TYPE Review

PUBLISHED 08 March 2024

DOI 10.3389/ffuel.2024.1378361

Critical review of the role of ash

OPEN ACCESS content and composition in
EDITED BY
Abul Kalam Hossain,
Aston University, United Kingdom
biomass pyrolysis
REVIEWED BY
Justin Thomas, Lokeshwar Puri, Yulin Hu* and Greg Naterer*
Czech Technical University in Prague, Czechia
Vikas Sharma, Faculty of Sustainable Design Engineering, University of Prince Edward Island, Charlottetown, PE, Canada
University of Brighton, United Kingdom

*CORRESPONDENCE
Greg Naterer,
gnaterer@upei.ca In the face of environmental challenges (e.g., dramatically increasing greenhouse
Yulin Hu,
yulinhu@upei.ca
gas emissions and climate change), it is utmost of importance to sustainable
energy systems. Biomass consisting of agricultural and forest waste, municipal
RECEIVED 29 January 2024
ACCEPTED 28 February 2024
solid waste, and aquatics, has been identified as alternative and promising fuel
PUBLISHED 08 March 2024 sources. Thermochemical conversion approaches like pyrolysis can turn various
CITATION
types of biomass into three valuable product streams, namely, bio-oil, biochar,
Puri L, Hu Y and Naterer G (2024), Critical review and syngas. To date, past review articles have considered the major operating
of the role of ash content and composition in parameters of kinetics, chemistry, and the application of pyrolysis products.
biomass pyrolysis.
Front. Fuels. 2:1378361. However, ash content is one of the key biomass components that lacks
doi: 10.3389/ffuel.2024.1378361 investigation on its influence during biomass pyrolysis with respect to
COPYRIGHT
products yield and properties. This review article examines: i) the ash content
© 2024 Puri, Hu and Naterer. This is an open- and composition in different types of biomass; ii) effects of ash content on
access article distributed under the terms of the catalytic pathway and biomass thermal degradation; iii) ash related problems in
Creative Commons Attribution License (CC BY).
The use, distribution or reproduction in other the thermal degradation of biomass; and iv) available deashing techniques for
forums is permitted, provided the original biomass. The review aims to provide new understandings and insights regarding
author(s) and the copyright owner(s) are the effects of ash content and composition on biomass pyrolysis.
credited and that the original publication in this
journal is cited, in accordance with accepted
academic practice. No use, distribution or KEYWORDS
reproduction is permitted which does not
comply with these terms. pyrolysis, products yield, products properties, biomass, ash

1 Introduction
Given the environmental impact of fossil fuels such as oil, coal, and natural gas, there is a
need to develop alternative energy sources which fulfil the world’s growing energy needs.
Alternative energy sources should be economical and sustainable, biomass is a promising
renewable energy source. Compared to other types of sustainable energy (e.g., solar and
wind), biomass is a carbon-rich energy source. Among the different types of biomass,
lignocellulose including agricultural and forestry residue and energy crop has been
extensively utilized as a raw materials to produce biofuels and biochemicals via
different conversion technologies (M. Guo et al., 2015; Manikandan et al., 2023;
Braghiroli and Passarini, 2020). Monir et al. (2022) applied a mixture of empty fruit
bunches of palm oil, coconut shell, and forest waste to produce syngas along with bioethanol
through a hybrid gasification and syngas fermentation. Valizadeh et al. (2022) and Li et al.
(2021) turned woody sawdust and rice husk, respectively, into bio-oil (a substitute to
petroleum crude oil) by pyrolysis. The main advantages of using lignocellulosic biomass as a
fuel source include its abundance, carbon neutrality, and economical processing. Aside
from lignocellulosic biomass, algae that belongs to the third generation of biofuels offers
benefits of high biomass productivity, fast growth rate, an ability to be cultivated in
wastewater or brine water, high lipid yield, and presences of valuable biochemicals (e.g., β-
carotene, lutein, and astaxanthin) (Adeniyi et al., 2018). As suggested by da Rosa et al.

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Puri et al. 10.3389/ffuel.2024.1378361

(2023), there is a parallel drawn between algae in both energy and fuel source in boilers to replace petroleum crude oil and can also be
food markets. Algae biorefineries are used in food, chemical and further upgraded to hydrocarbon fuels to reduce the consumption of
energy markets. petroleum crude oil. Another application of bio-oil is the recovery of
To date, different types of biomass conversion technologies have a wide spectrum of chemicals like phenolics, alcohols, and acids (Hu
been developed ranging from biological methods, chemical, to and Gholizadeh, 2020).
thermochemical methods. A summary of the main categories of Due to the complexity in biomass composition and the
biomass conversion are shown in Figure 1. Thermochemical multiphase reactions involved in the pyrolysis process, a full
techniques like pyrolysis could be a more effective approach for understanding of the associated chemical reaction pathways is
biomass processing (W. Li et al., 2017). This could be related to the challenging. Previous studies have used characteristic biomass
inherent benefits of pyrolysis such as its ability to use a variety of compounds like cellulose (Hu et al., 2022; Fliri et al., 2023; Shao
feedstock; minimize environmental effects; and the co-production of et al., 2023), hemicellulose (D. Chen et al., 2022; Hu et al., 2024),
bio-oil, biochar, and syngas (Osman et al., 2023). In contrast, a lignin (Folgueras et al., 2023; Genuino et al., 2023; Pienihäkkinen
prolonged reaction time is needed in the biological conversion et al., 2023), lipid (Bartoli et al., 2021; Bartolucci et al., 2023), protein,
methods. For example, mesophilic anaerobic digestion typically and their monomers like glucose, xylose, phenol (Lago et al., 2022;
requires 25–30 days to convert organic waste into biogas and Cruz-Reina et al., 2023), and amino acids in either individual,
digestate. During biological conversion, it is also significant to binary, or tertiary systems to study the underlying reaction
properly control the culture medium (e.g., pH, temperature, and mechanism. Past review papers have been previously reported by
the existence of inhibitory chemicals) over the entire reaction to (Osatiashtiani et al., 2022; Al-Balushi et al., 2023; Sierra et al., 2023;
avoid microorganism inactivity and reaction failure. Another Silos-Llamas et al., 2023; Xing et al., 2023). Past studies have
limitation is the requirement for an additional treatment before examined the effects of reaction parameters on biomass pyrolysis
fermentation, such as enzymatic hydrolysis or saccharification to with respect to products distribution and properties (Kan et al.,
break down big carbohydrate’s molecules into fermentable simple 2016), catalyst usage (Grams et al., 2023), bio-oil upgrading
sugars (Awasthi et al., 2023). (Fermoso et al., 2017), and the applications of biochar (Ghodake
Pyrolysis is a thermochemical conversion process in an inert et al., 2021) and gaseous products (X. J. Lee et al., 2020).
condition with or without the presence of a catalyst. As illustrated in Aside from organics (e.g., cellulose, hemicellulose, and lignin),
Figure 1, in a typical biomass pyrolysis, biomass is initially pre- biomass also contains a certain amount of inorganics. Past studies
treated by size reduction, washing, and drying, and then loaded to a have discussed the catalytic effects of ash fraction on biomass
pyrolysis reactor (e.g., auger reactor and fluidized bed reactor). pyrolysis by affecting the bio-oil and biochar yield and products
During the reaction, pyrolysis vapor is released from the volatiles properties. In other studies, it was found that the presence of ash in
fraction of biomass upon thermal degradation, followed by bio-oil helped reduce NOx emissions upon combustion and lower
condensation to separate bio-oil and gaseous products (Gahane the number of O-containing functional groups in bio-oil (Kim et al.,
et al., 2022). Bio-oil (also called pyrolysis oil) can be used as a cleaner 2021; Wang et al., 2021). Moreover, ash fraction present in biomass

FIGURE 1
Summary of biomass conversion methods to produce value-added bioproducts and applications.

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often leads to slagging, fouling, bed agglomeration, and corrosion TABLE 1 Summary of ash content in different forms of agricultural waste
(Islam et al., 2021; Melikoglu et al., 2023).
problems during the biomass thermal degradation including
pyrolysis. Most previous studies focused on the ash-related Agricultural waste Ash content (wt%, d.b.)
properties in biomass combustion (Vassilev et al., 2014; L; Wang
Jute stick 0.3
et al., 2012; Nunes et al., 2016; Niu et al., 2016) and potential
applications of biomass ash in concrete manufacturing and Sugarcane bagasse 1.4
agriculture (Pode, 2016; Silva et al., 2019; Olatoyan et al., 2023). Hazelnut shell 1.9
However, to the best of our knowledge, past literature has not
examined the influence of ash content and composition on biomass Walnut shell 1.9

pyrolysis in terms of products yield and properties. Pistachio shell 1.9

Therefore, in this review article, i) the ash content and
Wheat straw 2.2
composition in different types of biomass including agricultural
waste, forestry waste, municipal solid waste, and aquatic biomass, Orange filter cake 3.7
will be examined; ii) the effects of ash content on catalytic pathway Pomegranate filter cake 3.9
and biomass thermal degradation will be reported; iii) ash related
Poplar branch 4.1
problems including slagging, sintering, fouling, bed agglomeration,
and corrosion, will also be reviewed; and iv) lastly, deashing Hazelnut glume 8.9
techniques covering biological processes, acid leaching, and
Corn stalk 10.0
additives addition, will be investigated.
Rice straw 10.1

Rice husk 16.0

2 Ash content and composition in
different types of biomass
and composition of the commonly used types of biomass in
To evaluate the ash’s effect on biomass pyrolysis, it is important pyrolysis, including agricultural waste, forestry waste, municipal
to understand the content and main composition of ash fraction of solid waste, and aquatic biomass, will be discussed.
commonly used types of biomass in pyrolysis. This is helpful for
selecting the appropriate type of biomass for pyrolysis and deciding
on whether a deashing pre-treatment is needed. In general, the ash 2.1 Agricultural waste
fraction present in different sources, ranging from agriculture,
forestry, to municipal, exhibits variations in the content and Agricultural waste is usually the result of harvesting on the farms
chemical composition. These differences occur due to and slaughterhouses. Examples of agricultural waste include rice
geographical location, local ecosystem, cultivation conditions, as husk, corn straw, sugarcane bagasse, hazelnut glume, and pistachio
well as the surrounding environment. shell. Slaughterhouse waste is another stream of agricultural waste
Ash usually contains alkali and alkaline earth metals (AAEMs), and includes the animal waste generated from the slaughtering
heavy metals, non-metals, and other elements. Their composition process. Other examples of slaughterhouse waste are feathers,
and reactivity affect the thermal degradation pathway of biomass. hatchery waste, blood, bedding material, shell, and animal litter
The alkali salts present in the ash fraction of biomass could either act (Muduli et al., 2018).
as catalysts or inhibit the thermal degradation of major biomass In a detailed study by Melikoglu et al. (2023), the ash content in
biomolecules (Changi et al., 2015). The minerals present in the ash orange filter cake, pomegranate filter cake, corn stalk, sugarcane
could be bound onto an organic matrix of the biomass by bagasse, olive pomace, hazelnut glume, hazelnut shell, poplar
substituting with acidic H atoms in the carboxylic acid or branch, walnut shell, and pistachio shell was measured. The
phenolic groups and then subsequently form salts (Nik-Azar results are summarized in Table 1. It can be observed that all
et al., 1997). tested agricultural waste had either a medium or a low level of
In general, ash is composed of both major and minor mineral ash content, based on the category of ash content. Bagasse, hazelnut
elements. Major mineral elements include titanium (Ti), shell, walnut shell, pistachio shell, orange filter cake, pomegranate
phosphorus (P), aluminium (Al), potassium (K), iron (Fe), filter cake and poplar branch were found to be lower in ash content
calcium (Ca), magnesium (Mg), and silicon (Si), while minor than other agricultural waste. Olive pomace, hazelnut glume and
mineral elements include nickel (Ni), molybdenum (Mo), corn stalk fell into the medium ash content group.
mercury (Hg), copper (Cu), chromium (Cr), cadmium (Cd), Islam et al. (2021) showed that the ash content of rice husk, rice
barium (Ba), vanadium (V), and zinc (Zn). In comparison, the straw, jute stick, and wheat straw was determined to be 16 wt%,
existence of major mineral elements results in ash fouling and 10.19 wt%, 0.3 wt%, 2.21 wt%, respectively. Rice husk was found to
corrosion towards process equipment. By comparison, the contain the highest amount of ash (i.e., 16 wt%). Such a high ash
particle emission is primarily caused by minor mineral elements. content could lead to a series of industrial machinery problems such
Biomass can be classified into i) high ash-containing biomass as fouling, sintering, slag deposition, and agglomeration, and a
(ash wt% > 10 wt%), ii) medium ash-containing biomass (ash wt% = detailed explanation is provided in Section 4. Therefore, ash
5–10 wt%), and iii) low ash-containing biomass (ash wt% < 5 wt%) removal from rich husk might be necessary prior to pyrolysis or
(Stella Mary et al., 2016). In the following sections, the ash content other thermochemical conversion methods.

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TABLE 2 Summary of ash composition in agricultural waste (wt%, d.b.) (Vassilev et al., 2010).

Feedstock SiO2 CaO K2O P2O5 Al2O3 MgO Fe2O3 SO3 Na2O TiO2 Total ash
Miscanthus grass 56.42 10.77 19.75 5.54 0.79 3.01 0.94 2.28 0.47 0.03 3.0

Sweet sorghum grass 66.85 10.41 9.49 3.47 0.81 3.12 0.58 3.47 1.74 0.06 4.2

Barley straw 50.78 9.89 28.18 2.97 0.67 2.87 0.95 2.22 1.39 0.08 5.3

Corn straw 49.85 14.73 18.53 2.42 5.06 4.49 2.53 1.84 0.16 0.29 7.7

Oat straw 37.79 12.03 26.84 6.14 4.69 4.45 2.17 4.93 0.72 0.24 5.9

Wheat straw 50.35 8.21 24.89 3.54 1.54 2.74 0.88 4.24 3.52 0.09 7.1

Coconut shell 66.75 2.41 8.48 1.54 8.48 1.54 6.16 0.01 4.62 0.01 3.2

Cotton husk 10.93 20.95 50.2 4.05 1.32 7.59 1.92 1.72 1.31 0.01 3.4

Sugarcane bagasse 46.79 4.91 6.95 3.87 14.6 4.56 11.12 3.57 1.61 2.02 2.1

TABLE 3 Total ash content (wt%, dry basis) and ash composition (mg/kg, dry basis) of woody biomass (Dibdiakova et al., 2015).

Total ash content

Steam bark 1.78

Branch twigs 1.56

Branch base 0.48

Stem bark 0.22

Ash composition Steam bark Branch twigs Branch base Stem bark

Al 860 779 115 860

Ca 239,749 125,095 241,309 239,749

Fe 2,425 3,648 2,757 2,425

K 72,739 174,887 64,150 72,739

Mg 37,481 33,486 45,526 37,481

Mn 47,704 19,467 25,575 47,704

Na 10,608 19,233 7,201 10,608

P 37,942 81,096 33,092 37,942

S 20,460 18,052 18,133 20,460

Si 3,712 14,725 7,210 3,712

Zn 3,057 2,383 3,297 3,057

In addition to the total ash content, the detailed chemical In the following section, the effect of such chemical species on
composition of ash fraction present in the biomass is another biomass degradation and product distribution is discussed. In recent
critical factor affecting the subsequent biomass thermal studies, the ash fraction derived from agricultural waste has been
degradation by pyrolysis. The ash composition of various types valorized into value-added bioproducts. Shen (2017) discussed the
of agricultural waste has been explored in other previous studies. A potential of using silica derived from rice husk for soil remediation,
summary of the ash composition of different agricultural waste is pollutant removal, and fabrication of silicon materials.
provided in Table 2. As shown in Table 2, corn straw contained the
highest ash content (7.7 wt%) compared to other agricultural
waste. The most dominant species in the ash fraction of corn 2.2 Forestry waste
straw were SiO2, CaO, and K2O. This also occurs for other
agricultural waste such as Miscanthus grass, sweet sorghum Forestry waste is derived generally from deforestation and
grass, and barley straw. wildfires, including soft and hard stems, branches, foliage, barks,

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TABLE 4 Ash composition derived from forest residue biomass (Bosch et al., TABLE 5 Ash content in various municipal waste (Islam et al., 2021).
2022).
Ash content (wt%, d.b.)
Content (wt%,d.b.)
Plastics waste 0.23
Ash 1.27
Polyethylene 1.46
Composition (mg/g,d.b.)
Electronic waste 1.83
Al 0.31
Wastepaper 2.68
Ca 2.81
Furniture waste 2.70
Cu 0.02
Tire waste 3.28
Fe 0.70

K 0.43
TABLE 6 Composition of municipal solid waste (Márquez et al., 2023).
Na 0.53

Zn 0.09 Content (wt%,d.b.)

*d.b. represents dry basis. Ash 27.0 ± 1.2

Composition (wt%,d.b.)

chips, lumps, pellets, sawdust, and other various wood species SiO2 29.0

(Vassilev et al., 2010). Compared to agricultural waste, woody CaO 25.0

biomass is a more common feedstock used in pyrolysis for fuel
Al2O3 5.6
generation. The ash content in forestry waste is usually much lower
than that present in agricultural waste. Tables 3, 4 shows the ash Na2O3 4.6
content and composition identified in forestry residue. SO3 4.6
Table 3 indicates that the dominant species in the ash fraction of
woody biomass (i.e., Pinus Sylvestris) are Ca, K, Mg, Mn, P, and Si. In K2O 4.5

particular, the content of K, Na, and P in the twigs were observed to *d.b. represents dry basis.
be considerably higher than those in the steam wood, bark, and
branch. Stem bark contained the highest amount of ash content biochar. Previously, Sotoudehnia et al. (2020) turned waste
(1.78 wt%). This result could lead to unwanted ash melting and corrugated cardboard into biochar and bio-oil by pyrolysis at
slagging when using twigs in the boiler or furnace (Dibdiakova 350°C–450°C with a feed rate of 0.5 kg/h. Lim et al. (2022) co-
et al., 2015). pyrolyzed plastics and food mixtures for producing bio-oil under
The ash content and composition derived from forest residue flue gas conditions. The content of ash in different types of MSW has
has also been studied by Bosch et al. (2022). The forest residue was been previously measured by Islam et al. (2021), as shown in Table 5.
derived from a local wood processing facility and was a mixture of It can be found that the ash content was in the range of 0.23–3.28 wt
sapwood, bark, tops, and branches. The results are shown in Table 4. %. Among the investigated feedstocks, tire waste was observed to
An amount of 1.27 wt% of ash content was found. This ash fraction contain the highest ash content of 3.28 wt%.
primarily was composed of Al, Ca, Cu, Fe, K, Na, and Zn. Compared Table 6 shows the chemical composition of MSW’s ash fraction.
to Table 3, the differences in ash composition between two forest It was found that alkali metals are formed with metal oxides where
residues could be caused by the differences in the type of wood, soil Al2O3 was found to be present in the largest quantity. When
quality used to grow the wood, as well as the wood cultivation compared to agricultural waste (Table 1) and woody biomass
conditions. (Table 3), a higher ash content can be found in the MSW
(i.e., 27 wt%). Specifically, MSW contains a significantly higher
content of ash that of woody biomass. An ash content of 1.27 wt
2.3 Municipal solid waste % is present in forest residue derived from a mixture of sapwood,
bark, tops, and branches (Table 4).
Generally, municipal solid waste (MSW) comes from three
major sources, namely, construction, industrial, and commercial
sources. Examples of MSW include paper waste, paper scraps, boxes, 2.4 Aquatic biomass
broken glassware, light bulbs, ash, leather elements, textiles, toxic
substances (e.g., paints, batteries), and hazardous solid waste (e.g., Researchers have found that aquatic plants can be an excellent
sanitary napkins and used syringes) (Islam et al., 2021). The resource for renewable energy production, due to comparatively
inappropriate treatment of MSW like incineration and a landfill high productivity compared land-grown plants, and land which is
results in a substantial amount of greenhouse gas emissions (Chen not required in the cultivation stage and hence without competition
et al., 2022; Nair et al., 2023). between food and fuel production (Miranda et al., 2017).
Recent studies have used pyrolysis to treat MSW and valorise It was found that water hyacinth has a growing rate at 100 dry
this organic waste into value-added bioproducts like bio-oil and tonnes/(ha·year) while switchgrass (i.e., one type of energy crop)

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TABLE 7 Total ash content of algae (Tibbetts et al., 2015). 0.81%–2.66%. S varied between 0.41 and 1.38 wt%. The presence of
such nutrients in the algae is primarily due to the fact that nutrients
Algae species Ash content (wt%, d.b.)
are one of the key elements in the algae cultivation stage, and thus
Chlorella 5.8 the nutrients will be uptake by algae.
Nannochloropsis granulata 6.7
Overall, it can be observed that forestry residue contains the
lowest ash content when compared with agricultural waste,
Botryiciccus brunii 7.2
municipal solid waste, and aquatic biomass, as illustrated in
Spirulina 7.8 Table 9 To reduce the operational challenges associated with
high ash content, woody biomass can be a more suitable
Porphyridium aerugineum 8.9
feedstock than other types in thermal degradation treatment. In
Acutidesmus dimorphus 14.5 the following sections, the influences of ash content and particular
Tetraselmis chuii 16.2 ash composition on catalytic pathways and biomass thermal
degradation during pyrolysis treatment are reviewed.
Neochloris oleobundans 16.7

Phaeodactylum tricornutum 17.0

3 Effects of ash content on catalytic
pathway and biomass thermal
degradation
only produces about 25 dry tonnes/(ha·year) (Wullschleger et al.,
2010). Together with a tailorable biosynthesis pathway, algae could Ash has shown significant effects on various thermochemical
be another promising feedstock for producing biofuels and conversion methods including pyrolysis, in terms of the reaction
biochemicals by pyrolysis (Banerjee et al., 2020; X; Wang et al., pathways and products distribution and properties. From past
2022). The ash content and composition of different algae species literature, ash content/composition primarily affects pyrolysis
are summarized in Tables 7, 8 respectively. As indicated in Table 7, with respect to i) the reaction rate; ii) bio-oil yield and
the different species resulted in a variation in the ash content. The properties; iii) composition of biochar; and iv) the total biomass
ash fraction in the algae strains ranged from 5.4 wt% to 17.0 wt%. conversion (Antal, 1983; Scott et al., 2001; Wright et al., 2010;
The highest ash content of 17 wt% was observed in the Bridgwater, 2012; Mayer et al., 2012; Carpenter et al., 2014).
Phaeodactylum tricornutum.
Tibbetts et al. (2015) examined the micro and micromineral
content of various algae species. Results showed that Ca varied in the 3.1 General description of ash fraction
range of 0.26–2.99 wt% and P was found to lie in the range of
0.73–1.46 wt%. It can be observed that Na content was found to be As earlier mentioned in Section 2, ash usually contains alkali and
one of the highest amongst other macronutrients with a range of alkaline earth metals (AAEMs), heavy metals, non-metals, and other

TABLE 8 Ash composition of different algae species (Tibbetts et al., 2015).

Phaeodactylum Nannochloropsis Botryococcus Porphyridium Tetraselmis

tricornutum granulata braunii aerugineum chuii

Macro-mineral (wt%, d.b.)

Ca 0.26 ± 0.00 0.09 ± 0.00 0.10 ± 0.00 0.64 ± 0.01 2.99 ± 0.00

P 1.17 ± 0.00 0.73 ± 0.00 1.45 ± 0.02 1.39 ± 0.01 1.46 ± 0.00

Mg 0.71 ± 0.00 0.26 ± 0.00 0.36 ± 0.0 0.55 ± 0.01 0.43 ± 0.00

K 2.3940.01 1.50 ± 0.0 0.750.01 0.67 ± 0.01 1.86 ± 0.01

Na 2.66 ± 0.02 1.03 ± 0.00 0.94 ± 0.02 0.81 ± 0.02 0.89 ± 0.00

S 1.38 ± 0.01 0.58 ± 0.0 0.41 ± 0.01 0.64 ± 0.01 1.38 ± 0.00

Micro-minerals (mg/kg)

Cu 54.8 ± 0.4 17.8 ± 1.2 35.2 ± 1.4 45.3 ± 1.1 102.2 ± 0.7

Fe 4772.7 ± 22.4 1,394.8 ± 0.0 6,203.1 ± 97.2 11,100.7 ± 221.1 1773.7 ± 14.7

Mn 45.1 ± 0.2 150.8 ± 0.0 453.7 ± 7.5 258.5 ± 4.4 191.4 ± 0.7

Se 0.5 ± 0.0 0.5 ± 0.1 n.d n.d 0.5 ± 0.1

Zn 50.0 ± 0.4 32.0 ± 2.3 27.8.0.5 41.0 ± 0.6

*d.b. represents dry basis.

*n.d. represents not detected.

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TABLE 9 Average value of ash content of four types of biomass (average et al., 2013; Carpenter et al., 2014). In particular, Yip et al.
value based on past literature).
(2010) observed that Ca and two alkali metals (i.e., K and Na)
Biomass Average ash content (wt%, d.b.) were retained in the biochar product and all demonstrated
catalytic activity during biomass thermal degradation. The
Forestry waste 1.27
order of catalytic performance was K>Na>Ca.
Municipal solid waste 2.03

Agricultural waste 4.27

3.1.3 Heavy metals
Are characterized by relatively high densities, atomic weights, or
Aquatic biomass 10.28 atomic numbers. Some heavy metals identified in the ash fraction of
biomass are listed below. Fe is one of the heavy metals identified in
the biomass ash and exists in the form of Fe2O3 (Mlonka-Medrala
elements. This section will discuss the general impact of ash fraction et al., 2020). Pb is another type of heavy metal that could be present
on biomass thermal degradation and pyrolysis products yield and in the biomass since it can be incorporated into biomass during the
properties by categorizing the ash fraction into alkali metals, alkaline growth period. Past literature found that Demol Timber and sewage
earth metals, heavy metals, non-metals, and other elements. sludge contained a Pb content of 6,300 mg/kg and 150 mg/kg,
respectively (Nzihou and Stanmore, 2013).
3.1.1 Alkali metals
consist of Li, Na, K, Rb, Cs, and Fr, which have their outermost ⁃ Fe: It has shown to increase the rate of reaction of cellulosic
electron in an s-orbital. They are highly reactive at standard degradation (Radlein and Quignard, 2013; Thy et al., 2013;
temperature and pressure (STP) and exist as shiny and soft. Carpenter et al., 2014), which in turn causes an increase in the
Among them, K and Na are considered the most critical species biomass conversion and the bio-oil yield.
in the ash fraction of biomass, causing unwanted reactions. Upon ⁃ Pb: A possible catalytic influence of Pb has been reported by
biomass thermal degradation, these alkali metals are evaporated and several researchers. In the thermal degradation of cellulose and
then form aerosols such as KOH, KCl, K2SO4, NaCl, and Na2SO4 in lignin, its presence leads to the demineralization of cellulose
the gas phase. The resulting aerosols could lead to the formation of and lignin (Obernberger and Biedermann, 2002; Thy et al.,
ash agglomeration and slag (Mlonka-Medrala et al., 2020). The 2013; Carpenter et al., 2014).
detailed effects of K and Na on biomass thermal degradation and
bio-oil production are discussed below. 3.1.4 Non-metal elements
Elements that mostly do not exhibit metallic properties, such as
⁃ K: In a thermal degradation study of lignin, K induced a H, He, and N. They have a low density, high electronegativity, and
catalytic effect. Past literature also suggests that K is act as poor conductors for heat and electricity, unlike metals. For the
responsible for a high biochar yield but a low yield of tar. category of non-metal elements, Capablo et al. (2009) summarized
Tar is typically the heavy fraction of bio-oil. Lastly, several the content of non-metal elements like Cl and S for waste generated
studies have observed that K hinders the depolymerization from agricultural, forestry, and municipal, e.g., Cl and S for mash
process of main biomass components (Scott et al., 2001; from beer brewery, empty fruit bunch, and shea waste. Olive waste
Patwardhan et al., 2010; Mohan et al., 2006; Mourant et al., was 0.01 wt% and 0.22 wt%, 0.35 wt., % and 0.13 wt%, 0.07 wt% and
2011; Thy et al., 2013; Carpenter et al., 2014). 0.24 wt%, and 0.24 wt% and 0.13 wt%. Although their contents are
⁃ Na: It is known for high biochar production even with a low, the presence of such elements has demonstrated a significant
smaller Na concentration (i.e., down to a few ppm) in the raw impact on biomass thermal degradation. In addition, Blasing et al.
material, along with a lower yield and quality of bio-oil. This (2013) observed that P is another trace element that belongs to non-
observation could result from the Na-induced secondary metal existing in various biomass including willow, poplar, oak, pine
cracking of pyrolysis vapor and thus exhibits an adverse seed shells, hazel nut shells, and almond shells.
impact on bio-oil formation (Patwardhan et al., 2010;
Bridgwater, 2012; Radlein and Quignard, 2013; Thy et al., ⁃ S: typically causes catalyst deactivation. During pyrolysis, the
2013; Carpenter et al., 2014). deoxygenation reaction (i.e., one of the common chemical
reactions occurring in the biomass depolymerization) is
3.1.2 Alkaline earth metals inhibited due to the formation of H2 S vapour (Thy et al.,
Include Be, Mg, Ca, Sr, Ba, and Ra, which lies in the group 2 of 2013; Ruddy et al., 2014; Mohan et al., 2006; Gunawardena and
the periodic table. They are less reactive at STP compared to alkali Fernando, 2013; H; Chen et al., 2011; Bulatov and Klemeš,
metals and exist as shiny and slivery-white. For alkaline earth metals 2009; Zhang et al., 2010).
detected in the biomass ash, Ca and Mg have been reported to be the ⁃ Cl: The presence of Cl leads to an increase in the yield of
primarily reactive elements (Mlonka-Medrala et al., 2020; Yu levoglucosan (i.e., a six-carbon ring structure that is often
et al., 2021). produced from pyrolysis of cellulose); however, it could lead to
the catalyst poisoning and deactivation like S element
⁃ Ca and Mg: One previous study has reported that the catalytic (Atadana, 2010; Shimada et al., 2008; He et al., 2010;
effect of Ca and Mg on thermal degradation of lignin is minor. Mohan et al., 2006; Thy et al., 2013; Bridgwater, 2012).
In particular, they led to a lower tar and higher biochar yield ⁃ P: Along with the positive catalytic effect on biochar yield, it
(Patwardhan et al., 2010; Radlein and Quignard, 2013; Thy has also been found that phosphoric acid (H3PO4) promotes

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FIGURE 2
Reaction pathway of fast catalytic pyrolysis due to the presence of ash in the biomass.

the coke deposition, which not only poses a threat to catalyst demonstrates a negative impact on the in-situ catalytic pyrolysis.
deactivation but also causes fouling and corrosion the process Specifically, the deposit of ash either on the surface of the catalyst or
machinery (Ruddy et al., 2014). the inside of the catalyst’s porous structure leads to the catalyst
deactivation since it could position the active sites of the catalysts
3.1.5 Other elements and subsequently deactivate them (Bridgwater, 2012; Einvall et al.,
Si is a metalloid and does not belong to either metal or non- 2007). In particular, the presence of S and Cl elements in the ash
metal. As shown in Table 2, SiO2 is the most dominant species found fraction of biomass results in catalyst deactivation, as earlier
in the ash fraction of agricultural waste. Armesto et al. (2002) also mentioned in Section 3.1. Furthermore, other researchers have
found that the main trace element in the ash fraction of rice husk was mentioned the ash fraction of biomass could lead to a reduction
SiO2, C, K, and P, and similar results were previously reported by in the surface area of the catalyst (Lee et al., 2010; Song and Guo,
Fernandes et al. (2016). This chemical species has shown to have 2012; Batista et al., 2018).
negative effects on bio-oil yield but catalyses the char formation
(Bulushev and Ross, 2011; Carrier et al., 2013; Carpenter 3.2.2 Products distribution and properties
et al., 2014). In general, for pyrolysis at moderate temperatures
(i.e., 400°C–600°C), the metallic species are retained in the
porous structure of char particles, which can then catalyse the
3.2 Effects of ash on products yield and thermal degradation of biopolymer (Nzihou et al., 2019). Mullen
properties and catalyst used in pyrolysis and Boateng (2013) showed that above 90% of K and Na that
originally present in biomass were transferred to biochar fraction
In this section, the effects of ash fraction on pyrolysis products during pyrolysis reaction at 550°C. Wang et al. (2021) found that ash
distribution and properties, and the performance of the catalyst in could reduce the surface area of the biomass particles by depositing
pyrolysis are discussed. In an experimental study conducted by on the surface of biomass particles at a prolonged reaction time. This
Yildiz et al. (2015), the authors stated that the ash fraction affected might limit the heat and mass transfer within the biomass particle
pyrolysis process by four pathways. The catalytic thermal cracking of (Naterer, 2021) and subsequently affects the biomass conversion
primary pyrolysis vapours is triggered, which leads to a significant rate and products distribution and properties. As illustrated in
increase in the production of gaseous products and biochar but Figure 3, during the process of biomass thermal degradation,
negatively affects the bio-oil yield and properties. It reduces the pyrolysis vapor is continuously released from the biomass,
molecular size of the molecules in the vapor phase owing to the followed by an appropriate condensation stage. The pyrolysis
promoted cracking of the pyrolysis vapor. Thirdly, those molecules vapor is consequently separated into bio-oil (condensable
with reduced size could enter and block the catalyst’s pores or fraction) and gases (non-condensable fraction). Therefore, it is
channels, and consequently reduce the catalytic activity. Also, critical to avoid the cracking of pyrolysis vapor inside the
catalyst poisoning takes places due to the interaction with ash pyrolysis reactor if high-quality yield of bio-oil is the major
particles. An overview of the effects of ash fraction on catalysis objective. However, alkali and alkaline earth metals (AAEMs)
used in the pyrolysis and products distribution and properties is have been reported to be responsible for catalytic cracking and
displayed in Figure 2. thermolysis reactions which usually take place in the pyrolysis
vapour. This intensely affects the products distribution and bio-
3.2.1 Lowering catalytic performance oil properties (DeGroot and Shafizadeh, 1984; Mohan et al., 2006;
Recently, catalysts have been applied either in-situ or Shimada et al., 2008; Patwardhan et al., 2010; Eom et al., 2012; Tan
downstream for the pyrolysis process to facilitate biomass et al., 2013). Patwardhan et al. (2010) observed that even an ash
degradation or the formation of target pyrolysis products, content of 0.5 wt% led to a variation in the yield of levoglucosan.
respectively (He et al., 2010; Dayton et al., 2015; Al-Salem et al., Specifically, the authors investigated the effect of ash composition on
2017). Past literature has suggested that the ash fraction levoglucosan yield. The influence was followed in the order of: K+ >

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FIGURE 3
Flowchart describing biomass pyrolysis (Gahane et al., 2022).

bio-oil when conducting pyrolysis at higher temperatures

(i.e., 510°C–550°C). This phenomenon could be caused by the
existence of K present in ash. This promoted cleavage of the
glycosidic bond of cellulose via depolymerization and
fragmentation, leading to the formation of low molecular weight
and water-soluble molecules such acetone, acetic acid, formic acid,
and hydroxy acetaldehyde. These molecules are also the commonly
identified chemicals in the bio-oil. This leads to the phase separation
of bio-oil. The researchers also stated that K could lead to an
increased formation of phenolics compounds in bio-oil but
decreasing concentration of furfurals in bio-oil (Nowakowski and
Jones, 2008). K could trigger a different decomposition pathway of
cellulose by decreasing anhydro sugars and furans but promoting
phenols, as evidenced by GC-MS analysis. In an experimental study
performed by Kim et al. (2021), it was observed that bio-oil yield
FIGURE 4
Effects of different types of metallic elements on pyrolysis decreased significantly from 45.7 wt% to 29.9 wt% as the amount of
products yield. ash content increased. The study also concluded that the
concentration of phenolic monomers increased from 2.8 mg/g to
20.2 mg/g in the bio-oil.
Na+> Ca2+> Mg2+. Among the studied ash elements, K+ was found to Unlike the yield of bio-oil, the influence of ash on the yield of
show the strongest impact on pyrolysis of cellulose and levoglucosan biochar is contradictory. Yildiz et al. (2015) observed a reduction in
yield. Richardson et al. (2015) compared different types of metallic the biochar yield. However, Shimada et al. (2008) reported an
elements (e.g., Ce, Mn, Fe, Co, Ni, Cu, and Zn) on pyrolysis product improvement in the yield of biochar, which could be due to the
distribution obtained from eucalyptus wood at 500 °C. The results promoted effect of alkaline earth metals of ash, especially those
are shown in Figure 4. It was observed that all the metallic elements existing in the form of chlorides such as MgCl2 and CaCl2. Wang
led to a reduced yield of bio-oil compared to metallic elements-free et al. (2021) concluded that biochar yield decreased because of ash
biomass, while no significant difference was observed among seven melting at higher pyrolysis temperatures. Further research is still
metallic elements with respect to bio-oil yield. needed to clearly elucidate the effects of ash on biochar yield and
Patwardhan et al. (2010a) and Ronsse et al. (2012), reported a properties during the pyrolysis treatment. A table summarizing the
lower yield of levoglucosan was found in the presence of ash. Yildiz major influences of ash fraction on pyrolysis of biomass is displayed
et al. (2015) observed that the presence of ash resulted in a decrease in Table 10.
in the yield of biochar and bio-oil by ~ 2 wt% for each product,
whereas the non-condensable gas yields increased by 4 wt%. This
decrease in the bio-oil yield could be attributed to vapour cracking 4 Ash related problems
caused by ash. Also, it was found that ash promoted the production
of H2 and CH4 for both non-catalytic and catalytic pyrolysis. This Ash related problems are one of the main issues leading to the
trend indicated that the ash fraction of biomass facilitates the undesirable downtime of plant, as they cause instability within the
gasification of pyrolysis vapor to form H2 and CH4. Another operation (Sommersacher et al., 2013; Niu et al., 2019). In terms of
study by Gómez et al. (2018) reported, the phase separation of the ash composition, the presence of K in biomass has been reported

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TABLE 10 Summary of main ash effects on biomass pyrolysis.

Main effects of biomass ash in pyrolysis Causes

1) Lowers the catalytic activity for in-situ catalytic pyrolysis Ash deposit onto catalyst surface and/or block the porous structure of catalyst

Reduce the active sites of catalyst

Catalyst deactivation

2) Product distribution and properties Trigger craking of primary pyrolysis vapor and hence lowers bio-oil yield

Promote the formation of small and water-soluble molecules and phase separation of bio-oil

Contradicting results for ash’s effect on biochar yield

FIGURE 5
Schematic diagram to describe the main stages of ash formation upon biomass thermal degradation (Niu et al., 2016).

to be main cause of the ash related problems. Upon thermal generating heat, i.e., formation mechanisms of bottom ash and
degradation, K and other inorganics (e.g., P, Cl, Fe, Ca, and S) fly ash, the associated challenges of bottom ash and fly ash, and
present in biomass can be released into the vapor phase and the possible solution to reduce or limit bottom ash and fly ash (Tan
subsequently condensed and deposited on the surface of process et al., 2013; Vassilev and Vassileva, 2016; Kleinhans et al., 2018;
equipment to form solid ash. Another problematic ash composition Abioye et al., 2024). In the following sections, the formation
is Cl of biomass. Biomass with a high concentration of Cl could mechanisms of each ash related challenge include slagging,
result in the formation of hydroxides and carbonates at around sintering, fouling, corrosion, and beg agglomeration. It should be
800°C in the thermal conversion. This phenomenon could be highlighted that past literature lacks discussion regarding how ash-
attributed to the reaction between HCl and high volatile metals associated problems affect the pyrolysis product yield and
in the biomass at higher temperatures (Abioye et al., 2024). distribution, which could be one of the future research directions
The following figure illustrates the main stages involved in the in this field.
ash formation and transformation during biomass thermal
degradation. As indicated in Figure 5, upon thermal degradation,
the volatile fraction containing metallic compounds is first released 4.1 Slagging and sintering
by devolatilization, and then the solid char particles are formed. A
fraction of the alkali and alkaline-earth metals and volatile trace At operating temperatures above 1,000°C, the ash fraction of
elements are diffused out of the char particles. Among them, some biomass turns into molten ash which is then lumped or aggregated
metallic elements like K and Na, particularly K, result in a series of together. The phenomena of the formation of molten ash lumps are
ash-associated problems through nucleation, condensation, and called slagging (Bryers, 1986; Rong et al., 2017). Slagging is also
reaction such as slagging, sintering, fouling, beg agglomeration, related to sintering, which forms molten ash and, has glassy
and corrosion (Niu et al., 2016). properties during cooling (Bryers, 1986). In a typical furnace or
Past articles have limited their discussion about the ash effects boiler, slag could appear on the wall of furnace and superheater,
on thermal degradation of biomass in a furnace or boiler for which is primarily caused by the high Cl and K content. Specifically,

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FIGURE 6
Schematic diagram illustrating the slagging formation in a biomass fired furnace/boiler (Zhu et al., 2014) (Licence: CC BY 3.0 DEED).

the presence of a high concentration of Cl in the biomass could gas in the boiler. This further causes issues relating to the deposit
trigger the release of K from the biomass, and then results in the formation (Zhang, 2013). Míguez et al. (2021) reported that the ash
formation of KCl. The resulting KCl can further condense and fouling/deposition occurred in four steps: i) solid bed freed of
deposit on the surface of processing equipment by a series of inorganic materials; ii) the formation of aerosol; iii) the free
mechanisms like diffusion, electrophoresis, thermophoresis, inorganic compounds tend to travel to the surface of the process
inertial impaction, and gravity. The KCl can also bond slag and equipment; and iv) finally, the ash is deposited and accumulated on
later with the tube behaving like an adhesive. A schematic diagram the surface.
of the slagging formation is depicted in Figure 6 (Zhu et al., 2014).
Possible strategies can be applied to reduce slagging is adding
additives like kaolin (Davidsson et al., 2008) and biomass 4.3 Bed agglomeration
pretreatment via water washing and acid pickling (Werkelin
et al., 2010). The fundamental chemistry in agglomeration is the formation of
alkali silicate eutectics. The eutectic system is defined as a
homogenous mixture that has a melting point lower than those
4.2 Fouling of the components of the system. This occurs from the reaction
between SiO2 in the bed materials (silica sand is a very common bed
Fouling refers to the deposition of non-melting ash. A portion of material used in the fluidized bed reactor) or ash (as earlier
ash composition has a melting point that is higher than the mentioned, SiO2 can be identified in the ash fraction of certain
temperature at which fouling begins. This, the portion of ash type of biomass) with alkali metal oxides like K2O or Na2O. The
would turn into molten ash to cause slagging and sintering (Shao associated chemical reaction is K2O+ nSiO2 → K2O · nSiO2 (where,
et al., 2012; Rong et al., 2017). Fouling could occur when ash is n varies from 1 to 4) (Morris et al., 2018). The temperature at which
deposited in the convection section of the boiler, which consists of agglomeration occurs depends on the amount of biomass ash, but
the superheater, reheater tube, economizer, and air heater. With typically, the temperature should be higher than 800°C (T.M.
proper removal of ash deposit, it might lead to a decrease in the Nussbaumer, 2001; T; Nussbaumer et al., 2008). The images
furnace heat absorption but an increase in the temperature of flue describing the agglomeration of bed particles during thermal

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FIGURE 7
Images of bed agglomeration due to thermal degradation of high alkali biomass: (A) small agglomerate of bed particles (500–200 μm); (B) big
agglomerate of large bed particles (4 cm) (Kittivech and Fukuda, 2020) (Licence: CC BY 4.0 DEED).

FIGURE 8
Coating-triggered mechanism for agglomeration (Morris et al., 2018).

degradation of high alkali biomass are shown in Figure 7 (Kittivech could result from: i) the small ash particles that attach to the bed
and Fukuda, 2020). particles, ii) the alkali elements present in ash can condense, and iii)
In recent years, the mechanisms for forming bed agglomeration the interaction between these alkali elements and the surface of bed
caused by biomass ash include coating-triggered agglomeration and particles. Afterwards, the sintering occurs at this coating and further
melt-triggered agglomeration. For the first coating-triggered homogenizes and strengths the coating. Finally, the severity of the
agglomeration mechanism, Ohman et al. (2000) found that ash is agglomeration process is primarily determined by the temperature-
initially deposited on the bed particles and a coating is created. This driven adhesive force, which is controlled by the melting of this

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TABLE 11 Summary of deashing strategies that can be applied to biomass (Dhawan and Sharma, 2019).

Single acid washing HCl, HF, HNO3, HI, and H2SO4

Stepwise acid washing HF-HCl, HCl-HNO3, HF-HNO3, HF-FeNO3

Oxidizing agents and chelating agents H2O2, K2Cr2O7, NaOCl, Fe2(SO4)3, EDTA, pyroligneous acid

Alkali treatments NaOH, KOH, Na2CO3, CaO, and Ca(OH)2

Alkali-acid leaching NaOH-HF, NaOH-HCl, NaOH-H2SO4, KOH-HCl, NaOH-HCl-H2SO4

coating. Figure 8 describes this coating-triggered agglomeration include the fouling index, alkali index, slagging index and alkali ratio
mechanism for two different ash scenarios. (Abioye et al., 2024). Different de-ashing strategies have been widely
For the second melt-triggered agglomeration mechanism, developed and adopted for coal, and have the potential to be used for
Olofsson et al. (2002) reported the temperature of some localized biomass, as summarized in Table 11 (Dhawan and Sharma, 2019).
hot spot is above 1,000°C, which is higher than the operating
temperature of ~670°C–870°C. This results in the formation of an
alkali silicate melt phase that could be originally obtained from both 5.1 Biological processes
biomass ash and bed particle. The largest agglomerate (i.e., size of
50–60 mm) was exhibited as a glass-like form, suggesting prolonged Biological processes have been frequently used to remove ash
exposure to a high temperature. from biomass. Amongst those techniques, bioleaching has been the
most successful and most regularly used one. This is due to the lower
utilization of chemicals and other resources (Krebs et al., 1997; Wu
4.4 Corrosion and Ting, 2006). In bioleaching, conversion takes place at a
microbial level, to convert solid compounds into soluble
Corrosion refers to the phenomena of accelerated chemicals, easing the following extraction and recovery stages
decomposition, in which ash particles containing compounds (Krebs et al., 1997). The microorganisms involved in bioleaching
such as K2CO3, K2SO4, SiO2, KCl, NaCl and CaSO4 settle on the are responsible for the formation of organic and inorganic acids,
surface of process equipment (Konist, 2023; G; Song et al., 2018; such as H2SO4, citric acid and gluconic acid (Krebs et al., 1997).
Sanusi et al., 2022; Obot, 2021; H; Chen et al., 2017). Generally, the Aspergillus niger is the most widely used microorganism (Bosshard
deposit of alkali chloride onto the superheater tubes results in et al., 1996; Q; Wang et al., 2009).
corrosion towards a boiler when burning biomass and other
organic waste. In addition to the corrosion issue, it can also
reduce the final steam temperature and hence the boiler 5.2 Leaching
efficiency (Enestam et al., 2013). To limit the corrosion challenge
associated with the alkali chlorides, particularly at high For the detaching of intrinsic inorganic species, such as alkali, Cl
temperatures, Cr has been added to the Fe- and Ni-based alloys, and S from biomass, leaching is widely used (Tonn et al., 2012; Niu
during which protective oxide layers containing Cr2O3 can et al., 2016). Water and acid leaching are the most popular solvents
significantly limit the corrosion caused by alkali chlorides. These used in the leaching as 90% of alkali metals and all alkali chlorides
protective oxide layers can be broken down due to the interaction are water and acid soluble (Wei et al., 2019). This method is
with gaseous KCl and NaCl to form K2CrO4 and Na2CrO4 (Li et al., commonly used, especially when ash deposition/fouling is a
2007). Chemical corrosion can occur if the ash fraction encounters problem in the process (Q. Guo et al., 2020).
moisture. Galvanic corrosion can be observed when metal alloys According to Gudka et al. (2016), woody biomass wood can be
react with ash. Furthermore, the phenomena of erosion-corrosion leached using water as the leaching agent. It was seen that hot water
are found when ash damages the oxide layers on the surface of washing led to an increase in the ash melting temperatures, i.e., an
process machinery (Míguez et al., 2021; Abioye et al., 2024). increase from 820°C to 1,400°C. The variations in the concentration
of ash composition were detected. For example, Mg dropped from
around 5 wt% to 60 wt%, but Na increased from 10 wt% to 90 wt%
5 Deashing techniques and S increased from 0 wt% to 90 wt%. Another study performed by
Carrillo et al. (2014) on sorghum biomass showed that water
High ash containing biomass demonstrates several challenges leaching resulted in the declination of ash content of around 20%
when applying it as a biofuel owing to the increase in the capital and and while lignin increased up to 53%. A 0.5 M nitric acid was utilized
operating costs (Hess et al., 2019). Biological approaches, leaching, by Feng et al. (2014) to remove ash from woody biomass (i.e., white
and adding additives have been identified as the most effective pine bark, white spruce bark, and white birch bark) at room
deashing treatment methods. The selection of an appropriate temperature for 8 h under stirring and a biomass/acid ratio of 1:
deashing strategy is dependent on the composition and yield of 20 (g/mL). The results indicated that acid leaching was effective in
biomass ash, the type of biomass, environment and other factors (L. removing K from all studied biomass and a reduction in the Ca
Wang et al., 2012; Boström et al., 2012). In general, the major factors concentration was observed in the white spruce and
that are taken into consideration for selecting the deashing methods white birch bark.

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Javed (2020) applied CH3COOH, HCl, and H2SO4 to pretreat Al2 O3 · 2SiO2 + M2 O + 2SiO2 → 2MAlSi2 O6 (9)
wheat straw to remove the ash fraction. It was found that acid
leaching pre-treatment showed a significant impact on the thermal
degradation properties of pre-treated what straw and an increase in
the energy content and C content of pre-treated what straw. Jiang
6 Conclusion
et al. (2013) also found that the physicochemical properties and
This review article discussed the ash content and composition
pyrolysis characteristics of biomass can be largely dependent on the
identified in the most common types of biomass in pyrolysis
deashing pre-treatment towards biomass. Specifically, after deashing
including agricultural and forestry waste, municipal solid waste,
pre-treatment, the functional groups present at the surface of
and aquatic biomass. The effects of ash content and composition on
biomass were removed, and the emission peak of some volatile
the biomass pyrolysis with respect to the catalytic performance in
fraction of pre-treated biomass was shifted. The authors reported
the catalytic pyrolysis process and products yield and properties
that alkali and alkaline earth metals demonstrated a catalytic effect
were reviewed. Besides, various technical challenges (e.g., slagging,
on biomass pyrolysis. Hess et al. (2019) conducted a techno-
sintering, fouling, bed agglomeration, and corrosion) caused by the
economic analysis for ash removal from high ash containing
ash fraction in the thermal conversion of biomass were reviewed,
microalgae. The results found that an increase in the ash content
along with a description of the possible deashing methods of
from 0 wt% to 70 wt% led to a doubling increase in the downstream
biological processes, leaching using water or acid, and additives
capital cost.
addition. Overall, this review has offered new insights and
understanding of the influence of ash content and composition
on biomass pyrolysis, laying a useful groundwork for future research
5.3 Additives in this field.

Additives are usually added to the biomass ash with an aim of

enhancing the melting temperature of ash. It is known that the
additives have an impact on ash chemistry and hence the physical
Author contributions
properties such as the melting point (Konist, 2023; L; Wang et al.,
LP: Writing–original draft. YH: Writing–review and editing.
2014; Míguez et al., 2021). Some types of additives are aluminium
GN: Writing–review and editing.
silicate based, S-based, and P-based (G. Wang et al., 2022).
Additives are usually the best solution to deal with ash related
problems as they have been shown to improve ash fusion
characteristics and sequester the species, which cause problems
Funding
during biomass thermal conversion (Roberts et al., 2019). Miccio
The author(s) declare that financial support was received for the
et al. (2019) added fireclay and quartzite to the olive husk. The
research, authorship, and/or publication of this article. Natural
results showed that no bed agglomeration was occurred when using
Sciences and Engineering Research Council of Canada (NSERC).
fireclay as the additive even at a prolonged reaction time. Another
study performed by Batir et al. (2019), using kaolin as an additive,
was able to sequester the formation of KCl and KOH. Two species
could lead to problems in the thermal conversion of biomass, owing
Acknowledgments
to the interaction with kaolin to form potassium alumina silicates.
The authors are grateful for the financial support of Natural
To date, kaolin has been found to be the most effective additive to
Sciences and Engineering Research Council of Canada (NSERC),
remove ash from biomass, particularly KCl. The active chemical
i.e., RGPIN-2022-03203, Development of next-generation
present in kaolin is kaolinite, Al2Si2O5(OH)4. It is thermally
technologies to produce clean and renewable transportation fuels.
decomposed at 450°C–600°C to form meta-kaolinite (a mixture of
alumina and silica and is shown as the amorphous structure) and
water is also released. The resulting meta-kaolinite can react with the
K species present in biomass ash to form potassium aluminium
Conflict of interest
silicates possessing a high melting temperature. The associated
The authors declare that the research was conducted in the
chemical reactions are shown below, Eqs 1–9 (Abioye et al., 2024):
absence of any commercial or financial relationships that could be
construed as a potential conflict of interest.
Al2 Si2 O5 (OH)4 → Al2 O3 · 2SiO2 + 2H2 O (1)
Al2 O3 · 2SiO2 + 2MCl + 2H2 O → 2MAlSiO4 + 2HCl (2)
Al2 O3 · 2SiO2 + M2 SO4 → 2MAlSiO4 + SO3 (3) Publisher’s note
Al2 O3 · 2SiO2 + 2MOH → 2MAlSiO4 + H2 O (4)
All claims expressed in this article are solely those of the authors
Al2 O3 · 2SiO2 + M2 O → 2MAlSiO4 (5)
and do not necessarily represent those of their affiliated organizations,
Al2 O3 · 2SiO2 + 2MCl + 2SiO2 + H2 O → 2MAlSi2 O6 + 2HCl (6)
or those of the publisher, the editors and the reviewers. Any product
Al2 O3 · 2SiO2 + M2 SO4 + 2SiO2 → 2MAlSi2 O6 + SO3 (7) that may be evaluated in this article, or claim that may be made by its
Al2 O3 · 2SiO2 + 2MOH + 2SiO2 → 2MAlSi2 O6 + H2 O (8) manufacturer, is not guaranteed or endorsed by the publisher.

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Glossary P Phosphorus

AAEMs Alkali and alkaline earth metals Pb Lead

Al Aluminum P2O5 Phosphorus pentoxide

Al2O3 Aluminum oxide Rb Rubidium

Ba Barium Ra Radium

Be Beryllium Si Silicon

Ca Calcium SiO2 Silicon dioxide

Cu Copper Sr Strontium

Cr Chromium SO3 Sulphur trioxide

Cd Cadmium Ti Titanium

CaO Calcium oxide TiO2 Titanium oxide

Cs Cesium V Vanadium

CH4 Methane Zn Zinc

CaCl2 Calcium chloride

CaSO4 Calcium sulfate

Cl Chlorine

Fe Iron

Fr Francium

Fe2O3 Iron oxide

GHG Greenhouse gas

GC-MS Gas chromatography-mass spectrometry

H Hydrogen

He Helium

Hg Mercury

K Potassium

K2O Potassium oxide

K2CO3 Potassium carbonate

K2SO4 Potassium sulphate

KCl Potassium chloride

KOH Potassium hydroxide

Li Lithium

Mg Magnesium

Mo Molybdenum

MgO Magnesium oxide

MSW Municipal solid waste

MgCl2 Magnesium chloride

NOx Nitrogen oxides

Ni Nickle

Na2O Sodium oxide

Na Sodium

NaCl Sodium chloride

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