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Fuel
journal homepage: www.elsevier.com/locate/fuel
ENEA, National Agency for New Technologies, Energy and Sustainable Economic Development, UTTRI S.S. 106 Ionica, km 419+500, 75026 Matera, Italy
PoroGen Corporation, 6C Gill Street, Woburn, MA 01778, USA
h i g h l i g h t s
" Production of biomethane from biogas produced from anaerobic digestion of organic matter.
" Possibility to use biomethane in the grid injection.
" Use of polymeric membrane for biogas upgrading.
" Cleaning biogas.
a r t i c l e
i n f o
Article history:
Received 10 May 2012
Received in revised form 30 July 2012
Accepted 31 July 2012
Available online 23 August 2012
Keywords:
Biomethane
Anaerobic digestion
Biomass
Landll gas
Organic waste
a b s t r a c t
Anaerobic Digestion (AD) is a biological process that takes place naturally when bacteria break down
organic matter in environments with or without oxygen. Controlled anaerobic digestion of organic waste
in enclosed landll will generate methane. Almost any organic material can be processed with AD, including waste paper and cardboard (of a grade that is too low to recycle because of food contamination), grass
clippings, leftover food, industrial efuents, sewage and animal waste. AD produces biogas which is comprised of around 60% methane (CH4) and 40% carbon dioxide (CO2). This biogas can be used to generate
heat or electricity and/or can be used as a vehicular fuel. If the intended use is for power generation the
biogas must be scrubbed to remove a number of impurities. After conditioning the biogas can be used for
onsite power generation, to heat homes or can be added to the national natural gas grid. In recent years
several research groups have shown the possibility of upgrading the biogas for biomethane production
[1]. This study will show the feasibility of integrating anaerobic digestion plant with onsite polymeric
membrane purication system for conditioned biomethane production.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
The anaerobic digestion is the technology that can convert the
agro-industrial waste chain, the municipal solid waste and/or
wastewater sludge into renewable energy. There are multiple characteristics that make this technology applicable to industrial energy generation processes. Nevertheless, improvements in both
environmental characteristics and overall process economics are
still required to make the technology acceptable broad base. An
important economic consideration is the fact that the biogas can
be produced at the biomass production site reducing transportation costs. The AD plants can be scaled down that makes the process ideal for rural area development. The biogas can be used in
a cogeneration system or used for biomethane production which
in turn can be sent to national natural gas network or used as a
biocombustible fuel in the automotive sector.
Corresponding authors. Tel.: +39 (0)835 974736; fax: +39 (0)835 974210
(A. Molino).
E-mail address: antonio.molino@enea.it (A. Molino).
0016-2361/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.07.070
2. The process
Anaerobic digestion is a natural biological process when bacteria break down organic matter in environments with little or no
oxygen. A controlled enclosed version of the anaerobic breakdown
of organic waste is a landll process which releases methane as
one of end products. Several research groups have shown that
the AD process can be split into three main stages: hydrolysis, acidogenesis and methanogenesis as show in Fig. 2.1 [2].
Anaerobic fermentation signicantly reduces the total mass of
waste, generates solid or liquid fertilizer and yields energy. It can
1004
be maintained at psychrophilic conditions (1216 C, e.g. in landlls, swamps or sediments), mesophilic conditions (3537 C, e.g.
in the rumen and in anaerobic digester) or thermophilic conditions
(5560 C; e.g. in anaerobic digesters or geothermally heated ecosystems). Disadvantages of the thermophilic anaerobic fermentation are the reduced process stability and reduced dewatering
properties of the fermented sludge and the requirement for large
amounts of energy for heating, whereas the thermal destruction
of pathogenic bacteria at elevated temperatures is considered a
big advantage [2]. The slightly higher rates of hydrolysis and fermentation under thermophilic conditions have not led to a higher
methane yield. No signicant change in the total methane yield
from the organic matter for fermentation temperatures ranging
from 30 C to 60 C have been reported [3,4].
In the rst stage of hydrolysis, or liquefaction, fermentative bacteria convert the insoluble complex organic matter, such as cellulose, into soluble molecules such as sugars, amino acids and fatty
acids. The complex polymeric matter is hydrolyzed to monomers,
e.g. cellulose to sugars or alcohols and proteins to peptides or amino acids, by hydrolytic enzymes, (lipases, proteases, cellulases,
amylases, etc.) secreted by microbes. The hydrolytic activity is of
a signicant importance in the high organic content waste and
may become rate limiting. Some industrial operations overcome
this limitation using chemical reagents to enhance the performance of the hydrolysis process. The application of chemicals to
enhance the rst step has been found to result in a shorter digestion time and it provides a higher methane yield [5].
2.1. Hydrolysis/liquefaction reactions
Lipids ? Fatty Acids
Polysaccharides ? Monosaccharides
Protein ? Amino Acids
Nucleic Acids ? Purines & Pyrimidines
methane
CO2
carbon dioxide
CO2
4H2
hydrogen
! CH4 2H2 O
water
The biogas products from the anaerobic digestion contain methane, carbon dioxide, hydrogen, hydrogen sulde, ammonia, siloxanes and other substances that may inhibit the anaerobic
digestion process or cause corrosion problems in pipelines of
plants or in the distribution network [79].
Several research groups have summarized technologies for biogas purication, in particular, for hydrogen sulde, ammonia and
siloxane removal [10]. At the end of the purication process the
biogas still contains hydrogen, carbon dioxide and trace of sulphidric acid and ammonia (<100 ppm) that must be removed from the
stream to produce biomethane.
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BIOMETHANE
FEED BIOGAS
PERMEATE
The separation system is comprised of the feed biogas compressor to upgrade biogas pressure derived from anaerobic digestion
from atmospheric pressure to 31 barg; the compressed biogas is
stored in a rst tank to stabilize feed pressure and to regulate
the gas ow to rst stage membrane module. The stabilized feed
gas is directed into the rst membrane module that removes carbon dioxide, water vapor and some additional impurities (hydrogen, hydrogen sulde, oxygen, ammonia) by permeation and
generates the non-permeate (retentate) product biogas comprised
primarily of methane. The product gas is generated at the target
methane purity, it is dried and is collected at about 30 barg pressure. To increase methane recovery the permeate gas from the rst
stage membrane module is processed through a second stage
membrane system.
The rst membrane module splits the feed gas stream into two
gas streams, the biomethane product non-permeate gas stream
with methane content higher than 95% by volume collected at a
high pressure of about 30 barg and the permeate gas stream that
contains majority of carbon dioxide, water vapor and additional
impurities collected at a low pressure of 2 barg.
This one can be recirculated at the compression stage and after
this it can be fed at the second stage membrane. With this second
membrane module it is possible to recover additional product
stream with methane concentration greater than 85% and a second
stage permeate with a low methane content can be used as a fuel
as shown in Fig. 3.5. The permeate stream from the second stage
can be alternatively vented since it contains all impurities removed
from the biogas, i.e. most of carbon dioxide, water vapor, hydrogen,
ammonia, sulphidric acid, and some nitrogen.
Polymeric membrane modules utilized in the two stage process
were provided by PoroGen Corp., a US based company that specializes in industrial separation process. PEEK-SEP hollow ber
membranes composed of poly (ether ether ketone) polymer were
used. The membranes are designed to remove acid gases and water
vapors from raw natural gas or biogas to improve gas quality.
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Days of load
Type of biomass
Volume
loaded (l)
Total volume
into reactor (l)
1
4
6
7
8
11
12
13
14
15
18
19
20
21
22
25
26
27
28
29
32
33
34
Pig manure
Pig manure
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
Fruit and vegetables
200
200
16
16.5
22
22
22
24
25
26
27
28
29
30
31
32
33
34
36
38
40
42
45
200
400
416
432.5
454.5
476.5
498.5
522.5
547.5
573.5
600.5
628.5
657.5
398.5
718.5
750.5
783.5
817.5
853.5
891.5
931.5
973.5
1018.5
Fig. 3.2. Experimental results for DA. Methane concentration and biogas production vs days of experimental test.
3. Experimental results
The ENEA Trisaia research center operates anaerobic digestion
plant of plug ow technology type, PFR, with throughput of 70 kg
Upgrading Plant
Fig. 3.1. Anaerobic digestion plant.
Control room
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Fig. 3.5. Two congurations for biogas upgrading with polymeric membrane system.
Table 3.2
Wobbe index specications for town gas, natural gas and LPG.
Family
Type of gas
Wobbe index
range (MJ/Sm3)
Wobbe number
range from [13]
1
2L
2H
3
Town gas/syngas
Natural
22.530
3945
45.555
73.587.5
2429
LPG
4853
7287
Table 3.3
Gas specications for gas grid injection in Germany.
Parameter
Unit
Value
Wobbe index
MJ/Nm3
Relative density
Dust
Water dew point
CO2
O2
S
C
vol.%
vol.%
mg/Nm3
46.156.5 H
37.846.8 L
0.550.75
Technically free
<t2 (where t is the earth temperature)
<6
<3 (in dry distribution grids)
<30
per day. The plant has been in operation for several years. The plug
ow reactor is comprised of a stainless steel cylinder 70 cm in
diameter and 350 cm long with an internal volume of about of
1.3 m3; the reactor is inclined at a 20 angle and contains a
40 dm3 gasometer at the elevated section of the reactor. The AD
plant in show in Fig. 3.1.
4. Future developments
Recently the biogas production system was upgraded and the
reactor was coupled with membrane gas separation system. Initial
process simulation shows that the gas generated by the reactor
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Iw V c =Gs 0:5
The Wobbe Index is used to compare the combustion energy
output of fuel gas of different quality for use in an appliance (re,
cooker, etc.). If two fuels have identical Wobbe Indices then for given pressure and valve settings the energy output will also be
identical. Typically variations of up to 5% are allowed as this would
not be noticeable to the consumer.
The Wobbe Index is a critical factor to minimize the impact of
the changeover when analyzing the use of substitute natural gas
(SNG) fuels such as propaneair mixtures.
There are three ranges or families of fuel gases that have been
internationally agreed upon based on the Wobbe index. Family 1
covers manufactured gases, family 2 covers natural gases (with
high and low ranges) and family 3 covers liqueed petroleum gas
(LPG). Combustion equipment is typically designed to burn a fuel
gas within a particular family: hydrogen-rich town gas, natural
gas or LPG.
The simulation results show that the biomethane produced by
cascade conguration has the Wobbe index in the range of 46
51 corresponding to the family 2H, i.e. similar to the natural gas.
It is thus possible to use this biomethane in the natural gas grid.
Currently there are no unied, European technical standards
which regulate the conditions for injecting biogas into the natural
gas grid [14].
The European Commission is currently working on developing
such standards and determining quality specications for the
biomethane (see Table 3.2). The regulations allows for injection
into natural gas grid of two types of biogas: Type H (High), a
gas having a high caloric value and type L (Low) having a
low heating value.
In some European Union countries, such as Germany, the quality specication for the biogas (biomethane) is based on natural
gas specications. Table 3.3 shows German biogas specications
for gas to be injected into gas grid.
As one can see the biomethane produced by AD process [16,17]
has the prerequisite quality for the gas grid injection, in fact the
only problem can be caused by the sulfur content in the biogas, because typically the sulphidric acid content in the biogas is 0.01
0.2% by volume depending on the organic matter processed. With
the POROGENs PEEK-Sep membrane is also possible to remove
H2S from the biomethane and obtain a product stream with suphidric acid content lower than 30 mg/Nm3.
5. Conclusions
Biomethane produced from biogas generated by anaerobic
digestion of organic matter is an alternative gas source to that of
the natural gas. The European Directive 2003/55 has authorized
connection to the natural gas grid. Of particular interest is the possibility to inject biomethane, rened biogas with quality comparable to that of natural gas (CH4 concentration greater than 95%),
which can be used in place of fossil fuels in all its network applications, and in transportation. To produce pipeline quality biomethane starting from the biogas generated by AD process it is
necessary to remove water, sulfur compounds, halogenated organic molecules, carbon dioxide, oxygen and metals.
Several research groups have shown that the biogas can be produced at about 810 cent per cubic meter of biogas, depending on
the organic matter source, with the methane content of 5560% (by
volume) while the upgrading cost is about of 78 cent considering
the cost of kWh of about 20 cent the total process cost is about
2022 cent for cubic meter of biomethane compressed to gas
grid at 30 bar. Italys market price of natural gas is xed by the
national authority for the electrical energy and gas use and is equal
to 40.09 cent/Nm3 referred to January 2010, will justify the
industrial feasibility of this process.
References
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dokumente/biogas%20upgrading.pdf>.
[2] Winter J, Temper U. Microbiology of the anaerobic wastewater treatment.
Sewage Waste Recycle 1987;38:1421.
[3] Hashimoto AG, Varel VH, Chen YR. Ultimate methane yield from beef cattle
manure: effect of temperature, constitute, antibiotics and manure age.
Agriculture Waste 1981;3:24156.
[4] Mursec B, Janzekovic M, Cus F, Zuperl U. Comparison of rollers after sowing of
buckwheat. J Achievements Mater Manuf Eng 2006;17:26972.
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