1 s2.0 S0961953420304670 Main
1 s2.0 S0961953420304670 Main
1 s2.0 S0961953420304670 Main
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.
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:
3
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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
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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]
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
* 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.
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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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.
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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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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.
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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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].
11
A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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.
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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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
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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]
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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
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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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A. Rafiee et al. Biomass and Bioenergy 144 (2021) 105935
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