Recent Progress Towards In-Situ Biogas Upgrading Technologies

Science of the Total Environment 800 (2021) 149667
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Science of the Total Environment
journal homepage: www.elsevier.com/locate/scitotenv
Recent progress towards in-situ biogas upgrading technologies

Jing Zhao a,1, Yu Li b,⁎,1, Renjie Dong b
a
Faculty of Science and Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands
b
College of Engineering, China Agricultural University, Qinghuadonglu No.17, 100083 Beijing, China
H I G H L I G H T S G R A P H I C A L A B S T R A C T
• In-situ biogas upgrading technologies

are reviewed.
• H2-addition technology is the most
prominent in-situ technology.
• Hydrogenotrophic methanogens are
critical microorganisms in upgrading
technologies.
• HFM reactor shows the highest average
CH4 content (92.5%).
• The combination between H2-addition
technology and HPAD/BES is promising.
a r t i c l e i n f o a b s t r a c t
Article history: Biogas is mainly produced from the anaerobic fermentation of biomass, containing methane with an extensive
Received 17 June 2021 range between about 50% and 70%. Higher methane content biogas has higher energy and heat value, which
Received in revised form 10 August 2021 needs biogas upgrading. There are mainly two types of biogas upgrading technologies (ex-situ and in-situ).
Accepted 10 August 2021
This manuscript presents a review of technologies on in-situ biogas upgrading. These technologies comprise
Available online xxxx
H2 addition technology (e.g., continuous stirring tank reactor (CSTR), hollow fiber membrane (HFM), nano-
Editor: Yifeng Zhang bubble (NB) technology, upflow anaerobic sludge blanket (UASB)), high-pressure anaerobic digestion (HPAD),
bioelectrochemical system (BES), and additives (e.g., ash, biochar, and iron powder). The results confirm the ex-
cellence of H2-addition technology, with the highest average CH4 content obtained (HFM: 92.5%) and one of the
Keywords: few full-scale cases reported (Danish GasMix ejector system: 1110 m3). Meanwhile, newly pop-up technology
Anaerobic digestion such as HPAD delivers appropriate CH4 content (an average of 87%) and is close to the full-scale application
In-situ biogas upgrading (https://bareau.nl/en/for-professionals/). More importantly, the combo between HPAD and H2-addition technol-
Biomethane ogy is prominent as the former improves the low gas-to-liquid obstacle confronted by the latter. Additionally, re-
CO2 removal
cently emerging BES can't stand out yet because of limited efficiency on CH4 content or constraint full-scale
Hydrogenotrophic methanogens
application behaviors (disability to operate at high current density). However, its combination with H2-
Abbreviations: AD, anaerobic digestion; AEM, anion exchange membrane; AM, acetoclastic methanogenesis; BES, bioelectrochemical system; CE, coulombic efficiency; CWSB, coarse
walnut shell biochar; CEM, cation exchange membrane; COD, chemical oxygen demand; CSTR, continuous stirring tank reactor; DM, dry matter; DET, direct electron transfer; DIET, direct
interspecies electron transfer; FWSB, fine walnut shell biochar; GHG, greenhouse gas; HPAD, high-pressure anaerobic digestion; HFM, hollow fiber membrane; HRT, hydraulic retention
times; HM, hydrogenotrophic methanogenesis; IEA, international energy agency; IET, interspecies electron transfer; LNG, natural-gas liquefaction; MEC, microbial electrolysis cell; MBR,
membrane bioreactor; NGG, natural gas grid; NB, nano-bubble; OLR, organic loading rate; PR, primary reactor; PB, photobioreactor; PtG, power to gas; PEM, proton exchange membrane;
SR, secondary reactor; STP, standard temperature and pressure; SMY, specific methanogenic yield; SHE, standard hydrogen electrode; TS, total solids; UASB, upflow anaerobic sludge blan-
ket; VFAs, volatile fatty acids; ZVI, zero-valent iron.
⁎ Corresponding author.
E-mail addresses: [email protected] (J. Zhao), [email protected] (Y. Li), [email protected] (R. Dong).
1
These authors contributed equally to this work.
https://doi.org/10.1016/j.scitotenv.2021.149667
0048-9697/© 2021 Elsevier B.V. All rights reserved.
J. Zhao, Y. Li and R. Dong Science of the Total Environment 800 (2021) 149667
addition technology to form the Power to Gas (PtG) concept is promising, and its commercial application is avail-
able (http://www.electrochaea.com/). Hydrogenotrophic methanogens are imperative players in all reviewed
technologies for the generation of upgraded CH4.
© 2021 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Different technologies used for in-situ biogas upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. H2 addition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.1. Mechanism, challenges, and opportunities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1.2. Existing reactor set-ups for H2-added biogas upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2. High-pressure anaerobic digestion (HPAD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.1. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.2. HPAD applications, challenges, and opportunities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.3. Bioelectrochemical system (BES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.1. Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.2. BES applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4. Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4.1. Ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4.2. Biochar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4.3. Zero valent iron (ZVI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3. Comparison between different in-situ technologies and predominant methanogens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.1. CH4 content and H2 conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2. Predominant methanogens in upgrading technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4. Existing full-scale in-situ applications and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
5. Summary and concluding remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Declaration of competing interest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1. Introduction CO2 and trace contaminants (H2S, N2, O2, water, and NH3) limit the ap-
plication of biogas. Thus, during the practical upgrading process, the re-
Fossil fuels dominate as the primary energy supply for industrial moval of CO2 is the primary goal. Meanwhile, such a method is also
processes and daily livelihood (Adnan et al., 2019). However, the accompanied by impurities removal (in most cases H2S and NH3) for
use of fossil fuels imposes a big threat to the environment, with the qualified biomethane production.
significant threat being greenhouse gas (GHG) emissions. Nowadays, To note, various upgrading treatments have been developed, which
many governments have released climate announcements aiming to can be grouped into in-situ and ex-situ technologies. Ex-situ technolo-
reduce GHG emissions. In 2018, the total primary energy supply gies include water scrubbing, pressure swing adsorption, physical
came globally from natural gas (23%), oil (31%), coal (27%), renew- scrubbing, chemical adsorption, cryogenic separation, membrane sepa-
able energy (18%), with small shares from nuclear. While in China, ration, and biological upgrading techniques (Angelidaki et al., 2018).
renewable sources contributed to less than 15% of total energy con- The number of biogas upgrading plants delivers an increasing trend in
sumption in 2019. The execution of the climate agreement signed the last two decades (Fig. 1). These ex-situ strategies are extensively im-
in 2019 would result in at least 70% of electricity obtained from re- plemented in large-scale biogas plants (5000 > Q ≥ 500 m3 biogas/day,
newable sources by 2030 (IEA, 2020). NY/T 337-2011) (Adnan et al., 2019; Angelidaki et al., 2018; Papacz,
Biogas is a credible renewable energy source that is generally 2011). However, ex-situ technologies need additional equipment and
produced from anaerobic digestion (AD) of biomass. The potential materials and periodic replacement of solution and membrane, which
to generate biogas from currently available substrates ranges be- are costly and heavily dependent on the size of the AD plant (Papacz,
tween 10,100 and 14,000 TWh at the global scale. If fully exploited, 2011). According to previous reports, ex-situ technologies only become
the produced energy will contribute to 6-9% of the world's primary economically and energetically feasible when the operational capacity
energy consumption and could be one of the proper substitutions of the AD plant exceeds 2400 m3 biogas/day (Adnan et al., 2019;
of fossil fuels (energy from biogas will replace 23-32% of the world's Sarker et al., 2018). For medium (500 > Q ≥ 150 m3 biogas/day) and
coal consumption) (WBA, 2019). In general, raw biogas consists of small-scale (150 > Q ≥ 5 m3 biogas/day, NY/T 337-2011) digesters,
50-70% of CH4 and 30-50% of CO2 as well as some trace components the upgrading equipment is neither available nor cost-effective (Li
such as H2S, N2, O2, CO, and NH3 (Adnan et al., 2019; Angelidaki et al., et al., 2017; Lindeboom et al., 2011; J. Zhao et al., 2020; L. Zhao et al.,
2018; Appels et al., 2011). 2020). Currently, 110,448 biogas facilities are operating in China, with
Except for CH4, other gasses in biogas are redundant, as they don't 6972 being large-scale, accounting for 6% of the total biogas installations
promote energy generation. It is believed that biogas with higher than (WBA, 2019). In this context, medium and small-scale biogas plants are
90% of CH4 increases its heating value and enables its quality as natural the dominant ones (94%), motivating the establishment of compatible
gas (Table S1) (Bassani et al., 2016). Therefore, high concentrations of in-situ biogas upgrading facilities.
2
Fig. 1. Biogas upgrading plants in IEA bioenergy among 37 member countries.

(Data obtained from http://task37.ieabioenergy.com/plant-list.html, IEA Bioenergy 2019, data in 2013 is lacking)
In-situ technologies include H2 addition (Bassani et al., 2016; Jensen large-transmission grids of H2 is nearly 1.5-1.8 times more than CH4
et al., 2021), high-pressure anaerobic digestion (HPAD) (Lindeboom (Wahid and Horn, 2021). Moreover, the volumetric energy density of H2
et al., 2011; J. Zhao et al., 2020; L. Zhao et al., 2020), bioelectrochemical (10.88 MJ/m3) is inherently lower than that of CH4 (36 MJ/m3)
system (BES) (Fu et al., 2020; Liu et al., 2017), and additives (e.g., ash, (Angelidaki et al., 2018). Thus, it would be attractive to use H2 to up-
biochar, iron powder) (Feng et al., 2014; Linville et al., 2017; Yin et al., grade biogas rather than using it as a fuel itself. The upgrading process
2019) (Fig. 2). Henry's law plays a vital role in in-situ upgrading tech- using H2 could exploit the biogas plants' existing facilities and reduce
nologies, especially in HPAD and H2 addition reactors. In the last decade, the initial investment cost. Furthermore, the conversion of excess CO2
in-situ upgrading technologies have attracted broad attention. Presum- to CH4 enhances the CH4 yield and the energy value of the output gas.
ably, it is ascribed to the exclusive advantages of much smaller carbon
footprints since CO2 is captured and converted to new products (Fu 2.1.1. Mechanism, challenges, and opportunities
et al., 2021). But recent progress on in-situ technologies has been rarely
gathered (Adnan et al., 2019; Angelidaki et al., 2018; Kadam and 2.1.1.1. Mechanism. Regarding the two major pathways of
Panwar, 2017; Sun et al., 2015). Thus, in this review, in-situ biogas- methanogenesis (acetoclastic methanogenesis (AM, Eq. (1)) and HM
upgrading technologies are presented regarding the principle, utiliza- Eq. (2)), HM is thermodynamically more favorable and stable than AM
tion, resultant CH4 content, microbial community, and practical applica- (Sarker et al., 2018). Several studies, including pilot-scale, have investi-
tion potential. By gathering relevant information, the ideal biogas gated hydrogenotrophic methanogens in bioreactors to upgrade biogas
upgrading facilities are exhibited to satisfy the requirement of medium to biomethane (Dupnock and Deshusses, 2021). In principle,
and small-scale AD plants. hydrogenotrophic methanogens use 4 mol of H2 as the electron donor
and 1 mol of CO2 as the carbon source and electron acceptor to produce
2. Different technologies used for in-situ biogas upgrading 1 mol of CH4 through the so-called Wolfe cycle (Fig. S1) (Eq. (2)) (J.
Zhang et al., 2020a). Or, CO2 is converted into acetic acid, catalyzed by
2.1. H2 addition homoacetogenic bacteria via the Wood-Ljungdahl pathway (Eq. (3)),
and then acetoclastic methanogens use acetic acid to generate CH4
H2 addition is one of the most exploited techniques in the laboratory (Eq. (1)) (Fig. S1) (Fu et al., 2021). It is noteworthy that HM is widely
for biogas upgrading (Table 1), which relies on the hydrogenotrophic distributed within the methanogenic community. Except for
methanogenesis (HM) pathway to convert H2 and CO2 to CH4. The ori- Methanosaeta, other prominent methanogens such as Methanosarcina
gin of H2 should be derived from a renewable source to make the entire (both AM and HM), Methanobacterium, Methanculleus all could use the
process renewable. Thus, the exploitation of renewable electricity HM pathway for CH4 production.
(windmills and photovoltaics) for water electrolysis (harvest H2 as a re- Typically, conventional AD (without apparent inhibition) produces
sult) is tempting (Angelidaki et al., 2018; Bassani et al., 2016). This around 30% CH4 via the HM pathway (Nzila, 2017). When the
method also stores the surplus renewable energy, known as the conditions are not optimal, acetoclastic methanogens are generally
power to gas (PtG) technology. H2 itself is already considered a valuable inhibited (these archaea are considered more sensitive to toxicants or
fuel for the future energy market. changes in environmental conditions compared with hydrogenotrophic
Nevertheless, technology and infrastructure for large-scale H2 stor- methanogens). This results in the dominance of the HM pathway, but it
age and delivery are not mature. The low density of H2 (0.09 kg/m3) will lead to acetate accumulation, which ultimately will also inhibit the
hampers its transportation as it requires larger pipes and more com- hydrogenotrophic methanogens. In some situations (for example, high
pression power compared to CH4 (0.657 kg/m3) at similar operational ammonia, high temperature), syntrophic acetate oxidizers may become
conditions (Wahid and Horn, 2021). Moreover, the capital cost of the dominant acetate-utilizers, oxidizing acetate to CO2 and H2, which is
3
Fig. 2. Different technologies used for in-situ biogas upgrading (A) H2 addition in an AD plant, (B) high-pressure anaerobic digestion (HPAD), (C) bio-electrochemical technologies, and
(D) additives from corn stover biochar is shown as an example.
(SEM images from (Shen et al., 2017))
further consumed by HM (Duarte et al., 2021; Dyksma et al., 2020). Methanothermobacter are dominant archaea (Table 1). The pure culture
Moreover, the addition of H2 directly to AD also switches the methano- of these microorganisms could act as bioaugmentation culture to accel-
genic metabolic pathway towards the HM pathway (Table 1). In H2- erate the HM process, promoting the conversion rate of H2 and CO2 to
supplemented systems, Methanoculleus, Methanobacterium, and CH4 (Dahl Jønson et al., 2020).
4
J. Zhao, Y. Li and R. Dong
Table 1
Summary of H2 addition for biogas upgrading.
Reactor type Substrate Operation Conclusion Microbes H2 CH4 production CH4 (%) Reference
condition utilization rate
efficiency
(%)
Two-stage CSTR Cow manure 55 °C ①CH4 production rate was maximum at 140 rpm and – 13%-39% 0.03-0.14 41% (26% for inlet) (Wahid and Horn, 2021)
food waste 10 L (6 L)a 12.2 mL/min gas recirculation rate. L/L/d
H2:CO2 (2:1, 4:1) Primary + ②H2 gas-to-liquid transfer rate should be improved.
upgrading
reactor
CSTR H2:CO2 (2:1-10:1) 38 °C ①High H2 content caused pH increase Methanobacterium 58%-99% CH4 production 77-100% (59% for (Agneessens et al., 2017)
Sludge and straw 2L ②High H2 content caused acetate accumulation, which increased control)
HRT 20 days was produced by the homoacetogens. 136%-199%
Pressure < 1.2 ③Pulse H2 injection enhanced H2 uptake rates.
bar
CSTR+HPAD Food waste Pressure 3, 5, 7 ①The pH dropped when pressure increases. Methanobacterium >96% 0.8-1.4 biogas 92% (52.4% for (Kim et al., 2021)
H2 bar ②The addition of H2 helped increases pH in the HPAD Methanosarcina L/L/d control)
3.0 L(2.3 L) reactor. Methanosaeta
37 °C ③High amount of H2 caused CH4 yield drop and VFAs
accumulation due to lack of CO2 and high H2 partial
pressure
CSTR Cattle manure, H2 Batch, 118 mL ①The H2 consumption rate was affected by PH2, and – >80% 3.7-67.8 mL/L/h 65% (62% for control) (Luo et al., 2012)
Propionate, butyrate Continuous, 4.5 L mixing intensity. 22% higher than
55 °C ②The addition of H2 increased pH due to consumption of control
bicarbonate, which then inhibits methanogenesis.
③The propionate and butyrate level were not
significantly affected by the H2 addition.
CSTR H2:CO2:CH4 = 37 °C, 55 °C ①Thermophilic condition had a higher (60%) H2 Methanobacteriales 2.9-22.8 0.9-5.3 95% (Luo and Angelidaki,
5
60:15:25 1 L (0.6 L) bioconversion rate than mesophilic condition. L/L/d L/L/d 2012)
②Gas-to-liquid mass transfer was the rate-limiting
factor for efficient H2 utilization.
CSTR Manure, acidic 1 L (0.6 L) ①The best stirring speed was 150 rpm, and using a Methanothermobacter 1.2-1.5 0.76-0.89 L/L/d 75% (57% for control) (Luo and Angelidaki,
whey, H2 Continuous ceramic diffuser was better than the column. L/L/d 2013a)
55 °C ②The addition of H2 had a positive effect on the
HRT 15 days methanogenesis but no obvious effect on the
acetogenesis.
Batch Glucose, H2 37 °C ①The best ratio of H2:CO2 was 4:1. Methanobacterium 2.32 0.59 94% (67% for control) (Wahid et al., 2019)
0.5 L ②pH increased above 8, which influenced the process mL/L/h mL/L/h
Batch mode stability. 98%
③High H2 content caused VFAs accumulation and
reduced CH4 yield.
Batch Maize leaf substrate, 52 °C ①High H2 addition could inhibit VFAs degradation. Methanobacterium >92.2% 118-127 89% (64% for control) (Mulat et al., 2017)

H2 120 mL ②High H2 addition stimulated homo-acetogens for 471-510 mL/L/d
Batch mode production acetate from CO2 and H2. mL/L/d
CSTR Grass silage 55 °C Elevated H2 concentration hampered the in-situ - 33-72% 0.33-2.52 60% (Voelklein et al., 2019)
9.5 L acetogenesis process L/L/d
OLR: 3-8 g VS/L/d
Batch Cattle manure, H2 118 mL (40 mL) ①High ammonia inhibited methane production in both Methanothermobacter - 320 mL/(gVSS/h) CH4 yield was highest (Wang et al., 2020, 2016)
NH4Cl (1 and 7 g Batch mode mesophilic and thermophilic conditions. thermautotrophicus when the PH2 was 0.5
NH+4 -N/L) 37 °C, 55 °C ②Ammonia level increase, the pathway change from AM atm
PH2: 0, 0.25, 0.5, 1 to HM, and syntrophic bacteria increase.
atm ③H2 injection under high ammonia concentration could
promote the growth of some hydrolytic and
fermentative bacteria
④The ammonia toxicity was alleviated at thermophilic
conditions.
(continued on next page)

Table 1 (continued)
efficiency
(%)
Batch Glucose, H2 37 °C, 55 °C, 150 ①Stop the methanogenesis step, using CO2 to produce Moorella sp.4 <90% - 77% (Omar et al., 2019)
rpm chemicals, such as VFAs.
540 mL (100 mL) ②thermophilic inoculum had a higher ability to inhibit
methanogenesis and produced higher acetate.
③Gas ratio H2:CO2 = 2:1 was the best ratio to get high
CH4 content and acetate yield.
CSTR H2 (3-30 mmol) Fed-batch ①More acetic acid produced by the addition of H2. - - - 65-72% (Sarker et al., 2020)
Cattle manure semi-continuous ②Poor Gas-to-liquid transfer was a significant problem.
6.6 L (5 L)
39 °C
Batch H2:CO2:CH4 37 °C ①thermal treatment didn't suspend the methanogenic Acetoanaerobium noterae >98% - 96% (Omar et al., 2018)
4 ratio Batch mode activity of the inoculum. 10 (acetate produce)
540 mL (100 mL) ②chemical treatment enhanced biogas upgrading and
acetate production.
③Gas ratio H2:CO2 = 2:1 wan best to gas high CH4
content.
Batch Food waste 160 mL (75 mL) ①H2 addition improved biomethane yield and biogas - - 12.1% higher 77.2% (65%) (Okoro-Shekwaga et al.,
5% H2, 95% N2 37 °C quality from food waste. than the control 2019)
Batch mode ②High acidification potential of food waste helped to
buffer excessive pH increase.
CSTR H2:CO2 = 4:1 37 °C, (11.6 L) ①CH4 yield increased by 29.6% after H2 addition. Methanosaeta (AM) 1.93 L/d 29.6% after H2 70% (62%) (Zhu et al., 2020)
Swine manure ②H2 was mainly indirectly converted into CH4 via Clostridium addition
homoacetogensis. (homoacetogenic)
CSTR H2 1 L (0.5 L), 200 CH4 increase by more than 3-fold than the original. Methanobacteriales - 2.76 L/L/d 95% (50% for initial) (Tao et al., 2019)
6
(simultaneous rpm, 37 °C,HRT Need to add some buffer to prevent an inhibitory rise of Methanomicrobiales
in-situ and ex-situ) 15 days pH.
OLR 2, 3, 4, 5 g
COD/L/d
CSTR H2:CO2 = 0:1, 1:1, 35 °C ①Temperature was a crucial factor in impacting the 35 °C: Methanosaeta 0.9-1.9 L/d CH4 yield was 62-70% (M) (Zhu et al., 2019b)
4:1 55 °C succession of microbial community structure. 55 °C: Methanosarcina, (M) 13% higher than 66-78% (T)
(11.2 L) ②Continuous stirring was harmful to the stabilization of Methanoculleus 1.9-6.4 L/d control.
the mesophilic system. (T)
CSTR H2:CO2 = 4:1 60 °C, 700 rpm Pressure increased the H2 mass transfer flux. Methanothermobacter <97% 21 L/L/d 62% (17%) (Martin et al., 2013)
101 kPa & 122 thermautotrophicus
kPa
Single (R1) or H2 3L ①H2 addition helped single rector increased the CH4 Single: 303-648 142-152 Single: 51.6% (44.6%) (Fontana et al., 2018)
two-stage CSTR Cheese whey 150 rpm, 55 °C content by 7% (power-to-methane). Methanothermobacter mL/L/d mL/gCOD Two-stage:
(R2&R3) permeate, cheese HRT 15 days ②In the two-stage CSTR, some short-chain fatty acids wolfeii 39.7% (57.3%)

waste powder were produced, which could be used for Two-stage:
power-to-chemical. Coprothermobacter
proteolyticus
Anaerobaculum
hydrogeniformans
CSTR H2:CO2 = 1:1-4:1 55 °C ①Continuous mixing was favorable for thermophilic Methanoculleus 1.88-6.63 222.3-291.6 L/kg 80% (Zhu et al., 2019a)
Sodium formate 11.2 L in-situ biogas upgrading by H2. Methanobrevibacter L/d VS
②After H2 added, strict HM played a crucial role in the Methanobacterium
in-situ biogas upgrading system.
③Formate was more beneficial for acetogenesis of
propionate degradation compared to H2.
CSTR H2, CO2, CO = 4:1 330 mL (100 mL) ①Thermophilic condition increased CH4 production rate. 37 °C: Acetobacterium - 0.24 mol/mol H2 81-92% (Grimalt-Alemany et al.,
37 °C, 60 °C ②At mesophilic condition, AM contributed to 65% of CH4 sp., Methanospirillum 2020)
production. hungateii
60 °C: Thermincola
carboxydiphila,
AM : CH3COO− þ H2O ! CH4 þ HCO3− , ΔG00 ¼ −31 kJ=reaction ð1Þ As Eq. (4) implies, rt can be promoted by kLa. The value of kLa is influ-
enced by reactors' configuration and operating conditions (Rusmanis
HM : 4H2 þ CO2 ! CH4 þ 2H2O, ΔG00 ¼ −130:7kJ=reaction ð2Þ et al., 2019). Thus, kLa can be modified by changing the H2 diffusion device
(Luo and Angelidaki, 2013a; Yun et al., 2017), adjusting the mixing speed
Homoacetogensis : 4H2 þ 2CO2 ! CH3COOH þ 2H2O, ΔG00 (Luo and Angelidaki, 2013a), and adopting gas recirculation (Guiot et al.,
¼ −104:5 kJ=reaction ð3Þ 2011). Modified reactors design such as upflow anaerobic sludge blanket
(UASB) reactor and nano-bubble diffuser can be potential options for
diffusion devices. Furthermore, HPAD could be introduced to increase
2.1.1.2. Challenges and opportunities. Although biological biogas
the gas-to-liquid transfer rate (based on Henry's constant) of CO2/H2
upgrading offers technical advantages, H2-added biogas upgrading is
(the H2 utilization rate reaches up to 99%) (Agneessens et al., 2017;
still challenging (Bassani et al., 2016). The primary constraints and cor-
Rusmanis et al., 2019). Additionally, the application of biogas recirculation
responding solutions are demonstrated below:
through the membrane for gas sparging has increased H2 and CO2 conver-
2.1.1.2.1. Increased pH induced by CO2 consumption. Together with the
sion efficiency up to 95% in different trials (Alfaro et al., 2018; Alfaro et al.,
injection of H2 into the digester, the depletion of CO2 proceeds, leading
2019; Díaz et al., 2015). All these intensifications are designed to inten-
to a rise of pH due to the removal of bicarbonate (a primary form of CO2
tionally enhance the contact (prolong the contact time) between
in the liquid phase). Bicarbonate (HCO-3) acts as a critical buffer in AD.
hydrogenotrophic methanogens in the liquid phase and H2 in the gas
Hence, it also causes volatile fatty acids (VFAs) accumulation and in-
phase. The following section will thoroughly elaborate on the different re-
hibits the activity of hydrogenotrophic methanogens (Mulat et al.,
actor types, as well as varying modules (Section 2.1.2, Fig. S3).
2017; Wahid et al., 2019). Thus, it is one of the main drawbacks of in-
situ H2 addition configuration. To overcome this technical challenge, re-
2.1.2. Existing reactor set-ups for H2-added biogas upgrading
searchers adopted co-digestion with acidic waste to compensate for the
increase of pH (pH > 8), such as food waste (Okoro-Shekwaga et al.,
2.1.2.1. Continuous stirring tank reactor (CSTR). CSTR is the most common
2019) and cheese whey wastewater (Fontana et al., 2018). In addition,
type of reactor used in AD. A set of impellers controlled by a motor vigor-
the combination of H2 injection and HPAD could be an excellent way
ously stirs the reactor. Gas retention and interface area are maximized
to solve high pH in H2-injected reactors. Since injected H2 could use sur-
through the reduction of bubble size via intensive mixing. High-speed
plus CO2 dissolved in the liquid phase of HPAD to mitigate the decreas-
mixing requires high energy input that could break biomass granules
ing pH and further convert CO2 into CH4 internally. Kim et al. (Kim et al.,
and the structure/cell of the microorganisms, which further causes acetic
2021) claimed that after the addition of H2 into the HPAD reactor, the
acid accumulation in the system (Rusmanis et al., 2019; Wahid and Horn,
CH4 content increased up to 92.1% compared to 77.4% of the control,
2021). It has been suggested that the optimal speed used in the upgrading
and pH increased from 6.7 to 8.7 at 5 bar when treating food waste.
system is around 140-170 rpm, with the CH4 production rate being 0.9-
Thus, these two technologies could make up for each other's
5.3 L/L/d (Luo and Angelidaki, 2013a; Wahid and Horn, 2021). Although
shortcomings.
an improved mixing speed could increase CH4 content from 57% to 75%
2.1.1.2.2. Increased H2 partial pressure causes inhibition. Another es-
(Luo and Angelidaki, 2013a), it still does not meet the CH4 quality for
sential aspect that needs to be considered during the H2 injection pro-
the natural gas grid (NGG). Therefore, gas recirculation and gas diffusion
cess is the concentration of H2. The HM pathway is only
device are required to help further increase CH4 content. In this regard,
thermodynamically feasible when H2 concentration is deficient (10-4-
Wahid and Horn (Wahid and Horn, 2021) obtained the highest CH4 pro-
10-6 atm) (Zhao et al., 2018). High H2 concentration inhibits
duction rate (0.13 L/L/d) when the gas was recirculated at 12.2 mL/min,
methanogenesis and promotes the accumulation of electron sinks
and the CH4 concentration increased from 77% to 80%.
such as butyrate, propionate, lactate, and ethanol in the reactors
(Angelidaki et al., 2018; Omar et al., 2019). Thus, H2 concentration is a
2.1.2.2. Hollow fiber membrane (HFM) reactor. HFM reactor relies on hol-
vital parameter in the H2 addition reactors. The optimal H2 to CO2
low fibers to realize bubbleless gas transfer (Fig. S3) (Luo and Angelidaki,
ratio is still ambiguous at the moment. Some researchers demonstrated
2013b). The inner diameter (e.g., 200 μm) and outer diameter (e.g., 280
that the best ratio of H2 to CO2 was 2:1 when simultaneous biogas
μm) of hollow fibers are tiny, enabling substantial fibers (e.g., 320 fibers).
upgrading and biochemical production could be achieved (Omar et al.,
These characteristics allow hollow membrane high surface area
2018; Omar et al., 2019). While other researchers found the best ratio
(e.g., 844 cm2) (J. Zhao et al., 2020; L. Zhao et al., 2020). When H2 goes in-
was 4:1 for biogas upgrading or biomethane production (Rachbauer
side the fibers, the pressure in the thread could force the H2 to penetrate
et al., 2016; Wahid et al., 2019). A systematic evaluation of varying H2
the liquid phase from the tiny pores on the membrane without bubble
to CO2 ratios with different common substrates and different inoculum
formation. Thus, the HFM reactor could increase the H2 conversion effi-
sources should be carried out to determine the optimal ratio.
ciency to around 98%, which improves the low H2 gas-to-liquid transfer
2.1.1.2.3. Low gas-to-liquid transfer rate. The H2 gas-to-liquid transfer
rate (J. Zhao et al., 2020; L. Zhao et al., 2020). The gas sparging through
ratio should be well studied in H2 addition reactors for efficient uptake
HFM results in kLa values of 430/h for H2 (Díaz et al., 2015). Meanwhile,
of H2 (in the gas phase) by hydrogenotrophic methanogens (in the liq-
the microbes could attach to the outer membrane to form biofilm.
uid phase) (Agneessens et al., 2017; Díaz et al., 2015; Luo and
Wang et al. (Wang et al., 2013) indicated that Methanosaeta and
Angelidaki, 2012). In such a sense, Henry's constant is 7.8 × 10-3 mol/
Treponema (homoacetogens-related genus) prevailed on the biofilm,
L/MPa for H2, which is remarkably lower than that of CO2 (0.318 mol/
while Methanoculleus was prevalent in the liquid. Such observation
L/MPa) (standard temperature and pressure (STP), 0 °C and 1 atm).
suggested that homoacetogenesis and AM were the main pathways on
Therefore, the efficiency of the H2 utilizing rate strongly depends on
the biofilm, while HM was the main pathway in the liquid phase
the H2 gas-to-liquid transfer rate, as determined in (Eq. (4)) (Bassani
(Wang et al., 2013). The presence of acetic acid, Methanosaeta, and
et al., 2016):
homoacetogens-related bacteria indicated that HM and AM pathways
co-existed in H2-added HFM reactors (Li et al., 2020; Wang et al., 2013).
rt ¼ 22:4kL a H 2gTh −H2l ð4Þ Nevertheless, Luo and Angelidaki (Luo and Angelidaki, 2013b) reported
that the biofilm was harmful to the process because it blocked the diffu-
where; rt is the H2 gas-to-liquid mass transfer rate, (L/(L.day)); 22.4 is sion of H2 to the liquid to some extent. And the biofilm contributed
gas volume to mole ratio (1 mol gas corresponds to 22.4 L gas at STP); merely 22-36% to the H2 consumption in the CH4 formation process.
kLa is gas transfer coefficient (per day); H2gTh is H2 concentration in This result is conflicting with another study using HFM for H2S removal,
the gas phase (mol/L); H2l is H2 dissolved in the liquid phase (mol/L). where only the biofilm promoted the oxidation of the gaseous substrate
7
Table 1 (continued)
efficiency
(%)
Methanothermobacter
sp.
Batch H2:CO2 = 4:1 24 °C, 35 °C, 55 ①Main limitation was the low-gas-to-liquid transfer Methanothermobacter 643-994 112-309 mL/L/d - (Figeac et al., 2020)
°C, 65 °C rate and solubility of H2. mL/L/d
600 mL (200 mL) ② High temperature enhanced CH4 production rate,
210 rpm while it increased the instability of the system.
③The optimal temperature range 35 °C -55 °C.
Batch H2:CO2 = 4:1 55 °C, 65 °C ①The efficiency was better at 65 °C than 55 °C. Methanothermobacter – 0.46 L/L/d 85%-92% (Guneratnam et al.,
1.14 L ②Reseeding of the process was required as when 2017)
Batch mode inoculum ages, efficiencies decreased
CSTR H2, sludge 1.4 L (0.3 L) ①Acetate accumulation increased at increasing OLR. Methanomicrobiales 60-80% 8-18 mmol/L/d 71%-94% (50%) (Agneessens et al., 2018)
38 °C P②Homoacetogeneis consumed up to 60% of H2 at a low
HRT 20 days CO2 level and became less critical after repeated H2
injections.
Biofilms H2:CO2 = 4:1 38 °C ①H2 addition resulted in CO2 limitation and pH increase. Methanoculleus <2 8 L/L/d 95% (50% for control) (Maegaard et al., 2019)
1.2 L (0.3 L) ②HM was highly dependent on CO2 concentration. nmol/cm3/s
③A methanogenic biofilm was established on carrier
materials.
Two-stage CSTR R1: Cattle manure 37 °C, 55 °C ①At thermophilic conditions, higher efficiency of CH4 Methanoculleus 37 °C: 178 37 °C: 38 mL/L/d 37 °C: 89% (69.7%) (Bassani et al., 2015; Treu
R2: H2 and biogas R1 (1.5 L) production and CO2 conversion were recorded. Desulfovibrio mL/L/d 55 °C: 92 mL/L/d 55 °C: 85% (67.1%) et al., 2018a)
from R1 R2 (2 L) ②The addition of H2 favored the proliferation of 55 °C: 470
potential homoacetogens mL/L/d
Two-stage CSTR Cattle manure (PR) 55 °C ①Acetate was produced by homoacetogens. Methanoculleus ND 85-113 mL/L/d 99% for SR (Treu et al., 2018b)
8
H2 (SR) PR: 1.5 L (biogas ②The pH of SB was higher than that of PR. Methanothermobacter (from H2) (67% for PR)
reactor), HRT 15
days
SR: 2 L
(upgrading
reactor),
HRT 20 days
UASB Potato-starch 1.4 L ①H2 low gas-to-liquid mass transfer rate limited the - <1.873 1.188-1.528 L/L/d 82% (Bassani et al., 2016)
wastewater, H2 55 °C availability of H2 for methanogens L/L/d
②H2 distribution can be improved using porous insert 94%
devices, like a ceramic sponge.
③Gas recirculation and chamber configuration helped to
maximize CO2 conversion to CH4.
UASB H2:CO2 = 4:1 4.5 L ①Packing material that provided efficient cell - 55% 3.9 m3/m3/d ceramic ball: 65% (Daglioglu et al., 2020)

Packing materials 37 °C immobilization can increase biomethane efficiency. (ceramic) (ceramic) glass pipe: 78%
(ceramic ball, glass ②Glass pipe (85%) has higher H2 utilization efficiency 85% (glass) 4.8 m3/m3/d
pipe) than ceramic ball (55%) (glass)
UASB reactor + Synthetic UASB: 1 L ①pH increased. - - - >90% (51.7% for (Luo et al., 2014)
degassing unit wastewater (15 g/L Degassing unit: ②The COD removal efficiency and CH4 yield were not control)
membrane glucose) 0.4 L affected by the gas desorption.
37 °C
Two-stage UASB Synthetic 35 °C ①Syntrophic bacteria and methanogens facilitated Methanoseata <99% - >90% (Xu et al., 2020)
wastewater, glucose OLR 1-5 biogas upgrading with syngas
H2/CO2/CO/CH4 gCOD/L/d ②CO in H2-rich syngas didn't inhibit methanogenesis.
2.1 L (0.7 L)
HRT 1 day
Two-stage R1:cattle manure, 53 °C ①VFAs accumulation in the in-situ reactor. Methanothermobacter - R2: 355-427 R1:87% (Corbellini et al., 2018)
R1: CSTR potato starch, H2 PR1: in-situ, (3 L), ②Hydrogenotrophic methanogens and homoacetogens mL/L/d R2:95%
R2: upflow reactor R2:digestate from R1 HRT 15 days were rich in reactors.
PR2: ex-situ, (850
mL)
UASB H2:CO2 = 4:1 37 °C. 55 °C, (6.3 ①The highest performance achieved by applying gas Methanoculleus <1.6 L/L/d 0.4-4.8 L/L/d 96% (Yun et al., 2017)
L) recycle under thermophilic conditions. chikugoensis (37 °C)
Methanothermococcus
(55 °C)
Top-mounted Manure, H2 1200 L ①H2 conversion rate was controlled by H2 gas-liquid - 24% - 63% (Jensen et al., 2018;
agitator 52 °C, mass transfer. 70.3 L/m3/h Jensen et al., 2021)
Venturi-based gas HRT 14 days ②venturi-based mixing system for H2 injection to
mix system facilitate H2 gas-liquid mass transfer in in-situ
biomethanation.
③Headspace recirculation improved H2 consumption
Biofilm plug-flow H2:CO2 = 4:1 0.75 L ①High rate methanogenesis was observed without Methanosaetaceae - <40 v/v/d <90% (Savvas et al., 2017)
reactor 37 °C gas-liquid agitation. Methanobacteriales
②More active methanogens existed on biofilm.
Ceramic H2:CO2 = 4:1 Pilot-scale, 60 L ①Ceramic MBR could efficiently transfer H2 to CH4, KLa Methanothermobacter 95% 0.22 - (Alfaro et al., 2018)
membrane loading rate 10-30 55 °C was 268/h. thermautotrophicus m3CH4/m3H2
LH2/m3/d ②CH4 production rate was 0.18 L/m3; H2 transform rate
was 95%.
HFM H2:CO2 = 4:1 40 L (31 L) ①H2 mass transfer to the liquid phase was identified as - 95% 0.22-0.23 m3/m3 95% (60% for control) (Díaz et al., 2015)
55 °C the limiting step for the conversion. H2
②Gas sparging through a membrane module can
efficiently increase the gas-to-liquid transfer rate.
HFM (CSTR) H2 1 L (0.6 L) ①Increase H2 flow rate could increase CH4 content. - - - 96.1% (53%) (Luo and Angelidaki,
Cattle manure and 55 °C, 150 rpm ②pH increased to 8.3, which hampered the AD. 2013b)
whey HRT 15 days ③Biofilm formed on the membrane will decrease H2
diffusion to the liquid.
HFM H2 35 °C, (20 L) ①94% H2 utilization efficiency. Methanoculleus sp. 100% Biogas 30 mL/L/d 73% (Alfaro et al., 2019)
Sewage sludge HRT 20 days ②CH4 production yield increased by 42%. Methanospirillum sp. (from H2) Had high CH4
③Gas recirculation and H2 supply through a submerged Methanolinea sp. production rate.
membrane for biogas upgrading. Methanobacterium sp.
9
HFM H2 and biogas (60% 200 mL reactor ①Acetate and ethanol generated by homoactogen Clostridium ragsdalei 95% - 97.6% (60% at initial) (J. Zhao et al., 2020; L.
CH4, 40% CO2) tube during the upgrading process. P11 Zhao et al., 2020)
250 mL (150 mL) ②Increase PH2 could help further increase CH4 content.
biogas reactor
Bench-scale,30
°C, pH 7.0-7.5
HFM H2:CH4:CO2 = 7.85 L (7 L) The optimum ammonia nitrogen for biogas upgrading Methanobacterium 91-99% CH4 yield 94.1% (Li et al., 2020)
66:18:16 55 °C was 5.5 g/L Methanosaeta increase
NH4Cl (3.5-6.5 g/L) 35.2-64%
HFM Coke oven gas (92% 3 L (2 L), CSTR ①HM and AM existed in the reactor, HM existed in the Methanoculleus 96% 554-1305 mL/d 99% (Wang et al., 2013)
H2, 8% CO) 37 °C, 200 rpm liquid part, and AM lived on biofilm. Methanosaeta
Sewage sludge HRT 10 days ②pH increased after H2 addition. Treponema
(homoacetogenetic)
NB Waste activated 0.25 L batch ①NBs with the negative zeta potential could be stable in - - 45 mL/g-VS/d 60% (55% for control) (Wang et al., 2019)

sludge study reactors for 2 weeks.
Air-NB, N2-NB, 36 °C ②The CH4 production enhanced by 14-21%, H2-NB had
CO2-NB, H2-NB the best performance.
NB Swine manure 0.25 L, Batch ①The cumulative CH4 production from the NB added - - 192-225 mL/g-VS 60% (50% for control) (Fan et al., 2020)
Air-NB, CO2-NB, mode reactor was 19-39% higher than the control group.
H2-NB 35 °C ②NB addition not only accelerated hydrolysis rates of
proteins and carbohydrates but also enhanced the
production of VFAs
Note:
‘-’ not mentioned;
PR: primary reactor;
SR: secondary reactor;
MBR: membrane bioreactor;
OLR: organic loading rate.
a
The volume in parenthesis is the working volume of the reactor.
(Sahinkaya et al., 2011; Zhao et al., 2011). Probably, such divergence requirements. By doing so, the CH4 content enjoys a substantial incre-
comes from the different hydraulic retention times (HRT) adopted in ment (from 58% to 82%) (Bassani et al., 2016).
those studies. When the HRT is short, few microorganisms exist in the
system, and thereby the gases are consumed primarily by the microor- 2.2. High-pressure anaerobic digestion (HPAD)
ganisms attached to the fibers. In contrast, the HRT in Luo's study is rela-
tively long (HRT 15 days), which permits the submerse growth (Luo and Compared to the regular pressure counterpart, high-pressure anaer-
Angelidaki, 2013b). Besides HRT, different mixing intensities also influ- obic digestion (HPAD) reactor can ultimately produce qualified biogas
ence the structure of biofilm. A high speed could decrease the thickness (CH4 content >88%). This strategy integrates biogas generation,
of biofilm. However, an increase in mixing power is not practical for AD upgrading, and pressurization in a single step (Lindeboom et al., 2011;
reactors due to the rise in operating costs. Moreover, this effort also J. Zhao et al., 2020; L. Zhao et al., 2020) or two-stage (Chen et al.,
leads to high gas permeation rate, which is not suitable for H2 conversion 2014b; Merkle et al., 2017b) (Table 2).
(Celmer et al., 2008). Thus, in the HFM reactor, there is a ‘trade-off’ when
setting parameters like HRT and stirring speed to maximize conversion 2.2.1. Mechanism
efficiency. The main principle of the HPAD technology is Henry's law, where
CO2 dissolves better than CH4 in the liquid phase when the pressure in-
2.1.2.3. Nano-bubble (NB) technology. NB technology has recently been creases. Henry's constant for CH4, CO2, H2S, and NH3 is 0.016, 0.318,
recognized as a unique biogas upgrading technology. NBs are gaseous 1.15, and 620 mol/L/MPa (STP, 0 °C and 1 atm), respectively (J. Zhao
spherical bubbles with a diameter ranging from 50 to 200 nm (ISO et al., 2020; L. Zhao et al., 2020). Moreover, the improved contact be-
20480-1:2017). The generated NBs are characterized with excellent tween CO2 and methanogens could also enhance CO2 uptake by
characteristics such as long residence time, improved gas solubility, methanogens. As a result, the CH4 content in the outlet gas increases
low buoyancy, high negative zeta potential, and high surface charge under pressure. Together with CO2, other pollutant gas (H2S and NH3)
(Lyu et al., 2019). Owing to these features, NBs are stable in solution also dissolves quickly into the liquid phase under pressure.
from days to months. Another intriguing characteristic of NB comes
from its capacity to enhance enzyme activity by promoting water mo- 2.2.2. HPAD applications, challenges, and opportunities
bility, such as hydride carrier Coenzyme F420 (hydrogenotrophic When the substrate is fixed, the CH4 content in the headspace biogas
methanogenesis). Based on the mechanism of NB, the application of responds linearly to the pressure within a range from 1 bar to 10 bar.
H2-NB seems tempting. In this regard, biogas upgrading by H2-NB has When the pressure is increased higher than 10 bars, other factors,
been evaluated in various studies (Bassani et al., 2015; Fan et al., such as pH and saturability, will take over the function of pressure to de-
2020; Wang et al., 2019). Fan et al. (2020) reported that the CH4 yield termine the CH4 content. Moreover, some researchers indicated that
was increased by 39.3%, and CH4 content was increased from 50% to when the pressure was increased to 31.5 bar, the specific methanogenic
60% in the H2-NB reactor. Wang et al. (Wang et al., 2019) found that yield (SMY) decreased by 30% compared to digestion at ambient pres-
the addition of NB water enhanced the CH4 yield by 14%-21%, and CH4 sure (Lindeboom et al., 2011). In fact, 10 bar (around 90% CH4) already
content was increased to 60% compared to 55% of the control reactor. meets the pressure requirement for NGG and natural-gas liquefaction
Since NB technology is still in its infancy, future investigation on the ef- (LNG) (J. Zhang et al., 2020a, 2020b; L. Zhang et al., 2020a, 2020b; Y.
fect of H2-NB in hydrogenotrophic methanogenesis is appreciated. Zhang et al., 2020). Further increase of pressure would only increase
the cost of this technology. Hence, in most cases (Table 2), the optimal
2.1.2.4. Upflow anaerobic sludge blanket (UASB) reactor. The UASB reactor operating pressure is set around 10-20 bar.
relies on the blanket formed by the granular sludge possessing highly
active biomass (Mainardis et al., 2020). Wastewater (low suspended H2O þ CO2↔H2CO3↔HCO3− þ H þ ↔CO32− þ 2Hþ ð5Þ
solids content) flows through the blanket from a bottom-up direction
and is thoroughly contacted with the anaerobic microorganisms Although HPAD technology can upgrade biogas, it relies mainly on
throughout the process (Fig. S3) (Bassani et al., 2016). Typically a physical principles to dissolve the CO2 in the reactor's liquid phase.
UASB process could provide higher CH4 content (91% after H2 addition) Thus the upgrading ability is determined by the volume of the liquid
in the biogas than a CSTR process does (86% after H2 addition) because phase. If the liquid is not changed frequently, its buffer capacity will
more contact time and area between microorganisms and H2 is reach saturation. When the buffer capacity is saturated, pH will drop
guaranteed in the UASB reactor (Corbellini et al., 2018; Nizami et al., below 6 in a single-stage system because of the formation of H2CO3
2012). The typical UASB configuration has been modified by introducing (Eq. (5)). Low pH hurts CH4 content (Lindeboom et al., 2012). Lemmer
packing materials, contributing to immobilizing functional microbes et al. (2015b) implemented a water scrubbing technique to increase
(hydrogenotrophic methanogens) (Daglioglu et al., 2020). Meanwhile, pH in the HPAD reactor. After decompression, CO2 is released from the
the packing materials used in the UASB reactor could further affect the liquid phase, and the liquid phase can be reused (Lemmer et al.,
CH4 content (78% vs. 65%) and H2 utilization efficiency (85% vs. 55%) 2015b; Merkle et al., 2017b). Water scrubbing increased pH from 6.5
for glass pipe and ceramic balls, respectively (Daglioglu et al., 2020). A to 6.7, and consequently, the CH4 content increased from 75% to 87%
longer gas retention time was monitored in the glass pipe bioreactors (Lemmer et al., 2015b). However, water scrubbing requires an addi-
(2.58 h compared to 2.08 h for ceramic balls), prolonging the contact tional recirculating system, which increases the overall investment.
time between gas and microorganisms. Like the HFM reactor, the Lindeboom et al. (Lindeboom et al., 2013b) applied silicate minerals
UASB reactor can be tall, increasing the contact time and promoting (e.g., wollastonite, olivine, and anorthosite) for CO2 scavenging. They
the H2 conversion efficiency. Meanwhile, the optimal upflow velocity demonstrated that pH increased from 6.0 to 7.5, and CH4 content in-
is essential in the UASB system, which helps provide adequate mixing creased to around 87% at 3-9 bar. However, this method required sub-
of the gas and biomass (Daud et al., 2018). However, the higher upflow stantial chemicals, and the produced precipitate might block the
velocity reduces the contact time between sludge and wastewater and outlet pipe. Alternatively, to avoid problems with pH, wastewater
smashes the sludge granules (Daud et al., 2018). Therefore, upflow ve- with high alkalinity content can be an option. J. Zhao et al. (2020) and
locity significantly impacts both biological performance and physico- L. Zhao et al. (2020b) stated that HPAD could be applied to treat highly
chemical effluent characteristics (Ozgun et al., 2013). Thus, the alkaline (14.4 g/L CaCO3) wastewater without pH modification. Hence,
optimal upflow velocity should be carefully determined in the UASB HPAD technology for biogas upgrading can be applied with close pH
system. Additionally, the gas collected from the top part could be monitoring or for the treatment of high-alkalinity waste streams. Or,
recycled into the UASB reactor until the CH4 content meets the HPAD can be coupled with external voltage to form bioelectrochemical
10
Table 2
Summary of high-pressure technology used for biogas upgrading.
Reactor type Substrate Operation Conclusion Microbes CH4 (%) Reference

condition
H2 addition Sewage sludge 1.5-3 bar, 35 °C ①Pressure could increase the gas-to-liquid transfer rate, H2 - 95.2% (Díaz et al., 2020)
(single-stage) H2 injection HRT 20 days conversion reached 99%.
35 L, 300 kPa ②Exogenous H2 could help upgrade biogas.
H2 addition Food waste, H2 3, 5, 7 bar, 37 °C ①pH decreased caused by high pressure Methanobacterium 92%(52.4% for control) (Kim et al., 2021)
3.0 L (2.3 L) ②Addition of H2 could increase pH Methanosarcina
Methanosaeta
Single-stage, CSTR synthetic wastewater 37 °C ①CO2 dissolved in the liquid phase under the pressure Methanosaeta concilii 88% (64% for control) (J. Zhao et al., 2020; L.
(glucose, acetic acid) 11 bar, 2 L ②HPAD reactor could deal with high alkalinity content Methanobrevibacter Zhao et al., 2020)
wastewater
Single-stage Propionic and butyrate 0.2 L, 35 °C Increasing PCO2 decreased the syntrophic propionic and - - (Ceron-Chafla et al.,
0.3-8 bar butyrate oxidation 2020)
Single-stage, batch NaCH3COO∙3H2O 30 °C, 3-90 bar The SMY decreased by 30% compared to atmospheric - 90-95% (Lindeboom et al., 2011)
conditions.
Single-stage, batch VFAs 30 °C, 1-20 bar Substrate and cation inhibition reduced conversion rates - >94% (Lindeboom et al., 2013a)
single-stage, batch Sodium acetate 30 °C, 1-20 bar PCO2 was below ideal theoretical equilibrium. - CH4 > 95% (pH 7); (Lindeboom et al., 2012)
pH was lower than 6. CH4 > 80% (pH 5-6)
Batch Glucose 30 °C, 1-10 bar The addition of silicate can buffer glucose acidification and - 75-88% (Lindeboom et al., 2013b)
sequestrate CO2.
Batch Sodium acetate, 30 °C, 1-20 bar PCO2 could inhibit propionate degradation (5 bar). Methanosaeta concilii; - (Lindeboom et al., 2016)
Glucose, Propionate Methanobacterium
11
formicicum
CSTR Activated sludge 37 °C,1-6 bar Phosphate solubility increased, COD removal decreased. Methanocellaceae 85% (Latif et al., 2018)
Two-stage, batch A mixture of grass and maize 37 °C, The initial pressures didn't significantly influence pressure - - (Lemmer et al., 2017;
Methane filter silage hydrolysate 10, 20, 30 bar, and increase, degradation of organics, and SMY. Merkle et al., 2017a)
1, 50, 100 bar
Two-stage, Maize silage 37 °C, continuous Water scrubbing can help increase pH from 6.5 to 6.7. - 75-87% (Lemmer et al., 2015b;
Methane filter 9-50 bar Merkle et al., 2017b)
flow rate: 0, 20, 40
L/day
Two-stage, Leachate from maize 37 °C The SMY dropped. - pH from 7.2 to 6.5, (Chen et al., 2014a;
Methane filter silage/grass and maize silage 1, 3, 6, 9 bar Higher NH4 lead to higher pH and CH4 content but lower CH4 from 66 to 75% Lemmer et al., 2015a)
SMY.
Two-stage HR: maize and grass silage HR: 55 °C ①HPAD cost savings of 20%. - 75%-94% (Bär et al., 2018)
(Hydrolysis reactor, HR; Methanogenesis MR(fixed-bed reactor): MR: 37 °C, 21 L ②Combine microfiltration and HPAD could further increase

reactor, MR) effluent percolate from HR <100 bar CH4 content.
③Microfiltration unit reduced the HRT in the HPAD process
to 1.5 days.
Two-stage, leachate from maize silage 37 °C ①Best performance was 9 bar and 12.5 kg m3d-1. - 74.5% (Chen et al., 2014b)
Methane filter reactor 1.5, 9 bar ②Higher OLR became unstable.
Two-stage, Food waste 37 °C, continuous pH decreased from 7.22 to 6.98, and COD removal decreased Methanosaeta, 91% (Li et al., 2017)
Biofilm reactor 3-17 bar 93 to 80%, the SMY decreased. Methanospirillum
electromethanogenic reactor Sodium acetate 55 °C, 50 bar The methane-production rate of the reactors showed an Methanothermobacter - (Kobayashi et al., 2017)
(Stainless-steel single-chamber Fed-batch applied-voltage dependence. Thermincola
reactors) 700 mV
Note: ‘-’ not mentioned.

Table 3
Bio-electrochemical technology used for biogas upgrading.
Reactor type CO2 removal Anode Cathode Operation Conclusion Microbes CH4 (%) Reference
efficiencies/CE condition
Two-chamber + 98% (enrich Solium acetate, CO2, 300 mL ①Pre-enriched inoculum enhanced biocathode CH4 Methanobrevibacter 0.586 mmol CH4/d (Dykstra and
PEM inoculum) Porous carbon felt, Porous carbon (250 mL), 22 °C production. arboriphilus for enriched (0.153 Pavlostathis, 2017b)
62% (control) anolyte felt, HRT 7 days ②The archaeal communities were similar, while the bacterial for control)
Catholyte, communities were different.
-0.8 V,
1.65 atm
CH4 produce
Two-chamber + 89%-135% (CE) Graphite felt Graphite felt 1.4 L (0.7 L)b ①CH4 production was enhanced at lower pH (pH 6.5). Methanothermobacter CH4 production (Lee et al., 2020)
PEM O2 produce Substrate: CO2 ②CH4 production rate was higher than this pure strain. sp. THM-2 (pure) rate is 6.36 L/m2/da
CH4 produce
-0.85, -0.90,
-0.95 V
Two-chamber + 88% (20A m-2) Na2SO4 solution HEPES buffer 0.2 L, 20 °C ①Upgraded cathode off-gas (CH4, H2) generated more - 45% (Acosta et al., 2020)
AEM 99% (anolyte), (catholyte) microbial protein than raw biogas.
12
(40A m-2) Iridium mixed metal Biogas from ②CO2 and CH4 were separated by electrochemical.
oxide coated R1, ③H2 content increased, and CH4 decreased when current
titanium-electrode Stainless- increase.
mesh steel wire
O2 produce mesh
H2& CH4
Two-chamber + 80-88% (CE) N2:CO2 = 4:1 Glucose Batch and Hydrogenotrophic methanogenesis and alkali production Methanobacterium >70% (Xu et al., 2014)
CEM Graphite electrodes -700 mV continuous followed by CO2 absorption were likely to be major Petrolearium
Graphite 37 °C, 1 L (0.8 contributors to biogas upgrading in these systems
electrodes L)
Single-chamber – Cow manure 35 °C ①Electrode promoted lignocellulose degradation - 84% (77% control) (Qu et al., 2014)
Stainless steel electrode Batch mode ②Electric polarity was: cathode > anode > blank
100-2500 mV ③Cathodic micro-voltage was: 250 mV > 500 mV > 100 mV
Two-chamber + 11-75% (CE) 410 mL 420 mL; 35 °C O2 diffusion from the anode compartment, which decreased Methanobacterium sp. 65-85% (Batlle-Vilanova et al.,

CEM H2O as electron donor -600, -800 mV Batch mode the reactor efficiency. 2015)
O2 produce Synthetic gas
(55% CH4, 45%
CO2)
Single-chamber & 60.2-80.9% Glucose Single-chamber ①Single chamber had higher VFAs concentration, especially - 98% (Liu et al., 2017)
Two-chamber + (electron Carbon felt 55 °C, 400 mL for propionate. (two-chamber)
CEM balance) 0 to -1.2 V (350 mL) ②Two-chamber reactor had higher CH4 content and more
Two-chamber stable.
55 °C, 500 mL
(350 mL)
Two-chamber + 25-33% (CE) Stainless steel mesh Stainless steel 0.5 L for each; ①No significant differences between different inocula for CH4 Methanobrevibacter 83% (Cerrillo et al., 2017)
CEM Sodium acetate mesh Continuous; production and CH4 recovery efficiency. CH4 production
NaHCO3 HRT 6.8 h; 23 ②Hydrogenotrophic methanogens were dominated in the rate 0.23 L/m3/d
-800 mV °C biocathode.
Single-chamber – Stainless steel mesh, Carbon cloth 38 °C, 600 mL The CH4 yield was enhanced by 48%. The CH4 production rate - 88% (Hagos et al., 2018)
Glucose, xylose, cellulose (400 mL) increased 1.65 times.
Single-chamber 66.7% (Energy Acetate (10 g/L) 180 mL ①CH4 yield increased 2.3 times, COD removal rate was Methanospirillum 98% (Bo et al., 2014)
efficiency) Stainless steel Batch mode tripled, and carbon recovery was increased by 56.2%.
0.4, 1.0 V ②The overall energy efficiency was 66.7%.
BES + H2 – Carbon cloth Carbon cloth AD1, 2.3 L ①Combination of MEC with AD improved AD performance. Methanobacteriales CH4 yield 500 mL/g (Yanuka-Golub et al.,
injection biogas and H2: MEC: 2.1 L ②H2 circulation contributed to the high quality and yield of Methanomicrobiales COD 2019)
AD1-MEC-AD2 CO2 = 4:1 (0.5-1.5 V) CH4. Methanosarcinales
AD2, 0.8 L, 37
°C
BES 6.7-25.4% (CE) Graphite fabric sheet with multiwall 0.5 V, 1.0 L ①CH4 production strongly depended on electroactive Methanocorpusculum 62.3-207 mL/d (Feng et al., 2018)
carbon nanotube and Ni 35 °C microorganisms' concentration in bulk solution. bavaricum
sludge ②IET was the main pathway that existed in the system. Clostridium quinii
High-pressure + 70% sodium acetate 55 °C, 50 bar The methane-production rate of the reactors showed an Methanothermobacter CH4 production (Kobayashi et al., 2017)
single-chamber (current-capture stainless-steel Fed-batch applied-voltage dependence. Thermincola rate 168
BES efficiency) 700 mV mmol/m2/d
Two-chamber + 85.2% (CE) Carbon paper Carbon paper 0.15 L for each, ①This system combined biogas purification, H2S removal, Methanococcus 98.3% (Fu et al., 2020)
PEM FeSO4·7H2O CO2 Batch & and sulfur recovery. maripaludis S2 CH4 production
Continuous, 37 ②Fe2+ could simulate sulfide removal and CH4 formation rate 20.6 μmol·h−1
°C
BES – Carbon cloth stainless Bench-scale ①Remove H2S and increase CH4 content. - 87% (Lin et al., 2016)
Dairy manure 25 °C, 35 °C ②3 V was better for H2S removal.
1, 2, 3 V 160 mL (100 ③Stainless steel electrodes removed most sulfide without
mL) interfering with CH4 production.
Two-chamber + 100% Iridium mixed metal Stainless steel 0.5 L (0.2 L) for ①Membrane electrolysis allowed to simultaneously remove - >98% (Verbeeck et al., 2019)
AEM oxide coated wire mesh each CO2 and add H2 to the biogas.
titanium-electrode CH4:CO2(H2S) ②H2S absorption in the alkaline catholyte removed up to 98%
mesh = 60:40 of the incoming H2S.
Two-chamber + 1.5-3.5% (CE) Carbon felt Granular 55 °C, 500 mL ①Ammonium removal in the MEC anode compartment Methanomassiliicoccus CH4 production (Cerrillo et al., 2018)
CEM Digested pig slurry graphite (265 mL) achieved 14.46 g N-NH4+ m−2 d−1, removal efficiency rate 79 L/m3/d
N2 produce biogas 18-30%.
H-cell reactor 10% (Nitrogen titanium mesh drums Steel brushes <550 mV ①N2 will replace with O2 produce at the anode. - (56% COD removal (Siegert and Tan, 2019)
13
removal Wastewater No membrane ②The drums were better in removing COD, while steel rate)
efficiency) Batch mode brushes produced CH4 faster.
Two-chamber + 105 mmol/d Anolyte 800 g graphite 0.86 L ①CO2 adsorption in BES cathode was driven by net alkalinity - 34 meq/Ld (Zeppilli et al., 2016)
AEM 85 (CE) Acetate granules 0.2, -0.1 V generation. 47%
Catholyte ②Alkalinity generation was due to selective ion transport
CO2 N2 = 3:7 across separation membranes.
62 mmol/d ③AEM allowed a higher CO2 removal due to HCO-3 transport 83 meq/Ld
Two-chamber + 53% (CE) from cathode to anode. 81%
PEM
Two-chamber + 11-19% (CE) Carbon felt Carbon felt Batch, 22 °C ①The CH4 yield was 2.9-fold higher. Methanobrevibacter 0.60-2.73 mmol (Dykstra and
PEM + 62-97%(cathode anolyte -0.65 to -0.80 300 mL (250 ②ZVI assisted in the start-up of an elctromethanogenic arboriphilus CH4 Pavlostathis, 2017a)
zero-valent Iron capture V mL) biocathode and maintained microbial activity during voltage Proteobacteria
(ZVI) efficiency) Sodium interruptions.
80-99% acetate acetate

removal rate CO2, 1.65 atm
Catholyte
ZVI:1, 2 g/L
Note: ‘-’ not mentioned; CE: coulombic efficiency; MEC: Microbial electrolysis cell.
a
The CH4 production per unit cathode surface area.
b
The volume in parenthesis is the working volume of the reactor.
HPAD to convert the surplus dissolved CO2 into CH4 (Kobayashi et al., and two-chamber BES, are available. Single-chamber BES is featured
2017). Another option is the combination of HPAD and H2 addition, as by membrane-free characteristics (without anion exchange membrane
underlined above (Section 2.1.1.2). (AEM) and cation exchange membrane (CEM)). In this context, Qu et al.
The methanogenic community in HPAD might be affected by various (2014) investigated the effect of the individual electrode (anode or
internal conditions such as pressure, pH, and temperature. Lindeboom cathode) at different micro-voltages (100, 250, 500, 2500 mV) on the
et al. (2011) claimed that methanogens are resistant to pressure and AD of cow manure in single electrode-assisted fermenters (Li et al.,
could tolerate an external pressure of up to 100 bar. But the relevant 2021; Qu et al., 2014). They affirmed the enhancement of the average
knowledge of the methanogenic community at elevated pressures is CH4 content (77.9%) in the voltage-added (2500 mV) cathode-assisted
rare. Whereas the change of pH induced by the dissolution of CO2 under reactors than that of the control (67.4%). In another study, Bo et al.
high pressure could strongly affect the activity (SMY decreased by 30%) (2014) argued that the CH4 content could excess 98%, and CH4 yield
and composition of the methanogenic community (50% Metahanosaeta was increased 2.3 times through the addition of only a small voltage
at 11 bar) in the HPAD system (Li et al., 2017; Lindeboom et al., 2011, (1.0 V) in a barrel-shaped single chamber BES. The merit of single-
2016; J. Zhao et al., 2020; L. Zhao et al., 2020). As for temperature, chamber BES comes from its simple set-up, no additional membrane
Methanosaeta, Methanospirillum, Methanobrevibacter are abundant at unit, and low voltage input (due to its low internal ohmic resistance).
mesophilic conditions, while Methanothermobacter is rich at thermophilic However, the concern arises considering the production of O2 at the
conditions (Kobayashi et al., 2017; Li et al., 2017; Lindeboom et al., 2016; J. anode if the applied voltage exceeds the principle voltage required for
Zhao et al., 2020; L. Zhao et al., 2020). water split (1.23 V at the standard condition), which is harmful to the
Collectively, the development of HPAD reactors offers some clear ad- oxygen-sensitive methanogens. One solution could be the supplemen-
vantages for biogas upgrading. However, low pH caused by the dissolved tation of electron donors (COD, H2S, NH+ 4 ) other than water since
CO2 is still a significant bottleneck for the wide distribution of this tech- these compounds can be oxidized to provide electrons at a potential
nique. Conversion of the dissolved CO2 into CH4 could be ideal for solving much lower than that of water. For instance, the applied voltage to ox-
this problem and decreasing CO2 emissions. Reduction of dissolved CO2 idize NH+ 4 (136 mV) can be much lower than for the water splitting
could be achieved through the direct addition of H2 or bioelectrochemical (1.23 V) with appropriate catalysts in place (Table S2) (Siegert and
technology implementation. Despite current constraints confronted by Tan, 2019). The AD process and BES integration have been tested
HPAD, continuous operation of the HPAD reactor would considerably re- using real effluents as anodic substrates (Zeppilli et al., 2017), allowing
duce capital expenditure (around 20%) compared to a conventional AD, simultaneous N2 production at the bioanode and CO2 removal at the
including ex-situ upgrading and biomethane injection into the NGG biocathode. In another study, Fu et al. (2020) used a single BES reactor
(Budzianowski and Postawa, 2017; Sarker et al., 2018). to treat synthetic wastewater for simultaneously CO2 reduction and sul-
fur recovery. This system comprises a ferrous ion (Fe2+) mediated abi-
2.3. Bioelectrochemical system (BES) otic anode for H2S oxidation and a methanogen-inoculated biocathode
for CO2 removal. In the anodic chamber, H2S was removed and selec-
BES for biogas upgrading has several advantages. The process can be tively converted into elemental sulfur particles. The CH4 production
performed at low temperatures; the process produces less sludge and re- rate of 20.6 μmol/h and high upgrading level (98.3% CH4) was achieved
quires no aeration cost, making the process eco-friendly (Kumar et al., in the cathode chamber. This system holds great potential for practical
2017). application as concurrent biogas upgrading and sulfur recovery can be
achieved.
2.3.1. Mechanism Alternatively, the dual-chamber BES can be adopted for biogas
BES harbors the oxidation reaction at the bioanode (take wastewater upgrading regardless of the potential to maximize the upgrading rate
chemical oxygen demand (COD) as an example: CxHyOzN + (2x-z) H2O and efficiency. In this context, Liu et al. (2017) evaluated the biogas
→ xCO2 + [y + (2x-z)] [e- + H+] + NH3 (Eq. (6)), while the reduction upgrading efficiency of single-chamber and two-chamber reactors. Com-
of CO2 to CH4 at the biocathode is also known as electromethanogenesis. pared with single-chamber BES, two-chamber BES was more stable, with
Electromethanogenesis can proceed via several known mechanisms lower VFAs concentration (420 vs. 775 mmol/e), higher CH4 yield (CH4
(Fig. S2) (Fu et al., 2021): 1) Interspecies electron transfer (IET): H2 pro- yield was enhanced by 40% vs. 10% compared to control), and significantly
duced at the cathode at the expense of H+ reduction, which is catalyzed higher CH4 content (98% vs. 60%). Thus, they concluded that two-
by extracellular enzymes: 2H+ + 2e− ⇋ H2 (Eq. (7)), H2 can then be cap- chamber BES reactors are more suitable for continuous biogas upgrading
tured by hydrogenotrophic methanogens for CO2 reduction: CO2 + 4H2 in future research and application (Liu et al., 2017). Besides applied volt-
⇌ CH4 + 2H2O (Eq. (2)) (Fig. S2C). When the applied voltage is sufficient age, different membrane types could also influence the reactor's behav-
to overcome thermodynamic limitations and losses, H2 can also be pro- iour. Zeppilli et al. (2016) stated that in AEM-BES, 5.4 g/L∙d of CO2 was
duced abiotically at the cathode. 2) Direct electron transfer (DET): removed through the membrane due to molecular diffusion and ionic
Cheng et al. (2009) proved the existence of DET, where methanogens transport. In contrast, in the proton exchange membrane (PEM)-BES,
can use electrons directly to reduce CO2 into CH4 by physical contact on only 3.2 g/L∙d of CO2 was removed by the osmotic overflow.
cathode without the intermediate production of H2. CO2 + 8H+ + 8e−
⇋ CH4 + 2H2O (Eq. (8)) (Cheng et al., 2009; Hagos et al., 2018) 2.3.2.2. Biocathode materials. Currently, biocathode materials mainly
(Fig. S2D). 3) Homoacetogenesis plus AM: H2 and CO2 are first converted include carbonaceous fabric materials, metal-based materials, and a com-
into acetate by homoacetogenic bacteria, and then the formed acetate is bination of them. In a recent study, Zhen et al. (2018) compared five dif-
degraded by AM to generate CH4 (Fig. S2E). At relatively low external po- ferent carbon-based cathode materials (carbon stick, carbon twined with
tential, DET dominates in electromethanogenesis. In this context, it en- Ti wire or covered with carbon fiber, graphite felt, and carbon cloth)
ables BES to get rid of the common gas-to-liquid transfer rate problem regarding their long-term performance in CO2 electromethanogenesis.
in exogenous H2 injection technologies to a certain extent. In the subsec- Results indicated that carbon stick covered with graphite felt enjoyed
tions, factors influencing the efficiency of the conversion of CO2 into CH4 the most pronounced CO2 reduction rate (90%), significantly higher
(biogas upgrading efficiency) are discussed (Table 3). than that of carbon stick (40%). Such phenomenon was owing to the pro-
liferation of the robust electromethanogenic cathodic biofilm brought by
2.3.2. BES applications the composite electrode, enabling more effective CO2 utilization and elec-
tron uptake. Likewise, Kim et al. (2017) reported an improved CH4 con-
2.3.2.1. Single-chamber or two-chamber BES?. According to the reactor tent (83%) obtained in a Ni-doped granular activated carbon biocathode
configurations, two types of BES reactors, namely single-chamber BES than that of the control (73%).
14
2.3.2.3. Mineral addition for CO2 sequestration. Besides reactor configura- contribute to the accelerated carbonation reaction and high alkalinity.
tions and cathodic materials, which can promote the conversion rate of Linville et al. (2017) stated that biochar addition increased alkalinity
CO2 into CH4, the implementation of cheap chemicals coupled with BES as CaCO3 increased from 2800 mg/L to 4800-6800 mg/L, providing pro-
can be an alternative for further CO2 reduction and acceptable CH4 con- cess stability for AD of food waste. Besides, the material for biochar af-
tent. In this context, J. Zhang et al. (2020a, 2020b), L. Zhang et al. (2020a, fects the CO2 adsorption capacity. Linville et al. (2017) believed that
2020b) and Y. Zhang et al. (2020) adopted wollastonite to achieve in- fine walnut shell biochar (FWSB) had higher adsorption capacity than
site CO2 sequestration by forming calcite precipitates. As a result, they coarse walnut shell biochar (CWSB) due to the increased surface and
attained the ultimate CH4 content of 95.9% (control without wollaston- ash content. The FWSB could remove 61% of the CO2 (85.7% CH4),
ite: 90%), followed by an enhancement of CH4 yield (16.9%) (J. Zhang whereas the CWSB could deduct 51% of the CO2 (78.9% CH4) produced
et al., 2020a, 2020b; L. Zhang et al., 2020a, 2020b; Y. Zhang et al., from the AD process. In another study, the corn stover biochar-
2020). Moreover, the generated precipitates barely aggregated on amended digesters produced near pipeline-quality biomethane (>90%
biocathode and did not significantly affect the morphology of cathode CH4 and <5 ppb H2S), and CO2 removal by up to 86.3% (Shen et al.,
biofilm. 2015); Shen et al. (2017) and Wei et al. (2020) also introduced corn sto-
Collectively, BES can be introduced for biogas upgrading, especially ver biochar to upgrade biogas and raised the CH4 content to 95% and
when the electricity is coming from renewable sources (windmill, pho- 87.3%, which were much higher than previously reported results. How-
tovoltaic, etc.). However, most BES is temporarily limited to lab-scale, ever, the negative effect of high dosages of biochar was unveiled due to
indicating the requirement of an improved upgrading efficiency (oper- high concentrations of mono- and divalent cations released from bio-
ation under high current density) before its full-scale application char into the digester. Another function of biochar is that it could act
(Rousseau et al., 2020). as a kind of carrier material for immobilized functional bacterial/
methanogens (Clostridia, Methanothermobacter) and further increase
2.4. Additives the CH4 production rate (increased by 20-70%) (Wei et al., 2020; Yang
et al., 2020; J. Zhang et al., 2020b). Furthermore, keeping CO2 in the bi-
2.4.1. Ash carbonate/carbonate form in the aquatic phase encourages CH4 forma-
Sludge ash, a substance originating from municipal solid waste in- tion via CO2 reduction by hydrogenotrophic methanogens (Yang et al.,
cineration, has been reported as an AD booster for improved biogas pro- 2020).
duction (Montalvo et al., 2017; Yin et al., 2018). This is because it
contains many trace metal elements (Zn, Ni, Fe, etc.) (Yin et al., 2019). 2.4.3. Zero valent iron (ZVI)
Trace elements from ash are essential components of enzymes and co- ZVI is another additive used in the AD system to upgrade biogas and
factors in CH4 production. Moreover, the high concentration of alkali increase CH4 yield, which could provide Fe element as a cofactor of en-
oxide metals (CaO, MgO, etc.) enables the high buffer capacity of ash, zymes and promote the DIET pathway (both conductive material and
which can efficiently prevent VFAs accumulation and provide a suitable indirectly provide conductive pili/cytochromes) (Fig. S2), thus enhanc-
environment for the growth of methanogens. Nevertheless, a high dos- ing more conversion of VFAs to CH4 (Romero-Güiza et al., 2016; J. Zhang
age of sludge ash into the system should be avoided, as it suppresses the et al., 2020a, 2020b; L. Zhang et al., 2020a, 2020b; Y. Zhang et al., 2020).
activity of methanogens. The anaerobic corrosion of ZVI (oxidized to Fe2+ or Fe3+) donates elec-
In comparison, stepwise addition of sludge ash is recommended. A trons that can be used directly for CO2 reduction by methanogens, or can
study conducted by Yin et al. (2019) indicated a linear correlation be- lead to the formation of H2, enhancing the abundance and activity of
tween ash dosages and CO2 sequestration. The gradual addition of ash hydrogenotrophic methanogens. Additionally, its reductive character
may not stimulate the hydrolytic and acidifying enzyme activities im- also decreases the oxidation-reduction potential, inducing a more favor-
mediately but favors the action of coenzyme F420, compared to the in- able environment for the activity of anaerobic microorganisms (J. Zhang
stantaneous addition group. As a result, the stepwise addition of ash et al., 2020a, 2020b; L. Zhang et al., 2020a, 2020b; Y. Zhang et al., 2020).
enriched the proportion of Methanomassiliicoccus (34.48%) and pro- For instance, Feng et al. (Feng et al., 2014) claimed that the addition of
moted amounts of CO2 captured (Yin et al., 2019). After adding the ZVI effectively enhanced protein and cellulose decomposition. The CH4
sludge ash to the AD system, the CH4 yield was improved by up to content was improved from 58.5% of the control reactor to 68.9%, and
26.6%, and the CH4 content was boosted from 76.1% to 86.6% at thermo- CH4 production was enhanced by 43.5% (Feng et al., 2014).
philic conditions (Yin et al., 2018). At mesophilic conditions, the CH4 Charalambous and Vyrides (Charalambous and Vyrides, 2021) declared
yield was strengthened by 39.2%, and the CH4 content was enhanced that the CH4 content was increased to 97% compared to 74% for ZVI-free
from 69.1% to 79.4% by stepwise adding the ash (Yin et al., 2019). reactors. Other researchers reported that the total CH4 production was
increased by 123-231% compared to the control system without the
2.4.2. Biochar ZVI amendment. The content of the headspace CH4 was around 5
Biochar possesses a high surface area (105 m2/g), a high ash content times higher than that of the control (Dykstra and Pavlostathis, 2017a;
(45.2% dry weight), and high concentrations of oxide metals (14.2% K2O, J. Zhang et al., 2020a). Besides, ZVI could remove H2S (S2- + Fe2+ →
3.9% CaO, and 4.2% MgO of the ash content, respectively) (Shen et al., FeS ↓) (J. Zhang et al., 2020a, 2020b; L. Zhang et al., 2020a, 2020b; Y.
2015). The trace element (Fe, Co, Ni, Mn) in biochar could act as a cofac- Zhang et al., 2020).
tor to enhance the biogas upgrading process (Romero-Güiza et al., 2016; As mentioned above, ash, biochar, and ZVI all could increase CH4 con-
Wambugu et al., 2019). Moreover, the pores in biochar could adsorb CO2 tent, but the capacity of ash/biochar is limited. The biogas (80-86% CH4)
(Shen et al., 2015). Additionally, the microorganisms could attach to the produced from the ash addition reaction still cannot meet the applica-
surface of biochar to avoid being washed out. Owing to these advan- tions' requirements. Thus, ash, biochar, or ZVI could be a kind of additive
tages, biochar improves CH4 concentration and production rate used in other reactors (e.g., BES) to increase the CH4 content further.
(Table 4) (Masebinu et al., 2019). The sludge-based biochar and ash
share an identical element composition. However, the mechanisms for 3. Comparison between different in-situ technologies and predomi-
the enhancement are different. Notably, the introduction of biochar pro- nant methanogens
motes the direct interspecies electron transfer (DIET) pathway (Fig. 2D
and Fig. S2), which seldomly happens in ash-addition reactors (Yin 3.1. CH4 content and H2 conversion
et al., 2019). Moreover, the alkaline metals of biochar lead to a slight in-
crease of pH (alkaline pH) in the biochar-added digesters, which con- CH4 content is the primary indicator in the biogas upgrading tech-
verts excess CO2 to bicarbonate/carbonate. The reaction would nologies, representing the quality of biogas. Fig. 3 summarizes the CH4
15
Table 4
Additives used for biogas upgrading.
Additives Surface Pore Diameter Reactor type Substrate Operation Function of additives Microbes CH4 (%) Reference
(m2/g) volume of pores condition
(cm3/g) (nm)
Sludge incineration 14.2 0.047 Particle 2 L (1.5 L) Waste activated 1.5 g/g DM ① Stepwise addition of ash enhanced CH4 production by 35.8% Methanomassiliicoccus 79.4% (69.1% (Yin et al., 2019)
ash size: 100 rpm sludge 55 °C and facilitated CO2 sequestration as calcite sediment for control)
0.1-0.3 ② Relative activity of coenzyme F420 was improved by 43.8% in
mm stepwise addition.
Sludge incineration 14.2 0.047 Particle Batch mode sludge 0.6-1.5 g/g DM ① Optimal AD performance was achieved at ash dosage of 0.9 - 55-90% (Yin et al., 2018)
ash size: 2 L (1.5 L) 55 °C g/g DM.
0.1-0.3 ② CH4 production increased by up to 26.6%.
mm ③ Ash accelerated sludge hydrolysis and fermentation.
④ CO2 sequestration was linearly correlated with ashes dosage.
Ash (thermal power – – Particle Batch Primary sludge and 35 °C ① Particle size of 1-1.4 mm had the highest degradation of - 28-96% (Montalvo et al., 2017)
plant) size: 250 mL secondary sludge organic matter and highest CH4 production
0.8-2.36 (200 mL)
mm
Corn stover biochar 302.6 0.11 5.9 Batch: 160 Primary sludge Biochar:1.82-3.06 ① Accelerated primary sludge hydrolysis and enhanced CH4 Methanolinea 81.3-87.3% (Wei et al., 2020)
mL g/g TS production (8.6-17.8%). Methanosaeta (67.5% for
Continuous: 55 °C ② Increased buffering capacity, conductively, and alleviated Rgodobacter control)
CSTR HRT 15 days NH3 inhibition. Paludibacter
1.8 L(1.5 L) Proteinclasticum
Walnut shell biochar Fine Fine Fine Bench-scale Food waste Biochar: 0.96-3.83 ① Increased alkalinity from 2800 to 4800-6800 mg/L - 77.5-98.1% (Linville et al., 2017)
(WSB) WSB: WSB: WSB: 650 mL g/gVS ② The FWSB had a better CO2 adsorption capacity of 61%
86.5 0.16 7.06 (550 mL) 37 °C, 55 °C
Coarse Coarse Coarse
WSM: WSM: WSM:
16
792.7 0.11 3.67

Corn stover biochar ND ND ND 0.5 L CSTR Sludge from WWTP 0.25-1.0 g/day ① Biochar addition increased CH4 production rate by up to Methanosarcina 95%(max) (Shen et al., 2017)
Two-stage R1: 37 °C, 25-37%. Clostridia
R2: 55 °C ② Increased fertilizer value of the digestate
HRT 5-15 days ③ CO2 removal by up to 86.3%.
Corn stover biochar 315.3 0.09 6.5 Two-stage Sludge from WWTP R1: 37 °C, HRT 1.2 ① Biochar addition sequestered CO2 and enhanced CH4 yield. - >90% (Shen et al., 2015)
days ② Biochar addition increased alkalinity and mitigated NH3
R2: 55 °C, HRT 12 inhibition.
days
1.82-3.64 g/g TS
Woody biochar PBC: PBC: 0.19 PBC: 5.07 600 mL Sludge 37 °C, 55 °C ① CO2 sequestration by up to 32.4-66.2%. - 79-92.3% (Shen et al., 2016)
Pinewood (PBC) 310.19 WOBC: WOBC: (550 mL) PBC: 2.49-4.97 g/g ② Biochar addition increased alkalinity, and alleviated free
White oak biochar WOBC: 0.15 4.92 DM ammonia by up to 10.5%
(WOBC) 296.81 WOBC: 2.2-4.4 g/g
DM

Digestate biochar(DB) DB: DB: 2-50 Batch mode H2:CO2:N2 = 4:1:1 3.0 g ① Biochar as a carrier material for immobilized HM. Methanobacterium - (Yang et al., 2020)
and corn straw 334.91 0.02-0.13 300 mL 37 °C ② CH4 production increased by 20-70% Spirochaetes
biochar (CSB) CSB: CSB: 120 rpm
279.93 0.02-0.11
ZVI 0.05 ND Particle Two-stage Alkaline-pretreated 35 °C, 120 rpm ① ZVI effectively enhanced the decomposition of protein and HM 68.9% (58.5% (Feng et al., 2014)
size: 0.2 250 mL Waste activated ZVI: 1, 4, 20 g/L cellulose. Homoacetogens for control)
mm working sludge ② The activities of key enzymes increased 0.6-1time.
volume ③ CH4 production raised by 43.5%, and the sludge reduction
ratio increased by 12.2%.
ZVI (powder and scrap – – – Batch mode Cheese whey 36 °C, 100 rpm ① Addition of powder ZVI (25 g/L) or scrap ZVI (50 g/L) - 97% (74% for (Charalambous and
type) 250 mL (100 25, 50, 100 g/L enhanced production and SCOD removal, resulting in the control) Vyrides, 2021)
mL) substantial conversion of VFAs.
② 50 g/L scrap ZVI was most cost-effective than 25 g/L powder
ZVI.
Note: ‘-’ not mentioned; DM: dry matter.

content from the reviewed papers and is classified by different H2 conversion efficiency (%) is an essential parameter in H2 addition
upgrading technologies. HFM combined with H2 addition has the upgrading technologies. The HFM reactor has higher H2 conversion effi-
highest CH4 content (92.5% on average). While HPAD performs ciency (97%) than CSTR (83%) and UASB reactors (93%) (Fig. 3B). Pre-
slightly worse, with an average of 87% CH4 content obtained. sumably, the HFM reactor has higher CH4 content (>92%) because
UASB+H2, BES, and additives exhibited a similar CH4 content (81- more CO2 could combine H2 to generate CH4 through the HM pathway.
83%). Although the highest CH4 content could increase up to 100% In these H2 addition technologies, H2 supplement needs extra equip-
in H2 with CSTR technology (Treu et al., 2018b), it has the lowest av- ment and energy (water electrolysis). Thus, using BES alone could be at-
erage CH4 content due to the substrate and H2 injection methods (NB tractive because it combines H2 production and biogas upgrading in one
is not discussed here as only one case is reported regarding H2 addi- system. Or, BES coupled with pressure should be highlighted as it solves
tion). Compared with other technologies, HFM is more stable to pro- the gas-to-liquid transfer problem if the dominant pathway in BES is IET
duce high-quality biogas. instead of DET (Kobayashi et al., 2017).
Fig. 3. Comparison of different in-situ upgrading technologies (A) Maximum CH4 percentage (%) from various reviewed papers, (B) average CH4 percentage and H2 conversion efficiency
(%) of different H2 addition technologies, (C) the show-up frequency of methanogens (occurrence number, y-axis) among these reviewed papers, (D) The influence of operating
temperature on the show-up frequency (occurrence number, x-axis) of methanogens under mesophilic and thermophilic condition, respectively among the reviewed papers).
17
3.2. Predominant methanogens in upgrading technologies group modified the gas injectors into the GasMix ejector system and
attained a pronounced H2 consumption efficiency (49%), with a maxi-
Microorganisms, especially methanogens, are key players in the bio- mum CH4 content of 65% (Jensen et al., 2021). Concomitantly, the reac-
gas upgrading process. Methanothermobacter, Methanobacterium, tion heat of the upgrading process entailed significant savings regarding
Methanosaeta, Methanculleus, and Methanobrevibacter are the most pre- the heat of the biogas reactor. Despite those merits, the incomplete H2
dominant methanogens in these reviewed papers (Fig. 3C). Except for transfer implied a necessity for a subsequent ex-situ technology for
Methanosaeta, other methanogens could all produce CH4 through the final biogas upgrading. Researchers should examine whether or not
HM pathway. Therefore, the HM pathway plays a crucial role in the bio- such in-situ technology could serve as a low-cost first step in the biogas
gas upgrading process, especially in H2 addition technologies. In com- upgrading system to reduce the necessary capacity of subsequent ex-
parison, the existence of acetoclastic Methanosaeta is probably due to situ upgrading technologies in the future.
homoacetogenic bacteria (e.g., Treponeme, Clostridium ragsdalei P11). For HPAD, our group is currently collaborating with a Dutch company
In other words, homoacetogenic bacteria use H2 and CO2 to produce ac- (BAREAU; https://bareau.nl/en/for-professionals/) on the establishment
etate, and then Methanosaeta consumes acetate to produce CH4 (Wang of a medium-scale HPAD in a wastewater treatment plant for simulta-
et al., 2013; L. Zhao et al., 2020). Therefore, in some H2/CO2 addition re- neous biogas upgrading and nitrogen removal (by annomax) (Basic infor-
actors, acetate can also be identified (Omar et al., 2018; Omar et al., mation of HPAD: volume: 1 m3; pressure: 19-20 bar; H2 injection rate:
2019; Sarker et al., 2020). 2000 L/d; pH: 6.5-7.5). The output-pressured biogas contains 95% of
Methanothermobacter is a thermophilic methanogen that uses CO2 CH4 that can be directly injected into the gas grid if the contaminants
and H2 as the substrate to produce CH4 and grows best at a temperature (H2S, NH3) are adequately removed. Furthermore, we will consider pro-
between 55 °C and 65 °C. In thermophilic reactors, Methanothermobacter ducing H2 from the electrolysis of AD effluent or wastewater via BES. Rel-
can make up to 50% of the biomass. It is noteworthy that HM has a higher evant technical and economic assessment is in progress to see if these two
proportion in thermophilic reactors (20 cases reported) than in compatible technologies can make HPAD competitive in the market.
mesophilic ones (17 cases reported) (Fig. 3D). Some researchers reported For BES, sole large-scale BES has not yet been reported, probably due
that thermophilic conditions presented a higher CH4 production rate and to its technical incompetence to make the process economically feasible.
H2 bioconversion rate in H2 addition reactors (Figeac et al., 2020; Grimalt- According to the estimated capital costs of BES (reactor type: single-cell;
Alemany et al., 2020; Luo and Angelidaki, 2012; Yun et al., 2017; Zhu et al., current density: 1000 A/m3), the capital costs (€/kg COD) of a BES is 8,
2019b). In BES, Methanobacterium and Methanobrevibacter prevailed which is significantly higher than the product revenue (0.2 €/kg COD)
(Geppert et al., 2016). (Rozendal et al., 2008). Such a considerable gap requires a breakthrough
in reactor configurations, anode and cathode materials, solution
4. Existing full-scale in-situ applications and future perspectives conductivity, and screening of efficient electroactive microorganisms.
Despite the obstacles confronted by BES, a combination of BES for H2
Compared with a thorough investigation of large-scale ex-situ tech- production (water electrolysis) and subsequent biomethanation (H2
nologies, relevant examination of in-situ technologies, mainly technical addition technology) might be a viable effort. Under such circum-
and economic feasibility analysis, is scarce for the moment. However, stances, Cambrian Innovation (http://cambrianinnovation.com/
some researchers/companies have devoted themselves to bridge the resources/) and Electrochaea (http://www.electrochaea.com/) are two
gap between lab-scale in-situ trials and corresponding large-scale leading companies that made progress by developing industrially appli-
installations. cable, bioelectrically enhanced anaerobic treatment systems. One com-
For H2 addition in-situ technology, Jensen et al. (2018) firstly mercial project (with a basis for the design of 1 MW) in Solothurn,
coupled the venturi-based H2 injectors (Landia®GasMix) with a full- Switzerland established by Electrochaea has accomplished several
scale manure-based AD digester (working volume 1110 m3) for in- goals: 1) stable operation of >1200 h, CH4 production >13,800 Nm3;
situ biogas upgrading. They affirmed the positive correlation (r = 2) excellent output gas quality (>97% CH4 in product gas) that exceeds
0.95) between H2 consumption efficiency (10-26%) and H2 injection standards for grid injection; 3) Load factor tests: 0%-100% capacity test-
rate (20-65 m3/h). They highlighted the significance of gas-to-liquid ing achieved. These achievements will inspire the corresponding efforts
mass transfer, which can be improved by a high H2 injection rate, for more efficient development of BES systems, at either lab-scale prin-
small gas bubbles, and improved recirculation rate (Jensen et al., ciple analysis or large-scale application. The larger plants built by these
2018). However, they stated that the current H2 consumption rate dis- companies will be crucial for a techno-economic assessment of the tech-
abled venturi-based technology to constitute a stand-alone in-situ nology, especially when the electricity is readily available from renew-
upgrading system, requiring substantial improvement. The same able energy facilities (windmill, photovoltaic, tidy, etc.). Moreover, an
Table 5
The merits and challenges of different types of biogas upgrading technologies.
Technologies Merits Challenges
H2 injection • High H2 conversion rate and high CH4 content. • pH inhibition, pH increases up to >8.5 due to bicarbonate consumption.
• Versatile reactor configurations and can be combined with other in-- • The limited the gas-to-liquid mass transfer rate.
situ technologies. • High H2 level inhibits HM, and acetate accumulates.
• Applicable at full-scale AD plant. • Require external addition of H2.
• High capital and operation costs (e.g., HFM).
High pressure • Efficient removal of gas impurities (CO2, H2S, and NH3). • Automatic system control, safety.
• Increase the gas-to-liquid transfer rate. • A large amount of CO2 in the liquid phase causes pH decline.
• Close to the full-scale application (coupled with H2 addition)
BES • H2 produced within the reactor, with little or no external H2. • Limited gas-to-liquid mass transfer rate.
• Act as surplus renewable energy storage in terms of CH4. • Limited to lab-scale (can't be operated at high-current density yet).
• Promotion of hydrolysis, acetogenesis, and methanogenesis. • Not economically feasible yet.
• Environmentally-friendly
Additives • Simple set-up • A large quantity of heavy metals is present in the reactors, which may adversely
• Trace element as cofactors for improved methanogenesis. affect methanogenesis.
• Carrier for microorganisms to attach and further increase the CH4 • Need cost-effective and environmental-friendly additives.
production rate.
• Increase buffering capacity, conductivity and alleviate NH3 inhibition.
18
investment screening on the spatial deployment of two types of PtG bio- Acknowledgment
gas upgrading installations (biogas upgrading and CO2 methanation)
has been carried out on a national scale in Danish (Nielsen and Skov, Part of the work is supported by the China Scholarship Council
2019). They concluded that biogas upgrade paths had the lowest costs (CSC).
of the two approaches (3.1 M€ for biogas upgrade vs. 7.0 M€ for CO2
methanation) at the current cost level. More importantly, the method Appendix A. Supplementary data
could be an excellent reference for other countries, given the availability
of the same type of data. Supplementary data to this article can be found online at https://doi.
Unfortunately, a relevant large-scale sample of NB technology org/10.1016/j.scitotenv.2021.149667.
has not been documented yet. But such upgrading holds great
promise as it may fix the frustrating gas-to-liquid problem in H 2 References
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Science of the Total Environment 800 (2021) 149667

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