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Biomass and Bioenergy 144 (2021) 105935

Contents lists available at ScienceDirect

Biomass and Bioenergy


journal homepage: http://www.elsevier.com/locate/biombioe

Biogas as an energy vector


Ahmad Rafiee a, b, *, Kaveh R. Khalilpour c, James Prest d, Igor Skryabin e
a
Department of Theoretical Foundations of Electrical Engineering, Faculty of Energy, South Ural State University, Chelyabinsk, Russia
b
DanaCluster Pty Ltd., Sydney, Australia
c
School of Information, Systems and Modelling, University of Technology Sydney, Australia
d
ANU College of Law, Fellows Rd, Australian National University, Canberra, Australia
e
ANU Energy Change Institute, Oliphant Building, Mills Road, Australian National University, Canberra, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: Biogas is a sustainable energy vector with diverse input sources (e.g. landfills and anaerobic digestion of waste
Biogas upgrading materials, wastewater treatment sludge, manure from animal production, or energy crops) and diverse appli­
Biomethane cations. The nature of the substrate and the design of the biogas production process determines the composition
Physicochemical
of raw biogas. All types of biogas must be cleaned and upgraded before delivering to the consumers and in
Techno-economics
Waste-to-energy
practice, the key challenge of the biogas supply chain is its cleaning and upgrading to consumers quality. The
physicochemical technologies used to clean and upgrade the raw biogas are reliable, mature and at high tech­
nology readiness levels.
This paper critically reviews the biogas supply chain including feedstock supply, biogas production and
upgrading/cleaning processes, potential hazards of biogas contaminants, product specification based on appli­
cations, and biogas/biomethane uses. The biogas cleaning and upgrading technologies with emphasis on cost
comparison are assessed. In summary, the upgrading technology alternatives and their associated costs are found
substantially affected by the project-specific circumstances. For instance, upgrading with chemical scrubbing
might be preferred in the availability of cheap on-site thermal energy. If the biomethane is planned to be injected
into high-pressure natural gas pipelines, those upgrading methods operating at relatively high pressures (e.g.
membranes) would be preferred. If the biomethane injection point to the gas grid is located distant from the
production site, the distribution cost will also play a determinative role in the overall biogas supply chain
economics. Among all these factors, plant capacity seems to be a pivotal element in the economics of biogas
supply chain. Amendments to national and sub-national support schemes are also an important factor affecting
investment decisions.

1. Background The so-called waste-to-energy (WtE) has multiple advantages. Not


only it addresses the waste disposal challenge, but it also offers a good
Meeting the climate change mitigation targets requires a rapid opportunity for energy security, as both the processes for production and
transition from fossil fuels to renewable electricity and renewable fuels. consumption of energy can be located in the same geographic location,
Increased urbanization rate, growing population, and economic evolu­ unlike fossil fuels. WtE can be considered as a semi-renewable source of
tion are significantly altering the perspective of national solid waste energy and an alternative (or at least a compliment) to fossil fuels which
materials in terms of waste composition, generation pace, and waste account for over 80% of the global energy consumption [2]. WtE pro­
treatment processes [1]. Over a few decades of research and industrial cesses comprise any waste treatment technology that generates any form
actions, today there is general consensus that conversion of the waste to of energy i.e. heat, electricity, or liquid transport fuels (e.g. diesel, petrol
energy is a promising waste management option. or kerosene) from a waste material feedstock.

Abbreviations: AD, anaerobic digestion; CCS CO2, capture and storage; CHP, combined heat and power; DCM, di-chloro-methane; DEG, di-ethylene glycol; DMC,
di-methyl carbonate; DME, di-methyl ether; DMEA, di-methyl ethanolamine; EG, ethylene glycol; EU, European Union; FF, fresh feedstock; FT-GTL, Fischer-Tropsch
gas-to-liquid; GHG, greenhouse gas; HRAR, high rate anaerobic reactors; MBR, membrane bioreactors; IPCC, intergovernmental panel on climate change; LF, landfill;
MCFC, molten-carbonate fuel cell; MEA, mono-ethanolamine; MSW, municipal solid waste.
* Corresponding author. Department of Theoretical Foundations of Electrical Engineering, Faculty of Energy, South Ural State University, Chelyabinsk, Russia.
E-mail address: a.rafiee82@gmail.com (A. Rafiee).

https://doi.org/10.1016/j.biombioe.2020.105935
Received 26 July 2020; Received in revised form 2 December 2020; Accepted 8 December 2020
Available online 16 December 2020
0961-9534/© 2020 Elsevier Ltd. All rights reserved.
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

Bioenergy refers to power, heat, transport fuels, and gas that is blend of gases (primarily methane and CO2) is released, known as biogas
produced from biological sources [3]. It is the third principal source of [6]. Some decades ago, biogas was perceived as “poor man’s fuel” [7],
energy in the world, nearly emission-neutral [4] and can have a positive but today it has emerged as one of the major options in the international
impact on promoting and balancing existing and future energy systems energy planning context. The biogas production process has several
[5]. Dairy waste, agricultural waste, wastewater treatment plants, urban advantages including its feedstock flexibility which can also include
food waste and garden waste, landfill (LF) gas and municipal solid waste MSW. In fact, when MSW is dumped in the nature, it goes under bio­
are the principal categories for use. logical dissociation and generates biogas the release of which to the
When an organic waste is decomposed in the absence of oxygen, a atmosphere creates significant environmental impact. The released

Fig. 1. a) Global renewable installed capacity (left axis) and share of biogas installed capacity (right axis) in the total renewable installed capacity during 2000–2017
(data source: [14]). b) Global electricity production from renewable resources (left axis) and share of biogas in renewable electricity generation (right axis) during
2000–2017 (data source: [14]).

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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

methane has over 20–times more global warming effects than CO2 for a
100-year time horizon. But, once the gas is produced in a process, it
becomes a potential alternative energy source, especially for rural
communities. Regardless of its energy value, biogas even if flared will
release CO2 which has substantially less environmental impact than
methane. Last but not least, access to distributed biogas resources sup­
ports the energy (gas and electricity) grid decentralization movement
and improves the higher uptake of variable renewable technologies such
as photovoltaics (PV) and wind. The actual advantage and also necessity
would be in the modulation capability of the renewable electricity
production in order to compensate for the variability in the PV or wind
energy. Other environmental benefits of biogas are:

• Protection of the environment by replacing inorganic fertilizer,


conservation of forest vegetation, reduction of air & water pollution,
and so on [8,9].
• Green energy production in form of heat, power, vehicle fuel, and
Fig. 2. Installed biogas capacity by country as of 2017 (data source: [15]).
trigeneration [10].
• Reduction of greenhouse gas emissions by substituting conventional
Thailand, China, France, and Turkey.
fossil fuels [9].
As also evident from Fig. 2, Europe is the world leader in terms of the
• Disposal of organic matters including household wastes, industrial
installed biogas plant capacity and biogas-based power generation
and municipal solid wastes, and agricultural residues [10].
[16–18]. In 2017, the total number of biogas plants in Europe was 17783
• Supply of base-load energy to the gas and electricity networks.
[16]. At the same year, the number of biomethane plants in Europe was
540 of which 340 were feeding into grid [16]. The majority of the bio­
Full utilization of the sustainable biogas potential can supply nearly
methane generation plants were in Germany (195 plants) followed by
20% of the worldwide natural gas demand. Currently, the sustainable
UK (92 plants) and Sweden (70 plants) [10]. The biogas production in
biogas and biomethane potential is 570 and 730 million tonnes of oil
Europe was 18.4 billion Nm3 (N represents normal conditions i.e. T =
equivalent (Mtoe), respectively [11].
20 ◦ C, P = 1 atm) that represented a share of 4% in natural gas use [16].
Given the increased political prominence of hydrogen and policies
It has been anticipated that the biogas production will reach 20 billion
and measures to promote it, the contribution of biomethane to energy
Nm3 by 2020 [19]. A review of biogas upgrading technologies in Europe
security and a low emissions future energy mix could be projected. In the
and share of EU transport sector in 2030 can be found in Refs. [20].
search for ‘renewable gas’ the question of the relative economics of
Biogas upgrading technologies are based on pressure swing adsorption,
biomethane versus renewable hydrogen becomes important. Bio­
water scrubbing and chemical scrubbing. Biogas upgrading to bio­
methane has the advantage over hydrogen since natural gas grids and
methane will reach 18 billion cubic meter per year in 2030 (about 9.5
appliances will not require modification, because of the similarity of
times higher than that of 2017). This is equivalent to nearly 10% of the
biomethane to natural gas. The necessary changes of the infrastructure
EU’s projected natural gas import for 2030. Biomethane will contribute
would be rather low up to a H2 share of around 10% (molar or volu­
to about 3% of the natural gas consumption of EU countries in 2030
metric concentration) [12]. The mole fractions of hydrogen in
[21]. It is expected that the maritime and road transport customers will
non-conventional gas in France is 6%, Austria 4%, Germany 5%, and
use a large share of the produced biomethane in the EU.
The Netherlands 12% [13].
In summary, biogas is a sustainable energy vector with several
Actual biomethane production in 2018 was about 35 Mtoe. Based on
benefits including 1) renewable source of energy, 2) lower discharge of
the current policies, the biogas consumption in 2030 and 2040 will be
methane to the air in comparison to LFs or traditional manure man­
around 95, and 150 Mtoe. The sustainable development scenarios are
agement, and 3) having a high-quality digestate by-product used as
even more optimistic and project biogas consumption to reach nearly
fertilizer [22].
190 and 325 Mtoe in 2030 and 2040, respectively. Currently, most of the
Although the literature is rich on biogas upgrading technologies,
biogas is used for onsite power and heat generation. But, as we move in
there exists growing attention to the investment analysis and opera­
time, the amount of biogas being upgraded to biomethane increases and
tional cost reduction of the upgrading routes. The current study reviews
biomethane production becomes the main biogas-processing pathway,
and evaluates the various aspects of biogas as an energy vector such as
leaving onsite power and heat application as the second.
biogas production pathways, conventional and prospective upgrading
Fig. 1 (a) depicts the evolution of the global renewable installed
technologies (including physical, chemical, and biological [23]) with
capacity (bar chart) and the share of biogas (line chart) in the global
their basics of operations, advantages/disadvantages, energy needs,
renewable installed capacity between 2000 and 2017. The installed
methane recovery efficiency, market penetration, biogas market­
renewable capacity in 2010 was 754 GW and increased to 2182 GW in
s/applications in addition to economics of various upgrading technolo­
2017. The share of biogas technology in the global renewable installed
gies. The cost of biogas upgrading depends on raw biogas capacity, the
capacity increased from 0.32% to 0.90% during 2000–2012. Thanks to
concentration of contaminants in the raw biogas, local circumstances,
the fast developments in other renewable technologies such as wind and
energy and water cost, envisaged lifetime of the investment, and so on.
PV, despite growth in biogas installations, its share in the renewable
Furthermore, this paper covers the biogas composition for various
technology mix showed a little decline reaching 0.79 in 2017. Fig. 1 (b)
feedstocks, standard requirements of upgraded biogas for the grid in­
represents the global electricity generation from renewables (bar chart)
jection, biogas conversion to chemicals, upgraded biogas product
and the share of electricity generation from biogas (line chart) between
specifications, the potential hazards of biogas contaminants during
2000 and 2017 [14]. The global electricity generation from renewable
production or upgrading, and final use of the upgraded biogas and CO2.
resources increased from 2850 TWh in 2000–6191 TWh in 2017. This
The rest of the paper proceeds as follows. Section 2 describes the
changed the global share of biogas in electricity generation from 0.46%
biogas supply chain including biogas feedstock, biogas production, and
to about 1.42% in this time period.
the products/by-products (methane, CO2, chemicals) obtained from
Fig. 2 shows the installed biogas capacity (MWel) by country as of
biogas. Section 3 addresses the potential hazards of biogas
2017. Germany with over 6 GWel is on top, followed by the US, UK, Italy,

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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

contaminants, final product specification, biogas upgrading processes, Table 2


in addition to physical/chemical/biological approached for biogas The reduction of GHG emissions of biogas source compared to fossil fuels [31].
upgrading. Costs of biogas upgrading via various technologies are Feedstock GHG reduction vs. fossil fuels [%]
elaborated in Section 4, followed by conclusions in Section 5.
Maize 75
Sugar beet (incl. tops) 85
2. Biogas supply chain Grass 86
Organic household waste 103
Waste from the food industry 119
The biogas supply chain is composed of feedstock supply, biogas Manure 148
processing, production and upgrading/purification, in addition to final
markets/applications, biogas uses or products (e.g. biomethane injec­
tion to gas grid, biomethane conversion to chemicals, etc.). Biogas sector for biomass development is the forestry sector with 87% of the
feedstocks (elaborated in Section 2.1) may be in solid or slurry forms in supply (fuelwood 67% of the biomass feedstock, followed by charcoal
addition to concentrated and dilute liquid form. Some examples are 7%, recovered wood 6%, and wood industry residues 5%). The second
agricultural residues, livestock manure, organic waste materials, and sector is the agriculture sector (animal/agricultural by-products and
sewage sludge. The raw biogas must be cleaned and upgraded in various energy crops) with share of 10% to biomass supply. The third one
degrees to meet the consumers’ gas composition standards (such as mole contributes to 3% by generating energy from MSW and landfill gas. In
fractions of H2, CO2, O2, and H2S in the upgraded biogas). Thereby, the 2015 and in terms of total biogas plants per feedstock in the EU, about
selection of cleaning and upgrading technologies (see Section 3.3 and 71% of biogas was produced from agriculture sources, followed by 16%
3.4) depends on the upgraded biogas demand, the levels of raw biogas from sewage, 9% from LFs and the rest from other sources [19]. Europe
contaminants, and project-specific circumstances. has more than 50% of the global agricultural area, and nearly 55% of the
A list of existing production and upgrading plants in Europe and global waste to energy conversion [32]. The biomass supply source
around the world based on various features (such as the feedstock, final varies among the continents and for biogas as a renewable energy
application of biogas, upgrading technology, the methane content of the source, Europe is an evident leader [32].
upgraded gas, plant capacity and date of plant commencement) is
available in Refs. [24,25]. In addition, a list of providers of upgrading
technologies is available in Ref. [25]. This list includes the manufac­ 2.2. Biogas production
turers of PSA units, water/chemical scrubbers, organic physical scrub­
bing units, membrane modules, cryogenic units, and small-scale biogas Biogas is produced from different routes and environments. Its
upgrading installations. Ref. [25] also gives the number of upgrading composition is a function of several factors such as the nature of the
units by types in several European countries. substrate used to produce biogas, and the process design [33]. The
various routes of biogas production are:

2.1. Biogas feedstock • Anaerobic digestion (AD) is known as the biological conversion
process in an oxygen-free environment and is carried out in four
The content of fats, proteins, and carbohydrates in the substrates has steps including hydrolysis, acidogenesis, acetogenesis, and meth­
an obvious direct impact on the biogas production system and the sub­ anogenesis (Fig. 3), [34,35]. Various types of waste materials such as
sequent upgrading sequence. Table 1 lists the methane and biogas yield food waste, agricultural and industrial wastes, MSW, wastewater,
obtained from various feedstocks. It shows that depending on feedstock and crops can be used as feedstock for the AD process [29,36].
type, methane yield can vary between 51% and 65%. The range of • Anaerobic degradation in LFs (natural decomposition of waste). An
produced biogas volume is even much wider spanning from 25 to 202 LF site is a location dedicated for dumping garbage, rubbish or other
m3 per tonne of fresh feedstock. sorts of solid wastes. With the growing waste production from
Subsequently, the actual greenhouse gas (GHG) emissions reduction homes, offices, hospitals, schools, and markets, landfilling has been
depends on the substrate source used. Table 2 lists the GHG emissions the most common disposal approach. LFs are either left to pile in
reduction of some feedstock with maize being the lowest (75%) and heaps or buried. While LFs are the most cost-efficient method of
manure being the highest (148%). disposing waste materials, they are associated with environmental
In 2014, the total biomass supply was 59.2 Etta Joule (EJ), i.e. 10.3% risks. Soil, water, and predominantly air are dirtied by the deposition
of the global energy supply, with annual growth of 2.3% [32]. The key of waste materials in the LFs [37]. In addition, decomposition of
organic materials in the oxygen-free environment is slow which in
Table 1 long-term has negative effects on the next generations. There are five
Methane and biogas yields of various feedstock materials [26–30]. distinct types of landfilling including LF as a deposit of inert waste,
Feedstock Methane yield Biogas yield [Nm3/tFF] (FF: fresh aerobic, semi-aerobic, hybrid, and anaerobic [38]. To produce
[Vol %] feedstock) biogas from LFs, complex biochemical conversion processes
Distillers grains with 61 40 including different phases should be designed.
solubles • Novel AD technologies including high rate anaerobic reactors
Grass silage 54 172 (HRAR), membrane bioreactors (MBR), and integrated HRAR- MBR,
Pig manure 60 60 [39].
Sweet sorghum 54 108
Cattle manure 60 45
Corn silage 52 202 Depending on the source, biogas can contain contaminants including
Liquid pig manure 65 28 sulphur compounds (H2S, sulphides, disulphides and thiols), haloge­
Forage beet 51 111 nated compounds, nitrogen and organic silicon species.
Organic waste 61 100
The biogas obtained from a conventional LF is a complex mixture of
Beet 53 88
Liquid cattle manure 60 25 compounds [42]. A typical composition of LF gas may contain: methane
Poultry manure 60 80 (35–65%), CO2 (15–50%), N2 (5–40%) that seeps into the LF gas during
Whey 15 330 recovery, O2 (0–5%), H2 (0–3%), H2O (0–5%), CO (0–3%), H2S (0–100
Cattle slurry 12.8 200 ppm), NH3 (0–5 ppm), halocarbons (20–200 ppm), volatile organic
Flotation sludge 21.6 540
compounds, VOC (0–4500 mg/m3), and siloxanes (0–50 mg/m3). A

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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

for domestic stoves [47]. If the purity of the biogas is not of impor­
tance, other upgrading technologies can be employed.
• Heat/Power: Otto, diesel engines, and gas turbines can be fueled by
biogas. About 30–40% of the biogas energy is converted to power
while the remaining energy can be extracted as heat. With the
exception of the Otto engines, biogas can used in dual-fuel engines.
In a dual-fuel engine, biogas and diesel are used to maintain the ef­
ficiency of the diesel engine as high as possible. Among the conti­
nents, Europe is the main producer of bioelectricity and heat from
biogas [32].
• Fuel for vehicles: upgraded biogas can fuel light- or heavy-duty
vehicles such as cars, buses and trucks. The odorized and pressur­
ized biogas (to nearly 200 bar) is used as fuel in vehicles. A higher H2
content in biogas is allowed to be used to fuel vehicles. The use of
biogas as a vehicle fuel is considered as the best way to reduce fossil
fuel consumption [31].
• Injection to gas pipelines: To inject biogas to the gas transmission
networks, it must meet the related standards and requirements listed
in Table 4. The injection of a high-quality upgraded biogas (bio­
methane) to gas grids is the optimal solution to distribute bio­
methane in the countries with an extensive natural gas network [48].
Injecting biomethane into national gas networks creates new mar­
kets and applications. Biomethane and natural gas can be mixed
liberally and are wholly interchangeable. Virtual ‘green gas’ distri­
bution networks are simply implementable to produce green elec­
tricity and heat.

2.3.2. CO2
CO2 is one of the key species of the Earth’s texture and can be found
in its core, crust, as well as in the atmosphere. The increased CO2
emissions are the main rationale for anthropogenic climate change. CO2
capture and storage (CCS) has received much attention over the last two
decades as one of the main climate change mitigation options. The total
Fig. 3. Anaerobic digestion process model [28,40,41]. CO2 emitted to the air is nearly 32.2 giga tonnes/annum and the major
CO2 emitter sectors are power/heat production (42.4%), transportation
simpler biogas may be obtained from the degradation of livestock (23%), manufacturing industries and construction (19%), residential
manure in an oxygen-free environment, sewage sludge or (5.8%), services (2.7%), and others (7.1%) [50,51]. The current global
agro-industrial wastes which encompasses methane (53–70%), carbon CO2 utilization amounts up to about 200 million tonnes/annum.
dioxide (30–47%), N2 (0–3%), O2 (0–1%), H2O (5–10%), H2S (0–10 Implementing the carbon tax policies make the CO2 capture inevitable
ppm), NH3 (0–100 ppm), hydrocarbons (0–200 mg/m3), and siloxanes and the CO2 would be available at a low or even negative price. This may
(0–41 mg/m3). CO2, H2O and N2 are the main contaminants of biogas. In interrupt the current trend of CO2 valorization and consequently in­
Ref. [43], the chloride amount in LF gases was reported to be 118–735 crease the CO2 utilization in the current and/or new industries. CO2 can
and total fluorine amounted 63–256 mg/m3. be transported via pipelines from CO2 sources to the CO2 demanding
Table 3 represents the biogas properties obtained from digesters and industries (CO2 sinks). The concentration of CO2 to be transported via
LFs. For the purpose of comparison, the last three rows in Table 3 pro­ pipeline must be above 95% [47]. CO2 utilization pathways can be
vide the market natural gas composition in three markets including divided into chemical and physical. Physical CO2 utilization routes
Denmark, The Netherlands, and the North Sea. The biogas produced in include use of it in carbonated drinks, fire extinguisher, dry ice, refrig­
closed digesters shows higher methane content and considerably lower erant, solvent, welding medium, process fluid, algae farms for photo­
N2 and O2 levels than an LF-derived biogas [44]. synthesis, and enhanced oil/gas recovery. CO2 can be chemically
utilized in the following processes: synthesis gas production, methanol
production, di-methyl ether (DME) production, urea synthesis,
2.3. Biogas end-use market di-methyl carbonate (DMC) production [52], polyurethane production
[53], Fischer-Tropsch gas-to-liquid (FT-GTL) products [54,55], syn­
Methane and CO2 are the major constituents of biogas. In this sec­ thetic methane production [56], chemical looping dry reforming [57],
tion, we discuss the various uses of methane and CO2. mineralization [58], and so on. A literature review of physical and
chemical utilization pathways can be found in Refs. [50]. The CO2 from
2.3.1. Methane the biogas upgrading processes can be used in the CO2 demanding in­
The typical applications of low/medium/high quality gas obtained dustries such as for chemicals production [54,55,59–66]. CO2 utilization
from cleaning/upgrading of biogas are represented in Fig. 4. Upgraded for production of synthetic methane, methanol, and Fischer-Tropsch
biogas can be utilized to produce: derived liquids were addressed by Abdin et al. [59]. Assen and
co-workers [63] studied the direct and indirect utilization of CO2 in the
• Heat: The high quality biogas (biomethane) can be combusted in polyurethane supply chain. The CO2 utilization for polyols (direct route)
boilers/stoves. The generated heat can be used for space heating, is 0.30 kg CO2/kg polyurethane while for indirect route is 1.7 kg CO2/kg
process heating, and so on. Biogas can also be used in boilers without polyurethane. Conversion of CO2 to synthesis gas (syngas) via catalytic
the need to upgrade it [47]. Chemical absorption upgrading tech­ partial oxidation of methane was considered by Chen [64]. The
nology is the most suitable way to produce high quality biomethane maximum syngas production was reported at CO2/O2 ratio of 0.2 when

5
A. Rafiee et al.
Table 3
Typical composition of biogas from AD, LF gas and natural gas [45].
Biogas CH4 (%) CO2 (%) O2 (%) N2 (%) H2 H2S (ppm) Heavy Ammonia Other (mg/Nm3) Physical properties Ref.
(%) hydrocarbons (%) (ppm)
Density LHV Wobbe index Methane
(kg/m3) (MJ/ (MJ/Nm3) number
NM3)

LF 35–65 (45) 15–40 0–5 5–40 (15) 0–3 0–100 (<100) 0 5 Total chlorine: 1.3 16 18 >130 [31]
(40) (1) 20–200
LF 30–60 (45) 15–40 0–10 0–50 (15) 0–2 0–1000 (<100) 0–5 (5) mg/ BTX: 0–500 0.8 21 27 144 [13]
(40) (1) (1.5) mg/m3 m3 Total chlorine: 0–800
Total fluorine: 0–800
(10)
Siloxanes:0–50
LF 47–57 37–43 <1 <1–17 36–230 Halogenated [46]
compounds: 0.3–1.3
Organic silicon
compounds: 0.7–4
Benzene: 0.6–2.3
Toluene: 1.7–5.1
AD 60–70 (65) 30–40 0 NA (0.2) 0 0–4000 (<500) 0 100 Total chlorine:0–5 1.1 23 27 [31]
6

>135
(35)
AD 50–80 (65) 15–50 0–1 0–5 (0.2) 0–2 100–10000 0–100 (100) BTX: 0–20 0.8 22 26 135 [13]
(35) (<600) mg/m3 mg/m3 Total chlorine:0–100
Total fluorine: 0–100
(0.5)
Siloxanes: 0–50
AD 53–70 (63) 30–47 0 0.2 0 0–1000 (<1000) 0 <100 0–5 1.2 23 27 >135 [44]
(47)
AD 55–58 37–38 <1 <1–2 32–169 Organic silicon [46]
compounds: < 0.4
Benzene: 0.7–1.3
Toluene: 0.2–0.7
Danish 85–92 (90) 0.2–1.5 – 0.3–1 – 1.1–5.9 (3.1) 9 – – 0.82 39 55 73 [31]
Natural (0.7) (0.3)
gas
Dutch 81 1 14 3.5 0.8 32 44 – [24,
Natural 44]

Biomass and Bioenergy 144 (2021) 105935


gas
North Sea 86.6–88.8 1.9–2.3 <0.01 0.9–1.1 0–5 (1.5) 8.3–8.5 (8.3) BTX:0–1750 0.7 35 50 76 [13]
natural gas (88.8) (2.3) (1.1) mg/m3
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

Table 4
Standard requirements of upgraded biogas for injecting to gird or fueling vehicles of several countries [13,24,31,34,49].
Market France Germany Sweden* Switzerland Austria The
specifications Netherlands
L Gas H Gas L Gas Grid H Gas Grid Biogas type Biogas type Lim. Unlim.
A B Injection Injection

CH4 (%) 97 ± 1 97 ± 2 >50 >96 >80


CO2 (%) <2 <2 <6 <6 <6 <6 <2
O2 (%) <0.01 <0.01 <3 <3 <1 <1 <0.5 <0.5 <0.5 <0.5
H2 (%) <6 <6 <5 <5 <5 <5 <4 <12
CO2+O2+N2 (%) <4 <5
Sulphur (mg/Nm3) <100 <100 <30 <30 <23 <23 <30 <30 <5 <45
Water (%) 32 (mg/m3) 32 (mg/m3)
NH3 (mg/m3) 20 20
Water dew point <-5 <-5 < ground <ground T*-5 T*-5 <-8 (@40 − 10 (@10
(◦ C) temp temp bars) bars)
Wobbe index (MJ/ 42.48– 48.24– 37.8–46.8 46.1–56.5 44.7–46.4 43.9–47.3 47.7–56.5 43.46–44.41
Nm3) 46.8 56.52

* Biogas type A is used in ‘lean-burn’ engines i.e. heavy vehicles such as trucks and buses while type B is used in stoichiometric combustion engines of private cars. **T
= lowest average daily temperature on a monthly basis.

separator and an absorption unit to remove water. The dried syngas is


then fed into a methanol reactor. Methanol production via biological
conversion of biogas using methane-oxidizing bacteria (methanotrophs)
is investigated in Ref. [73].
Hydrogen can be produced via biogas dry reforming. In Ref. [71], the
preparation of the catalyst, the optimization of process conditions, types
of reactors, and the impact of biogas contaminants were reviewed. A
proprietary skid-mounted, small-scale DME production unit that con­
verts biogas (with up to 50% CO2 content) was developed by Oberon
Fuels [74]. The production capacity of the unit is 10,000 gallons/day.
Yang et al. [70] reviewed conversion of biogas to hydrogen/syngas,
methanol for gasoline production, ethanol and higher alcohols. For
biogas conversion to hydrogen/syngas, reforming technologies such as
dry reforming, steam reforming, and partial oxidative reforming were
discussed. Partial oxidation of methane, photo-catalytic conversion,
Fig. 4. LF gas utilization pathways. biological conversion and indirect conversion were addressed for
methanol production. For ethanol and higher alcohols production,
the oxygen to carbon ratio is one. In addition, 10–41% of CO2 can be direct approaches and indirect routes (such as syngas fermentation and
consumed for syngas production in the catalytic partial oxidation of catalytic conversion) were elaborated. A novel approach for simulta­
methane. Uner et al. reviewed photocatalytic water splitting and CO2 neous biogas upgrading and co-production of succinic acid and bio­
reduction to produce methane and methanol [65]. Conversion of CO2 to methane was addressed by Gunnarsson et al. [75]. Bacterial strain
FT-derived liquid fuels was addressed in Ref. [54,55,60]. CO2 was fed to actinobacillus succinogenes 130Z was used to produce high-purity
the reforming section of the GTL process. CO2 conversion to methanol methane.
was investigated in Ref. [66] where the CO2 stream came from a
power-plant CO2 capture process. Methanol production through CO2 3. Biogas upgrading
hydrogenation was studied in Ref. [67,68]. The methanol production
rate of the process with an inlet H2/CO2 ratio of 3 is nearly 59% higher Biogas upgrading is necessary because of two constraints: 1) product
than the process with an inlet H2/CO2 ratio of 2 [67]. The profit index of safety due to potential hazards caused by contaminants (see Section 3.1,
a two-stage reactor system is 2.05% higher than the process with one 3.2), and 2) product quality enforced by market specifications (see
reactor [68]. Section 3.1, 3.2).

2.3.3. Biogas conversion to chemicals 3.1. Potential hazards of biogas contaminants


In addition to the separation of CO2 content of biogas to increase its
methane content, there exists another approach to valorize the biogas Certain actions must be taken to minimize the emissions from AD
CO2 content to commodity fuels and chemicals such as methane [69,70], biogas plants [76]. These actions include the use of flares to avoid
methanol, and hydrogen [70,71]. In the biogas to methane process, the methane emissions, enhancing the thermal and electrical efficiency of
biogas stream is mixed with additional hydrogen coming from a solid CHP units, and to avoid leakage to the air [77,78].
oxide electrolysis cell (SOEC) and then is conveyed to a methanation CO2 release to the air takes place during combustion of biogas,
reactor [69]. Boiling water is used in the methanation reactor as the transport and storage of biomass, in addition to digestate use. Poeschl
reactor-cooling medium. Operation of a full-scale methanation reactor et al. [79] studied the CO2 release to the environment during the pro­
under favorable conditions for 1000 h is possible. To obtain pipeline duction of biogas from supply system of several feedstocks, biogas plant
quality gas, the optimal H2 to CO2 ratio to the methanation reactor must infrastructure, in addition to digestate management. Biogas production
be 3.9. from waste materials (such as pomace, cattle manure, food residues, and
Tamnitra and co-workers [72] simulated methanol production from slaughter waste) is more sustainable than utilization of energy crops. In
biogas. In their simulation, biogas is preheated, mixed with steam, and addition, management of digestate materials results in higher total
then is conveyed to a reformer. The reformer outflow is sent to a emission mitigation when an MSW feedstock is used.
Methane emissions from biogas processes do not have any health

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issue and there is no evidence of health issue between biological systems Table 5
and methane [80,81]. The main release points of methane in the biogas Potential hazards of biogas contaminants and recommended countermeasures
supply chain are biomass storage, incomplete combustion of biogas, and [7,13,29,83].
digestate management. Hazardous Hazard Countermeasure
Nitrous oxide emissions from biogas results in a considerable impact Component/agent
on global warming [82]. Halocarbons • Corrosive gases: affect the • Sampling and analysis
Biogas production and handling is associated with some safety con­ integrity of the system. of halocarbons.
cerns that should be considered during the biogas production process. • Production of furans and • Removal of
dioxins under combustion halocarbons.
The following hazards shall be kept to a minimum level [7,13]:
conditions: health issues. • Exclusion of materials
• Toxic and corrosive with high halocarbon
➢ The health of end-users and employees: direct toxicity with un­ combustion species: content.
burned gas and, indirect toxicity by biogas combustion, chemical influence on end-user
products, water and air pollution. equipment and health
issues.
➢ Operation of gas facilities and appliances, and gas grids integ­ High content of • Change of combustion • Adding heavier
rity: some hazards include corrosion and clogging of the grid CO2 properties, which affects the hydrocarbons.
equipment, clogging as well as the failure of end-user appliances, etc. performance and safety of • Mixing biogas with
final-user equipment. natural gas.
• Maintaining CO2
In some situations, the treatment processes may suffice to decrease
concentration within
the hazards to acceptable levels. In other occasions, specific treatments tolerable limits.
of the raw gas may be required. Table 5 indicates the potential hazards Ammonia • Corrosive gas: impact on the • Sampling and analyzing
of biogas contaminants during the biogas production process, gas integrity of the gas network. for ammonia.
treatment equipment, and so on. Water in combination with O2 or CO2 • Toxic compound: health • Removing ammonia
issues. from the gas.
can introduce system integrity problems. In addition, H2S in combina­
• Increased NOx emissions
tion with water and O2 produces H2SO4, that cause corrosion of gas after combustion.
storage tanks, gas pipelines, engines and compressors. The existence of Biological agents • Bio corrosion: affects the • Sterilization of the
NH3 and halocarbons corrodes pipelines and engines when biogas is integrity of the system. substrate material.
• Health hazard in case of • Filtration.
combusted [24].
presence of pathogenic • Increase digester
Biogas combustion releases pollutants to the air. For example, CO is agents retention time.
the key by-product of biogas incomplete combustion. Sulphur dioxide Polyaromatic • Effect on elastomer and • Monitoring and
pollutants depend mainly on the efficiency of desulphurization section hydrocarbons plastic material: system removal.
of the biogas upgrading plant. NOx emissions, non-methane volatile (PAHs) integrity issues.
• Carcinogen and toxic: health
organic compounds, and formaldehydes are other key pollutants of the
issues.
biogas combustion process. The emission factors of the mentioned pol­ • Soot formation when PAHs
lutants are given in Ref. [84,85]. are burnt.
The storage, management, and treatment of feedstock and digestate • Impact on safety and
performance of end-user
materials are the most important steps from the global warming point of
equipment
view in biogas production processes [76]. Most of nitrous oxide emis­ Siloxanes • Production of silica at • Sampling and
sions can be avoided when we use closed storage for manure in addition combustion conditions analyzing.
to co-digestion feeding strategy. Outspreading untreated biomass ma­ which affects the user • Elimination of materials
terials on the ground will release large quantities of methane, ammonia, equipment. with high silicon
content.
nitrous oxide, volatile hydrocarbons, etc. to the air.
• Removing siloxanes
from the biomass
3.2. Requirements for upgraded biogas product specification material or the biogas.
Phosphine (PH3) • Toxic compounds: health • Sampling and analysis.
and phosgene issues. • Removal of phosphine/
Table 6 summarizes the requirements used for biomethane utiliza­
(COCl2) • Corrosive species: Affect the phosgene from the
tion pathways and the associated optional upgrading technologies. integrity of the system. biogas.
Gas grids have also certain specifications for the protection of both • Exclusion of sources
pipeline assets and end-users. To guarantee the safety, operability and with high phosphine/
integrity of gas grids, conventional and nonconventional gases should phosgene content.

meet the least quality requirements. Each country may have its own
standards and requirements for the biomethane grid injection, and the fuel to ensure engine performance. Biogas containing organo­
vehicle use (see Table 4). Table 7 demonstrates the parameters that are chloride contribute to corrosion in combustion engines or vehicles while
constrained in the US legislation or within the EU directives for cross- under certain combustion conditions, the formation of furans and di­
border gas transmission. oxins is also possible [43].
Apart from methane and CO2, biogas may encompass water, H2S, O2, Depending on the specifications of end-users, the required compo­
N2, siloxanes, NH3, and particles. The energy content of biogas is pro­ sition and consequently the type of upgrading technology to be applied
portional to its methane content, thereby cleaning and upgrading of the is determined. It is also of great importance to minimize methane release
biogas (i.e. removing contaminants) rise the calorific value of the gas. In from the upgrading process to the air, water leakage from a water
the upgrading methods that CO2 is separated from the raw biogas, some scrubber, and any other stream exiting the plant. For instance, in the
of the other contaminants are also removed. However, mechanical wear absorber, some of the methane can be absorbed into the liquid and then
and corrosion of the upgrading equipment is avoided if the biogas is be released into the air with the gas stream. The absorption liquid used
cleaned before the upgrading process for CO2 removal. The hydrogen in the process needs to be treated with other wastewaters.
sulphide and halogenated compounds present in biogas can cause The techniques used to clean, and upgrade biogas are described
corrosion to engines. In the presence of water, sulphur compounds below. These technologies are available in standardized and pre-
corrode gas storage tanks, compressors, and engines. Engine manufac­ fabricated modules [87].
turers may set minimum limits on methane content (energy density) of

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Table 6
Gas quality and technological recommendations regarding biogas utilization [34,47].
Utilization pathway CH4 content (%) CO2 content (%) Contaminants Cleaning and upgrading technology

Domestic stoves Heating value comparable to – H2S < 10 ppm H2S: iron hydroxide/oxide.
natural gas CO2: chemical absorption.
Boiler – – H2S < 250 ppm H2S: biological desulphurization.
Internal combustion >30 – H2S: 545–1742 ppm. H2S: biological desulphurization.
engine Halides: 60–491 ppm.
Siloxanes: 9–44 ppm.
Dew point: Ta-6.7 ◦ C.
Stirling engine >35 – H2S < 2800 ppm. H2S: biological desulphurization.
Siloxanes: about 0.42 ppm.
Halides: 232 ppm.
Dew point: T-6.7 ◦ C.
Gas turbine/micro >35 – H2S: 10,000 ppm. Siloxanes: around 0.087 ppm H2S: biological desulphurization.
turbine (0.005 for micro- turbine).
Dew point: T-6.7 ◦ C.
Natural gas grid 70–98 1.0–8 H2S: 2–15 mg/m3; N2: 2–10%. H2S: impregnated activated carbon and iron
injection H2: 0.1–4%. hydroxide/oxide.
O2: 0.01–3%. CO2: PSA + membrane.
When O2 and N2 removal is required.
Chemical absorption + PSA if high methane
purity is needed.
Vehicle fuel >96 <3 H2S: 5 mg/m3. H2S: impregnated activated carbon along with
iron hydroxide/oxide.
CO2: chemical absorption/cryogenic separation.
Fuel cell SOFC: as much as possible. SOFC: as little as H2S: 1–5 ppm (MCFC) and 1 ppm (SOFC). H2S: impregnated activated carbon together
MCFC: no specification. possible. Siloxanes: few ppm. with iron hydroxide/oxide.
MCFC: <35
a
T: gas temperature, MCFC: molten-carbonate fuel cell, SOFC: solid oxide fuel cell.

3.3. Biogas upgrading processes


Table 7
Quality parameters in the proposed harmonized EU H-gas cross-border gas
The market of emerging as well as conventional technologies for
transmission grids [13,86].
biogas upgrading is currently changing because of the stringent
Parameter Value
composition specifications [88]. Biogas upgrading adds investment and
Wobbe index 13.6–15.81 KWh/m3 (25 ◦ C/0 ◦ C) operating costs to the overall process. As such, it is essential to choose
Relative density 0.555–0.7 the most suitable biogas upgrading method, and to optimize the process
Total Sulphur <30 mg/m3
with regard to minimum energy consumption and maximum methane
(H2S + COS) <5 mg/m3
Mercaptans <6 mg/m3 concentration of the upgraded gas. Physical or chemical upgrading
Oxygen <10 ppm methods need high energy requirements and/or chemicals. As a result,
Carbon dioxide <2.5% molar the development of alternative biogas upgrading technologies (e.g.
Water dewpoint < − 8 ◦ C at 70 bara
biological methods, microbial electrochemical) with lower operating
Hydrocarbon dewpoint < − 2 ◦ C over 1–70 bara
costs as well as environmental impacts has been triggered [44]. The
upgrading costs of the established methods depend on the selected
technology, and most prominently on the size of the plant [24]. There
are commercial plants for raw gas capacities below ca. 250 Nm3/h, and

Table 8
The required contaminants concentrations in the raw biogas in the various upgrading methods.
Upgrading technology H2S VOC O2/N2/H2 NH3

Chemical scrubbing Moderate concentrations. Moderate concentrations. Go to the upgraded gas. Moderate concentrations.
Main part goes to CO2 stream. Main part removed with the CO2 Main part goes to the CO2
Polish filter may be needed in upgraded and condensate streams. stream.
gas.
Water scrubbing Moderate concentrations. Moderate concentrations. Go to the upgraded gas. Moderate concentrations.
Main part goes to the stripper Main part removed with the Main part removed with process
air. condensate water.
and stripper air.
PSA Low concentrations Removal from raw gas is required. O2/N2 go to CO2 stream, Removal from raw gas is required.
H2 goes to product gas
Organic physical Moderate concentrations. Moderate concentrations. Go to the upgraded gas. Moderate concentrations.
scrubbing main part goes main part goes main part goes
to the stripper to the stripper to the stripper
air. air. air.
Membrane separation Low concentrations. Removal from raw gas is required. Go to the Usually removed with condensate
some amount goes to the CO2 and upgraded gas during drying the raw biogas.
product gas. stream.
Cryogenic separation Moderate concentrations. Moderate to high Go to the upgraded gas. Moderate to high
Removed during first stage concentrations. concentrations.
refrigeration. Removed during first stage Removed during first stage
refrigeration. refrigeration.

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plants larger than about 2000 Nm3/h are under construction. heated before desorption (see Fig. 7). In addition, CO2 solubility in
New technologies such as cryogenic upgrading [24], in-situ methane Selexol and Genosorb solvents are 5 and 17 times higher than in water.
enrichment in AD [89,90] and ecological lung [24] are also being Thereby, the diameters of the scrubbers are smaller than those of water
developed. Note that the stage of development of the upgrading routes scrubbers, since a lower flowrate of the organic solvent is needed.
might be quite different.
The required contaminants concentration of the raw biogas 3.3.3. Chemical scrubbing
conveyed to upgrading technologies are listed in Table 8 [91]. A detailed This upgrading process is fundamentally similar to water or organic
process description of the upgrading technologies can be found in Refs. solvent scrubbing (Fig. 8). The process configuration consists of a
[92–94]. A comparison of different upgrading techniques including PSA, packed bed (filled with structured or random packings) absorption unit
water scrubber, and amine scrubber for different raw gas capacities can (in which the CO2 is separated from the biogas) plus a stripper (regen­
be found in Ref. [24]. erator) equipped with a reboiler. This process is simpler than water/
In Europe and in 2015, water scrubbing method accounted for 34% organic scrubbing due to the enhanced process performance of using
of the upgrading market, followed by chemical absorption, and pressure CO2-reactive absorbents such as alkali aqueous solutions or alkanol
swing adsorption (PSA) with 25, and 20%, respectively (see Fig. 5) [19]. amines. The CO2 (and H2S) of the raw biogas react with the amine. The
Other mature technologies such as membrane separation, and physical absorber operates at 1–2 bar while the operating pressure of the stripper
absorption represent 13, and 8% of the market share, respectively [19]. is usually 1.5–3 bar. Steam can be used in the reboiler of the stripper.

3.3.1. Water scrubbing 3.3.4. Pressure swing adsorption (PSA)


CO2 removal via water scrubbers is a traditional approach in This technique is a dry method which is based on the selective
chemical engineering. This process is based on the reality that the water adsorption of CO2 over CH4 onto zeolite and polymeric sorbents, silica-
solubility of CO2 is approximately 26 times (at 25 ◦ C) higher than that of gel, activated alumina, or activated carbon [96]. Packed bed columns
CH4, [42]. The availability of cheap water supply is a determinative operating in parallel under pressurization, feed, blowdown and purge
element in the selection of this technology. The CO2 removal from the regime. The compressed raw biogas enters the adsorption column where
biogas produced in wastewater treatment plants can be performed in CO2 is retained and methane flows through the bed. When the adsorbent
single-pass water scrubbers operating at 6–10 bar. However, LF biogas is saturated with CO2, the feeding is stopped, the blowdown phase is
can be treated in a sequential water scrubber with tap water coupled to a initiated by decreasing the pressure to release CO2 which can be directed
two-stage desorption column in order to regenerate water. The absorp­ into an off-gas stream. For continuous operation of the process, four
tion column is filled with Pall or Raschig rings random packing and packed bed columns are being closed and opened consecutively (Fig. 9).
counter-current flow of water and gas minimizes the energy consump­
tion and the methane loss [95]. Water flowrate depends on operational 3.3.5. Membrane separation
pressure. In the desorption column, CO2 is removed from water by This separation technique is based on the selective permeation of gas
addition of atmospheric air. The regenerated absorbent is then returned components flowing through a semi-permeable membrane. Polymeric
to the absorption unit (Fig. 6). materials are preferred membranes over non-polymeric materials for
A typical flow of about 0.1–0.2 m3 water per Nm3 of raw biogas is upgrading the biogas due to the lower cost, stability at high pressures,
reported for single-pass water scrubbers. The water consumption of easy manufacture, and easy scalability. Most of the methane is retained
process designs with water recycling lies within the range of 0.18–0.23 while most of the CO2 permeates through the membrane. The biogas is
m3/Nm3 of biogas. Higher operating pressures result in lower water cleaned (to remove particles, H2O, H2S, VOCs, NH3, and siloxanes [97,
flowrates but increases compression, and pumping costs. Off-gas treat­ 98]) to avoid deterioration and clogging of the membrane stages,
ment processes such as biofilters, incinerators, or activated carbon filters compressed to 6–20 bar, and then is fed to membrane modules. The
used to minimize H2S, and CH4 emissions from the desorption column process may have several membrane stages.
entail additional costs to the process.
3.3.6. Cryogenic separation
3.3.2. Organic solvent scrubbing In this method, contaminants like H2S and CO2 are liquefied and
This upgrading technology is very similar to water scrubbers, except separated in three successive stages to remove them and also to optimize
that the use of solvent increases the CO2 solubility and thus capture. The the energy recovery [99]. The temperature of the compressed biogas to
organic solvent-based scrubbing needs a gas pre-treatment unit (to the first separator is − 45 ◦ C, to the second one is − 70 ◦ C and to the third
separate water) and several inter-cooling/-heating stages to guarantee separator is − 120 ◦ C.
an efficient operation i.e. the solvent is cooled before absorption and
3.3.7. Process configuration
No single technology can remove all contaminants in biogas.
Generally, each upgrading technology is capable of removing one or two
contaminants. Ultimately, based on the biomethane requirement as­
pects, a combination of processes is used to build the biogas upgrading
plant. The combination of the techniques used for cleaning and
upgrading biogas is illustrated in Fig. 10.
The physical/chemical processes used to remove biogas contami­
nants are described in Section 3.4.

3.4. Physical/chemical processes for contaminants removal

3.4.1. Water removal


The water content of biogas may condensate or form hydrates in
transmission lines and make corrosion and erosion issues [24]. Water
can be separated by cooling, compression, adsorption or absorption. By
Fig. 5. Evolution of the operational biogas upgrading plants in Europe dur­ decreasing the temperature or increasing the pressure, water condenses
ing 2001–2012. and is then removed, [45]. Water removal by adsorption can be achieved

10
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Fig. 6. Schematic of biogas upgrading using water scrubber.

Fig. 7. Schematic of biogas upgrading using organic solvent scrubber.

by SiO2, molecular sieves or activated carbon. The regeneration process hydroxides/chlorides to the digester liquid phase [104,105]. Use of
can be done by heating or a decrease in pressure. Absorption can be sodium and calcium hydroxide in the process causes the formation of
performed in glycol solutions (regenerated by heating) such as ethylene salts with elemental sulphur which cannot be regenerated.
glycol (EG), di-ethylene glycol (DEG), tri-ethylene glycol (TEG) or by the The H2S content of biogas can be eliminated by adsorption/oxidation
use of hygroscopic salts. to elemental sulphur or conversion to SO2 [33]. Mezmur and Bogale
used KOH/NaOH and activated carbon to reduce CO2- and H2S- content
3.4.2. H2S removal technologies of biogas by 82 and 99%, respectively [106]. In addition, charcoal and
The H2S present in the raw biogas can be removed by adsorption silica gel were employed to remove the moisture. The cleaned biogas
onto several materials including activated carbon iron oxide or hy­ was used for power generation.
droxide [100], membrane separation, calcium hydroxide Ca(OH)2 Membrane-based separation can also be used for the selective H2S
[101], ethylenediaminetetraacetic acid Fe-EDTA [102], in-situ precipi­ removal from biogas [107]. Polyimide, poly-sulphone and cellulose
tation in the digester via iron salt addition, and absorption [103]. The acetate are commonly used as membrane materials for the biogas
most straightforward method of controlling H2S concentration in the upgrading purposes [108]. Significant improvement in the desulphuri­
biogas is the in-situ desulphurization occurring in the biogas digester. It zation efficiency can be achieved if special rubbery polymeric mem­
can be done by dosing air/pure oxygen to the digester gas stream or iron brane material is used [109].

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that contain a silicon-oxygen bond (Si–O) and are used in shampoos and
deodorants. So, siloxanes can be found in raw biogas originated from
both sewage sludge treatment plants and LFs. Siloxanes, VOCs and
halocarbons can be separated from the biogas by adsorption on acti­
vated carbon [42,105]. Siloxanes can also be removed by cooling the
biogas, silica gel/activated aluminum, or absorption in a mixture of
liquid hydrocarbons [24]. Siloxanes can also be separated during the
H2S removal process. The adsorption on activated carbon must be run
under high pressure with low moisture contents of biogas. There are
some technical problems with the regeneration of activated carbon
materials. The reported siloxanes removal efficiency via adsorption on
activated carbon are 95% [105] and 74–83% [115]. In addition, using
cryogenic condensation of siloxanes, a removal efficiency of 25.9 and
99.3% can be obtained when the biomethane temperature is dropped to
− 25 and − 70 ◦ C, respectively [42]. The cryogenic condensation route
needs high investment and operating costs [113].
Use of ionic liquids in removing VOC compounds from raw biogas
was studied by Privalova et al. [116]. Experimental results suggest that
1-butyl-3-methylimidazolium acetate [BMIM] [AC] ionic liquid has a
better performance compared to aqueous amines solutions as it captures
65 wt% of the identified VOC compounds, whereas amine solutions
retain nearby 35 wt% only.

3.4.4. N2 and O2 removal technologies


Fig. 8. Schematic of biogas upgrading using chemical scrubber. N2 and O2 are present at high molar concentrations from LFs when
vacuum generation is used to collect the raw biogas as a consequence of
Table 9 represents the pros and cons of the physical/chemical H2S air infiltration. The technologies used for both N2 and O2 removal are
removal routes. adsorption with activated carbon, molecular sieves, pressure swing
H2S and CO2 can also be removed from the raw biogas using cryo­ adsorption, membrane and cryogenic separation. A fraction of N2 and O2
genic separation [110]. For large-scale biogas desulphurization, there can be separated during the desulphurization processes or via some of
exist three patented H2S removal processes i.e. Biopuric®, Thiopaq®, the upgrading routes. Removal of both N2 and O2 is cumbersome and
and H2SPLUS SYSTEM®, [111–113]. In these processes, the combina­ expensive. The concentration of these species in the upgraded biogas
tion of bioreactors and chemical scrubbers are used. should be too low unless the biogas is used for boilers or CHP units. The
corresponding pros and cons of the upgrading process routes used to
3.4.3. Halocarbons, volatile organic compounds (VOC), siloxanes removal remove N2 and O2 are listed in Table 10.
technologies
Halogenated compounds contain one or several halogen atoms 3.4.5. CO2 removal technologies
including chlorine, fluorine, iodine or bromine [114]. Examples of The CO2 content of biogas is about 25–50% on a volume basis and its
halogenated compounds are carbon chlorobenzene, tetrachloride, removal from biogas is essential to enhance the biogas energy density
tri-fluoromethane and chloroform. Halocarbons are often seen in the LF and heating value, and to mitigate the costs of pipeline/road/rail
biogas but rarely found in the AD biogas or from sewage sludge, and transportation. Physical/chemical methods used to remove CO2 from
organic wastes. Halocarbons are oxidized to corrosive products when the raw biogas are based on the physical or chemical transfer of the CO2
biogas is combusted. The corrosive combustion products together with to another gas, liquid- or solid-state material. The technologies used for
water can cause corrosion issues in downstream pipelines and appli­ CO2 removal are PSA, water scrubbing, organic physical/chemical
ances. In addition, furans (polychlorinated dibenzofurans and poly­ scrubbing, adsorption of gas molecules on adsorbent materials, cryo­
chlorinated dibenzo-p-dioxins), and dioxins can form if the time and genic separation, thermo-catalytic methanation, and membranes sepa­
temperature of combustion are sufficient. Siloxanes are chemical species ration. These technologies are mature and have higher efficiency

Fig. 9. Biogas upgrading using PSA.

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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

Fig. 10. The combinations of biogas cleaning and upgrading processes.

Table 9 Table 10
Pros and cons of physical/chemical H2S removal technologies. Pros and cons of N2 and O2 removal technologies.
H2S removal Advantages Disadvantages N2 and O2 Advantages Disadvantages
technology removal
technology
Adsorption using • Low operating cost. • Temperature should be
iron oxide or • High H2S removal controlled. Membrane • Low energy • Complex maintenance.
hydroxide efficiency, i.e. >99%. • Regeneration of adsorbent separation requirements. • High purchasing cost of
is expensive. • Compact design and membrane.
• H2S content of raw gas must light in weight. • Low CH4 separation efficiency
be < 100 ppm. • Easy operation. and high CH4 loss.
Adsorption on • High H2S removal • Activated carbon has a PSA • Low energy demand. • Water and H2S have to be
activated Efficiency. short lifetime. • CO2, N2 and O2 can be removed before the pressure
Carbon • Carbon regeneration is separated swing adsorption process.
performed at a high simultaneously. • Periodical regeneration of the
temperature. adsorbent is required.
Absorption (sodium • Operation under • Low liquid to biogas ratio is Cryogenic • Simultaneous removal • High capital cost and energy
hydroxide ambient pressure and needed. separation of multiple demand.
washing) temperature. contaminants.
• Water can be used as • CO2 is produced as a by-
solvent. product.
• High H2S removal
efficiency of 90–100%.
Membrane • High H2S removal • Concentration of H2S in the compared to the biological routes used for CO2 removal [110]. CH4
separation efficiency. raw gas must be <2%. recovery is an important factor from the economic and ecological points
• Simultaneous CO2
removal from the raw
of view [117].
gas. The water-scrubbing route is the most popular biogas upgrading
In-situ precipitation • Efficient at high H2S • High operating costs. process. Commercial water scrubbers from several suppliers can be
content of raw gas. • Not efficient at low H2S found in the market for a wide range of gas capacities [24]. In the
• Low investment cost. concentrations.
pressurized water scrubbing process, the raw biogas is compressed and
• Concentration of H2S in the
raw gas must be > 100–150 contacted with water counter-currently in a vertical column. In this
ppm. method, CO2, some quantities of methane and H2S of the raw biogas are
transferred to the water stream. The regeneration step involves a flash
depressurization, to recover methane [70], and a desorption column
operating under atmospheric pressure. The water scrubbing process is
simple and robust but the existence of nitrogen and oxygen in the

13
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

desorption column is a drawback. In addition, bacterial growth takes recommended to install a biogas pre-treatment process for the partial
place and cause clogging. Foaming in the scrubbers is another potential removal of those compounds prior to CO2 separation to avoid opera­
operational problem. tional issues.
Organic physical scrubbing process is extremely similar to water The highest methane recoveries can be achieved with chemical ab­
scrubbing technique unless an organic solvent such as polyethylene sorption compared to all other upgrading approaches (Table 11).
glycol (with higher solubility for CO2/H2S in addition to lower vapor Employing complex designs with membrane separation can yield
pressure) is used as an alternative to water [118]. Commercial processes methane recovery values of up to 99–99.5% at a higher investment cost
using polyethylene glycol (as solvent) are Purisol™, Selexol™, and [44]. It is important to note that lower methane loss can be obtained at
Genosorb™ [100]. Use of solvents reduce the size of absorption vessels, the expense of higher energy demand.
lessen pumping, and mitigate the solvent loss. The fixed capital investment costs of physicochemical CO2 removal
In chemical scrubbing technique, on the other hand, aqueous solu­ processes depend on the concentration of contaminants and plant size (i.
tions of several alkanol amines such as mono-ethanolamine (MEA), e. the economy of scale). Thereby, the higher the biogas upgrading ca­
diethanolamine (DEA), di-glycolamine (DGA), and di-methyl ethanol­ pacity, the lower the investment cost. The capital costs of membrane
amine (DMEA) interact with CO2 that increase the selectivity between separation process rapidly increase as the process is scaled down. The
CO2 and methane resulting in a very low absorption of CH4 s [105]. Most main operating cost of the separation technologies are the cost of elec­
of amine scrubbers operate near atmospheric pressure. The absorption tricity needed for mechanical equipment e.g. biogas compression and
step and chemical reactions are exothermic which heat up the solution pre-treatment, liquid pumping, cost of energy for solvent regeneration at
by around 25 ◦ C. Note that absorption equilibrium favored by low high temperatures in case of chemical absorption, etc. The maintenance
operating temperatures while chemical reactions favored by high cost of a membrane-based upgrading route is about 3–4% of the fixed
operating temperatures. So, optimal operating temperatures must be investment costs, while this value is nearly 2–3% for absorption and
found [100]. The solvent leaving the absorber is heated up for regen­ adsorption processes [42].
eration purposes and then is conveyed to the stripper column operating Acrion Technologies Inc. has built a process named CO2 Wash® for
at high temperature. A pre-desulphurization unit is needed to avoid the upgrading of the LF gas (Fig. 11) [129]. This process removes
poisoning the alkanol amine solvent. Thermal or oxidative degradation sulphur and halogenated compounds, siloxanes, and non-methane hy­
of the solution increases the equipment corrosion potential, chemical drocarbons from the LF biogas. The removed contaminants dissolved in
consumption, and release of hazardous degradation species [119–121]. the liquid CO2 of column bottom stream can be sent to incinerators
Several adsorbent materials such as activated carbon materials, ze­ together with the LF gas. The purified liquid CO2 with purity of 99.99%
olites, titano-silicates, silica gels, etc. can separate CO2 from methane and a gas stream comprising mainly methane and CO2 are the other
[122]. Water removal is necessary before the process to prevent the streams from the CO2 Wash® process. The siloxanes, chlorinated com­
poisoning of the adsorbents. The biogas feed must be pressurized to pounds as well as sulphur contents of the clean methane and CO2 stream
about 10 bar to have enough driving force in the process. Regeneration (top stream of the tower) are all below the detection levels of 5, 10 and
process can be carried out in a cycling operation [70]. Two to nine 100 part per billion (ppb), respectively.
cycling adsorbers are used in parallel arrangement to assure a contin­
uous operation of the process [24]. O2 and N2 can be separated simul­ 3.4.6. Other compounds
taneously with CO2 [47]. Solid particulates, as well as oil-like compounds present in the raw
Cryogenic separation can be used to remove contaminants from raw biogas, are separated via dust collectors [114]. Sludge and foam are
biogas. In this approach, ammonia, H2S are separated and then CO2 is separated via cyclones. A filter with 2 to 5-μm mesh size is appropriate
removed in liquid form. Further cooling causes CO2 sublimation and its for most downstream applications of the biogas. Ammonia (NH3) is
removal in solid form. This technology is very energy intensive [100]. removed when the biogas is dried or upgraded and a separate cleaning
In the thermo-catalytic methanation process, the CO2 and H2 content unit is not required. The methane loss of the upgrading process (i.e. the
of biogas can be converted to methane on nickel catalyst under 10–20 methane present in the off-gas stream) can be avoided by mixing the
bar [123,124]. The mole fraction of methane in the biomethane stream off-gas with air to be used for combustion [83]. Methane can be seen in
is 96%. Kirchbacher et al. simulated four process configurations to the off-gas of PSA columns, in air/water from water scrubbers with/­
investigate the impact of fermentation setup, recycling of off-gas and without water recirculation. Separating methane from the off-gas is
multi-stage membrane separation, pressure and gas hourly space ve­ done to make the upgrading plant economically viable and to avoid/­
locity [125]. The process configurations are process with no recycle, minimize the methane slip to the environment due to its strong GHG
process with basic recycle, process with recycle + preceding methane emission.
removal, in addition to process with recycle + two-stage membrane
separation. The results show that a two-stage biogas fermentation is
extremely beneficial, as it increases the hydrogen storage capacity by 3.5. Biological biogas upgrading technologies
about 70%. Upgrading of raw biogas obtained from the organic matter
of MSW by solar/wind-derived hydrogen was analyzed in Refs. [126]. There are two biological approaches for biogas upgrading: 1)
Two case studies were conducted for UK (high wind availability) and chemoautotrophic, and 2) photosynthetic. Most of these methods are at
Spain (high solar availability). The results suggest that the cost of biogas pilot stage or early stage of full-scale implementation [23].
upgrading in the UK is lower than in Spain with the current prices.
Membrane separation route is one of the conventional methods used 3.5.1. Chemoautotrophic approaches for CO2 conversion
to upgrade the LF gas. The first plants were constructed in the late 1970s. The CO2 content of biogas can be converted to methane by metha­
This technology is based on dissimilar solubility and diffusivity of nation process. Bioconversion of CO2 to methane is a cutting-edge so­
gaseous species in each membrane. The pre-treated raw biogas is pres­ lution for upgrading a raw biogas [130]. This approach not only reduces
surized to 5–30 bar and is conveyed to the membrane module [100]. the CO2 concentration but also increases the energy content of the
Membrane-based separation is simple to operate, safe and robust, the effluent stream by increasing the methane concentration. It is possible to
scale-up flexibility is high, and there is no need of hazardous chemicals upgrade a raw biogas with CO2 molar concentration of 60% to bio­
[70]. High CO2 removal efficiency (>95%), as well as low CH4 loss, are methane with methane mole fraction of 90% under thermophilic oper­
achieved when physicochemical technologies are used for biogas ation at 65 ◦ C [131] and 98% under mesophilic condition (at 37 ◦ C)
upgrading. Other chemical species can also be captured via physico­ [132]. In the hydrogenotrophic CO2 removal route, the CO2 part of raw
chemical methods from the raw biogas with CO2. However, it is biogas is microbiologically upgraded by reduction of CH4 with H2 [133]:

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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

Table 11
Investment costs, plant capacity, energy use, methane loss and final methane content of the upgraded biogas physical/chemical technologies [42,44,47,127].
CO2 removal Working Operating Methane Methane concentration Power demand Heat demand Plant capacity (Nm3/h),
technology pressure (bar) temperature (◦ C) loss (%) of the upgraded biogas consumption (kWh/ (kWhth/m3 raw [investment cost (€ h/Nm3)]b
[24] [24] (%) Nm3)a biogas) [87] [88]

Water 4–7 No <2 >96 0.2–0.3 0 100–500–1000


scrubbing [5500–2500–2000]
Chemical No pressure 160 0.1–1.2 >99 0.12–0.15 0.6 600–1800 [3200–1500]
absorption
PSAc 4–7 No – 96–98 0.25–0.6 0 600–2000 [2700–1500]
Membrane 8 10–30 [128] – 96–98 0.2–0.38 0 100–400
separation − 1000 [6000–2500–2000]
Physical 4–7 55–80 <2 96–98.5 0.2–0.51 0 250–1000
separation − 1500 [4500–2000–1500]
a
Electricity consumption can be stated as the amount of energy per volume of cleaned gas, raw gas, ton of CO2, etc. [47].
b
Capital costs, operating and maintenance costs (O&M) of upgrading technologies are available in Ref. [47].
c
H2S and water needs to be separated before the PSA-column [24].

[130]. Depending on the optimal temperature, there exist four


methanogens, 1) psychrotolerant (about 18 ◦ C), 2) mesophilic (about
37 ◦ C), 3) thermophilic (about 55 ◦ C), and 4) hyperthermophilic
(about 65 ◦ C) [130]. The main challenges of the in-situ biological
upgrading method are the methanogenesis inhibition at pH values
above 8.5, and oxidation of alcohols in addition to volatile fatty acids
[23].
• Ex-situ methanation refers to the provision of CO2 and H2 in an
anaerobic reactor containing hydrogenotrophic to produce methane
[23,135]. The advantages of this approach over in-situ technique are;
1) stability of the process since upgrading operation is taking place in
a separate section (unit), 2) simpler biochemical process, 3) it is not
dependent on biomass, 4) syngas can be used instead of pure CO2,
and 5) feasibility of supplying power to remote areas. The efficiency
of the biogas upgrading process is highly dependent on the reactor
type [23]. In addition, the operating temperature is an important
factor for the efficiency of the bio-methanation process. The main
challenge of this technology is the low mass transfer rate of the
present gas and liquid phases.
• Hybrid of in-situ and ex-situ processes: in this method, a fraction of
partially upgraded biogas from the in-situ upgrading process is
conveyed to an upgrading unit (ex-situ). This technique is less
developed compared to the in-situ and ex-situ approaches.

CO2 removal through microbial electrochemical is an innovative


method to upgrade biogas [136,137]. In microbial electrolysis cells,
electrons are released by bacteria and can be combined with protons to
produce hydrogen in the cathode [138]. The produced hydrogen can
upgrade biogas [139]. The in-situ upgrading approach is more effective
than the ex-situ system [136]. The performance of the in-situ method
can be further enhanced under continuous mode of operation.

3.5.2. Photoautotrophic approaches for H2S and CO2 removal


The photosynthetic CO2 removal route is an alternative technique
that sequester CO2 to increase the methane concentration. H2S removal
can be achieved by these methods, while over 54% of the raw biogas CO2
Fig. 11. Schematic view of the CO2 Wash® (Acrion). content is consumed [23]. Phototrophic organisms such as algae in
enclosed or open photobioreactors can catalyze the process. The
advantage of closed systems over open systems are high photosynthetic
4H2+CO2 → CH4 +2H2O (1) performance and low land/water needs. The main bottlenecks of closed
systems are high energy requirement and cost. An open system needs
Microbiological upgrading of CO2 in biogas to biomethane is per­ low resources for its construction and operation.
formed by each of the following three technologies: Photoautotrophic microorganisms such as prokaryotic cyanobacteria
and eukaryotic microalgae can convert CO2 utilizing water, sunlight,
• In-situ (biogas upgrading) by adding H2 from an external source into and nutrients to produce oxygen, heat and biomass [42]:
anaerobic digester enabling methanogenic Archaea to transform CO2
(40–60% molar concentration) to methane [134]. In this method, CO2 +H2O + sunlight (photons)+nutrients→O2
CO2 can be directly captured from the reactor, it has simple opera­ +CH1.63N0.14O0.43P0.006S0.005+waste heat (2)
tion, and is an alternative for storing excess renewable electricity

15
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

The produced active biomass for the production of value-added affected by the project-specific circumstances. For instance, upgrading
compounds [140] or as a feedstock to produce biogas [141]. Several with chemical scrubbing might be of much interest if cheap heat is
cyanobacteria or microalga such as Chlorella, Arthrospira and Spirulina available on-site. If the biomethane is injected to the high-pressure
have high photosynthetic efficiency and are mostly studied for biogas natural gas network, those upgrading processes working at relatively
upgrading. high pressure such as membranes would be preferred because the in­
In the photosynthetic H2S removal method, biogas is upgraded in jection costs can be reduced. Biogas production and biomethane con­
algal-bacterial photo-bioreactors [24,44]. It is a favorable replacement sumption may take place at different locations. If the biomethane
for the concurrent removal of CO2 and H2S in a single-step process. injection point to the gas grid is located away from the production plant,
the distribution cost should be considered.
2HS- + O2 → 2S0+2OH− (3)
The investment cost of upgrading technologies to remove CO2 from
2HS- +4O2→ 2SO2−
4 +2H
+
(4) the raw gas against the capacity of biogas is presented in Table 11 [88].
By constructing a power law equation for each technology, we find that
2HS- +2O2→S2O2−
3 + H2O (5) the chemical adsorption technology has the best economy of scale (when
the plant capacity is doubled, the investment cost increases by about
In this technology, H2S is oxidized to sulphate by sulphur oxidizing
24%). On the other hand, water scrubbing route has the poorer economy
bacteria (SOB) using the oxygen which is photo-synthetically produced
of scale (when the plant capacity is doubled, the investment cost in­
during bio-fixation of CO2 via microalgae. This process is described as
creases by about 44%). To remove CO2 from a raw biogas with flowrate
Eq. (6) [142]:
of 50 Nm3/h, the water scrubbing technology is the cheapest one, while
H2S + CO2 +nutrients + O2 → biomass + SO2−
4 /S + H2O (6) chemical absorption is the most expensive one. At a high biogas flowrate
of 2000 Nm3/h, the cheapest and most expensive technologies for
The H2S concentration decreases from the range of nearly removing CO2 are respectively physical separation, and chemical
3000–5000 ppm to 50–100 ppm [87]. Safety measures and precautions absorption.
are required to prevent the production of explosive gas mixtures [105]. In Ref. [92], the investment costs of five upgrading routes including
The dosing of iron hydroxides/chlorides forms and precipitates FeS, PSA, water scrubbing, amine scrubbing, membrane, and Genosorb®
which in turn significantly reduce the H2S concentration in the gas scrubbing versus the capacity of raw biogas are presented. All invest­
phase. ment costs excluding those for chemical scrubber include the cost of
Biogas can be biologically converted to liquid products such as ac­ off-gas treatment technology for methane degradation. In addition, the
etate, ethanol, and butanol [143,144]. A variety of microorganisms such costs of different upgrading technologies were discussed with the
as acetobacterium woodii, clostridium scatologenes, and the like can following assumptions [92]:
convert CO2 and hydrogen to liquid compounds [145].
• Investment and maintenance costs were based on the price of tech­
3.5.3. Halocarbons, VOC, siloxanes removal technologies nology providers in 2013.
LF biogas halocarbons including 1,1,1-trichloroethane, methylene • Plant annual availability of 96%.
chloride (di-chloro-methane, DCM), carbon tetrachloride (CCl4), • Operating lifetime of plants: 15 years.
dichlorodifluoromethane, and tetrachloroethylene are biodegraded at • Interest rate: 5%.
low concentrations under anaerobic, aerobic conditions [146,147]. The • Costs for planning, permission and additional construction was set to
biodegradability of VOC materials present in biogas such as benzene, 10% of investment costs.
toluene, volatile fatty acids is reported in Ref. [148]. • Insurance costs was assumed to be 0.5% of investment costs.
The removal of hexa-methyl-cyclo-tri-siloxane with a removal effi­ • Personnel cost for each technology and any plant size was €35/h.
ciency of up to 20% is reported in Ref. [149]. The removal of octame­ • Methane recovery rates and energy consumptions (w.r.t 55 and 65%
thylcyclotetraxilosane under anaerobic and aerobic conditions was methane content of the raw biogas) were based on warranty values.
addressed in Ref. [150]. The removal efficiency of 50–60% for aerobic • Desulphurization process (if required): H2S reduction by 100 ppm,
conditions and 15% under anaerobic conditions was reported. In €5/m3 of raw biogas capacity/year.
another study, the removal efficiency of 74% for octamethylcyclote­ • Costs for extra cleaning steps (e.g. NH3 or siloxanes removal) were
traxilosane was achieved by Li et al. [151]. not considered.

4. Costs of biogas upgrading Methane content of the raw biogas were changing from of 55–65%.
The heat cost of 3–5 €cent/kWhth and electricity cost of 12–18 €cent/
In nations and regions where policies and legislation have been kWhel were assumed.
introduced to incentivize the production of renewable gas, or renewable For the PSA system, the upgrading costs for raw biogas capacities are
heat, the cost of biogas upgrading can be offset or partially offset by the in the range 350–2800 Nm3/h. For water scrubbing technology, the raw
magnitude of the incentives, depending on their mode of application. gas capacities vary between 300 and 1400 Nm3/h. The raw gas capac­
For example, in Germany, a Feed-in Tariff is offered for electricity feed- ities of amine scrubber system and membrane technology range within
in associated with biogas installations including those involving CHP 250–2000 Nm3/h, and 250–750 Nm3/h, respectively. The comparison of
[152]. In the UK, the Renewable Heat Incentive is offered [153]. If these the investment costs of the five upgrading technology suggests that the
incentives are withdrawn it will obviously affect the relative economic PSA route has the highest investment cost for upgrading capacities of
attractiveness of biogas upgrading. Amendments to national and 250–2800 Nm3/h. At high upgrading capacities, the Genosorb® scrub­
sub-national support schemes are also important factors affecting in­ bing technology is the cheapest one. On the other hand, at low biogas
vestment decisions. There is evidence that investment in biomethane upgrading capacities, amine scrubbing is the cheapest in most of cases.
plants has slowed in Germany since amendments to the EEG law in 2018 Fig. 12 illustrates the costs for biogas upgrading (per Nm3/h of
[10]. biogas) to biomethane based on a company survey in 2012 [154,155].
Currently, the price gap between natural gas and biomethane varies As evident from this figure, the higher the plant capacity the lower the
significantly by region [11]. For example, the price gap in Asian specific investment cost. When the plant capacity is over 250 Nm3/h,
developing counties is the narrowest one while the price gap in the biogas upgrading using membranes results in higher investment costs.
North American counties is the highest one. On the other hand, for any upgrading capacity, water scrubbers offer the
The differences in upgrading costs of technologies are very much minimum upgrading cost among other technologies [155]. For the cases

16
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

authors considered three scenarios and five biogas upgrading technol­


ogies including water scrubbing, amine scrubbing, membrane separa­
tion, physical scrubbing with organic solvents and PSA. In the first
scenario, it was assumed that each biogas plant delivers the produced
biomethane via its in-situ upgrading infrastructure to the grid. In the
second scenario, it was presumed that the raw biogas of all biogas plants
is conveyed to a central biogas upgrading plant for the grid injection.
The last scenario states that biomass conversion to biogas, biogas
upgrading, and grid injection take place in a central facility. The results
indicate that the price of the injected biomethane of Scenario 3 (the most
favorable scenario) is nearly 19% higher than the natural gas.
Fig. 13 depicts the biomethane grid injection cost vs. the capacity of
the raw biogas. For each capacity, the minimum and maximum costs
represent the situations where the injection is to low- and high-pressure
Fig. 12. Specific costs for biogas upgrading in 2012.
gas networks. The economy of scale is mainly attributed to the capital
costs. Operational costs are less sensitive to the injection capacity. As
illustrated in Fig. 13, the difference between the minimum and
that the upgrading capacity is 20 Nm3/h, the specific investment cost
maximum costs stems from different compression costs of the bio­
based on a rough calculation is about $1.07/Nm3 CH4 while for the
methane. The biomethane injection costs into the gas grid increase
upgrading capacity of 200 Nm3/h, the specific investment cost drops to
considerably when the gas injection capacity is reduced. Further costs
$0.25/Nm3 CH4 [87].
for biomethane distribution via the gas network arise as a fee when the
Miltner and co-workers performed the techno-economic analysis of
gas is transported via the public gas grid. In Germany, for example, the
biogas upgrading (per standard m3/h of biogas) to biomethane via
fee varies between from $0.05–0.26/Sm3 methane.
pressurized water scrubbing, amine scrubbing, PSA, and membrane-
Techno-economic comparison of biogas production from various
based gas permeation [100]. Total upgrading cost comprises fixed in­
feedstocks in different countries is presented in Refs. [159]. The total
vestment costs (plant lifetime of 15 years), electricity price of 0.15
investment of two plants in Sweden with annual capacity of 100 and 20
€/kWh, annual availability of 98%, and maintenance costs. At low
ktonne of biomethane from pinewood and forest residues in 2014 were
biogas capacities, membrane-based gas permeation has the lower
estimated to be 65.1, and 60.5 M€, respectively. In addition, the in­
upgrading cost, while at high plant capacities the pressurized water
vestment cost of a plant in Sweden with capacity of 110,000 m3
scrubbing technology is the cheapest technology. Upgrading cost for a
MSW/year +3500 m3/day raw biogas in 2012 was 49.2 M$. In Ref. [87],
plant with a capacity of 250 Sm3 biogas/h is about 0.25 €/Sm3 bio­
the total production costs of biomethane for vehicle fueling by feedstock
methane, and it drops to 0.15 €/Sm3 biomethane for upgrading capac­
and capacity scale ranging from 100 to 2000 m3/h is addressed. The
ities above 2000 Sm3 biogas/h.
feedstock are energy crops, manure and industrial waste. The total
For the cases that biomethane is injected to natural gas grid, the most
production costs include costs of biogas production, cleaning and
important factors are network pressure, volumetric flow and distance to
upgrading, as well as distribution via the gas grid. In another study, the
the gas grid. The highest investment costs are contributed to compressor
economic feasibility of biogas upgrading of physicochemical upgrading
stations (ca. 60% of the investment [156]), metering/gas quality mea­
processes (section 3.3) on the market is studied (Fig. 14), [91]. In this
surement equipment and pipes construction costs. The major operating
figure, the lower and upper lines show the low and high fixed capital
costs are the costs of the gas conditioning (heating value adjustment by
investment of all existing physicochemical upgrading technologies
adding LPG) and power consumption of compressors. The fixed capital
versus the plant capacity. The lines approach to each other as the ca­
investment for connection to a 16 bar (medium pressure) network drops
pacity of raw biogas increases. Techno-economic analysis of LF biogas
from 12,240 to 2457 €/Sm3/h as the biomethane flowrate increases
upgrading with membranes and utilization for vehicle fuel is addressed
from 125 to 700 Sm3/h. The operating costs are dominated by the fixed
in Ref. [160]. The impact of feed composition, feed flow rate and
capital costs (up to 350 Sm3/h biomethane injection). Injection into a
pressure on gas processing cost was investigated. The raw biogas from
distribution network (pressure <1 bar) imposes low investment and
the LF contains 55% CH4, 38.9% CO2, 5% N2, 0.4% O2, 0.002% H2S and
operating costs. When the biogas pressure increases from 16 bar to 55
0.66% H2O.
bar (high-pressure pipelines), the compression costs will increase by up
to 50%. Table 16.8 and Fig. 16.4 of Ref. [156] illustrate examples of
5. Conclusions
costs for gas grid connections.
Stürmer et al. [157] compared total cost of biogas upgrading with
Biogas production from waste materials and renewables is a
four technologies including pressurized water scrubbing, PSA, gas
permeation, and amine scrubbing for three biomethane production ca­
pacities of 80, 150, and 500 Nm3/h. The scaling factor of the upgrading
technologies are pressurized water scrubbing 0.38, PSA 0.49, gas
permeation membrane separation 0.61, and amine scrubbing 0.56. The
scaling factor of the upgrading technologies + biomethane injection
facilities (compression units, transfer station, and gas pipe) are 0.38,
0.46, 0.55, and 0.51, respectively. This means that when the biomethane
production capacity is doubled, the increment cost increases of biogas
upgrading and injection using water scrubbing is the lowest one. In
addition, biogas upgrading via the membrane is the cheapest technology
at biomethane production capacities of 80, and 150 Nm3/h. On the other
hand, pressurized water scrubbing becomes the cheapest technology at
biomethane production capacity of 500 Nm3/h. In another study,
Paturska and co-workers performed an economic study for biomethane
Fig. 13. Biomethane grid injection costs based on cost analysis in Ger­
supply based on the Latvian natural gas infrastructure [158]. The
many, 2010.

17
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935

capacities among water scrubbing, PSA, membrane, and amine scrub­


bing. However, the pressurized water scrubbing is the cheapest tech­
nology at high biomethane production capacities. The biomethane
injection costs into the gas network increase noticeably with the ca­
pacity reduction.
The next step to this research is to develop an economical model for
biogas upgrading technologies. The inputs to the model will be biogas
composition and capacity, local technical data including electricity,
water, gas and utilities price, etc.

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