Journal of the Energy Institute 119 (2025) 101992

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Different pretreatment of biomass for gasification: A critical review

Yanbin Zhang a , Donghao Hou a, Xiyue Sun a , Xiaochao Zhu a,* , Beibei Yan a,c , Guanyi Chen a,b,c,d
a
School of Environmental Science and Engineering, Tianjin University, Tianjin, 300072, China
b
School of Mechanical Engineering, Tianjin University of Commerce, Tianjin, 300134, China
c
Tianjin Key Lab of Biomass/Wastes Utilization, Tianjin, 300072, China
d
School of Science, Tibet University, Lhasa, 850012, China

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

Handling Editor: Dr. Paul Williams Biomass presents inherent challenges, including high oxygen content, low energy density, and logistical diffi-
culties in transportation and storage. Furthermore, it undergoes adverse reactions during pyrolysis and gasifi-
Keywords: cation, such as ash accumulation, slagging, and corrosion, which compromise equipment efficiency. To augment
Biomass the efficiency of biomass utilization and elevate the yield and quality of gasification products, pretreatment is
Pretreatment
essential. Specifically, mechanical methods adjust biomass’s energy density, whereas microwave processing
Gasification
disrupts its cell wall structure via microwave radiation, enhancing microstructure porosity and decreasing
Syngas
Combination crystallinity. Chemical treatments, utilizing reagents such as acids, bases, deionized water, organic solvents, and
ionic liquids, modify cellulose crystallinity, lignin structure, biomass ash content, and regulate alkali and alkaline
earth metals (AAEMs) levels. Physicochemical methods leverage high temperature, pressure, and chemical re-
agents’ synergistic effects to facilitate changes in physical and chemical structures, thereby improving pre-
treatment and gasification efficiency. Biological pretreatment employs microorganisms or metabolically
produced enzymes to modify biomass’s physicochemical structure, enhancing gas productivity and lower heating
value (LHV) for subsequent gasification while significantly minimizing tar production. Given the diversity and
complex components of biomass, and their varying effects on gasification, selecting appropriate pretreatment
methods tailored to specific biomass types is critical. This article provides a comprehensive summary of pre-
treatment technologies preceding biomass gasification, detailing their mechanisms, advancements, merits, and
drawbacks. It also projects future research directions for gasification pretreatment, offering a theoretical foun-
dation and guidance for forthcoming biomass gasification studies and industrial applications.

1. Introduction Growing concerns over the environmental impacts and the unsustain-
able consumption of fossil fuels have prompted research into renewable
Due to rapid population growth, accelerating industrialization, ur- energy technologies. In recent years, there has been a rise in the share of
banization, and rapid socio-economic development, global energy con- renewables and an improvement in the electrification of end-use energy.
sumption is continuously increasing. According to the Energy Among the various forms of renewable energy, biomass energy
Information Administration, global energy consumption is projected to (bioenergy) is gaining global recognition due to its ubiquity, versatility,
rise from 634.58 × 1018 J in 2020 to 935.04 × 1018 J by 2050. Currently, and strong compatibility. The adoption of modern biofuels, which in-
fossil fuels like oil, coal, and natural gas remain the dominant sources of cludes the rapid expansion of solid biomass, liquid biofuels, and bio-
energy globally. In 2022, these fossil fuels constituted 82 % of the methane, significantly aids in the decarbonization of industries and
world’s total energy consumption, while renewable sources (excluding production processes that are challenging to decarbonize. According to
hydropower) accounted for 7.5 %, reflecting a roughly 1 % increase the International Energy Agency [2], biomass is projected to contribute
from the previous year. However, the over-reliance on fossil fuels not about 10 % to the global energy mix by 2035. By 2050, biofuels are
only accelerates the depletion of non-renewable energy reserves [1] but expected to supply around 27 % of transportation fuel globally. Table 1
also worsens environmental damage. Their extensive use significantly provides a breakdown of biomass energy’s contribution to primary en-
contributes to climate change and the degradation of ecosystems. ergy consumption in various nations, alongside their carbon emissions.

* Corresponding author.
E-mail address: [email protected] (X. Zhu).

https://doi.org/10.1016/j.joei.2025.101992
Received 20 October 2024; Received in revised form 8 January 2025; Accepted 8 January 2025
Available online 10 January 2025
1743-9671/© 2025 The Energy Institute. Published by Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar
technologies.
Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

The data highlights the immense potential for utilizing biomass energy annually, with 143 million tons incinerated. Waste oil production stands
on a global scale. In China, biomass resources primarily come from at 10.551 million tons, of which 527,600 tons are used for energy.
straw, livestock and poultry manure, forestry residues, household waste, Sewage sludge yields 14.47 million tons of dry weight per year, with
waste oil, and sewage sludge. The theoretical quantity of straw resources 1.1469 million tons utilized for energy. The primary methods of biomass
is approximately 829 million tons, of which about 694 million tons are utilization in China include power generation, clean heating, biological
collectible, with 88.215 million tons used for combustion. Livestock and natural gas, liquid fuels, and fertilizer substitution, collectively
poultry manure totals 1.868 billion tons (excluding wastewater), with contributing to a reduction of approximately 218 million tons of carbon.
211 million tons utilized for biogas production. Forestry residues ac- Biomass gasification refers to the process in which biomass raw
count for 350 million tons, with 9.64 million tons for energy production. materials (firewood, sawdust, wheat straw, rice straw, etc.) are pressed
Additionally, 310 million tons of household waste are collected into shape or simply crushed and processed, and then sent into the

Table 1
The percentage of biomass energy in primary energy consumption and the main types of biomass used in various countries around the world.
Country The percentage of substances in the The main sources of organic matter raw materials Carbon emissions
primary energy consumption structure (Million tons)in 2020

Asia Myanmar 33 % Forest timber 48.7

Laos 15.5 % Wood fuel 7.4
Charcoal
Pakistan 40.3 % Sustainable reuse of resources 0a
the Philippines 14.6 % Agricultural residues such as plant residues, animal manure, etc 0a
Jordan 0.8 % Agricultural residues (food, fruit, vegetable residues), animal 0a
manure, and municipal solid waste
Indonesia 3.6 % Rubber waste, palm oil residue, etc 0a
Sri Lanka 34.8 % Bagasse and firewood 18.5
Armenia 2.2 % Forest timber 0.32
Iran 0.5 % Solid matter mainly composed of agricultural solid waste and animal 0a
manure, Biogas
Thailand 18.7 % Rice husks, sugarcane bagasse, agricultural waste, firewood, and the 0a
liquid and residual substances produced during the process of
firewood processing
Malaysia 1.3 % Diesel fuel and biogas 0a
Turkey 0.9 % Abandoned materials (tree heads, dead trees), agricultural residues, 0a
animal manure, and urban solid waste

Africa Burundi 95 % Firewood and charcoal (71.7 %) agricultural residues (such as crops, 7.7
fruits, and vegetables)(28.3 %)
Madagascar 77.2 % Fuel wood, charcoal, plants and agricultural residues 20
Uganda 88.9 % Fuel materials, solid fuels 69.2
Togo 77.2 % Firewood, charcoal, and vegetable waste, etc 7.4
Rwanda 91.9 % Firewood and charcoal(67.7 %), agricultural residues (food, fruits, 6.6
vegetable residues)(32.3 %)
Tanzania 28.7 % Firewood and charcoal 8.8
Djibouti 25.5 % Firewood 0.8
Zimbabwe 91.9 % Firewood 145.4
Kenya 59.6 % Firewood and charcoal 68.2
Ghana 27.6 % Firewood and charcoal 13.9
Nigeria 92.7 % Firewood, charcoal, manure, crop residues, etc 953.7
Morocco 6% Firewood and charcoal 5.8
Algeria 0.01 % Firewood and charcoal 0.0017
Botswana 25.3 % Rice husks, bagasse, agricultural waste, firewood, and the liquid and 1.04
residual substances produced during the wood process
Mauritius 2.0 % Firewood and charcoal(2.9 %) 1.9
Bagasse(97.1 %)

Latin Nicaragua 6.3 % Firewood, bagasse, rice husks, coffee husks, flower husks, etc 0.6
America Bolivia 12.1 % Feces and green residue 0a
Guatemala 57.6 % Firewood and bagasse 35.8
Jamaica 5.4 % Bagasse, firewood, and municipal solid waste 0.4
Ecuador 1.8 % Firewood(43.8 %) and bagasse(56.2 %) 1.1
Paraguay 26.9 % Firewood(80.4 %) and bagasse(19.6 %) 11.3
Columbia 11.4 % Firewood, biodiesel, and crop waste represented by bagasse 11.3
Peru 14.0 % Firewood, animal manure, and crop waste represented by sugarcane 11.4
bagasse
Cuba 2.8 % Firewood, sugarcane products, biogas, charcoal, and alcohol, etc 1.7
Brazil 31.6 % Firewood(21.0 %) and bagasse(38.0 %) 181.6
Argentina 4.03 % Firewood and bagasse 4.1
Panama 7.5 % Firewood, bagasse, biogas, charcoal, and alcohol, etc 0.9
Chile 20.9 % Crop waste 0a
Uruguay 43.9 % Wood(21.08 %) and wood waste(74.01 %) 2.2

Europe Moldova 26.9 % Agricultural residues (including plant roots, stems, leaves, straw, 0a
grapevines, etc.)
Estonia 35.7 % Forest biomass, agricultural biomass, and municipal solid waste 0a

Oceania The Independent State of 31.6 % Wood waste, and charcoal, etc 8
Papua New Guinea
a
The entire life cycle has a "zero carbon" attribute, and overall carbon emissions should not be included in the overall carbon accounting process.

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

gasifier under oxygen deficiency conditions for gasification and cracking density of biomass, reduces transportation and storage costs, and min-
to obtain combustible gas and essence treatment to obtain product gas. imizes the risk of blockages in the feeding line [7,8].
Under specific thermodynamic conditions, partial air (or oxygen) and Since the 21st century, the primary goal of biomass pretreatment
water vapor facilitate the pyrolysis, oxidation, reduction, and reforming methods like grinding and densification has been to transform biomass
reactions of the high polymers in biomass. The tar produced during into briquettes for combustion. In gasification processes, these pre-
pyrolysis is further thermally or catalytically cracked into small hydro- treatment techniques improve efficiency by increasing the surface area
carbon molecules, resulting in gases containing CO, H₂, and CH₄ [3]. of biomass particles, thus enhancing heat transfer. This, in turn, boosts
Lignocellulosic biomass, such as crop straw, optimizes the conver- reactions such as the Boudouard reaction, the water-gas shift reaction,
sion of volatile substances into gaseous fuels through gasification. The and carbon conversion, leading to greater H₂ and CO production while
resulting gas can be used for heating, power generation, producing high minimizing CO₂ and tar emissions [9]. Research indicates that grinding
value-added liquid fuels, and providing centralized gas supply for resi- biomass particles to about 0.5 ± 0.1 mm results in optimal gasification
dents. However, lignocellulosic biomass has several disadvantages, performance [10,11]. At the same bed temperature, smaller particle
including high oxygen content (approximately 40 wt%), low energy sizes result in higher dry gas yield and carbon conversion efficiency.
density (15–20 MJ/kg), and difficulties in transportation and storage. Its Additionally, smaller particles lead to more complete biomass gasifica-
structure is tight and complex, with highly crystalline cellulose mole- tion reactions and higher H₂ yields. Furthermore, tar production de-
cules and various binding forces between cellulose, hemicellulose, and creases as particle size decreases. However, when particle size falls
lignin. These characteristics lead to adverse reactions during gasifica- below 0.4 mm, the improvement in gasification is negligible, while en-
tion, such as high energy consumption, inefficient gasification, excessive ergy consumption for grinding increases, raising costs.
tar production, reduced gas heating value, and pipeline blockages and Valdes et al. [12] conducted grinding, torrefaction, and granulation
corrosion. To improve biomass resource utilization and enhance the treatments on empty fruit bunch (EFB) to investigate changes in its air
yield and quality of thermal conversion products, pretreatment methods gasification performance. The results indicated that, under equivalence
are employed. Biomass pretreatment involves altering the physical and ratios (ER) ranging from 0.25 to 0.4, pelletized EFB generated higher
chemical properties of biomass through physical, chemical, or biological amounts of CO, H₂, and CH₄, achieving the highest cold gas efficiency
methods. This process reduces the volatile content, increases energy (CGE). Additionally, ground and granulated EFB was more easily
density and grindability, and enhances gasification, thereby improving transported to the reaction device, reducing agglomeration and sinter-
gas quality and yield while minimizing by-product formation (e.g., tar ing. Meanwhile, granulation can more effectively utilize by-products
and ash clumps). These methods reduce cellulose polymerization and from the gasification process, reduce energy loss, and improve the
crystallinity by disrupting the lignin and hemicellulose binding layers, quality of the synthesis gas. Wood and wood pellets from Pinus elliottii
adjusting the composition, and increasing the effective specific surface treated with densification increased gas production and heating value
area [4]. Non-lignocellulosic biomass, such as sewage sludge and food during CO₂ gasification [13]. Similarly, pelletized canola residue
waste, contains a large number of nitrogen-containing compounds, increased CO and H₂ production during steam gasification [14]. For
which can generate significant pollution during the gasification process. low-quality wood chip assessments, appropriate particle size distribu-
Pretreatment methods for this type of biomass primarily target the ni- tion is essential for effective gasification and power generation [15].
trogen content, aiming to reduce or convert it into precursors that are However, excessively large particle sizes reduce mass transfer efficiency
less likely to form NOx, NH₃, and HCN [5]. Additionally, and heat transfer during biomass gasification.
non-lignocellulosic biomass often has high moisture content, leading to Biomass mechanical pretreatment is effective for the gasification of
increased energy consumption during gasification. Therefore, the pre- lignocellulosic biomass, as it alters the polymerization degree, flow
treatment process should also address energy consumption concerns. characteristics, and mechanical properties of the biomass. Common
As an essential component of the biomass gasification process, mechanical pretreatment methods include drying, crushing, granula-
biomass pretreatment has seen significant advancements in recent years. tion, and solidification molding, which can be selected based on specific
These discoveries are expected to generate new research directions in process requirements. These methods are generally simple, cost-
biomass gasification technology and provide theoretical guidance for effective, and environmentally friendly. However, challenges include
industrial applications. This review summarizes recent advancements in inconsistent particle quality and high energy consumption associated
pretreatment technologies for biomass gasification and highlights the with equipment such as dryers, crushers, and granulators, in addition to
associated research findings. Additionally, it discusses the advantages the elevated maintenance costs of these systems.
and disadvantages of various biomass gasification pretreatment tech-
nologies and identifies the conditions under which these methods are 2.2. Microwave processing method
most applicable, offering prospects for targeted regulation of biomass
gasification. Microwave radiation pretreatment technology is a novel method that
utilizes electromagnetic waves with wavelengths ranging from 1 to
2. Physical pretreatment 1000 mm and frequencies between 0.3 and 300 GHz to disrupt the cell
wall structure and ultrastructure of lignocellulose, thereby loosening the
Physical pretreatment methods reduce the particle size, degree of cellulose tissue. Early studies (see Table 2) indicate that microwave
polymerization, and specific surface area of biomass by altering its fine radiation forms hotspots on polar groups within biomass cellulose
structure. Common physical pretreatment techniques include mechani- components, leading to continuous internal ion explosions that accel-
cal crushing, microwave treatment. erate the reorganization of the crystal structure [16,17]. Other research
suggests that microwave heating generates pressure within both hy-
2.1. Mechanical method drated and non-hydrated components [18]. Additionally, microwave
pretreatment involves the oscillation of dipoles, breaking hydrogen
Mechanical methods, such as grinding and densification, are among bonds between cellulose molecules, reducing crystallinity, and causing a
the most traditional pretreatment techniques. Mechanical grinding re- loss of swelling properties [19], as illustrated in Fig. 1 [20].
duces the size and crystallinity of straw biomass while increasing its Liang et al. [21] found that under microwave pretreatment, the
specific surface area, thereby enhancing the contact area between the surface of pine sawdust experienced fragmentation, and its microstruc-
biomass and active substances such as catalysts and enzymes in subse- ture underwent perforation and deformation. The pretreatment
quent reactions [6]. Mechanical treatment has minimal effect on the destroyed the lignin structure on the surface of pine sawdust, making the
chemical structure of biomass. Densification effectively increases the cellulose more prone to pyrolysis. Additionally, literature indicates that

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

during microwave pretreatment, inherent alkali metal and alkaline Table 2

earth metal (AAEM) ions in biomass partially dissolve and convert into Effect of microwave pretreatment of lignocellulosic biomass on gasification.
water-soluble ions. These ions can catalyze the steam gasification pro- Feedstock Microwave Gasification Gasification effect References
cess of distiller’s grains. After microwave pretreatment (600 W, 6 min), condition condition
the cellulose and lignin structures of distiller’s grains were disrupted, Spirit- 0, 200, 400, 850 ◦ C, Microwave [22]
and AAEM ions partially dissolved into water-soluble forms, increasing based 600, 800 W steam pretreatment
gas production during steam gasification by 13.46 % [22]. The gas yield distillers’ 0, 3, 6, 9, 12 (MWP) alters the
and H₂/CO ratio increase with increasing microwave power and dura- grains min surface
(SDGs) morphology of
tion, while the CO/CO₂ ratio exhibits the opposite trend. Furthermore, SDGs and converts
microwaves also have a torrefaction effect. After microwave torre- intrinsic AAEM
faction, moisture and volatile matter in biomass were effectively ions into water-
removed, enhancing its gasification performance [14]. soluble forms. The
optimal
Microwave pretreatment utilizes microwaves to modify the physical
conditions for this
properties of biomass (e.g., moisture content, microstructure) to process are 600 W
enhance gasification efficiency. Microwaves offer advantages such as for 6 min.
rapid and uniform heating, along with strong penetration capabilities. Chlorella 750 W, 1 min 800 ◦ C, For Chlorella, [23,24]
However, they also involve high energy consumption and substantial vulgaris Fe2O3 chemical looping
gasification (CLG)
investment costs, limiting their commercial and industrial applications reactivity
for straw biomass. Therefore, further optimization is required to reduce improved by 6.79
these costs. % after microwave
Biomass physical pretreatment technologies use mechanical forces, pretreatment,
which also
light, or electricity to alter material properties or states. The physical
lowered its
pretreatment method is the most commonly used biomass treatment activation energy,
process in industrial applications. It is particularly suitable for biomass enhancing the
with low moisture content and viscosity. For large-sized biomass, size CLG process.
reduction can be achieved through grinding, while granulation and Herb 200–300 ◦ C, 800 ◦ C, The use of [25,26]
residue 200–1000 W, steam microwaves
other densification methods are employed for small-sized biomass.
(HR) 5–20 min during HR
These techniques are typically characterized by easy operation and fast torrefaction
processing speeds. Physical pretreatment does not require chemical resulted in
additives, thus reducing environmental pollution and waste disposal increased higher
heating value
burdens. However, it is not effective for biomass with high moisture
(HHV) for the
content or viscosity and is more suited for lignocellulosic materials. torrefied material.
Moreover, physical pretreatment mainly alters the physical form of the Optimal
biomass, without significantly changing its chemical composition or conditions for MT
structure. Common physical pretreatment methods, such as grinding included a
temperature of
and granulation, require significant mechanical energy, especially when
225 ◦ C, a time of
processing hard woody biomass, resulting in high energy consumption. 8.755 min,
The microwave pretreatment method, which modifies the microstruc- moisture content
ture, suffers from high equipment costs and energy consumption. Future at 21.192 wt%,
and microwave
research in this area should prioritize reducing energy use and equip-
power at 400 W.
ment costs. Canola 250 W for 10 800 ◦ C, The highest gas [14]
residue min at 90 g of steam, ER = yield (24.4 mol/
3. Chemical pretreatment (CR) feeding load 0.4 kg), syngas yield
(22.1 mol/kg),
carbon conversion
The chemical pretreatment method involves decomposing the
efficiency (CCE) of
chemical bonds in lignocellulose using chemical reagents to reduce the 85.1 %, a lower
degree of polymerization and crystallinity of biomass, thereby promot- heating value
ing its degradation. Common chemical pretreatment methods include (LHV) of 2396 kJ/
Nm³, and gas
the use of acids, alkali, water, ionic liquids, low eutectic solvents, and
energy ratio (GER)
organic solvents. of 29.2 % were
achieved through
3.1. Acid treatment method steam gasification
of torrefied
pellets.
Acid pretreatment is the most studied approach for processing straw
biomass. This method can be categorized based on acid concentration
into dilute acid pretreatment at higher temperatures and concentrated between cellulose and lignin, reduces cellulose crystallinity, and in-
acid pretreatment at lower temperatures [27]. Concentrated acid pre- creases porosity, improving cellulose accessibility, as shown in Fig. 2.
treatment can cause significant equipment corrosion, making dilute acid Acid pretreatment is the most widely studied method for treating
pretreatment more suitable for industrial applications. The efficiency of straw biomass. It can be categorized into two approaches based on acid
acid pretreatment depends on various factors, including biomass feed- concentration: dilute acid pretreatment at higher temperatures and
stock size, solid-to-liquid ratio, acid concentration, pretreatment time, concentrated acid pretreatment at lower temperatures. Concentrated
and temperature. Both mineral acids (sulfuric, hydrochloric, and nitric acid pretreatment, however, can lead to significant equipment corro-
acids) and organic acids (such as phosphoric, acetic, and maleic acids) sion, making dilute acid a more suitable option for industrial application
can be used. Dilute acid pretreatment hydrolyzes hemicellulose and and promotion.
cellulose in their amorphous regions by releasing hydrogen ions (H⁺), The efficiency of acid pretreatment is primarily influenced by factors
resulting in monosaccharide formation. This process weakens the bond

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Fig. 1. Mechanism involved in microwave pretreatment of lignocellulosic biomass [20].

such as the size of the biomass feedstock, solid-to-liquid ratio, acid as sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium
concentration, pretreatment time, and temperature. Both mineral acids, hydroxide (Ca(OH)₂), and ammonium hydroxide (NH₄OH), to lignocel-
such as sulfuric, hydrochloric, and nitric acid, and organic acids, lulosic biomass materials. This process enhances the internal surface
including phosphoric, acetic, and maleic acid, can be utilized for acid area through swelling, disrupts ester bonds and other chain structures
pretreatment. During dilute acid pretreatment, the amorphous regions among hemicellulose, cellulose, and lignin, and reduces the crystallinity
of hemicellulose and cellulose are attacked by hydrogen ions (H⁺) and polymerization degree of cellulose. Consequently, this pretreatment
released through acidolysis, leading to hydrolysis into monosaccharides. decomposes and modifies the structure of lignin and facilitates the sol-
The degradation of hemicellulose weakens the bond between cellulose vation of hemicellulose [34–37]. Li et al. [32,38] utilized NaOH to
and lignin, reduces the crystallinity of cellulose, and enhances the pore pretreat pine wood (PW), successfully dissolving its hemicellulose.
structure, facilitating the attachment of cellulose [28], as illustrated in Additionally, sodium was artificially introduced during the NaOH
Fig. 2 [29]. In the chemical chain gasification of biomass, acid treatment treatment, which catalyzed the gasification process, ultimately
can increase the proportions of carbon (C) and hydrogen (H) elements increasing both gas production and carbon monoxide (CO) generation
while reducing the content of alkali and alkaline earth metals. This during gasification (see Fig. 3) and showing a decrease in the char yield.
treatment also enhances the production and proportion of CO, CH₄, and Meanwhile, compared with the raw materials, the gasification CGE and
H₂ during gasification [30]. Biomass pretreated with acid exhibits overall energy efficiency of alkali treated pine wood have also been
decreased activation energy [31], increased gasification heating value, significantly improved. Related studies are summarized in Table 3.
improved carbon conversion rates, enhanced cold gas efficiency (CGE), Beyond sodium, researchers have also incorporated potassium (K) and
and a significant rise in the proportion of CO in the gasification gas [32], calcium (Ca2⁺) during the pretreatment. The findings indicated that
as shown in Table 3. sodium carbonate (Na₂CO₃), potassium carbonate (K₂CO₃), and calcium
During biomass gasification, acid treatment boosts the proportions of carbonate (CaCO₃) significantly enhance the total gas yield, synthesis
carbon (C) and hydrogen (H) while reducing the levels of alkali and gas yield, H₂/CO ratio, and carbon conversion rate during lignin steam
alkaline earth metals, enhancing the production and proportions of CO, gasification. Among these, Na₂CO₃ exhibited the most effective catalytic
CH₄, and H₂. Biomass treated with acid exhibits lower activation energy, impact, followed by K₂CO₃, while CaCO₃ demonstrated the least effec-
higher gasification heating values, improved carbon conversion rates, tiveness. Furthermore, K₂CO₃ notably reduced the formation of poly-
and enhanced cold gas efficiency (CGE), as highlighted in Table 3. Acid cyclic compounds in the resulting tar [39].
treatment also modifies the structure of cellulose, hemicellulose, and Alkali pretreatment shares similar applications, advantages, and
lignin while effectively washing out alkali and alkaline earth metals drawbacks with acid pretreatment. Future research should also inves-
(AAEMs) from the biomass. Studies have shown that treating empty fruit tigate alkali types and concentrations, while refining the process to
bunches (EFB) with 0.1 wt% HNO₃ significantly improves gasification minimize costs.
performance, enhancing carbon conversion rates, CGE, and the heating
value (HHV) of the produced gas [33]. Acid pretreatment also impacts
biomass pyrolysis char in similar ways [34]. 3.3. Water washing (leaching) method
Acid pretreatment is applicable to various biomass types, including
lignocellulosic biomass and sludge. It alters the structure of lignin, cel- As previously discussed, alkali and alkaline earth metals (AAEM) can
lulose, and hemicellulose, adjusts the content of alkali and alkaline earth serve a catalytic role in the gasification process. However, research in-
metals, and offers benefits such as reduced activation energy, higher dicates that as the content of AAEM increases, its catalytic effect on
gasification heating value, improved carbon conversion, and enhanced gasification initially enhances and then diminishes. To optimize the
CGE. However, acid pretreatment generates harmful gases and waste- catalytic effect during gasification, water washing treatment is
water, contributing to environmental pollution. Some acids may also employed to regulate the AAEM content in biomass [30,33,41] while
increase the metal content in biomass. Moreover, the method requires simultaneously reducing the inorganic component concentration in the
corrosion-resistant equipment, adding to costs, and involves additional gasification residue [42], as detailed in Table 3. In the process of
steps such as separation and drying before gasification. Future research biomass water washing pretreatment, water acts as a solvent and un-
should focus on optimizing the types, concentrations, and processes of dergoes chemical reactions with the components in biomass, while
acid pretreatment to lower costs. reducing water-soluble substances (water-soluble organic matter, ash
content, etc.), increasing the specific surface area of biomass, ultimately
achieving the purpose of pretreatment, as illustrated in Fig. 4 [43].
3.2. Alkali treatment method Furthermore, integrating water washing with other pretreatment
methods, such as torrefaction and acid treatment, can further enhance
Alkali pretreatment involves the addition of alkaline reagents, such the gasification process, increase gas production, and minimize ash

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Fig. 2. (a) - SEM images of elephant grass pretreated with H2SO4 at 121 ◦ C for 30 min, (A) - untreated; (B) - pretreated with 5 %; (C) - pretreated with 10 %; (D) -
pretreated with 20 %; (b) - XRD analysis of rice straw before and after dilute acid pretreatment; (c) - FTIR analysis of Denanath grass before pretreatment (1), after
pretreatment by 1 % HCl (2), after pretreatment by 1 % HCl assisted by ultrasono (3) [29].

Table 3
Effect of Acid/alkali/water pretreatment of biomass on gasification.
Feedstock Acid/alkali treatment Gasification condition Gasification effect References
condition

Pine wood sawdust (PWS) 1.0 wt%,3.0 wt% AcOH, Fe2O3, 700–900 ◦ C Production and proportion of CO, CH4, and H2 increased [30]
1.0 g: 30.0 mL, 6 h
The empty fruit bunch (EFB) Water, 0.1 wt% HNO3 700–1000 ◦ C, O2/N2 HHV: 3019 kcal/m3 [33]
Carbon conversion: 68 %
CGE: 52 %
Grass 25 g + 400 mL AcOH, CO2, 850–950 ◦ C activation energy: [31]
85 ◦ C, 15 min leaching: 161.7 → 141.5 kJ/mol
Pine wood (PW) and high- 2 M HCl/NaOH, 48 h 1173K, CO2 Co-gasification of HDPE-AcWPW and HDPE-AlTPW at PW fractions of 22 % [38]
density polyethylene and 55 % resulted in energy values of 34.3 and 30.1 kJ/g, respectively.
(HDPE)
Pinewood (PW) pellets 2 M HCL: H-PW-1 CO2, 800 ◦ C Acid pretreatment of pinewood improved CO production, raising syngas [32]
2 M NaOH: Na-PW energy by more than 19.6 % compared to untreated samples. Additionally,
2 M HCL + water: H-PW- syngas energy and cold gas efficiency (CGE) increased by 44.6 % when using
2 alkali pretreatment with higher AAEM-Na content.
Spirit-based distillers’ grains 0, 200, 400, 600, 800 W 850 ◦ C, steam optimum operating condition: 600 W, 6 min [22]
(SDGs) 0, 3, 6, 9, 12 min, red
mud (RM)
Wine and vine residues Water, 88.8 g/L, 12 h 800 ◦ C, 0.85 L/min O2 A 36 % reduction in tar yield, along with a 17 % rise in CO and a 30 % increase [45]
+9.5 L/min N2 in H₂, was observed, along with a 12 % improvement in LHV.
Cornstalk 80 C, 80 mL deionized
◦
Steam, 900 ◦ C CO: 27 %, CH4: 11 % [44]
water, 6 h;
6 g CS-2+40 mL, 5 mol/
L, 60 ◦ C, 50 min HCl
Wheat, barley, corn, and (1) 50 g feedstock +0.5 L 15 vol% steam +5 vol The combination of washing and torrefaction effectively reduced the elements [42]
colza straw water 24 h % CO2, 950 ◦ C responsible for ash-related issues, improving ash behavior. Integrating
(2) 250 ◦ C torrefaction 1 torrefaction and carbonization with steam gasification proved to be an
h innovative approach to produce H₂-enriched syngas with minimal tar from
agricultural biomass.

generation [42,44]. 3.4. Organic solvent treatment method

Water washing (impregnation) pretreatment is effective for gasifi-
cation of lignocellulosic biomass by regulating the AAEM content and Organic solvent pretreatment involves the application of organic
reducing water-soluble organic matter and ash. However, it generates solvents—such as methanol, ethanol, ethylene glycol, glycerol, formic
wastewater, contributing to environmental pollution and increasing acid, acetic acid, acetone, formaldehyde, tetrahydrofuran, phenol, and
downstream treatment costs. Future applications should consider inte- amines—to straw biomass, with organic alcohols being the most prev-
grating water washing with other pretreatment methods to mitigate alent [46]. Under specific temperature and pressure conditions, these
these issues. solvents can hydrolyze and disrupt the internal bonds of lignin, as well
as the bonds between lignin and hemicellulose and the glycosidic bonds
in hemicellulose, thus altering the structure of lignin and increasing the
internal surface area. Typically, this method incorporates acid, alkali, or

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

salt catalysts to lower the temperature and pressure required for the Overall, biomass chemical pretreatment significantly modifies the
reactions. The organic solvents employed in pretreatment can be recy- structure of lignin, cellulose, and hemicellulose, improving gasification
cled through distillation, resulting in reduced pretreatment costs. Secer efficiency and reducing tar production. It generally reacts quickly and
et al. [47] found that using N-Methyl-2-pyrrolidone (NMP) as an organic can be completed in a relatively short period. However, the high cost of
solvent enabled the gasification of sorghum to produce hydrogen-rich chemicals, environmental pollution from wastewater and exhaust gases,
gas at a relatively low temperature of 350 ◦ C. and the need for biomass separation and drying post-treatment are
The lignin produced through organic solvent pretreatment exhibits notable challenges. In industrial production, chemical pretreatment of
consistent molecular weight, high hydrophobicity, and the absence of biomass must address requirements such as preventing equipment
sulfides, making it a valuable high-quality industrial by-product. How- corrosion. Additionally, to ensure effective chemical pretreatment,
ever, many solvents still possess drawbacks, including volatility, flam- biomass raw materials should not be excessively large. Due to the spe-
mability, explosiveness, and high cost, which impose significant cific requirements of the biomass gasification process, such as moisture
requirements on the reaction environment. Consequently, the develop- content, post-chemical pretreatment processes must include solid-liquid
ment of new green solvents with superior performance and lower costs separation to remove chemical reagents, reagent recovery, and further
has emerged as a critical area of research in organic solvent drying of the biomass. These steps contribute to increased equipment
pretreatment. costs and energy consumption. Research should focus on reducing costs,
optimizing processes, and minimizing pollutant generation.
3.5. Ionic liquid treatment method
4. Physicochemical pretreatment
Ionic liquids (ILs) are salts typically consisting of large organic cat-
ions and small inorganic anions. Compared to conventional solvents, ILs The physicochemical method leverages the synergistic effects of high
possess unique physical and chemical properties, such as polarity, hy- temperature and pressure, along with chemical reagents, to enhance the
drophobicity, low volatility, low melting points, high stability, and efficacy of biomass pretreatment. In contrast to conventional physical
excellent solubility [48]. During pretreatment using ILs, strong inter- and chemical pretreatment methods, this approach facilitates modifi-
molecular and intramolecular hydrogen bonds form between the anions, cations in both physical properties and chemical structures, including
cations, and the hydroxyl groups in cellulose and other components in bond breakage and intermolecular interactions, through the simulta-
lignocellulosic biomass, as illustrated in Fig. 5 [49]. The presence of neous application of elevated temperature, pressure, and chemical re-
electron-withdrawing groups in the alkyl chains of the cations enhances actions [52]. Currently, commonly employed techniques include
cellulose dissolution, leading to greater cellulose precipitation and torrefaction, hydrothermal pretreatment, and steam explosion methods.
lignin solubilization [48,50]. After IL pretreatment, the heating value of Additionally, ammonia fiber explosion and CO2 explosion methods are
materials like used coffee grounds increases while ash content decreases. also utilized.
In subsequent gasification, CO production rises, and cold gas efficiency
surpasses that of untreated samples, indicating the potential of IL pre- 4.1. Torrefaction treatment method
treatment in thermochemical conversion processes [51].
In a study by Dastyar et al. [49], ILs, specifically triethylammonium Torrefaction pretreatment involves gradually heating biomass in an
hydrogen sulfate, were used to pretreat heavy metal-stabilized bio- oxygen-deprived environment at temperatures ranging from 200 to
masses (HMCBs) before catalytic gasification. This pretreatment 300 ◦ C. This heating causes significant dehydration and breakdown of
increased the gas production rate and the H₂/CO ratio by 32 % and 153 lignocellulose, resulting in biomass becoming more brittle and hydro-
%, respectively. Moreover, pretreatment with different ILs improved the phobic, with lowered O/C and H/C molar ratios and higher energy
cooling efficiency of spent coffee grounds, resulting in higher CO yields density, making its properties more similar to coal [53]. Recent studies
and lower ash content [51]. (see Table 4) have explored various combinations of torrefaction with
Although ionic liquids exhibit remarkable pretreatment effective- gasification, leading to insights on ideal conditions, mechanisms, and
ness, their considerably higher costs compared to organic solvents, along how different types of biomass react to the process.
with challenges in recovery, significantly hinder their commercial As shown in Fig. 6 [54], torrefaction breaks down hemicellulose,
viability in industrial applications. cellulose, and lignin at different temperature ranges. Initially, biomass

Fig. 3. Mechanistic effect of AAEMs on gaseous products at different temperatures [40].

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Fig. 4. Structure evolution and mechanism for CO2 gasification of biochar from (a) raw biomass and (b) leached biomass [43].

had the highest H₂/CO molar ratio (1.83), carbon conversion efficiency
(90.33C%), and cooling efficiency (109.24 %). Torrefied WS also had
reduced tar content, indicating that combining torrefaction with steam
gasification produces H₂-rich syngas with minimal tar. Other studies,
such as those by Lee et al. [58] and Zheng et al. [59,60], found that
torrefied biomass required more energy for gasification but resulted in
increased gas production and reduced tar when paired with
co-gasification or the use of oxygen carriers.
Researchers have also explored torrefaction in different environ-
ments. Yan et al. [61] showed the viability of torrefaction using flue gas,
while Zhang et al. [62] demonstrated that CO₂ torrefaction of industrial
waste sludge improved its co-gasification with Yangchangwan coal.
Torrefaction pressure was also studied, with results showing that
gas-pressurized torrefaction of rice straw lowers co-gasification activa-
Fig. 5. Mechanism of HMCB fractionation and demineralization using trie- tion energy and enhances CO production. When conducted in an
thylammonium hydrogen sulfate [49]. oxidizing atmosphere, the lower heating value (LHV) of sewage sludge
gas increased from 13.51 to 17.15 MJ/m³ [63]. Similarly, Tong et al.
loses moisture and light volatile compounds between 150 and 200 ◦ C. [64] applied gas pressurized torrefaction to rice straw, finding that it
Around 200 ◦ C, hemicellulose begins to degrade through deacetylation improved carbon conversion and reduced activation energy for
and depolymerization, producing acetic acid that aids further break- co-gasification.
down. At the same temperature, the amorphous parts of cellulose start to In terms of pollutant control, torrefaction effectively removes chlo-
decompose, increasing biomass crystallinity, while the crystalline sec- rine from biomass and reduces hydrogen sulfide (H₂S) emissions during
tions of cellulose require temperatures above 270 ◦ C for depolymeriza- gasification [65]. Moreover, temperatures above 300 ◦ C can convert
tion. Lignin, which is structurally more complex than hemicellulose or nitrogen in biomass into volatile compounds such as ammonia (NH₃)
cellulose, begins softening at temperatures between 160 and 190 ◦ C. and hydrogen cyanide (HCN) [66]. This transformation also stabilizes
When temperatures rise to between 150 and 300 ◦ C, lignin’s ether bonds nitrogen functional groups, preventing them from forming NH₃ and HCN
break, with the aliphatic side chain cleaving near 300 ◦ C, leading to during subsequent gasification processes.
methoxy group removal and substantial depolymerization at higher However, not all types of biomass respond well to torrefaction. Some
temperatures. lose a significant amount of volatile matter, leading to reduced gas
In a study conducted by Wannapeera et al. [55], it was found that as production and energy content during gasification. For instance, torre-
torrefaction temperature increases, oxygen-containing groups in Leu- fied argan nutshells exhibited decreased gasification efficiency, with
caena leucocephala decompose, primarily as water. Prolonged torre- lower LHV in both gas and energy yields [67]. Similar results were
faction led to more CO₂ and condensate production. Similarly, Fan et al. observed with empty fruit bunches (EFB), where torrefaction reduced
[56] examined the torrefaction of xylan, a hemicellulose component, the production of H₂ and CO₂ [68]. Additionally, torrefied starchy food
and observed a significant decrease in its comprehensive pyrolysis index waste produced more gas than untreated waste only at temperatures
(CPI) as temperatures rose from 200 to 280 ◦ C, with a corresponding exceeding 900 ◦ C [69,70].
reduction in CO₂ gasification activity. This decline resulted from devo- In conclusion, torrefaction is a promising pretreatment technique for
latilization, polycondensation, and the formation of a condensed aro- biomass gasification, significantly altering biomass properties and
matic structure. enhancing syngas quality while minimizing tar production. Steam ex-
Wang et al. [57] evaluated wheat straw (WS) pretreated by torre- plosion technology, on the other hand, uses high temperatures and
faction, comparing its steam gasification at different torrefaction tem- pressures (180–240 ◦ C, 1–3.5 MPa) over a short period, followed by
peratures. WS torrefied at 500 ◦ C showed the highest H₂ concentration rapid pressure release. Unlike hydrothermal treatment, steam explosion
(54.21 vol%) and syngas purity (85.59 %), while WS treated at 280 ◦ C relies on steam to mix with biomass at high temperatures, with pressure

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Table 4
Effect of torrefaction pretreatment of biomass on gasification.
Feedstock Torrefaction condition Gasification condition Gasification effect References

Wheat straw 200–500 C, 1 h

◦
Steam, 900 C ◦
Integrating torrefaction/carbonization with steam gasification [57]
provided a novel and effective route to manufacture H2-enriched
syngas with extremely low tar content from agricultural biomass.
Kenaf 250 ◦ C, 30 min CO2 Using TK as feedstock required less energy in the gasification process [58]
compared to RK.
Eucalyptus 280 ◦ C, 40 min 850 ◦ C, NiFe2O4: Torrefaction combined with CLG was found to be an efficient strategy [59,60]
feedstock = 1.25 to enhance syngas production while minimizing tar formation.
Coal, cotton stalk, red 200, 250, 300 ◦ C, 1:1 torrefied biomass/ Entrained flow co-gasification experiments demonstrated better [71]
pinewood, hazelnut shell 20, 40, 60 min coal blends, 1200 ◦ C, syngas quality, higher cold gas efficiency, and improved carbon
O2 11.5 SLM conversion with torrefied biomass compared to coal-only gasification.
Wheat straw pellets 250, 260, 270 ◦ C, Sand or 3 oxygen carriers Pretreating biomass resulted in a better H₂/CO molar ratio and [72,73]
(OCs) reduced carbon conversion.
Woodchips 250 ◦ C 800, 850 and 900 ◦ C, High H₂ content and high heating value were obtained in the gas [74]
steam, air-steam product.
Spruce wood branches 240–300 ◦ C 800 ◦ C, steam The quality of product gas improved when combining gasification [75]
with torrefaction and CO₂ capture.
Wheat straw (WS), Shengli 200–400 C ◦
850 C, steam
◦
For WS-400/SL blends, H₂+CO yields and carbon conversion rose by [76]
lignite (SL) 3.95 % and 18.32 %, respectively.
Palm kernel shell (PKS) and 270 ◦ C, 1 h 767 ◦ C, steam, biomass The PKSTo/MBPr produced a higher H2 composition of 31.3 %, which [77,78]
low-rank Malaysian coal blending ratio of 52 % was more than PKSUn/MBUn sample of 19.1 % at 45 min reaction
(MB) time.
Mixture of spruce, pine, and fir 240, 270, 300, 330 ◦ C, 50 OC(10 wt%, 30 wt%, 50 Torrefaction altered the gas product distribution in BCLG, increasing [79]
(SPF) sawdust min wt%), 900 ◦ C the H₂/CO ratio from 1.06 to 1.30.
Palm kernel shells (PKS), 280 ◦ C, 2 h 800, 850, 900 ◦ C, CO2 Both HHV and fixed carbon content rose while volatile matter and [80,81]
mesocarp fibres (MF), empty 300 ◦ C, 0.5 h moisture content decreased post-torrefaction. Gasification of torrefied
fruit bunches (EFB) and non-torrefied oil palm biomass using CO₂ enhanced the
Boudouard reaction, promoting CO formation. Conversely, using
steam as the gasification agent significantly increased H₂ production
compared to CO₂.
Wheat straw (WS) 220, 240, 260, 280, and Steam, 900 ◦ C This study presents a promising sustainable method by integrating [82]
300 ◦ C, 1 h biomass torrefaction/carbonization with gasification-steam
reforming, using gasification biochar to improve H₂-enriched syngas
production while reducing tar.
Pine sawdust (PS) 260, 280, 300, and 320 ◦ C, 1300 ◦ C, air PS-280: the best gasification performance. [83]
11 min All torrefied PS samples generated less hydrocarbon gases than raw
PS.
Food waste 230, 260, 290 ◦ C, 1 h 700 ◦ C, steam, steam: Syngas yield and H₂ production from food waste torrefied at varying [84]
FW = 1.25 temperatures ranged from 0.95 to 3.49 m³/kg and 0.6–2.15 m³/kg,
respectively.
Rice (RI), cabbage (CA) and 280 ◦ C, 30 min Steam, 800 ◦ C, 15 min Torrefaction increased H₂ and CO production from individual food [85]
pork (PO) waste types (PO and CA), but inhibited CO formation from RI. It also
enhanced cold gas efficiency (CGE) for mixed food wastes, improving
syngas quality, except for RI and PO mixtures.
Corn stalk 200–550 ◦ C, 30 min Steam:CS = 2:1, 900 ◦ C, Enhancing the physicochemical properties of MTD-char, such as O/C [86]
and K content, significantly improved steam gasification and
water–gas shift reactions in biomass, yielding high-quality syngas.
Japanese cedar 300, 350, 400 ◦ C, 60 min ER = 0.1, 0.2, 0.3 At a temperature of 300 ◦ C, CAR exhibited a 9.9 % lower CGE and [87]
600, 800, 1000 ◦ C air approximately half the tar concentration. The highest CGE and CCE
values (81.2 % and 90.0 %) occurred at an equivalence ratio (ER) of
0.2 and a gasification temperature of 1000 ◦ C.
Grass 250 ◦ C, 40 min, N2 CO2, 850–950 ◦ C Activation energy: wet: 161.7 → 86.9 kJ [31]
dry: 161.7 → 124.3 kJ/mol
Wet torrefaction was more effective than dry torrefaction and leaching
at improving gasification properties. The enhanced pore structure and
volume in treated biomass likely contributed to better char reactivity
and conversion during gasification.
Industrial solid waste sludge 180–400 ◦ C, Ar/CO2, 1100–1400 ◦ C, CO2 The optimal torrefaction temperature for SL pretreatment in a CO₂ [62]
(SL) 10–60 min atmosphere was 300 ◦ C.
Rice straw (RS) Gas-pressurized (GP) 1200 C, CO2
◦
GPRS facilitated carbon conversion in coal into CO and reduced co- [64]
torrefaction: 250 ◦ C, 1.7 gasification activation energy.
MPa, 15 min
Sewage sludge 319.9 ◦ C, 1 h, oxidizing steam Torrefaction also improved the heating value and quality of producer [63]
atmosphere gas, with the severity of the torrefaction process resulting in a good
torgas quality and relatively high chemical energy transfer.
Wheat straw (WS), 260 ◦ C, 30–40 min 950 ◦ C, steam Torrefaction acted as a de-chlorinating method, reducing pollutants [65]
and preventing accelerated corrosion in thermochemical processes.
rapeseed cake (RC) 200, 250 and 300 ◦ C, 1 h 900 ◦ C, OC/Fuel mass Torrefaction slightly reduced the output of nitrogen species like NH₃ [66]
ratio = 0, 0.5 and 1 and HCN.
Argan nutshells 220, 250 ◦ C 850 ◦ C, air, air-steam Torrefaction of argan nutshells did not enhance gasification, with no [67]
improvements in gas production, H₂/CO ratio, or syngas energy
content.
Empty fruit bunch (EFB) 300 ◦ C 680, 780 ◦ C, steam Torrefied biomass saw a mass reduction, leading to lower syngas [68]
yields. The torrefaction temperature and pretreatment affected the
(continued on next page)

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Table 4 (continued )
Feedstock Torrefaction condition Gasification condition Gasification effect References

chemical equilibrium during gasification. Higher temperatures and

torrefaction promoted the heterogeneous water-gas reaction.
Leftover rice 240–300 ◦ C, 30 min Steam, 600-1000 ◦ C Though gas production from torrefied leftover rice was low at low [69,70]
temperatures, it increased with higher gasification temperatures due
to enhanced char reforming. At 1000 ◦ C, the CGE of torrefied rice
exceeded that of raw rice.

Fig. 6. Reaction mechanisms occurred in the course of biomass torrefaction [54].

being instantaneously reduced through an explosion valve. This method decreases, while both surface area and pore volume increase markedly.
causes hemicellulose to break down due to acetic acid hydrolysis, while Additionally, increased H₂ production during steam gasification raises
lignin undergoes depolymerization, leading to weaker cellulose bonds. the heating value of the gas. The hydrothermal char formed during
Pressure release creates shear forces that break glycosidic and hydrogen pretreatment also serves as an effective catalyst for tar cracking, pro-
bonds, significantly altering the biomass both physically and moting tar degradation and significantly reducing tar production [5,92].
chemically. Hydrothermal pretreatment also effectively removes N elements from
sludge, thereby reducing NH3 formation during gasification [5,93].
In this treatment process, water functions as both a reactant and a
4.2. Hydrothermal treatment method reaction medium, eliminating the necessity for additional chemical ad-
ditives. The primary factor influencing the effectiveness of biomass
Hydrothermal pretreatment involves maintaining water in a liquid hydrothermal pretreatment is temperature, followed by raw material
state under high temperatures (160–240 ◦ C) and high pressures to particle size and reaction time [89,94]. Therefore, stringent control of
promote the hydrolysis of lignocellulose. This process is facilitated by in- reaction temperature and high-quality reaction vessels are essential for
situ hydronium ions generated through water autoionization and the biomass hydrothermal pretreatment process.
hydrogen ions released from hemicellulose, leading to the formation of
acetic acid. During hydrothermal pretreatment, an increase in temper-
ature significantly alters the surface morphology of biomass; most 4.3. Steam explosion method
hemicellulose degrades, some lignin is lost, insoluble lignin migrates
between the layers of the cell wall, and cellulose becomes evenly Steam explosion technology is a two-stage treatment process that
distributed within the cell wall [88]. Recent studies on hydrothermal involves subjecting lignocellulosic biomass to high temperatures and
coupled gasification are summarized in Table 5. Following hydrother- pressures (180–240 ◦ C, 1–3.5 MPa) for durations ranging from a few
mal treatment, the biomass-derived hydrothermal char exhibits favor- seconds to several minutes, followed by rapid pressure relief. In contrast
able gasification performance. Moreover, the degree of coalification in to hydrothermal treatment, steam explosion utilizes water in the form of
corn straw improves with higher hydrothermal temperatures, which steam mixed with biomass during the high-temperature steaming phase.
results in decreased O/C and H/C ratios [89]. Additionally, the chemical The primary distinction from hydrothermal treatment is that the steam
structure of biomass shifts towards that of a coal-like structure due to explosion method instantaneously reduces the pressure within the re-
enhanced aromatization during the hydrothermal process [90], as action vessel to atmospheric levels via an explosion valve. During the
illustrated in Fig. 7 [91]. Hydrothermal pretreatment also enhances the high-temperature phase, hemicellulose breaks down through hydrolysis
synergistic effects of rice straw in co-gasification with coal [89]. Hy- caused by acetic and other acids released from acetyl groups, while
drothermal pretreatment of microalgae enhances both its energy density lignin depolymerizes, weakening the bonds within the cellulose. In the
and heating value, with the hydrogen content in the hydrothermal decompression phase, the rigid fiber structure is disrupted, turning it
carbon increasing significantly (from 28.9 % to 48.6 %). This improves into a fibrous, dispersed material due to water evaporation and expan-
energy recovery rates during the subsequent steam gasification process sion. The rapid pressure reduction also creates shear forces that break
and increases the H₂/CO ratio (from 0.81 to 1.72) [90]. glycosidic and hydrogen bonds, altering the physical and chemical
For non-lignocellulosic biomass, hydrothermal pretreatment en- properties of the biomass. Sui and Chen [101] further divide this process
hances structural integrity and gasification performance. During this into four distinct stages: gas displacement, gas penetration, gas cooking,
process, the content of volatile compounds in sludge significantly and gas explosion, as shown in Fig. 8. Steam explosion treatment

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

significantly changes plant cell wall structures, producing a slurry-like properties to more closely resemble coal. Physicochemical pretreatment
material [102,103]. Meanwhile, after steam explosion, the carbon increases the volatile matter content of biomass, reduces lignin content,
content of biomass typically increases while oxygen content decreases, and thus improves gasification efficiency while reducing by-products (e.
promoting the generation of CO and CnHm during the gasification g., coke, tar), ultimately improving gas production quality. However, the
process. high-temperature and high-pressure operating conditions complicate
Compared to other pretreatment techniques, steam explosion is more the process, increasing both equipment and energy consumption costs.
energy-efficient and environmentally friendly [104], as it does not To ensure uniform heating in the pretreatment reactor, biomass raw
require recycling steps, thus reducing environmental costs [103]. material size should be appropriately reduced in industrial production.
However, the process’s effectiveness is highly dependent on the particle Biomass treated through physicochemical pretreatment can be directly
size and crystallinity of the biomass, which can result in significant sent to industrial gasifiers for processing. Future research should focus
material loss and incomplete lignin removal during treatment. on reducing equipment costs and refining processing conditions.
In conclusion, physicochemical pretreatment methods that leverage
high temperature, pressure, and chemical reagents can substantially
improve biomass gasification by altering its physical and chemical

Table 5
Effect of hydrothermal pretreatment of biomass on gasification.
Feedstock Hydrothermal treatment Gasification Gasification effect References
condition condition

Corn straw (CS) and rice husk (RH) 150 g biomass+ 1 L Biomass: coal = 1:1 Low-quality biomass-derived hydrochar was shown to be a [89]
deionized water, (mass) stable alternative to conventional fuels.
180–240 ◦ C, 30–90 min CO2
Oil-palm empty fruit bunches (Raw-EFB) Steam, 200 ◦ C, 2.0 MPa, 30 700–900 ◦ C, air or The fuel properties of hydrochar improved, with HHVs of HT- [95]
min CO2/O2 (79 %:21 %), EFB and HTW-EFB reaching 22.1 and 21.5 MJ/kg,
respectively.
Wood waste (WW) and food waste 30 g biomass+ 150 mL 850, 900, 950 ◦ C, Co-hydrothermal carbonization resulted in hydrochar with [96]
digestate deionized water, 250 ◦ C, 2 h CO2 abundant surface functional groups and metal content, such
(WW:FWD = 1:1, WW:FWD1 = 1:1, WW: as calcium, which reached 124.25 mg/g.
FWD2 = 1:1, WW:FWD3 = 1:1, WW:
FWD1 = 2:1, WW:FWD1 = 3:1)
Herb tea waste (HTW, lignocellulosic type) 120–300 ◦ C, 30 min 900 ◦ C, CO2 Hydrothermal carbonization (HTC) improved fuel quality and [97]
penicillin mycelial waste (PMW, non- enhanced aromatic structures.
lignocellulosic type)
sewage sludge (SS, ash-rich type)
coal
Shenfu bituminous coal (SF) 200 ◦ C, 15.0 bar, 30 min 1300 ◦ C, CO2 The synergistic effect in stage 2 was more apparent for SF- [98]
Rice straw (RS) 220 ◦ C, 22.5 bar, 30 min RS200 and SF-RS220 than SF-RS240, primarily due to
240 ◦ C, 35.0 bar, 30 min differences in AAEM concentration.
Nannochloropsis sp. feedstock: deonized water 700–900 ◦ C, steam, Combining hydrothermal pretreatment and steam gasification [90]
= 1:4(mass) S/B = 1-3 in a single step showed great potential for promoting
180–220 ◦ C, 2–12 h, N2 hydrogen-rich syngas production and increasing energy
recovery from low-lipid microalgae.
Grass 25 g biomass + 450 mL CO2, 850–950 ◦ C Heating values rose by 8.3 % in dry torrefied grass and by [31]
water, 220 ◦ C, 60 min 13.5 % in wet torrefied grass. Pre-treatments reduced the
activation energy of raw grass biomass from 161.7 kJ/mol to
124.3 kJ/mol for dry torrefied samples and to 86.97 kJ/mol
for wet torrefied samples.
Oedogonium intermedium, bagasse, grape 3.0 g biomass +17.0 g 800–1000 ◦ C, 90 vol HTC increased energy density and fixed carbon-to-volatile [99]
pomace deionized water % CO2/10 % N2 matter ratios while decreasing catalytic metal concentrations
180 ◦ C, 6.6 bar, 1 h (K and Na). Reactivity of char from grape marc and
220 ◦ C, 10.1 bar, 1 h macroalgae declined after HTC at 180–260 ◦ C, while bagasse
260 ◦ C, 26.5 bar, 1 h reactivity decreased after HTC at 220 and 260 ◦ C but
improved after treatment at 180 ◦ C.
Activated sludge 200, 220, 240, and 260 ◦ C, 900 ◦ C, steam The surface area and pore volume of untreated sludge [92]
0.5 h increased by 7.66 and 1.73 times after treatment at 200 ◦ C,
leading to a 4.2 % rise in H₂ content in syngas derived from
char, despite some loss of volatile species.
Sewage sludge 40 g SS 700–900 ◦ C, 20 % During the HTC process, about 50 % of the nitrogen in sludge [93]
160 ◦ C, 3.3 MPa CO2/80 % N2 was removed, and the cold gas efficiency in the co-gasification
200 ◦ C, 3.6 MPa, of a 1:1 hydrochar/leaves blend increased to 66 %.
240 ◦ C, 3.9 MPa
4–12 h
Sewage sludge 180, 200 and 220 ◦ C, 30 700–900 ◦ C, 20 % CO₂ gasification of SS-derived hydrochar significantly [5]
min CO2/80 % N2 reduced tar formation from 10.9 % to 6.8 %, while the heating
CaO (Ca/C(mol) = 0.05, value of the syngas improved from 14.1 to 15.7 MJ/Nm³.
0.075, 0.1)
Sewage sludge 180, 200, 220, 240, and 1100 ◦ C, CO2 HTC temperature had a greater impact on the fuel properties [94]
280 ◦ C for 120 min, of hydrochar than HTC duration.
30, 60, 90, and 120 min at
280 ◦ C
Sewage sludge 180, 200, 220 ◦ C for 1 h 900 ◦ C, oxidizing The product gas from hydrothermally treated sludge cakes [100]
feedstock: deonized water agent had a higher lower heating value (0.98 MJ/Nm³) and better
= 1:4(mass) cold gas efficiency (5.8 %). Moreover, the hydrothermally
treated sludge cake generated less tar compared to untreated
sludge during gasification.

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Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Fig. 7. Variations of coal and biomass microcrystalline structure after HTP [91].

5. Biological pretreatment selecting suitable microorganisms for biological pretreatment can spe-
cifically degrade difficult-to-gasify components like lignin and cellulose,
Biological pretreatment involves using microorganisms’ metabolism enhancing gasification reactivity. Despite these advantages, challenges
or enzymes produced by metabolism to alter the physicochemical such as longer pretreatment times and low hydrolysis rates limit its
structure of biomass. Anaerobic pretreatment of corn straw effectively broader application. Additionally, although biological pretreatment
disrupts its highly embedded inert structure, enhancing straw porosity does not require high temperatures or pressures, it necessitates stable
and increasing gas production rate and gas lower heating value (LHV) in and specific temperature, pH, and humidity conditions to maintain
subsequent pyrolysis and gasification processes, while significantly microbial activity. Optimizing the drying process for solid sludge is also
reducing tar production (see Fig. 9) [105]. essential for energy evaluation in combined systems, requiring further
The concept of integrating anaerobic digestion with thermochemical refinement. In industrial applications, biomass raw materials should not
conversion was pioneered by the F. Monlau team, who first proposed be too large to allow adequate contact with microorganisms. Further-
and demonstrated the feasibility of gasifying digestion products [106, more, the biomass must be free from harmful substances that could harm
107]. Subsequently, led by Chen Guanyi at Tianjin University, another microorganisms, preventing microbial death and ensuring effective
team extensively researched the anaerobic digestion pretreatment pretreatment. Additionally, devices for solid-liquid separation and
coupled with gasification. Studies revealed that a 14-day anaerobic biomass drying must be integrated between biological pretreatment
digestion pretreatment of corn straw yielded optimal LHV gas (6.83 equipment and industrial gasification furnaces. The separated liquid
MJ/Nm³) in air gasification at 800 ◦ C, achieving a gasification efficiency should be recycled to reduce the cost of biological pretreatment, and the
(CGE) of 73.62 %, and reducing tar production by approximately 35 %. biomass must be further dried to meet gasification standards. Therefore,
Preliminary energy and economic evaluations of this coupling process future studies may focus on using machine learning models to simulate
indicated a 44 % cost savings and a 25 % increase in net profit compared anaerobic digestion and gasification systems, analyzing existing data to
to traditional biomass gasification systems [105,108,109]. Apart from establish correlations and improve system management and perfor-
Tianjin University, other research teams have also investigated similar mance [112].
coupling processes with comparable outcomes [110]. Moreover, studies
have explored the use of kitchen waste for anaerobic fermentation 6. Discussion
gasification, demonstrating significant improvements in overall energy
output, including electricity and heat, as well as increased biochar Currently, research across various fields, including economics,
production [111]. environmental science, and energy, has demonstrated the value of
This approach offers benefits such as low energy consumption, cost several pretreatment technologies. From an economic perspective,
efficiency, and reduced dependence on chemicals. Furthermore, although torrefaction, mechanical crushing, and pelletization processes

Fig. 8. Mechanism of biomass steam explosion process [101,103].

12
Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

increase production costs, they reduce transportation and storage ex- can be employed. By integrating these methods, biomass can be gasified
penses, leading to lower overall production costs [54,113]. In the to produce syngas with higher heating value and cleanliness.
biomass gasification power generation process, torrefaction technology The impact of various pretreatment methods on biomass gasification
has also proven to be economically viable [114]. Environmentally, products can vary significantly, providing insights for directional gasi-
torrefaction can help reduce greenhouse gas emissions and maximize the fication research. Selecting appropriate pretreatment methods based on
potential of biomass for bioenergy production [54,113]. Table 6 pro- the target gasification products allows for targeted regulation of gasifi-
vides a preliminary comparison of different preprocessing methods, cation outcomes. For instance, if carbon monoxide (CO) is identified as
listing their scope of application and advantages and disadvantages, and the primary gasification product, acid treatment, alkali treatment, ionic
providing reference for evaluation in fields such as economics and liquid treatment, or steam explosion can be considered as primary
environment. methods [32,38,51,103]. Conversely, if hydrogen (H₂) is designated as
Studies comparing hydrothermal pretreatment and acid treatment the target product, options such as ionic liquid treatment, torrefaction,
show that hydrothermal treatment consumes 1.5 times more energy and a combination of microwave and alkali treatments may be prefer-
[115]. Several factors affect the efficiency of biomass gasification, with able [22,47,57]. If the objective is to reduce ash content in gasification
one key factor being that the efficiency increases as the moisture content products, methods like water washing, ionic liquid treatment, and steam
of the biomass decreases [116]. As a result, pretreatment methods with explosion should be considered [42,51,103]. To minimize tar produc-
high water usage, like acid, alkali, and water washing, are mainly tion and gas pollutants, hydrothermal treatment and torrefaction can be
applied to biomass anaerobic digestion. If these methods are used for effective strategies [5,57,59,65,66,92]. In future research on biomass
biomass gasification, drying the biomass afterward becomes essential. gasification pretreatment, different methods should be organically
From a device perspective, different preprocessing techniques combined according to the research focus and target products to achieve
impose specific design requirements. Mechanical pretreatment requires directional gasification.
grinding and forming equipment capable of fine particle size and
equipped with screening devices to meet durability and wear resistance 7. Conclusion and prospection
standards. Acid/alkali treatment demands equipment with high corro-
sion resistance. Hydrothermal and steam explosion pretreatment tech- Currently, biomass gasification technology has reached a level of
nologies require devices capable of handling high temperature and maturity, with established industrial process routes. The primary
pressure. Biological pretreatment requires microbial reactors that can research focus is on enhancing gasification efficiency, producing high-
monitor and provide stable and suitable living conditions for microor- heating-value and clean syngas, and minimizing harmful substances
ganisms. In conclusion, the device requirements for various pretreat- such as tar. Various pretreatment methods are employed to modify the
ment techniques contribute to increased equipment costs. Developing composition and structure of biomass, aiming to improve its conversion
high-quality, cost-effective pretreatment equipment will be crucial for efficiency into syngas and reduce the formation of tar and NOx during
advancing the biomass gasification process towards industrial-scale gasification. Given the diversity in biomass types and compositions,
application. selecting appropriate pretreatment methods and devices to optimize
Additionally, to enhance the effectiveness of biomass gasification, gasification is critical. Additionally, integrating different pretreatment
different pretreatment technologies can be combined. For example, techniques based on their underlying principles is a key area for future
combinations such as torrefaction with palletization [14,117], torre- research. When considering economic, energy, and environmental fac-
faction with washing [42,65,73], alkali treatment with hydrothermal tors, combining pretreatment technologies should prioritize reducing
treatment [118], and microwave treatment with alkali treatment [22] energy consumption, lowering costs, and achieving clean production.

Fig. 9. Scanning electronic images (SEM) of (a) CS (magnification of 1000), (b) CS (magnification of 2000), (c) ADCS-14d (magnification of 1000) and (d) ADCS-14d
(magnification of 2000) [105].

13
Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Table 6
Comparison of pretreatment techniques.
Methods Scope of Advantages Disadvantages Requirements for equipment
application

Mechanical Lignocellulosic (1) Easy to operate; (1) Uneven particle quality; (1) Fine grinding equipment;
method biomass (2) Low investment cost; (2) High power consumption; (2) Forming and granulation equipment
(3) Environmental Protection (3) The maintenance and upkeep costs of
the equipment are relatively high.

Microwave Lignocellulosic (1) Fast heating speed (1) high energy consumption; (1) Customized microwave oven
processing biomass; sewage (2) Heating is more uniform (2) significant investment costs
method sludge; (3) Has strong penetrability

Acid treatment Lignocellulosic (1) Change the structure of cellulose, (1) Generate a large amount of harmful (1) Anti-corrosion equipment;
method biomass; sewage hemicellulose, and lignin gases and wastewater, causing (2) Equipment for dewatering and drying
sludge; (2) Adjusting the content of alkali metals pollution to the environment. of biomass materials
Alkali treatment Lignocellulosic and alkaline earth metals (AAEM) in (2) Chemical treatment can adsorb a large
method biomass; sewage biomass amount of metallic substances,
sludge; leading to an increase in the metal
element content in biomass.

Water washing Lignocellulosic (1) Adjusting the content of alkali metals Generate a large amount of harmful gases Equipment for dewatering and drying of
(leaching) biomass and alkaline earth metals (AAEM) in and wastewater, causing pollution to the biomass materials
method biomass environment.
(2) Reducing water-soluble substances
(water-soluble organic matter, ash con-
tent, etc.)
(3) Increasing the specific surface area of
biomass

Organic solvent Lignocellulosic (1) Effectively disassembling the (1) The existing acidic organic (1) Devices for preventing volatilization,
treatment biomass components of lignocellulosic biomass pretreatment systems often rely on combustion/explosion, and corrosion
method to achieve dissolution of lignin and high reaction temperatures and acid (pre-treatment equipment, storage
hemicellulose while retaining cellulose concentrations to achieve complete devices)
solids removal of lignin and hemicellulose (2) Distillation recovery device
(2) Organic solvent pretreatment has the components, which increases the
advantages of easy synthesis, low cost, complexity and cost of the treatment.
non toxicity, good recyclability, and (2) Many solvents still have drawbacks,
biodegradability including volatility, flammability,
(3) Environmental Protection explosiveness, and high cost, which
place high demands on the reaction
environment.

Ionic liquid Lignocellulosic (1) Different types of ionic liquids can (1) The synthesis energy and economic Ionic liquid recovery equipment
treatment biomass; sewage dissolve cellulose and lignin, effectively cost of ionic liquids are relatively high
method sludge; breaking down lignocellulose linked by (2) Although ionic liquids can effectively
covalent bonds, hydrogen bonds, and dissolve and treat biomass, their
van der Waals forces, and increasing the selectivity for different components in
reaction area of cellulose. biomass, such as cellulose and lignin,
(2) Most ionic liquids are liquid at room is low, which may affect the purity and
temperature, with stable performance, quality of the final product
almost no vapor pressure, and are non- (3) Although ionic liquids have shown
toxic and harmless, making them one of potential in biomass pretreatment,
the new environmentally friendly their application on an industrial scale
methods applied in biomass is still in the research and
pretreatment development stage and requires
further research and optimization

Torrefaction Lignocellulosic (1) Realize deep dehydration and structural High energy consumption and operating Torrefaction reactor (High temperature
treatment biomass; sewage damage of lignocellulose, convert it into costs and pressure resistance) with gas supply
method sludge; more hydrophobic and brittle biomass, system
and reduce the O/C and H/C molar
ratios,
(2) Increasing energy density, properties
closer to coal, improving the grinding
performance of biomass, and reducing
transportation and storage costs
(3) Reduce greenhouse gas emissions and
decrease gasification tar

Hydrothermal Lignocellulosic (1) Improve the fuel quality of biomass The reaction temperature, pressure, and High temperature and high pressure
treatment biomass; sewage (2) Increase the C content of raw materials time need to be strictly controlled. resistance
method sludge; and reduce the O content
(3) Improve heating value and achieve
significant ash removal effect
(4) Improve the physical and chemical
properties of biomass

Steam explosion Lignocellulosic Energy saving and environmental protection (1) Specific equipment and skills are Typical setup of steam explosion includes
method biomass; sewage required a boiler that produces steam, an
sludge; automatic control for steam pressure and

(continued on next page)

14
Y. Zhang et al. Journal of the Energy Institute 119 (2025) 101992

Table 6 (continued )
Methods Scope of Advantages Disadvantages Requirements for equipment
application

(2) Need to consider the adaptability of reaction time, a reactor with high
raw materials temperature/pressure steam, a blow
down chamber.

Biological Lignocellulosic (1) No pollution to the environment (1) Biological treatment requires a longer Microbial reactor
pretreatment biomass; sewage (2) Biological treatment technology is processing time, resulting in lower
sludge; relatively mature and has lower production efficiency.
investment costs. (2) Biological treatment requires the
(3) Organic gases such as biogas generated manipulation of professionals and has
through biological treatment can be a high level of technical expertise.
utilized as biomass energy.

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