration is accomplished by volatilization of R2 NH H2 !R2 NH2 HS heat 4
the adsorbed compounds either by increased
temperature with steam or by lowering the bed There are dierent types of absorbents which are
pressure. Activated carbon has been used for acids or bases. During H2S scrubbing process, H2S
CO2 and H2S removal from biogas. as well as CO2 are discharged as exhaust product,
so additional treatment processes would be needed
4.1.7. Scrubbing before nal disposal. The heat produced by the
In a scrubber, transfer of pollutants from a gas exothermic reaction during the absorption step is
stream to an aqueous phase is accomplished by used to preheat the absorbent in the desorption
intense contacting of the polluted gas with water step. Usually, the absorption tower works at low
or an absorbent solution within a packed col- or ambient temperature to favor solubilization
umn (Figure 3). Mass transfer depends on the while desorption is favored at higher tempera-
concentration, the air/water partitioning (Henry tures. By this means, the absorbent can be
law) coecient and the mass transfer resistance regenerated. Absorbants commonly used include
of the scrubber system. Scrubbing has been used mono-ethanolamine, di-ethanolamine, di-glycol-
extensively for H2S and CO2 removal from the amine, methyl-di-ethanolamine, di-isopropanol-
biogas prior to its use. Some specic absorbent amine, hot potassium carbonate, methanol,
compositions are presented: propylene carbonate, N-methyl-2-pyrrolidone.
100

4.1.7.3. Chemical precipitation with FeCl2. The 3H2 S 8KMnO4 ! 8MnO2 3K2 SO4 2H2 O
H2S contained in the gas stream is absorbed in a 2KOH at pH > 7:5 11
scrubber with a solution of FeCl2 and the
dissolved H2S is precipitated as FeS according
with the following reaction (Sarner 1990): 4.1.7.7. Hydrogen peroxide oxidation. The oxida-
tion rate of sulde with hydrogen peroxide is rel-
Fe
2 H2 S ! FeS 2H

5
atively slow (Cadena & Peters 1988). Twenty to
The Fe+2 is not regenerated during the process 30 min contact time is normally required for a
which means considerable reagent consumption. complete reaction. The mechanisms of oxidation
of H2S by hydrogen peroxide are not well under-
4.1.7.4. Chlorine oxidation. After H2S has been
stood; however, it is suggested that direct oxida-
absorbed in a scrubbing tower, it may be oxi-
tion of sulde by hydrogen peroxide depends on
dized with sodium hypochlorite to produce either
the reaction with oxygen released during gradual
elemental sulfur or sulfate, depending on pH,
decomposition of hydrogen peroxide. H2S must
according to the following reactions (Cadena &
be dissolved in water (scrubbing tower) prior to
Peters 1988):
its oxidation.
HS OCl ! S0 OH Cl at pH<7:5 6
H2 O2 H2 S ! S0 2H2 O at pH<8:5 12
  
HS 4OCl ! SO2
4 H 4Cl at pH > 7:5
7 2H2 O2 S2 ! SO2
2 2H2 O at pH > 8:5
13
Chlorine is not regenerated in the process, so it
may result in a high operational cost. Moreover,
in the presence of organic compounds, chlorine 4.1.8. Catalytic oxidation with Fe3+
oxidation is not attractive due to the formation (LO-CAT process)
of undesirable organic chloride compounds. In this patented process, ferric and ferrous ions
are chelated with EDTA to avoid precipitation
4.1.7.5. Ozone oxidation. H2S or VOCs are dis-
as FeOH or FeS (Thomson 1980). This allows
solved in water within a scrubbing tower and then
the ferric ion regeneration using air (O2) so H2S
they are oxidized by ozone (Chen & Morris 1972).
oxidation and reagent regeneration are simulta-
The sulfur oxidation is practically instantaneous
neous in two dierent columns.
and due to ozone instability in situ generation is
required. Ozone is a powerful oxidant but is H2 S 2Fe3  ! S0 2Fe2  2H 14
expensive.
HS O3 ! S0 OH O2 8 2Fe2  0:5O2 H2 O ! 2Fe3  2OH 15

HS 4O3 ! SO2


4 4O2 H

9 4.1.9. Oxidation with FeO
This treatment is based on the interaction of
H2S with a dry packed bed of Fe2O3 and
4.1.7.6. Potassium permanganate oxidation. After
FeO that may be in the form of iron residues
H2S is scrubbed, it can be oxidized using potas-
(turnings, blast furnace), natural minerals or
sium permanganate (Cadena & Peters 1988). This
iron oxide embedded wood shavings (Constant
method is not attractive since it has a high cost
et al. 1989). Diverse sulfur compounds are
and the manganese oxide must be adequately
formed as reaction products. Regeneration may
disposed of to avoid a negative environmental
be done by oxidation with an air stream
impact. In addition, dierent sulfur compounds
through the packed bed or in smaller applica-
are produced depending on pH.
tions, by exposing the spent material to the
air in an open space. The regeneration reac-
3H2 S 2KMnO4 ! 3S0 2H2 O 2MnO2 tion is exothermic, so some precautions should
2KOH at pH<7:5 10 be taken.
101

H2S oxidation: of wastewater treatment process. A methane and


sulde oxidizing bacterial consortium would
Fe2 O3 3H2 S ! Fe2 S3 3H2 O 16
make this technology feasible.
A combination of physical-chemical and
FeO H2 S ! FeS H2 O 17 biological processes may be applied for biogas
Fe2O3 and FeO regeneration: treatment applications, if the undesirable
compounds such as H2S are transferred in a
Fe2 S3 3=2O2 ! Fe2 O3 3S0 18 scrubber tower into a biologically active aqueous
phase. In such case, the microorganisms will
FeS 0:5O2 ! FeO S0 19 metabolize those compounds, as a source of
nutrients or energy for growth and maintenance,
This method has been widely used for biogas producing more biomass and carbon dioxide,
cleaning in small and medium size facilities. water, sulfate or sulfur, nitrate, etc. depending on
the pollutant. The overall eciency of the
4.1.10. Pressurized water process is determined by the relative rates of the
This rather simple method has been used for physical, chemical and biological processes
CO2 and H2S removal from biogas. A involved.
pressurized packed scrubber column is fed with Although the basic mechanisms are the same
water and biogas in a counter-current pattern, for all biological methods, there are dierent
water being sprayed at the top. The spent water equipment congurations to achieve transfer of
with high concentration of dissolved gases is pollutants and their biodegradation.
regenerated at ambient pressure in another
column or mixed tank, where CO2 and H2S 4.2.1. Biolter
should be recovered or properly disposed of. In biolters, an air mixture passes through a
moist packed bed that contains microorganisms
4.2. Biological methods growing as a biolm on the surface and crevices
of the support (Figure 4). The biolm activity is
Biological gas treatment systems are based on determined by its microbial density and the envi-
the capacity of microorganisms, including ronmental conditions, such as temperature, nutri-
bacteria, yeast and fungi, to transform certain ent availability, pH and humidity. The humidity
organic and inorganic pollutants into compounds of the biolm is one of the critical aspects that
that have very low impact on health and should be controlled in order to maintain biolog-
environment. For odor control applications, ical activity (Lang & Jager 1992).
pollutants are mixed in an air stream, so The supports can be either bioactive or inert.
microbial degradation involved is generally Natural bioactive supports, such as soil, peat,
oxidative in nature and end products are carbon
dioxide, water, sulfate, and nitrate, depending on
the odorous compound. This is not the case
when biogas cleaning is the objective, as no
oxygen is present on the mixture and addition of
air should be avoided due to the risk of forming
an explosive mixture. However, some biological
process could be applied if a strict control of air
addition can be guaranteed. This particular
method should be developed for methane
removal prior to biogas venting at small size
anaerobic municipal sewage treatment facilities,
where no reliable are system can be applied
due to the low biogas production. Moreover,
considering the simplicity of biolters, this
technology would be in congruence with this type Figure 4. Schematic diagram of an open biolter.
102

compost, bark etc., can retain water and generally transfer and the control of the xed biomass. Air
contain enough mineral nutrients to support an can be fed tangentially to the disks or through
initial active microbial population (Cardenas- perforations in a hollow shaft (Rudolf von Rohr
Gonzalez et al. 1999). They are relatively & Ruediger 2001).
inexpensive and easy to obtain and have been
used for many applications. However, natural
4.2.4. Bioscrubbers
supports may degrade with time and loose their
In bioscrubbers, pollutants in a gas phase are
structure and water retaining capacity inducing
removed by absorption in a recycling water
channeling and the loss of performance (Morgan-
stream in a scrubber tower (Van Groenestijn
Sagastume et al. 2003a). In some cases, re-mixing
2001a). Subsequently this pollutant laden water
the support with fresh material and nutrients
is regenerated by microorganisms in a bioreactor
allows recovery of activity, but eventually it will
with supplementary oxygen, and then returned to
need to be entirely replaced (Morgan-Sagastume
the contactor. Nutrient addition and pH are con-
et al. 2003b). With proper maintenance, the
tinually controlled in the bioreactor in order to
support can be used for several years.
maintain microbial growth and high activity. The
excess biomass and byproducts are purged from
4.2.2. Biotrickling lters
the system. Scrubbers are designed to favor mass
In this device, polluted air is passed through a
transfer from air to liquid phase, while maintain-
packed non-submerged column where liquid is
ing a low pressure drop (<3 cm H2O/m). The
continuously down-ow recirculated through
contactors can be packed towers, venturi
the packing. The pollutant is rst solubilized in
scrubbers, spray towers, etc. Bioreactors are
the falling liquid lm and transferred to the
usually activated sludge systems.
microorganisms that grow attached to the sur-
face of these supports. The liquid provides
moisture, nutrients, pH control to the biolm 4.2.5. Membrane bioreactors
and allows the removal of inhibiting products. In a membrane bioreactor, the pollutant in the
Eventually, excess biomass is sloughed o by gas phase is transferred through a membrane to
the trickling liquid and stable operation can be a biolm attached on the other side of the
achieved. barrier, where nutrients and oxygen are
The supports are inert packing materials, provided. The basic congurations are hollow
random or structured, which are similar to those bers and at sheets. In hollow bers the gas is
used in traditional scrubbers (plastic Raschig or usually passed through the lumen of the ber
Pall rings and saddles) although others such as and the biomass is on the shell side. These
volcanic scoria or polyurethane foam have been reactors have been used for other waste treat-
tested (Van Groenestijn 2001b). The air may be ment applications where the stream conditions
directed upow or downow which is counter- exclude the possibility of direct contact with the
current or cocurrent with the liquid ow, biomass (Van Groenestijn & Hesselink 1993;
respectively. To maintain low pressure drop and Ergas 2001).
reduce clogging, the support should have high Membranes can be made of very diverse
porosity and specic surface ratio lower than materials and have dierent chemical and physi-
400 m2 m)3. cal properties (solubility, selectivity, mechanical
strength, pore size, thickness and porosity). A
4.2.3. Rotating biological contactors distinct characteristic of the membrane bioreac-
Rotating biological contactors were developed tors is the fact that the polluted gaseous stream
initially for wastewater treatment In this device, and the biomass is physically segregated which
polluted air passes through the headspace of an allows the use of waste gas treatment in certain
assembly of discs mounted on a rotating shaft extreme applications such as indoor air.
that serve as biolm support. The shaft is rotated
(around 2 rpm) and the discs are partially sub- 4.2.6. Suspended cell bioreactor
merged in water containing nutrients and other In the suspended cell bioreactors the polluted air
additives. The movement of the discs favors mass is bubbled in the bulk liquid containing suspended
103

microorganisms. Several congurations can be product is identied as a polysulde and is


proposed (Bielefeldt 2001). The characteristics of obtained at a maximum removal rate of
the reactor, such as biomass concentration, air 3.92 mmol (H2S)/g(dry cells)h. The main
feed and sparger design, are generally imposed by advantage of this microorganism is based on its
the requirements of the wastewater treatment. In high growth rate, facilitating starting up and
an activated sludge process, the biological activity control of the population in a reactor. As sulfate
in the mixed liquor may be used to simulta- is not produced, the decrease of pH and the
neously treat the wastewater and the dissolved consequent eects on the microbial consortia are
polluted air. not a problem.

4.3. Microorganisms of particular interest 4.3.3. Thiobacillus denitricans


for H2S removal This chemoautotrophic facultative microorgan-
ism with simple nutritional requirement can grow
Among the H2S oxidizing microorganisms, in a heterotrophic environment. The use of these
Thiobacillus seems to be particularly suited for microorganisms has two disadvantages: the slow
engineering applications due to its simple nutri- growth and the sulfate production that is accu-
tious requirements, its high eectiveness and mulated in the reactor that may eventually in-
resistance to toxic substances and the wide pH hibit the microorganism (Sublette & Sylvester
interval it can tolerate (Cadenhead & Sublette 1987; Ongcharit et al. 1990).
1990). The most common reaction is a direct oxi-
dation of sulde to sulfur and sulfates by means 4.3.4. Thiobacillus thioparus, T. versutus,
of oxygen provided by air. In other cases (Thioba- T. neopolitanus and T. thioxidans
cillus denitricans) nitrate reduction to N2 allows These microorganisms have been used in pilot
the oxidation of sulde to sulfate. Particularly, plants oering similar characteristic in their
Thiobaillus ferroxidans raises a very simple and behavior. They do not have a clear advantage
eective process for H2S treatment in which the over Thiobacillus denitricans, as their growth
oxidant is regenerated by the microorganisms. rates are lower, but they have a lower require-
Some relevant microorganisms are the following: ment of ammonium (Cadenhead & Sublette
1990).
4.3.1. Chlorobium limicola thiosulfatophilum
4.3.5. Thiobacillus ferrooxidans
2H2 S CO2 hv ! 2S0 CH2 O H2 O 20 The oxidation of the H2S to S0 is carried out
with ferric sulfate according to the reaction:
An autotrophic anaerobic microorganism that
uses light as energy which may be a disadvantage H2 S Fe2 SO4 3 ! S0 2FeSO4 H2 SO4 21
due to the associated costs (Cork & Ma 1982).
The system does not depend on oxygen, as oxi- Ferric sulfate can be regenerated from ferrous
dation of H2S takes place in an anaerobic med- sulfate using Thiobacillus ferrooxidans as follows:
ium in the presence of CO2. The system favors 2FeSO4 H2 SO4 0:5O2 ! Fe2 SO4 3 H2 O
growth of Chlorobium due to the high concentra-
tions of H2S in the reactor, which works like a 22
bactericidal compound inhibiting the growth of The rst reaction is highly quantitative avoiding
other anaerobic bacteria that could compete, the discharge of H2S. The oxydation reagent is
such as methanogens. The main advantage of regenerated, so operational costs are reduced.
this process are the useful reaction products that Moreover, if sulfur is recovered, water would be
are obtained from H2S and CO2. the only by-product of the reactions. In general,
the operation costs of this process, called BIO-
4.3.2. Xanthomonas sp. chain DY44 SR (Figure 5), are around one third of those of
Chemoheterotrophic aerobic microorganism conventional processes such as scrubbers and
reported by Cho et al. (1992). The H2S oxidation adsorption columns. This arrangement avoids
104

Figure 5. Schematic of the BIO-SR process.

the problems associated with other H2S oxida- 5. Biogas as an energy source
tion microbiological processes as H2S does not
have an inhibiting eect on Thiobacillus ferroox- Biogas is a useful energy source that can be and
idans and SO24 is not accumulated in the med- aid to diminish the operation costs involved in
ium. (Satoh et al. 1988; Asai et al. 1990 and the wastewater and sludge conditioning
Sontah et al. 1990). processes. Nevertheless, as already mentioned,
domestic wastewater has such a low COD
4.3.6. Mixture of Thiobacillus and concentration that biogas reuse is sometimes
heterotrophous microorganisms economically unfeasible. In any case, biogas
In the Biocyd process, polluted air passes produced in anaerobic reactors, if it is not used,
through a packed reactor in which a biolm should be ared or treated in order to avoid
mixed culture of sulfooxidants as well as het- venting it to the atmosphere.
erotrophic bacteria has been developed (Torres Hence, two mayor topics are considered in
et al. 1993; Revah et al. 1995; Hugler et al. this section:
1999). The reactions are, at the beginning, a Raw biogas treatment in order to obtain a
partial oxidation of sulde to sulfur: If the lev- certain quality accordingly to the required
els of oxygen are high and sulfur is not re- standards for driving gas engines or biogas
moved from the reactor, the reaction continues red boilers.
to sulfate: Raw biogas conditioning in order to obtain a
2H2 S O2 ! 2S0 2H2 O 23 biogas quality for a proper burning in a are if
its reuse has been found to be economically
unfeasible.
2S0 2H2 O 3O2 ! 2H2 SO4 24
Biogas produced in anaerobic digestion
processes can be used for several purposes:
Figure 6 shows a diagram of this arrangement. direct gas use in boilers or heating devices,
105

Figure 6. Schematic of the BIOCYD process.

fuel for an engine directly coupled to a power At present, no common standard has been
generator, dened for biogas upgrading to natural gas, but
cogeneration of heat and power, it can be assumed that the European standards
upgrade of biogas to specications of natural shall be the guidelines for most countries. Never-
gas in order to run motor vehicle engines or to theless, methane concentration should be at least
supply a local gas network. 95% and H2S concentration should be kept
In all these cases, water and H2S removal below 5 mg/m3. However, quality requirements
should be provided. In addition, if the gas is to for vehicle fuel from biogas may not be the same
be used in gas engines, or if it is upgraded to a in dierent countries.
natural gas quality, the biogas should be en-
riched with methane, so CO2 should be removed 5.1. Biogas treatment requirements
as well. Table 3 lists typical requirements for gas
engines. The treatment degree of raw biogas will dier
according to the type of biogas end use. Treat-
ment procedures, already discussed in the previ-
Table 3. Typical requirements for gas engines (AD-NETT ous section, should also be selected depending on
2000) the biogas ow. Table 4 shows some typical
Component Dimension Range applications:

Energy content MJ/m3 1321 5.2. Biogas storage prior to its use
Variation of energy MJ/m3 02
content At the site of any anaerobic digestion facility,
Maximum temperature C 4060 two gas streams are produced that need treat-
feed ment: biogas and ue gas (headspace in reactor,
Minimum delivery mbar 2580 tanks and ventilation devices). Biogas that is
pressure produced as an end product in anaerobic digest-
Biogas humidity % <7080 ers is normally stored and utilized on site. Some
H2S content mg/m3 <10002000 medium and large scale industrial wastewater
Chloride and uor (total) mg/m3 <6080
treatment plants with an anaerobic reactor as the
106

Table 4. Dierent treatment degrees for biogas utilization (adapted from Nyns & Thomas (1998))

Type of end-use Removal of water Removal of CO2 Removal of H2S Pressure requirements (bars)

Electrical power generator PC NPC PC


Motor, Turbine
Thermal power P N NPC
Co-generation PC NPC PC
Vehicle fuel C C C 200
Natural gas for district heat C C C 6070

N = no treatment; P = partial treatment; C = complete treatment.

main biological wastewater treatment process the storage volume is calculated according to the
produce valuable biogas as a by-product that can demand of the equipment if biogas is going to be
be used as well. In most cases, biogas storage used. Figure 8 shows an anaerobic lagoon cover
should be provided. This can be done in dierent that can be considered a low pressure wet gas-
types of storage facilities like: holder.
a water sealed, oating gasholder,
a separate gas bag or a covered gasholder, 5.3. Biogas aring
the digester headspace with a foil membrane,
a separate steel gas tank for high pressure If biogas utilization is not possible, biogas
storage. combustion with ares is required since direct
According to the storage pressure, a more emission of biogas into open air must be
comprehensive classication can be as follows avoided for safety, health and environmental
(Constant et al. 1989): reasons. In fact, even if the anaerobic treat-
Low pressure gasholders. The biogas pressure is ment plant has a biogas utilization facility, a
kept below 50 mbar. Wet gasholders and dry aring system should be installed in order to
gasholders are the common types of these safely dispose of biogas during its maintenance
low-pressure units. and repairs.
Medium pressure tanks. These are usually steel When aring is the only end point of bio-
tanks where the biogas is storage at 1020 bar gas, storage may not be needed; however,
pressure. Contrary to most low-pressure some conditioning steps will still be required,
gasholders, the medium pressure tanks are of depending on the biogas source and the envi-
variable pressure and xed volume. ronmental regulation at the particular place. In
High pressure gas cylinders. Biogas is stored in such case, conditioning steps could include de-
steels cylinders of low volume (less than 50 l) foaming, water and H2S removal and even
at a pressure that varies from 150 to 350 bar. compression if biogas pressure at the are inlet
Wet gasholders are generally oating covers is too low.
or inverted vessels made out of steel. Some reac- Many countries have their own standards and
tors or digester have a signicant head space vol- regulations for emissions coming from biogas
ume that may be used for gas storage. Typical aring facilities, being the standards adopted by
volume ranges from 50 to 5,000 m3. the USA and the European Community the most
Dry, low-pressure gasholders are separated advanced and comprehensive ones. For instance,
from the anaerobic reactor/digester; they are gen- the Dutch emission guidance (NER 3.5/90.1)
erally manufactured using a rubber or polymeric considers the following restrictions for permanent
material. These gasholders may be installed un- ares (AD-NETT 2000):
der covers or housing structures in order to pro- The outlet temperature of the ue gas has to
tect the plastic liner. The full storage volume be at least 900C.
ranges from 1 to 1,000 m3. Some gas holder The residence time in the are has to be at
arrangements are shown in Figure 7. least 0.3 s.
Many designers consider a one-day storage The are has to be of the closed type (no
volume if the biogas facility is small. Otherwise, visible ame). However, if ares are only being
107

STEEL GASHOLDER < 50mb

GAS < 50 mb

0.05 0.3 bar

ANAEROBIC DIGESTER

ANAEROBIC REACTOR/DIGESTER
WET GASHOLDERS

GAS

10 bars

GAS CUSHION
PRESSURE REDUCER
WEIGHT

GAS
COMPRESSOR

< 50 mb

DRY GASHOLDERS

Figure 7. Dierent gasholder types (Constant et al. 1989).

Figure 8. Anaerobic pond cover (low pressure, low prole wet gasholder).

used during periods of equipment maintenance, The maximum limit of H2S and other organic
the use of a simple open or half-open are is sulfur compounds in the biogas to be ared is
allowed. 50 ppmv. If this limit is exceeded, sulfur has to
108

Figure 9. Open biogas are (left) and enclosed biogas are (right).

be removed from the biogas to less than the tank bottom, where they are evacuated on a
50 ppmv or a removal eciency of at least regular basis. These separators are very useful
98%. To prevent the formation of dioxins, the when installed at the suction side of a roots-type
halogenated hydrocarbons content has to be biogas compressor in order to stop small parti-
lower than 150 mg/m3. cles from entering the equipment, causing prob-
Totally enclosed ares are very expensive, lems related to excessive overheating.
mainly due to its refractory material used as an Apart from the foam separator, a sediment/
inside covering, so open ares are commonly water trap intended to eliminate part of the
used in Third World countries. In spite of this high moisture content of the biogas. These
fact, it is expected that in the near future aring traps are usually installed to provide additional
of biogas will be restricted to enclosed ares. safety by removing the remaining solids and
Figure 9 shows the two are types. liquid from the gas stream. They can be
sucient if the biogas solids or foam content is
5.4. Biogas piping and accessories limited, as in anaerobic reactors treating
municipal wastewater.
The common accessories in a conventional bio- A low pressure check valve. The check valves
gas line may include the following elements are recommended at every single biogas source
(WPCF 1987): lines in order to isolate them from the others if
A pressure relief/vacuum relief valve at the a general system collects from more that one
anaerobic digester/reactor cover, paired up to production source.
a vertical ame arrester in order to avoid a A biogas ow metering device. Nowadays the
spark from entering the digester/reactor. thermal mass owmeter type is the most
A foam separator tank to eliminate dust and commonly used.
small solid particles that are carried on along A back pressure regulator with a horizontal
with the biogas. In these tanks, usually water is ame arrester and thermal shut-o valve in
sprayed in order to carry solid particles down to order to avoid biogas ashbacks, located as
109

close as possible (less than 3 m) to the ame out that in many anaerobic reactors or digesters
source (a are, a boiler, etc.). in developing countries much simpler arrange-
A waste gas burner. As mentioned earlier, this ments are used. Adaptation to local conditions
burner can be of two types: open atmospheric should be encouraged, as long as safety require-
are or totally enclosed are. The latter is the ments are not compromised.
recommended one, although more expensive. When sizing the gas piping and equipment,
As many manometers as required by the the following parameters should be considered
process. The usual type is the well column (WPCF 1987):
manometer, lled with oil with a specic Biogas design ow at minimum, normal and
gravity similar to water, or mercury for a maximum conditions. These data are manda-
higher pressure application. It is recommended tory to properly size biogas piping, equipment
to install at least two manometers: one at the and storage facilities.
biogas source and another one at the are Biogas pressure at the generation site. This is
inlet. very important in order to determine if a com-
It should be pointed out that water conden- pression step is required. Most open ares are
sates along the biogas lines, so some drip traps specied to operate with an inlet pressure of 6
must be installed in every point where water in H2O (at the very least). In the same way,
accumulation is expected. For instance, the water most biogas boilers needs a minimum biogas
trapped by the sediment tank is usually pressure of 12 in H2O (red tube boilers), or 4
eliminated on a regular basis using a manual drip in H2O (water exible tube boilers) at the inlet
trap. The horizontal ame arresters are heat connection.
dissipation units and also they accumulate water, For a proper operation of an open are, the
so some manufacturers supply them with manual minimum pressure at the are outlet should be
drip traps. It is recommended to install a drip 2 in H2O. This is a simple rule of thumb, so
trap at the lowest point of the line and at the for a detailed calculation procedure it is recom-
base of the are tube. This trap can be an auto- mended to refer to the technical literature
matic or manually operated unit. about the subject.
A typical, fully equipped, biogas aring sys- Pipe diameter, length and tting. According to
tem is shown in Figure 10. It should be pointed the Manual of Practice No. 8 (WEF 1999) the

TYPICAL FIARING SYSTEM FOR TWO BIOGAS SOURCES

Q:78.34 m3/h : 4.0"

BIOGAS FROM DIGESTER 1

PI PI

STAINLESS STEEL CARBON STEEL PSV


Q:156.67 m3/h : 6.0"
FI AF01
TSD1

PURGE
TS01 Sediment and Condensotes trap PURGE

: 4.0 " AF01 Flame arrester/thermal shut-off valve


Q:78.34 m3/h
FI Thermal mass flowmeter

BIOGAS FROM DIGESTER 1 PI Manometer


PSV Pressure relief valve

Low pressure check valve

Butterfly valve

Figure 10. Typical aring system for two biogas sources.


110

piping should be sized with a maximum gas valve will usually have the following smaller
velocity below 3.7 m/s. This velocity will nominal diameter taking the line diameter as
prevent liquid and solid carry-over that may reference.
damage equipment downstream. Additionally,
the number of pipe bends and long piping runs Some additional rules of thumb are the
should be minimized to reduce pressure losses. following:
The calculation procedures are described in All gas piping should be sloped a minimum of
other technical references beyond the scope of 2% for proper drainage. Drip traps should be
this work, but generally speaking they consider located at all low points, and in long pipe
the following stepwise approach (WPCF 1987): runs.
Estimate the biogas production. Flame arresters should be installed as close to
Determine the operating pressure necessary for the source of ignition as possible. Those arrest-
all gas utilization equipment. ers can be located at a maximum of 3 m
Select the line size necessary to meet the veloc- upstream of the ignition source when used in
ity requirements. Determine pressure losses accordance with UL standards. This is due to
through each piece of equipment in the line the limited capacity of arresters to dissipate the
leading to the are. The sum of the pressure heat produced by the biogas combustion. The
required at the are inlet and the pressure drop higher the biogas volume in the pipe, the more
determines the minimum operating pressure dicult to the arrester to dissipate energy, so
necessary beneath the digester/reactor cover. ames may pass the arrester causing an explo-
Low pressure drop should be maintained sion.
across the entire system. Manufacturer A ame arrester should be specied in areas
manuals and catalogs should be consulted to where there is a possibility of air entrance,
determine the pressure drop at every accessory such as relief valves and vents. Where there is
within the biogas line. an open ame or possible sparking, e.g., ares,
In more complex systems, it is necessary to boilers or engine-generators, additional protec-
determine the minimum inlet pressures and tion utilizing thermal bypass shut-o valves,
pressure drops for each line before calculating and pressure (explosion) relief valves should be
the cover pressure. A gas storage device may specied along with the ame arrester.
be necessary to handle loads during periods of
low gas production. 5.5. Safety considerations
In general terms, the pressure relief valve on
the digester cover should be set to open at 0.5 The main risks involved in the storage and utili-
in H2O below the maximum operating zation of biogas are due to the high ammability
pressure. To ensure that the pressure relief of methane if combined with air in the proper
valve operates at a completely closed position, proportions. The low explosive level (LEL) for
the reactor/digester internal pressure should be methane is 5%, while the high explosive level
at 80% of the pressure setting of that valve. (HEL) is 15%. This means that a methane
For instance, if the valve is set at 13 in H2O, concentration as low as 5% is enough to cause
then the internal system pressure should be no an explosion if mixed with air. Conversely, a
more than 10.5 in H2O. Otherwise, the relief methaneoxygen gas mixture with a methane
valve may not be completely losed. concentration higher than 15% will not have
A pressure regulator valve is recommended to enough oxygen to burn.
maintain a proper pressure at the are inlet or at Methane ammability is then the main concern
the gas utilization equipment. As a rule of for the specication of equipment, instrumenta-
thumb, the regulator valve will be set at a tion and control elements within the anaerobic
pressure calculated using the maximum system reactors/digesters area (biogas piping lines, biogas
pressure (internal biogas pressure at the reactor/ utilization equipment and aring system).
digester) minus the pressure losses calculated for According to Bradfer (2002), the safety stan-
the whole piping and accessories in the system. dards that apply to biogas handling as a risky
When properly sized, the pressure regulator compound can be depicted as follows (Figure 11).
111

Figure 11. Biogas classication according to European and USA standards. Adapted from Bradfer (2002).

Every engineering procedure for the design Some integrated anaerobic/anoxic aerobic
and specication of any biogas handling sys- processes has been proposed for nitrogen
tem shall consider those standards as the safety removal; some of them requires an external car-
reference system. bon source in order to reach a low euent con-
centration of total nitrogen. Methanol, ethanol,
acetic acid has been used for this purpose, with
6. Biogas as substrate (electron donor) the drawback of their additional costs. Methane,
for denitrication of wastewaters a free, endogenous carbon source has been under-
estimated, as few research studies have been pub-
Nitrogen control is increasingly reinforced in lished on that subject (Davies 1973; Sollo et al.
developing countries, and it is the second step in 1976; Rhee & Fush 1978; Werner & Kayser 1991;
wastewater treatment policies. As a result, muni- Thalasso et al. 1995; Houbron et al. 1999; Rajap-
cipal sewage treatment should now consider, in akse & Scutt 1999; Costa et al. 2000; Eisentraeger
many cases, a proper removal of nitrogen and et al. 2001; Santos et al. 2004; Islas-Lima et al.
even phosphorous as well. 2004).
Anaerobic sewage treatment may be regarded Even if some discussion still prevails on the
as a suitable core technology for sustainable biochemical pathways and the denitrication
wastewater management and resource recovery rates (Mason 1977; Costa et al. 2000; Islas-Lima
(Lettinga et al. 1997). Several process arrange- et al. 2004), there is enough evidence that
ments have been proposed for nitrogen, phospho- methane may be used as external carbon source
rous and sulfur removal, all considering an for denitrication, achieving removal rates
anaerobic or anoxic step (Metcalf & Eddy 2003; similar to those obtain with classical substrates,
Villaverde 2004). In must of these processes, an such as methanol or ethanol (Werner & Kayser
organic electron donor must be supplied. This is 1991; Thalasso et al. 1995; Houbron et al. 1999).
the case of denitrication, where raw wastewater, The requirements for a proper denitrication
endogenous cell reserves or external carbon sour- process with methane are a good gas transfer
ces may fulll that need (Morgan-Sagastume to the liquid phase and a limited concentration
et al. 1994; Metcalf & Eddy 2003). of dissolved oxygen, around 1 mg/L (Werner
112

& Kayser 1991; Thalasso et al. 1995; Houbron this may be a long and complex process. CERs
et al. 1999; Costa et al. 2000). are sold between e 3 and 10 per ton of CO2
The use of methane for nitrogen removal is equivalents, depending on the stage of the project
another potential advantage of anaerobic resource cycle (UNEP 2005).
recovery integrated technologies that still have to
be validated in full scale plants. The resulting
reduction in operational cost would be another 8. Conclusions
advantage for the application of anaerobic sewage
treatment in developing countries. In order to favor a wider adoption of anaerobic
process for municipal sewage in developing
countries, odor control and biogas utilization/
7. Biogas and the Kyoto Protocol disposal should be properly addressed. However,
anaerobic sewage treatment should not be
Biogas emissions from anthropogenic sources are considered as an energy producer, unless a sig-
a threat to the gaseous composition of the nicant wastewater ow is treated.
atmosphere and contribute to the greenhouse H2S is the most characteristic bad odor con-
gases inventory. Livestock exploitations, rice stituent in biogas and at the surroundings of
production, sanitary landlls and waste organic anaerobic digesters and wastewater treatment
treatment facilities are important sources of facilities; many research works on odor control
methane. This gas is being accumulated in the consider H2S as the reference compound.
atmosphere at a higher rate than CO2 (0.6 versus Treatment technologies options for biogas
0.4% per year for the 1984 1994 decade) their cleaning and odor control are relatively exten-
concentration in the atmosphere being 1720 ppbv sive. The choice of a particular technology
and 350 ppmv, respectively for year 1994 (UNEP should consider technical and economical factors
1999). as well as environmental and safety aspects.
For this and other reasons, the common prac- From a technical standpoint, variables such as
tice of biogas venting at small- and medium-size stream (ow, temperature and humidity) and
anaerobic municipal wastewater treatment plants pollutant characteristics (composition, concentra-
should be avoided. The potential application of tion, reactivity, solubility and biodegradability)
modern and adapted anaerobic technologies in have to be evaluated.
developing countries could be hindered if this An important advantage of biological treat-
aspect is not solved. On the other hand, a facility ment methods over physical and chemical
for biogas conversion to energy (electricity) may technologies is the fact that biological processes
apply for the clean development mechanism can be operated at local temperature and
(CDM) of the Kyoto Protocol. As a result, pressure, within a wide range of pollutants at
developing countries may implement sustainable medium to low concentrations. Biological puri-
technologies and receive an income for their cation facilities are also ecologically friendly and
fscertied emission reductions (CERs) from less expensive if compared with most physical-
developed countries. The CDM is established in chemical treatments.
Article 12 of the Kyoto Protocol. In most of small anaerobic municipal
In order to register a specic project under treatment plants, biogas is vented, transferring
the CDM, the concept of additionality should be pollution from water to the atmosphere and
met, as dened in the 2001 Marrakesh Accords. contributing to the greenhouse gas inventory. To
A CDM project should prove that it reduces overcome this problem, biological processes, such
anthropogenic greenhouse gases emissions below as compost biolters, should be developed for
those levels that would have occurred if the methane removal prior to biogas venting, consid-
project was not implemented. Moreover, the ering the simplicity of this technology, in congru-
project developer should demonstrate that with- ence with anaerobic treatment options. A
out the CDM, the project is not the most feasible methane and sulde oxidizing bacterial consor-
economic option or that barriers can be tium would make this small scale technology
surmounted if the CDM registration is obtained; feasible.
113

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recovery processes can be accomplished if meth- sulde by Xanthomonas sp. Strain DY44 Isolated from Peat.
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ane is used as electron donor for denitrication Constant M, Naveau H, Ferrero GL & Nyns EJ (1989) Biogas
and nitrogen control purposes. Although this End-Use in the European Community. Elsevier Science
scheme must still be validated in full scale plants, Publisher, England
Corbitt RA (1990) Air quality control In: Corbitt RA (Eds)
the resulting reduction in operational cost would
Standard Handbook of Environmental Engineering (pp
be another advantage for the application of 41004115). McGraw Hill, New York
anaerobic sewage treatment in developing Cork DJ & Ma S (1982) Acidgas bioconversion favors sulfur
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