Applied Energy 342 (2023) 121195

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Tunable H2/CO syngas production from co-gasification integrated with

steam reforming of sewage sludge and agricultural biomass: A
experimental study
Ge Kong , Xin Zhang , Kejie Wang , Linling Zhou , Jin Wang , Xuesong Zhang *, Lujia Han
Engineering Laboratory for AgroBiomass Recycling & Valorizing, College of Engineering, China Agricultural University, Beijing 100083, 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

• Biowaste to tunable H2/CO syngas was

developed through co-GSR technology.
• Co-GSR of binary WS/SS using self-
derived biocarbon for tunable syngas
production.
• Steam co-gasification got H2-rich syngas
with a tunable H2/CO ratio of 1.77 –
3.35.
• Co-GSR of the blend within 10% of SS
gained the highest gas yield (94.74
mmol/g)
• Co-biochar C[WS + SS] showed a higher
H2 proportion (57.79%) and H2/CO
ratio (2.89)

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

Keywords: Biowastes to tunable H2/CO syngas is a promising way to produce clean energy carrier. This study proposed a
Co-gasification new concept of improving the production of tunable H2/CO syngas and tar abatement via co-gasification inte­
Inline steam reforming grated with inline steam reforming (co-GSR) of wheat straw (WS) and sewage sludge (SS) over self-derived
Tunable H2/CO syngas
gasification/co-gasification carbon materials (G/CGCMs). Binary mixtures with varying WS/SS mass ratios
Gasification/co-gasification carbon materials
Tar elimination
were initially subjected to steam co-gasification, achieving H2-enriched syngas with the tunable H2/CO molar
Biowaste ratio of 1.77 – 3.35. By introducing C[WS] in co-GSR process, the synergistic interactions between binary mixture
and C[WS] on the cumulative gas yield, H2 yield, and syngas yield were more predominant by using WS/SS-9/1
as the feedstock, reaching 94.74, 51.53, and 77.99 mmol/g. Moreover, co-GSR of WS/SS-9/1 presented the
highest CCE (98.77C%) and CGE (121.63%), suggesting the C content in the binary mixture and C[WS] was
almost entirely converted and reformed into gaseous product. Correspondingly, WS/SS-9/1 subjected to co-GSR
was also found to gain the lowest tar yield (5.99 g/Nm3). These observations were possibly because the addition
of 10% of SS in the blend could not only assure the sufficient C and volatile contents in the blend, but also ensure
the sufficient supply of alkali metals and alkaline earth metals (AAEMs) from SS as a catalyst to facilitate catalytic
cracking and reforming of intermediate tar from decomposition of 90% of WS. When G/CGCMs were applied in
both GSR and co-GSR processes, co-biocarbon C[WS + SS] used in the GSR of SS could garner a higher H2
concentration (57.79vol%) and H2/CO ratio (2.89). In addition, plausible reaction pathways and mechanisms

* Corresponding author.
E-mail address: xszhang@cau.edu.cn (X. Zhang).

https://doi.org/10.1016/j.apenergy.2023.121195
Received 30 November 2022; Received in revised form 15 March 2023; Accepted 21 April 2023
Available online 3 May 2023
0306-2619/© 2023 Elsevier Ltd. All rights reserved.
G. Kong et al.
regarding co-GSR of binary WS/SS mixture in the presence of G/CGCMs were discussed and elucidated. Simply
put, this study provides a newly sustainable route to produce tunable H2/CO syngas towards a clean and sus­
tainable waste management way.
1. Introduction
H2 as a new clean energy carrier is expected to eventually replace
petroleum fuels [1,2]. Approximately 96% of H2 is produced from fossil
fuels by steam reforming of natural gas, but massive CO2 is emitted into
the atmosphere in the manufacturing [3,4]. At present, biowaste-to-H2 is
regarded as an alternative and carbon–neutral way to combat the energy
crisis [5]. Among prevalent biowastes, sewage sludge (SS) is a complex
microbial heterogeneous semi-solid mixture containing high levels of
organic matter [6,7]. A vast number of SS is produced annually, and the
disposal of SS is a thorny issue [7]. Traditional disposal methods, such as
landfilling and incineration, are no longer sustainable due to environ­
mental and economic restrictions [8]. Since SS contains abundant hy­
drocarbons and inorganic materials, it shows a great potential for
pyrolysis or gasification to produce clean fuel [9]. So far, most attention
has been paid to obtain H2-riched syngas from SS gasification [10].
It is also recognized that 11.4 billion tons of crop residues are pro­
duced annually, 40% of which are agricultural crop residues [11].
Wheat straw (WS) as a dominant agricultural waste is hard to be valo­
rized due to the high ash content (e.g., silica). WS has been extensively
investigated in gasification for gas production [12]. For instance, Nanda
et al. investigated gasification of wheat straw in subcritical and super­
critical water, and the improved gas yield was achieved when different
catalysts were used in the process [13]. Thus, the utilization of SS and
WS as raw materials for H2 production will not only mitigate the
shortage of fossil fuel resources but also efficiently solve landfill disposal
problem of the biowastes [14].
For the versatile application of H2, it can be mixed with CO for syngas
production, which can not only be directly used for power generation
[15], but also be considered as an essential platform feedstock to syn­
thesize a wide range of valuable fuels or chemicals through well-
established industrial processes [16,17]. It is discerned that syngas
with a tunable H2/CO ratio is essential for the synthesis of chemicals by
using different Fischer-Tropsch synthesis (FTS) operation modes [17].
For instance, a H2/CO ratio of 1 is fit for hydroformylation process [18];
while a H2/CO ratio of 2 is perfectly suitable for the synthesis of
methanol and hydrocarbons through FTS process [19]. Although gasi­
fying biomass with steam can produce H2-rich syngas and promote tar
cracking reforming [20]. However, it is still difficult to obtain tunable
H2/CO syngas, which is the main bottleneck restricting the development
of biomass gasification technology.
Instead, co-gasification of biowastes (e.g., sewage sludge, livestock
manures, and black liquor) with either lignocellulosic biomass or coal
can significantly solve this problem and achieve excellent gasification
performance (like high gas yield and high syngas purity) [21]. For
instance, when coal was co-gasified with sawdust, the ash content in
biomass could server as inherent catalysts to augment the carbon con­
version efficiency [22]. Moreover, Hu et al. reported that during steam
co-gasification of horticultural waste and sewage sludge, H2 concen­
tration was promoted as SS ratio in the blend was increased probably
due to the catalytic effect of Na as well as the reduction and steam
oxidation of Fe species predominantly existing in SS; and the phenom­
enon was more pronounced at the higher temperatures [23]. As such,
Huang et al. proposed a concept of co-gasification of wet sewage sludge
and terrified biomass (spruce and birch) for producing hydrogen-rich
syngas; and the maximum H2 yield (33.6 mol/kg) was achieved from
co-gasification of wet sewage sludge and terrified spruce [24]. In addi­
tion, Yan et al. performed co-gasification of municipal sewage sludge
and cotton stalk with 10% TDS-600 for syngas production and obtained
the maximum syngas yield (0.808 m3/kg) at an optimized gasification
2
Applied Energy 342 (2023) 121195
temperature of 850 ◦ C and steam volume fraction of 20% [25]. Never­
theless, it is noted that SS and WS have not been subjected to steam co-
gasification process for H2-rich gas production so far.
Typically, introducing a catalyst or assisted-reforming agent in steam
gasification can accelerate the catalytic cracking and reforming re­
actions, contributing to gas production and tar elimination. Ni-based
catalysts are often considered as effective catalyst for catalytic
cracking and reforming [26], but the high cost of Ni is not highly
competitive for its commercialization [27]. In aspect of catalysts, the
catalysts with high mechanical strength, high melting point, good
chemical stability, and low cost should be considered.
In this regard, biochar has certain catalytic ability of catalytic
cracking and reforming due to its specific surface area, oxygen-
containing functional groups, and alkali metals and alkaline earth
metals (AAEMs) [28]. At present, biochar is often mixed with biomass or
directly used as a feedstock for steam gasification. For example, it was
observed that steam co-gasification of Japanese cedarwood and its
commercial biochar with different mixing ratios exhibited synergistic
effect on tar reduction, possibly due to the highly porous structure and
high content of AAEMs in biochar [29]. Recently, our group has devel­
oped a new route of torrefaction/carbonization-enhanced gasification-
steam reforming by using a biochar as both an assisted-reforming agent
and a co-reactant, which could promote the H2-rich gas production and
tar removal [30].
In view of the above, WS and SS showed enormous potential as
feedstocks to prepare gasification/co-gasification carbon materials (G/
CGCMs) for biomass gasification. Herein, a novel concept is proposed for
tunable H2/CO syngas production and tar abatement through utilizing
G/CGCMs as the assisted-reforming agents and co-reactants for co-
gasification integrated inline steam reforming (co-GSR). In this study,
the G/CGCMs maintained the high C content and enriched AAEMs,
which allowed it to be used as the gasification co-reactants and assisted-
reforming agents. Importantly co-GSR technology could thoroughly
converted binary feedstocks into tunable H2/CO syngas. To the best of
our knowledge, the application of G/CGCMs from WS and SS for biomass
gasification has never been conducted. In particular, co-GSR of binary
WS/SS mixture in the presence of their self-derived G/CGCMs for
tunable H2/CO syngas production has not been verified experimentally.
Herein, we developed a novel co-GSR of binary WS/SS blend with the
aid of self-derived G/CGCMs to pursue tunable H2/CO syngas produc­
tion and tar abatement. First of all, gasification performance from steam
co-gasification of binary feedstocks as a function of WS/SS mass ratio
was explored. Subsequently, binary mixtures with varying WS/SS ratios
were subjected to co-GSR to evaluate the effect of gasification carbon
material on gas formation behaviors and tar elimination performance.
Furthermore, the gasification performance from the dual-stage gasifi­
cation-steam reforming (GSR) and co-GSR processes over G/CGCMs was
examined. Ultimately, reaction pathways and mechanisms regarding co-
GSR in the presence of G/CGCMs were discussed in detail. Overall, this
work offered the inspiration of efficiently converting WS and SS into
tunable H2/CO syngas whilst minimizing tar formation by using green,
sustainable, and cost-effective G/CGCMs.
2. Materials and methods
2.1. Materials
Wheat straw (WS) was provided by CAU experimental station in
Beijing, China. Sewage sludge (SS) was supplied by a municipal waste­
water treatment plant of Beipai Group in Beijing, China. Both WS and SS
G. Kong et al.
were dried at 105 ◦ C for 24 h, and then they were ground into approx­
imately 40 mesh by using a high-speeder grinder. The binary feedstocks
were prepared by thoroughly mixing WS and SS. To thoroughly explore
the gasification performance from steam co-gasification of binary
feedstocks, the broad WS/SS mass ratios ranging from 0:10 to 10:0 were
applied in this study. WS/SS-X/Y represents the weight ratio of WS and
SS, the detailed labels are listed in Table S1.
2.2. Preparation of gasification/co-gasification carbon materials (G/
CGCMs)
The facile synthesis of G/CGCMs is shown in Fig. 1a. Our recent
study has proven that biochar gained through a fast gasification manner
at 900 ◦ C with a residence time of 15 min presented the optimal
Fig. 1. Schematic diagrams: (a) the preparation of G/CGCMs and (b) the steam co-gasification or co-gasification integrated with inline steam reforming (co-GSR)
experimental set-up and reaction system configuration.
3
Applied Energy 342 (2023) 121195
performance in gas production and tar reduction [31]. Therefore, to
prepare gasification carbon materials from fast gasification process, 20 g
of raw WS or SS was first placed in a quartz boat, which was kept outside
of the vertical furnace. Then, the quartz reactor was purged with Ar at
100 mL/min for 20 min, and it was preheated to 900 ◦ C and maintained
for 10 min. Subsequently, the quartz boat was pushed into the furnace
shortly and maintained for 15 min. Finally, the quartz boat was rapidly
pushed out and promptly cooled to room temperature. As such, the co-
biocarbon was prepared in a similar manner. The same amount of binary
WS/SS mixture in a mass ratio of 1:1 was used as feedstock to synthesize
co-biocarbon material. In this study, the gasification carbon material
obtained from fast gasification of WS or SS alone was denoted as C[WS]
or C[SS], respectively; while the co-gasification carbon material ach­
ieved from fast co-gasification of WS and SS was named as C[WS + SS].
G. Kong et al. Applied Energy 342 (2023) 121195

2.3. Direct steam co-gasification of WS and SS ( )

MJ
LHV = 0.126 × CO + 0.108 × H2 + 0.358 × CH 4 + 0.665×Cn Hm
Direct steam co-gasification of WS and SS blends is shown in Fig. 1b. Nm3
Our previous studies confirmed 900 ◦ C was the best condition for gas (3)
production and tar elimination [32,33]; and the degradation of biomass To quantify the gasification efficiency, the carbon conversion effi­
components mainly takes place at 250 – 450 ◦ C [34]. To accomplish ciency (CCE, C%) and cold gas efficiency (CGE, %) during steam co-
adequate steam reforming of volatiles to increase gas generation, a slow gasification process were used to examine the thermal conversion
gasification manner, starting from 250 ◦ C to 900 ◦ C, was operated in this degree.
study. Binary WS/SS mixtures with a consistent weight (1.5 g) was ∑
preloaded in a quartz basket, which was placed above the furnace. After CCE =
12
×
Vi
× 100% (4)
purging with Ar at 30 mL/min for 20 min, the quartz reactor was heated 22.4 mfeedstock × fC,feedstock
to 250 ◦ C and maintained for 10 min. Next, the quartz basket was pushed where Vi is the volume (L) of each compound; mfeedstock (g) represents
into the gasification stage in the upper zone of the furnace. At the same the mass of binary WS/SS mixture; fc (C%) is the weight fraction of
time, water with a flow rate of 0.2 g/min was injected into the reactor. carbon in the binary mixture.
Afterwards, the gasification zone was gradually heated to 900 ◦ C at During the co-GSR process, the carbon fraction in the G/CGCMs
10 ◦ C/min. When the gasification zone reached the desired temperature, should be taken into consideration in terms of CCE.
the experiment was prolonged for an additional 10 min to get the ∑
feedstocks and G/CGCMs exhausted for gas production. Eventually, the CCE =
12
×
Vi
× 100% (5)
gas was collected and the volume was measured. 30 mL of ethyl acetate 22.4 mfeedstock × fC,feedstock + mcarbon × fC,carbon
was utilized to dissolve the tar sticked on the condenser. where mcarbon (g) represents the mass of G/CGCMs introduced in the
co-GSR process; fC,carbon (C%) is the weight fraction of carbon in the G/
2.4. Co-gasification integrated with inline steam reforming (co-GSR) of
CGCMs.
WS and SS over G/CGCMs
The CGE (%) of the direct steam co-gasification is defined as the ratio
of the calorific value of the gases to the calorific value of binary mixture
The co-GSR system was conducted to via a two-stage gasification-
gasified in the system:
reforming system, as displayed in Fig. 1b. Steam co-gasification of bi­
nary WS/SS blends was performed in the upper stage, while the catalytic CGE =
LHV gas × V
× 100% (6)
steam reforming occurred in the lower stage. Prior to the test, raw binary LHV feedstock × mfeedstock
mixture (1.5 g) was placed in the quartz basket above the upper stage,
where LHVfeedstock is the LHV of binary WS/SS mixture, LHVgas is the
and the carbon material with a constant weight of 0.75 g was preloaded
gas LHV (MJ/m3), which is determined by Eq. (3).
in the catalytic reforming stage. After purging the whole system, the
As such, the CGE of the co-GSR process is expressed as the ratio of the
upper and lower stages were heated to 250 and 900 ◦ C, respectively; the
calorific value of gas to the total calorific value of binary mixture and G/
system was then controlled for 10 min. The next steps were same as the
CGCMs:
procedures of direct steam gasification process.
LHV gas × V
CGE = × 100% (7)
2.5. Analytical techniques LHV feedstock × mfeedstock + LHV biochar × mbiochar

where LHV biochar is the LHV of G/CGCMs, which is also calculated by

The compositions of raw feedstocks (WS and SS) and G/CGCMs were
Eq. (3).
tested by proximate and ultimate analysis. The inorganic components in
The tar yield (Ytar ) is denoted as the total mass of tar (mtar ) to the gas
WS and SS were measured by XRF analysis. The physicochemical
volume (V):
properties of G/CGCMs were characterized by SEM, N2 sorption iso­
( g ) m
therms, and XRD analysis. The tar components were determined by GC/ Ytar =
tar
× 100% (8)
MS analysis. Gaseous products were identified and quantified by GC Nm3 V
analysis. All the analytic methods were specifically described in the
Supplementary. 3. Results and discussion

2.6. Data analysis 3.1. Characterization of biomass and G/CGCMs

The gas yield (Yi , mmol/g) is defined as the mole of gas i produced 3.1.1. Characterization of WS and SS
from 1 g of reactants (binary WS/SS mixture plus carbon material): To well understand the synergistic interactions between WS and SS
during steam co-gasification and co-GSR processes, the proximate and
Yi =
V
× xi (1) ultimate analysis of WS and SS was initially operated, as given in
22.4 × m Table 1. Apparently, WS had a higher volatile content (71.82%), which
where xi (vol%) is the volumetric percentage of gas fraction i was due to the strong presence of lignocellulose in WS. By contrast, SS
measured by GC; V (mL) is the collected gas volume; m (g) represents the was found to have a low volatile content (52.51%), which was attributed
mass of binary WS/SS mixture for steam co-gasification process or bi­ to the high share (38.81%) of ash. Regarding the ultimate analysis, a
nary mixture plus G/CGCMs supplied for co-GSR process. higher C proportion (43.09%) and H proportion (5.31%) were observed
The syngas yield (Ysyngas, mmol/g) is calculated as follows: for WS, while the contents in SS was correlated to the high ash content.
Broadly, the C content included in biomass plays a vital role in biomass
V
Ysyngas = × (xH2 + xCO ) (2) gasification performance; the higher C content usually results in a higher
22.4 × m gas yield [30].
The lower heating value (LHV) of gas was determined based on the As ash occupied a large proportion in biomass feedstocks (especially
following equation [35]. SS), characterization of ash would be helpful to assess the role of ash
during the steam co-gasification and co-GSR processes. It is well known
that ash in biomass mainly contains mineral species, significantly
affecting biomass gasification and/or steam gasification [36]. The XRF

4
G. Kong et al. Applied Energy 342 (2023) 121195

Table 1 and [WS + SS] was approximately 0.080 cm3/g larger than its micro­
Proximate and ultimate analysis of biomass feedstocks and their G/CGCMs. porous pore volume, reaffirming their predominant mesoporous struc­
Characteristics WS SS C[WS] C[WS + SS] C[SS] tures. These results should be attributed to the synergistic interaction
between WS and SS; specifically, the strong presence of AAEMs in SS
Proximate analysis (wt%)
Moisture 5.53 3.57 8.19 2.68 2.33 might act as a catalyst to facilitate the decomposition of volatile matters
Volatile 71.82 52.51 11.60 2.15 1.21 in WS, forming more porous structures. In addition, the pore diameter of
Fixed carbon a
13.72 5.11 52.52 31.21 15.75 C[WS + SS] showed a lower pore size (5.03 nm) than C[SS] (5.31 nm),
Ash 8.93 38.81 27.69 63.96 80.71 indicating the formation of more mesopores during co-gasification
Ultimate analysis (wt%)
C 43.09 33.58 62.22 39.58 18.58
process. It is discerned that the large surface with more mesopore
H 5.31 4.89 0.54 0.39 0.24 structures is more desirable in the steam gasification process since it
N 0.75 3.84 0.92 1.34 0.98 could enhance the physical adsorption and the contact between tar,
S
a
0.11 1.03 0.27 1.23 0.93 steam, and carbon material, contributing to a higher gasification rate
O 41.81 17.85 8.36 – –
[29]. The XRD patterns of G/CGCMs are demonstrated in Fig. 2d. The
H/C molar ratio 1.47 1.73 0.10 0.12 0.15
O/C molar ratio 0.73 0.40 0.10 – – sharp peak at ~ 28◦ was associated with Ca2P2O7 (JCPDS 73–0440). The
N/C molar ratio 0.01 0.10 0.01 0.03 0.05 reflection at 26.3◦ was assigned to Al2SiO5 (JCPDS 99–0068), which was
HHV (MJ/kg) 17.97 16.41 22.25 15.38 7.21 more enriched in C[SS] and C[WS + SS]; Al2O3 often serves as an strong
a
Determined by difference, O = 100 – sum of (C, H, N, S, and Ash), Fixed active site during biomass gasification [41]. The diffraction peaks at
carbon (%) = 100 – sum of (Moisture, Volatile matter, and Ash). around 31◦ and 50◦ were ascribed to K2O (JCPDS 27–0431), which was
more abundant in C[SS] and C[WS + SS]. Importantly, iron oxides were
analysis was conducted to exhibit the dominant inorganic components also found in C[SS] and C[WS + SS]. The significant existence of SiO2
in the ash residues, as listed in Table S2. It can be seen that the ash was also found in all G/CGCMs, which might endow G/CGCMs with
residue of WS was dominated by SiO2 (9.72%), K2O (7.90%), and CaO strong resistance to sintering at high gasification temperatures [42].
(3.48%), whereas the SS ash was enriched in SiO2 (12.61%), CaO The proximate and ultimate analysis was performed to further
(9.02%), Al2O3 (7.78%), and Fe2O3 (6.99%). The large amounts of determine the basic properties of G/CGCMs. As illustrated in Table 1, C
AAEMs in the form of oxides (e.g., Fe2O3, Al2O3, and CaO) was involved [WS] presented a much higher volatile content (11.60%) than C[SS]
in SS, which could serve as the catalyst to enhance the gasification rates (1.21%). On the contrary, both C[SS] and C[WS + SS] had the extremely
[37]. It should be noted that Si and P species can present an inhibitory low volatile content (~2%), which was caused by the release of volatile
effect on gasification performance [36]. Therefore, the characteristic matter during the fast gasification process [29]. In particular, the co-
difference between WS and SS would allow co-gasification of WS and SS biocarbon C[WS + SS] exhibited the higher value than the predicted
to be meaningful for manufacturing co-gasification carbon material and value. It can be explained by the reason that the mineral compositions in
gas. feedstocks can significantly affect the gasification performance. In
particular, AAEMs (e.g., K, Ca, and Na) can serve as catalytic active sites
3.1.2. Characterization of G/CGCMs to accelerate the gasification reactions [29,43]. More apparently, the
To deeply determine the physicochemical properties of G/CGCMs, relative ash content of the G/CGCMs was much higher than that of
namely C[WS], C[SS], and C[WS + SS], they were characterized by corresponding raw feedstocks. As listed in Table 1, C[WS] presented a
several technical methods. SEM analysis (Fig. 2a–c) of G/CGCMs was higher C content (62.22%) than raw WS, while C[SS] revealed a lower C
operated to determine the surface structures. As shown in Fig. 2a and b, content (18.58%) than raw SS. It was well discerned that a higher C
the original fibrillary arrangement of WS structure was retained, and the content in a reactant is more desirable for steam gasification because
honeycomb intra-pore structures on the entirety of C[WS] and C[WS + more C content can react with steam to form syngas.
SS]. The honeycomb structures could be derived from the release of
volatile matters during the gasification process. The surface micro­ 3.2. Optimization of steam injection rate
structures of G/CGCMs were also measured by N2 adsorp­
tion–desorption isotherms, as plotted in Fig. 2e and f. C[SS] and C[WS + The steam injection rate usually plays a key role in steam gasification
SS] exhibited the obvious overlap of the start–end retention ring, and the process; thus, this parameter is deserved to be evaluated. The effect of
type of hysteresis loop was associated with the Type H3 loop, indicating the steam injection rate on gas formation behaviors is tubulated in
the strong formation of mesopores [30]. However, C[WS] revealed the Table S3. Apparently, the gas yields and H2 proportion exhibited a rising
low adsorbed quantities (Fig. 2e), implying its few porous structure; tendency from 49.11 to 58.78 mmol/g and 50.51 vol% to 52.63 vol%
these results well aligned with the SEM analysis. Furthermore, the respectively by augmenting steam injection rate from 0.15 to 0.25 g/
curves were in agreement with the observations, as described in Table 2. min. Notably, the cumulative gas yield and H2 yield achieved at 0.2 g/
The pore size distribution of G/CGCMs is shown in Fig. 2f. It was worth min approached to those obtained at 0.25 g/min. It was assumed that
noting that the pore size distribution of C[SS] and C[WS + SS] peaked at the steam injected into the system at 0.2 g/min could assure the suffi­
approximately 4 nm, affirming the co-existence of micropores and cient steam reacting with intermediate volatiles, fulfilling the thorough
mesopores; in contrast C[WS] did not exhibit a clear peak because of the steam reforming reactions to form gases. Further increasing the steam
less porous structure. injection rate would not significantly contribute to the gas reforming
The textual properties of G/CGCMs are tabulated in Table 2. Inter­ reactions. It was also worth noting that the highest H2/CO ratio (2.41)
estingly, co-gasification carbon material C[WS + SS] presented a higher was achieved at 0.2 g/min, which is good for the synthesis of high H2/
BET surface area (86.24 m2/g) than C[SS] (82.94 m2/g) and C[WS] CO syngas.
(12.13 m2/g). That was possibly because the AAEMs in SS could pro­ CCE and CGE used to explain the thermal conversion degree of co-
mote the destruction of aromatic rings in lignin and the dehydration of gasification. As regards CCE, 0.2 g/min exhibited the highest CCE
biochar to form abundant pores at high temperature [38,39]; besides, (67.06C%) as compared with 0.15 g/min (38.26C%) and 0.25 g/min
during co-gasification the metal oxides (like iron oxides) in SS can be in (50.28C%). Even though the CGE was increased in the range of 0.15 –
situ reduced by carbon atoms on the biochar surface, which can enhance 0.25 g/min and the result gained at 0.2 g/min was close to that obtained
the development of the pore structure [40]. Furthermore, C[SS] and C at 0.25 g/min. It should be recognized that increasing the steam injec­
[WS + SS] possessed the comparable pore volumes, which were larger tion rate would lead to more energy input, excessive steam might also
than C[WS]. It was also found that the mesoporous pore volume of C[SS] condense which caused the consumption of heat in the system [44]. As
further increasing the steam injection rate to 0.25 g/min would not

5
G. Kong et al. Applied Energy 342 (2023) 121195

Fig. 2. Physicochemical properties of G/CGCMs: (a-c) SEM images; (d) XRD patterns; (e) N2 adsorption–desorption isotherms; (f) pore size distributions.

3.3. Steam co-gasification of binary feedstocks with varied WS/SS ratios

Table 2
Textural characteristics of G/CGCMs.
3.3.1. Gas formation behaviors
Materials SaBET Sbmic Scmes Vdtotal Vbmic Vcmes Deavg To examine the interactions between WS and SS during steam co-
(m2/ (m2/ (m2/ (cm3/ (cm3/ (cm3/ (nm)
gasification process, steam co-gasification of binary feedstocks with
g) g) g) g) g) g)
varied WS/SS mass ratios was conducted first. The steam co-gasification
C[WS] 12.13 6.12 6.01 0.029 0.003 0.026 9.44
performance including H2/CO molar ratio, gas yields, CCE, CGE, and tar
C[WS + 86.24 35.03 51.21 0.108 0.015 0.093 5.03
SS]
yield is sketched in Fig. 3 and Table S4. As regards gas volumetric
C[SS] 82.94 30.77 52.17 0.110 0.014 0.096 5.31 concentrations (Table S4), WS revealed the lowest H2 proportion (49.62
vol%) from steam gasification of WS alone. The H2 proportion was
promoted to 53.77vol% when SS share was raised to 100% in the blend,
make great contribution to co-gasification performance, thus the steam revealing a similar trend to the study reported elsewhere [23]. At the
injection rate set at 0.2 g/min could be more suitable, considering the same time, the H2/CO molar ratio was gradually increased from 1.77 to
tradeoff between gas production and energy consumption. 3.35 (Fig. 3a); and it was clearly found that the experimental H2/CO
ratio was more significantly larger than the theoretical values when the
WS/SS mass ratio was maintained ranging from 4:6 to 6:4, indicating the

6
G. Kong et al.
Fig. 3. Gasification performance from steam co-gasification of binary feedstocks as a function of WS/SS ratio: (a) H2/CO molar ratio; (b) cumulative gas yield, H2
yield, and syngas yield; (c) CCE and CGE; (d) tar yield.
more positive synergistic interactions between WS and SS. It was pre­
viously reported that the synergistic effect of co-gasification can be
explained by several reasons, e.g., the catalytic effect of AAEMs [45], the
transfer of H/OH free radicals [46], and reactions between half-biochars
[47]. Particularly, the positive synergistic effect on H2/CO molar ratio
was mainly attributed to the reduction and steam oxidation of Fe species
as demonstrated before [23]. It was also inferred that the higher
amounts of WS (with the WS/SS ratios of 8:2 and 9:1) hampered the
synergistic effect of H2/CO ratio.
Regarding the influence of WS/SS ratio in the gas yields (Fig. 3b), it
was notable to observe that steam gasification of WS alone gained the
maximum gas yields, whilst steam gasification of SS alone led to the
lowest gas yields. That was mainly because the volatile content of WS
was much higher than SS. These outcomes were also in relation to the
higher ash content (38.81%) of SS and the lower ash content (8.93%) of
WS, as demonstrated in Table 1. Even though H2 proportion and H2/CO
molar ratio declined with the increasing share of WS in the blend, the H2
yield gradually increased with the increase of WS/SS ratio. Among these
binary WS/SS mixtures, WS alone subjected to steam gasification
garnered the highest cumulative gas yield, H2 yield, and syngas yield at
72.92, 36.18, and 56.59 mmol/g, respectively. As mentioned above, the
more C and volatile content was beneficial for the gas formation through
the complicated reactions. That was the main reason why WS alone as
feedstock could achieve the higher gas yields.
The CCE and CGE results from steam co-gasification of binary mix­
tures with varied WS/SS mass ratios are shown in Fig. 3c. Generally, CCE
and CGE gradually went up as the WS share in the blend was promoted.
Steam gasification of WS alone was found to achieve the highest CCE
(83.25C%) and CGE (113.60%), while steam gasification of SS alone
7
Applied Energy 342 (2023) 121195
gained the lowest values. That was possibly due to the fact that the
organic matters in SS contained more volatile organics such as carbo­
hydrates, lipid, and protein, which were more conducive to the forma­
tion of tar during the steam gasification. The deduction was confirmed
by the observations of tar yield, as shown in Fig. 3d.
3.3.2. Tar elimination performance
The tar yield from steam co-gasification of binary mixtures with
varying WS/SS ratios is illustrated in Fig. 3d. Interestingly, tar yield was
reduced with the increase of WS proportion in the blend, the lowest tar
yield (15.96 g/Nm3) was observed from steam gasification of WS alone.
In contrast, SS was more responsible for tar formation, achieving the
maximum tar yield (50.82 g/Nm3) when SS alone was subjected to the
steam gasification process. These results were correlated to the CCE and
CGE results, as described in the above section; namely more tar forma­
tion would reduce the C content in the feedstock to be converted into
gases, thereby lowering the CCE and CGE. It was also deduced that the
volatile organics in SS would be more prone to tar generation than those
in WS during steam gasification. Overall, comparing with other plat­
forms, e.g., co-pyrolysis or co-digestion, to valorize sludge and ligno­
cellulosic biomass, steam co-gasification was more advantageous due to
the more syngas production with an ultrahigh H2/CO molar ratio. Thus,
it was concluded that steam co-gasification of sludge and agricultural
biomass is a feasible and promising strategy to trade off tunable H2/CO
syngas production and tar formation.
G. Kong et al. Applied Energy 342 (2023) 121195

3.4. Co-gasification integrated with inline steam reforming of binary Table 4

feedstocks with varied WS/SS ratios over C[WS] Reactions occurred during dual-stage GSR and co-GSR processes.
Reactions Equation
3.4.1. Gas formation behaviors
Biomass decomposition reaction: (9)
To evaluate the influence of carbon material on gasification perfor­ Cx Hy Oz + heat→Gas + biochar + volatiles(tar) + steam
mance during the co-GSR process, C[WS] produced from fast gasifica­ Volatiles secondary cracking reaction: (10)
tion of WS was applied as a control for co-GSR process to determine the Volatiles(tar)→C + Cm Hn (smallervolatiles) + gas
role of carbon material in H2-enriched syngas production and tar Volatiles steam reforming reactions: (11)
n
removal. In this regard, the gasification performance from co-GSR of WS Cm Hn + mH2 O→mCO + (m + )H2
2
and SS over C[WS] in relation to WS/SS mass ratio is summarized in Water gas reactions: (12) and
Table 3. By introducing C[WS] in the catalytic reforming stage, the H2, Biochar(mainlyC) + H2 O⇌CO + H2 Biochar(mainlyC) + (13)
2H2 O⇌CO2 + 2H2
CO proportions and syngas purity were all elevated comparing with
Boudouard reaction: (14)
steam co-gasification of relative binary mixtures in the absence of C Biochar(mainlyC) + CO2 →2CO
[WS], as shown in Fig. 3. However, the CH4, CO2, and C2H4 concen­ Water-gas shift (WGS) reaction: (15)
trations descended when introducing C[WS] in the co-GSR process. That CO + H2 O⇌CO2 + H2
Steam methane reforming (SMR) reaction: (16)
was because the presence of C[WS] could not only serve as an assisted-
CH4 + H2 O⇌CO + 3H2
reforming agent to accelerate catalytic reforming reactions, but also Methane dry reforming (MDR)reaction: (17)
work as a co-reactant by reacting with steam through the complicated CH4 + CO2 ⇌2CO + 2H2
reactions (Table 4), resulting in the increase of H2, CO, and syngas
proportions. Despite the fluctuated syngas purity, the decrease of WS/SS
ratio was conducive to the slight increase of H2 concentration but reduction (see Table 3). In particular, it was observed that co-GSR of
decrease of CO proportion, thereby resulting in the minor increase of WS/SS-9/1 revealed the highest CCE (98.77C%) and CGE (121.63%),
H2/CO molar from 1.83 to 2.26. suggesting the C content in the binary mixture and C[WS] was almost
The cumulative gas yield, H2 yield, and syngas yield are also listed in entirely converted and reformed into gaseous product. This phenome­
Table 3. The gas yields were lifted to very high levels as compared to the non well aligned with the tendency of gas and tar yields.
gas yields obtained from steam co-gasification of corresponding binary
mixtures, as shown in Fig. 3b. One reason of gas promotion resulted 3.4.2. Tar elimination performance
from the water gas reactions and catalytic reforming reactions, the other Tar yield from co-GSR of binary mixtures with varied WS/SS ratios is
is due to the strengthened solid char conversion [23]. It was found that tabulated in Table 3. Comparing with tar yield from the direct steam co-
the synergistic interactions between WS, SS, and C[WS] on the cumu­ gasification process, it was significantly reduced from co-GSR by
lative gas yield, H2 yield, and syngas yield were more predominant for employing C[WS], resulting in a dramatical catalytic activity in tar
WS/SS-9/1, reaching 94.74, 51.53, and 77.99 mmol/g. It was possibly cracking and reforming. For instance, the tar yield from SS alone was
explained by the reason that the addition of 10% of SS could not only 9.21 g/Nm3, which was merely 18.12% of tar yield gained from direct
assure the sufficient C and volatile contents in the blend, but also ensure steam gasification of SS in the absence of C[WS]. It was reaffirmed that
the sufficient supply of AAEMs from SS to facilitate decomposition of the intermediate volatiles evolved from the decomposition of SS was
90% of WS. Moreover, with the aid of C[WS] in the catalytic reforming more readily cracked and reformed into gases over C[WS]. Among these
stage, more H2-enriched syngas was produced instead of tar generation. binary mixtures, WS/SS-9/1 subjected to co-GSR was found to gain the
It was concluded that the interactions between WS, SS, and C[WS] lowest tar yield (5.99 g/Nm3), which was correlated to the observations
during co-GSR process was in favor of H2-enriched syngas production of gas formation behaviors. Furthermore, it was confirmed that 10% of
and improved the solid char conversion; and the interactions was more SS introduced in the blend could provide effective catalytic role of
apparent when 10% of SS was added in the binary mixture. AAEMs for catalytic cracking and reforming of intermediate tar from WS
The CCE and CGE results from co-GSR in the presence of C[WS] as a decomposition. As a result, steam co-gasification integrated with inline
function of WS/SS mass ratio are also given in Table 3. It was noted that catalytic reforming by using carbon material as an assisted-reforming
CCE gained from co-GSR of varying WS/SS ratios was nearly 90% or agent and co-reactant is a promising strategy to promote H2-erniched
above and CGE from all binary mixtures were over 110%, which were syngas production and tar abatement.
much larger than those gained from direct steam co-gasification of bi­
nary mixtures in the absence of carbon material. These results indicated
that the introduction of C[WS] in the catalytic reforming stage could
possibly enhance the catalytic tar cracking and reforming to form gases,
which was evidenced by the enhancement of gas production and tar

Table 3
Gasification performance from co-GSR of WS and SS over C[WS] in relation to WS/SS ratio.
Feedstocks Gas yields (mmol/g) Gas concentration (vol%) H2/CO Syngas purity CCE CGE Tar yield
(%) (C%) (%)
Gas H2 Syngas H2 CO CH4 CO2 C2H4 C2H6 g/Nm3

SS 85.32 48.46 69.99 56.80 25.24 3.44 14.02 0.49 0.01 2.25 82.04 90.91 118.11 9.21
WS/SS-1/9 80.36 45.70 65.95 56.87 25.20 3.41 14.21 0.31 0.00 2.26 82.07 87.92 113.30 10.69
WS/SS-2/8 87.30 49.20 71.64 56.36 25.70 3.16 14.44 0.34 0.00 2.19 82.06 92.84 116.31 9.64
WS/SS-3/7 88.29 49.55 72.17 56.12 25.62 3.17 14.69 0.40 0.00 2.19 81.73 94.04 117.41 8.70
WS/SS-4/6 90.28 51.00 73.78 56.49 25.24 3.10 14.86 0.31 0.00 2.24 81.73 93.50 120.95 8.09
WS/SS-5/5 89.29 49.43 73.22 55.36 26.64 3.12 14.61 0.27 0.00 2.08 82.01 94.29 120.52 6.89
WS/SS-6/4 91.27 51.31 74.98 56.22 25.93 3.09 14.51 0.24 0.00 2.17 82.15 89.94 118.03 7.65
WS/SS-7/3 91.27 50.81 75.27 55.67 26.80 3.06 14.20 0.27 0.00 2.08 82.47 93.35 121.21 6.57
WS/SS-8/2 90.77 49.35 74.85 54.37 28.08 3.18 14.14 0.23 0.00 1.94 82.45 96.16 120.50 6.03
WS/SS-9/1 94.74 51.53 77.99 54.39 27.92 2.93 14.56 0.19 0.00 1.95 82.31 98.77 121.63 5.99
WS 94.25 50.65 78.36 53.74 29.40 2.78 13.90 0.18 0.00 1.83 83.14 94.88 120.69 6.32

8
G. Kong et al.
3.5. Co-gasification integrated with inline steam reforming of binary WS/
SS mixture over G/CGCMs
3.5.1. Gas formation behaviors
To manufacture clean H2-enriched syngas, WS or SS alone subjected
to dual-stage gasification-steam reforming (GSR) and WS/SS-5/5 sub­
jected to co-GSR were performed in the presence of all G/CGCMs to
investigate the effect of carbon material type on gasification perfor­
mance. The releasing properties of gas products are displayed in Fig. 4.
Noteworthily, the H2 and CO concentrations were both raised in the
presence of all G/CGCMs (Fig. 4a), which was probably caused by the
interactions taking place between biomass feedstocks, carbon material,
and steam through complicated reactions (e.g., water gas reactions), as
demonstrated in Table 4. It was clearly found that co-biocarbon C[WS +
SS] was responsible for the high H2 proportion, syngas purity, and H2/
CO molar ratio in spite of the feedstock supplied (see Fig. 4a and b).
Particularly, C[WS + SS] used for GSR of SS or co-GSR of WS/SS-5/5
could a higher H2 concentration and H2/CO molar ratio, reaching
57.79vol% vs 57.33vol% and 2.89 vs 2.71, respectively.
As expected, the cumulative gas yield, H2 yield, and syngas yield
were obviously improved by employing G/CGCMs in either GSR or co-
GSR process. As shown in Fig. 4c, C[WS] was more advantageous than
C[WS + SS] and C[SS] in terms of gas yields, indicating that C[WS]
worked as the assisted-reforming agent and co-reactant was more
favorable for gas production. That was possibly due to fact that the much
higher C content (see Table 1) was more likely to react with steam or
Fig. 4. Gasification performance from the dual-stage GSR and co-GSR processes over G/CGCMs: (a) evolved gas composition; (b) H2/CO molar ratio; (c) cumulative
gas yield, H2 yield, and syngas yield; (d) CCE and CGE.
9
Applied Energy 342 (2023) 121195
intermediate volatiles to yield more gases. It can be seen that GSR of WS
by using C[WS] presented the maximum cumulative gas yield (94.25
mmol/g), H2 yield (50.65 mmol/g), and syngas yield (78.36 mmol/g). It
should be noticed that co-GSR of WS/SS-5/5 in the presence of C[WS]
could also achieve comparable gas yields, especially H2 production
(49.43 mmol/g). Nevertheless, the GSR or co-GSR process in the pres­
ence of C[WS + SS] or C[SS] did not contribute to the gas formation,
which was due to the less C and volatile contents that could react with
steam and intermediate volatiles derived from decomposition of
biomass feedstocks to generate gas product.
Fig. 4d shows the CCE and CGE from dual-stage GSR and co-GSR in
the presence of varying G/CGCMs. Likewise, C[WS] was superior to C
[WS + SS] and C[SS] in terms of CCE and CGE results, reaching over 90C
% and 117%, respectively. Notably, GSR of WS and co-GSR of WS/SS-5/
5 in the presence of C[WS] exhibited comparably higher CCE (~94C%)
and CGE (~120%), indicating the almost completed carbon conversion
from solid to gas. Despite the feedstock, CCE obeying in the following
sequence: C[WS] > C[WS + SS] > C[SS]. When the binary mixture was
replaced by SS, CCE was lowered while CGE was not significantly
affected regardless of the type of carbon material used for the GSR or co-
GSR process. As explained above, SS consisted of more volatile organics
was much easier to form liquid tar. Overall, it was concluded that the
addition (≤50%) of SS in the binary mixture might not strongly affect
gasification performance, particularly the CCE and CGE results.
G. Kong et al.
3.5.2. Tar elimination performance
Tar yield from dual-stage GSR and co-GSR processes by using
different G/CGCMs in the catalytic reforming stage were measured, as
demonstrated in Fig. 5. It was obviously found that the tar yield was
considerably reduced from GSR or co-GSR process as compared to that
gained from direct steam gasification/co-gasification process. Note that
C[WS] showed the most decent tar reduction efficiency, achieving the
tar yield of below 10 g/Nm3 in spite of the biomass feedstocks. As SS was
prone to tar formation, the tar yield from direct steam gasification of SS
was 50.82 g/Nm3, and it was reduced by 81.21% when C[WS] was
introduced in the GSR process. The lowest tar yield (6.24 g/Nm3) was
observed from co-GSR of WS/SS-5/5 in the presence [WS], accompa­
nying with a tar reduction efficiency of (76.39%). Although the high
surface area and porous structure (see Table 2) of C[SS] and C[WS + SS]
could promote the dispersion of AAEMs and accelerate the diffusion of
intermediate volatiles into the inner active sites of C[SS] and C[WS +
SS], the more stable aromatic structure, higher fixed carbon percentage,
and higher C content (more details, see Table 1) could endow C[WS]
with a better tar elimination efficiency. Similarly, a dual-stage pyrolysis-
reforming process was conducted by using a char bed in the oxidation
zone to produce syngas and reduce tar formation [48], it was found that
99% of tar was eliminated, generating clean syngas. Besides, Anniwaer
et al. claimed that steam co-gasification of raw cedarwood and its
commercial biochar was found to have the synergistic effect on syngas
production and tar removal due to the catalytic effect of biochar [29].
3.6. Discussion and plausible mechanisms of co-GSR over G/CGCMs
Table 4 gives the chemical reactions that might take place during the
dual-stage GSR and co-GSR processes [49,50]. Eqs. 9 and 10 are the first-
order reactions, while Eqs. 11 – 17 are the second-order reactions [51].
It was worth noting that Eqs. 12 – 14 are solid–gas reactions, whilst Eqs.
15 – 17 are intermediate gas–gas reactions [51]. Given that steam was
sufficiently supplied in the process, the gasification performance was
Fig. 5. Tar yield from the dual-stage GSR and co-GSR processes over G/CGCMs.
10
Applied Energy 342 (2023) 121195
correlated to the essentials of WS/SS mass ratio.
In this study, the synergistic effect on the promotion of H2/CO ratio
during steam co-gasification was explained by the enhancement of the
complicated reactions, as illustrated in Table 4. Furthermore, Fe species
in SS was much higher than that in WS (Table 1). During the steam co-
gasification process, Fe species were possibly reduced by the reducing
gases from the thermal decomposition of WS with the higher volatile
content, and then the reduced Fe species might be oxidized by steam
through Fe-steam reaction to significantly increase H2 production
[52,53]. Thus, the synergistic interaction between WS and SS mainly
included the catalytic effect of AAEMs introduced by SS, enhancing the
volatile decomposition and tar cracking/reforming from WS decompo­
sition and thereby resulting in the higher H2/CO molar ratio from steam
co-gasification of WS and SS. Moreover, large amounts of reducing gas
generated from WS could cause the reduction of Fe species in SS, which
might improve the waster splitting reaction to yield more H2 [23].
During the co-GSR process, carbon material placed in the catalytic
reforming stage would work as an assisted-reforming agent and co-
reactant. It was noted that the presence of G/CGCMs could enhance
H2-enriched syngas production and tar abatement. It was manifested
that the C content in carbon material would particular in reactions (Eqs.
12–14) in the catalytic reforming stage. H2 evolution was promoted was
mainly caused by water gas reactions (Eqs. 12 and 13), water–gas shift
(WGS) reaction (Eq. 15), steam methane reforming (SMR) reaction (Eq.
16), etc. CO proportion was raised mainly via Boudouard reaction (Eq.
14), SMR reaction (Eq. 16), and water gas reactions (Eqs. 12 and 13).
The decreased CO2 and CH4 concentrations probably resulted from
Boudouard reaction (Eq. 14) and SMR reaction (Eq. 16), respectively.
The increase of CO and decrease of CO2 could in turn move the equi­
libriums of WGS reaction toward yielding more H2. Some similar liter­
ature data obtained from co-gasification process of sewage sludge/
wheat straw with other materials are summarized and demonstrated in
Table 5. It is clearly found that the co-GSR process by using G/CGCMs as
assisted reforming agents and co-reactant are superior to other processes
G. Kong et al. Applied Energy 342 (2023) 121195

Table 5
Comparison of gas formation behaviors of the representative studies and this work.
Biomass Other Mass Gasification /Reforming Catalyst Gas yields (mmol/gfeedstock) Gas Syngas H2/ Ref.
material ratio temperature (℃) type concentration purity (%) CO
(vol%)

Gas H2 Syngas H2 CO

Wet sewage Forestry 3:7 900 – ~31.54 11.67 ~21.13 ~37 ~30 ~67 1.23 [54]
sludge waste
Wheat straw Lignite 5:5 900 – ~37.95 ~17.84 ~27.70 47 26 73 1.81 [51]
coal
Horticultural Sewage 0.78:0.22 900 – 49.11 28.70 38.90 58.44 20.77 79.21 2.81 [55]
waste sludge
Sewage sludge Wheat 5:5 600 Ni-Fe-La/ 26.79 11.96 17.01 44.65 18.84 63.49 2.37 [56]
straw CSC
Wet sewage Pine 6:4 900/800 NiO/MD ~31.40 14.44 ~23.24 ~46 ~28 ~74 ~1.64 [57]
sludge sawdust
Sewage sludge Wheat 1:9 900 C[WS] 94.74 51.53 77.99 54.39 27.92 82.31 1.95 This
straw study
5:5 C[WS + 70.93 40.67 55.67 57.33 21.15 78.48 2.71 This
SS] study

in light of the cumulative gas yield, H2 and syngas yields, as well as H2/
CO.
It should also be noted that the presence of AAEMs species in the
carbon materials can enhance the catalytic tar cracking reaction [29]. It
was reported that the AAEMs, such as K2CO3 and CaO, played a signif­
icant role in catalytic tar reduction [58]. It was proven that the H/O/OH
free radices can break the bonds between AAEMs and the carbon matrix,
leading to the generation of active sties on the carbon material surface,
which can promote the tar cracking and reforming into syngas [59]. Tar
is usually formed through a series of complex chemical reactions and
molecular structure changes during biomass gasification [60]. It can be
commonly divided into three stages: at the first stage, primary tar
compounds (e.g., phenol, benzene and toluene) derived from the
decomposition of lignocellulose are polymerized into heterocyclic tar
compounds and aromatic tar compounds; at the second stage, as-formed
aromatics would be tuned into intact aromatic rings via dehydrogena­
tion, dealkylation and decarboxylation; at the final stage, the combi­
nation of intact aromatic rings could activate the monocyclic aromatic
compounds to successively form the polycyclic aromatic tar compounds
with increasing ring numbers [60]. It was well also known that the
possible catalytic tar elimination mechanism over carbon material
consists of tar deposition, dehydrogenation (soot formed on the carbon
material surface), and soot gasification [61].
Herein, the possible reaction mechanism regarding co-GSR of binary
WS/SS mixture over G/CGCMs for H2-enriched syngas production and
tar abatement is shown in Fig. 6. The intermediate volatile components
were evolved from thermal decomposition of binary WS/SS mixture in
the gasification stage. Afterwards, the released volatile vapors together
with steam would pass through the catalytic reforming bed that was
filled with G/CGCMs and contacted with the active sites on the surface
of G/CGCMs. Intermediate volatiles were then adsorbed on the carbon
material surface and went through polymerization reaction, releasing
gas and leaving soot on the carbon material surface [29]. The soot
deposited on the carbon material surface could be consumed by steam
and tuned into gases. Overall, the water gas reactions, WGS reaction,
Boudouard reaction, SM reaction, etc. extensively took place on the G/

Fig. 6. The plausible reaction mechanisms regarding co-GSR of binary WS/SS mixture over G/CGCMs for H2-enriched syngas production and tar abatement.

11
G. Kong et al.
CGCMs surfaces, contributing to the formation of H2-enriched syngas.
In addition, the CO2/H2 mass ratio (ƞ, g CO2/g H2) in the gas
products is often used to verify the H2 production efficiency. Even
though CO2 concentration in gases gained from co-GSR of binary WS/SS
mixture by using the G/CGCMs were lowered to some extent, the CO2/
H2 mass ratio was still very high (>5 g CO2/g H2). To reduce CO2 pro­
portion and thereby enhance H2 production efficiency in the future,
some bifunctional catalysts (e.g., biochar-CaO, biochar-MgO, and
biochar-zeolite) might be more fitted, simultaneously accomplishing the
improvement of H2 production and the reduction of CO2 emission. Given
that G/CGCMs were almost exhausted after the co-GSR progress, the
spent G/CGCMs cannot be recycled for further use. Accordingly, the
more stable carbon materials (graphited carbon nanotubes) can be
developed to replace the G/CGCMs in the future so that the recyclability
and duration of the catalysts can be extended to a large extent.
4. Conclusions
This study proposed a new concept of promoting tunable H2/CO
syngas production and tar removal via co-GSR in the presence of G/
CGCMs. Steam co-gasification of binary mixtures with varying WS/SS
mass ratios achieved H2-enriched syngas with a tunable H2/CO ratio of
1.77 – 3.35. There was a more positive synergistic effect on the increase
of H2/CO ratio when the mass ratio ranged from 4:6 to 6:4. By intro­
ducing C[WS] in co-GSR process, H2-enriched syngas with a narrowing
H2/CO ratio of 1.83 – 2.26 was obtained by increasing the share of SS in
the binary blend. Importantly, co-GSR of WS/SS-9/1 gained the
maximum cumulative gas yield, H2 yield, and syngas yield, reaching
94.74, 51.53, and 77.99 mmol/g, respectively. Correspondingly, WS/SS-
9/1 subjected to co-GSR was also found to gain the lowest tar yield (5.99
g/Nm3). That was possibly because the addition of 10% of SS in the
blend could not only assure the sufficient C and volatile contents in the
blend, but also ensure the effective catalytic function of AAEMs from SS.
When G/CGCMs were applied in both GSR and co-GSR processes, co-
biocarbon C[WS + SS] used in the GSR of SS could garner a higher H2
concentration (57.79vol%) and H2/CO ratio (2.89). In addition, plau­
sible reaction pathways and mechanisms regarding co-GSR of binary
WS/SS mixture in the presence of G/CGCMs were elucidated. Overall,
this study developed a new, green, and facile route to produce H2-
enriched syngas with tunable H2/CO ratios and promote tar elimination,
which is promising for binary biowastes valorization and the down­
stream synthesis of valuable chemicals or fuels.
CRediT authorship contribution statement
Ge Kong: Conceptualization, Methodology, Software, Investigation,
Formal analysis, Writing – original draft. Xin Zhang: Investigation,
Methodology, Formal analysis. Kejie Wang: Investigation. Linling
Zhou: Investigation. Jin Wang: Investigation. Xuesong Zhang: Su­
pervision, Project administration, Funding acquisition. Lujia Han:
Project administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgements
This work was supported by National Natural Science Foundation of
China (52206290), the earmarked fund for CARS36, Jiangsu Province
12
Applied Energy 342 (2023) 121195
and Education Ministry Co-sponsored Synergistic Innovation Center of
Modern Agricultural Equipment (XTCX1005), the Natural Science
Foundation of the Jiangsu Higher Education Institutions of China
(20KJB416009), and China Postdoctoral Science Foundation
(2020M671367).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.apenergy.2023.121195.
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