Waste Management 79 (2018) 667–688

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

A review on the demineralisation of pre- and post-pyrolysis biomass and

tyre wastes
I. Iraola-Arregui a,⇑, P. Van Der Gryp b, J.F. Görgens a
a
Process Engineering Department, Stellenbosch University, Private Bag X1, Matieland 7602, South Africa
b
School of Chemical and Minerals Engineering, North-West University, Potchefstroom 2520, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Pyrolysis is an attractive technology to convert low-cost carbonaceous waste materials into fuels, energy
Received 13 March 2018 and other value added products goods. During pyrolysis, the inorganic minerals present in the feedstock
Revised 19 July 2018 can cause problems to the equipment and give side reactions. Besides, the minerals present in the chars
Accepted 15 August 2018
can hinder their possible applications. Therefore, it seems necessary to eliminate said contaminants in
Available online 24 August 2018
order to valorise the aforementioned goods. Demineralisation is a process widely used for purifying
materials that are contaminated with inorganic matter. Although this technique is commonly used with
Keywords:
waste materials that will undergo pyrolysis, or the products obtained from it, the studies analysing this
Demineralisation
Valorisation
practise are rather scattered.
Pyrolysis char The aim of this paper was to compile and review the current literature concerning the demineralisation
Lignocellulosic biowaste of carbonaceous waste (tyres and lignocellulosic biomass) materials. The chemistry involved, feedstock
Waste tyres type and the effect of performing the purifying step before or after pyrolysis were addressed in this work.
The review revealed that biomass samples should be demineralised before pyrolysis in order to affect
not only the char but also the bio-oil quality. Depending on the form in which the minerals are linked to
the structure, the solvent chosen will vary (from water to strong acids). However, water is the most pop-
ular option due to its price and easy disposal. In tyres, demineralisation should be performed after pyrol-
ysis using strong acid and subsequently base. Due to the crosslinked chemical structure, rubber is highly
resistant to chemicals thus the pre-treatment has to be avoided.
Ó 2018 Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
2. Demineralisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
2.1. Conditions of demineralisation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 669
2.1.1. Surface area. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.2. Particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.3. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.4. Contact time and leaching rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.5. Operation mode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.6. Agitation/mixing/mass transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.7. Method of operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.1.8. Solvent and pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.2. Chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 670
2.2.1. Water. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
2.2.2. Acidic. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
2.2.3. Alkaline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672
3. Demineralisation of (lignocellulosic) biomass waste and its pyrolysis char. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672

⇑ Corresponding author.
E-mail addresses: itziar@sun.ac.za (I. Iraola-Arregui), percy.vandergryp@nwu.ac.za (P. Van Der Gryp), jgorgens@sun.ac.za (J.F. Görgens).

https://doi.org/10.1016/j.wasman.2018.08.034
0956-053X/Ó 2018 Published by Elsevier Ltd.
668 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

3.1. Mineral content of lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 672

3.2. Demineralisation of lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
4. Demineralisation of waste tyres and its pyrolysis char . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
4.1. Metal content of waste tyres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
4.2. Demineralisation of waste tyres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 681
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 685

1. Introduction
We live in a consumer society where due to the fast way of life,
products have a very short service life. The world population is
increasing together with the lifestyle development and urbanisa-
tion. Urban area dwellers produce higher waste levels than rural
area inhabitants, who tend to reuse and recycle more (Hoornweg
and Perinaz, 2012). Therefore, the waste production rate is increas-
ing and will continue doing so in the future.
As a case in point, due to the high amount of cars required
nowadays, >1.5 billion tyres are produced per year in the world
(ETRMA, 2014; JATMA, 2016; RMA, 2015), which sooner or later
they will become a waste (Karakurt, 2014). Although tyres do not
present a danger to the health on their own, the inappropriate dis-
posal and mismanagement of big amounts can cause serious prob-
lems not only to the environment but also to human beings.
Tyres are thermoset materials that cannot be melted and repro-
cessed and are infusible, insoluble and have very high strength and
resistance to abrasion, heat, chemicals and degradation. These
properties make waste tyres highly difficult to recycle. Therefore,
the handling of used tyres is gaining a lot of attention (Torretta
et al., 2015). Due to the waste management legislation becoming
more and more severe, landfilling of waste tyres is getting banned
in numerous countries (EEA, 2009). There are several alternatives
for tyre recycling such as reclaiming and retreading, but they have
limited applicability. Recycling cannot address the full problem, as
it is a very high cost process resulting in products with question-
able characteristics (Antoniou et al., 2014).
Feeding a society that does not stop growing is also a challenge
from the point of view of waste as crop residues are the main
source of inedible phytomass (Smil, 1999).
Biomass is a non-fossil biogenic solid product generated by nat-
ural and anthropogenic processes. Biomass varieties can be classi-
fied according to their biological diversity, source and origin in:
wood and woody biomass, herbaceous and agricultural, aquatic,
animal and human wastes, contaminated biomass and industrial
wastes (semi-biomass) and mixtures (Vassilev et al., 2010). Waste
biomass is derived from several processing methods applied to
obtain biomass products (Easterly and Burnham, 1996). Biomass
wastes have been used all over the world since the old times in
several applications, such as farmyard manure, basketing, mat
making, and so on. In modern times, the development of synthetic
fibres, chemical fertilisers, etc. have replaced the use of this residue
(Prasad and Power, 1991), increasing the amount of biomass left in
the fields.
Aside from the waste disposal matter, an additional global con-
cern is the energy crisis. The energy content of waste can be recov-
ered by means of either biological processes (e.g. anaerobic
digestion) or thermo-chemical processes (combustion, pyrolysis
or gasification). Owing to its simplicity and environmental bene-
fits, pyrolysis is proving to be a promising form of waste recycling,
with the production of potentially valuable products (Collard and
Blin, 2014; Danon et al., 2015b). Pyrolysis is an attractive solution
for reducing waste volume, to conserve landfill space while allow-
ing energy recovery. It consist on the thermal decomposition of a
material in the absence of oxygen (inert atmosphere) to produce
gas (non-condensable low-molecular-volatiles including C1-C6
hydrocarbons, hydrogen, CO, CO2 etc.), oil (hydrocarbon liquid con-
taining water) and char (pyrolytic solid) fractions (Wampler,
1995). Yields and composition of pyrolysis products are affected
by the conversion conditions and the chemico-physical properties
of the raw material, type of reactor, residence time, etc. (Williams,
2013). For example, fast pyrolysis (high heating rates and short
vapour residence times) is preferred to maximise the oil yield
(Bridgwater, 2012a), opposed to slow pyrolysis which enhances
char production (Hodgson et al., 2016).
For pyrolysis to be an attractive process from a commercial
point of view, all the products obtained should have a market.
The gas fraction can be used as a fuel in industrial combustion pro-
cesses. For instance, it can be used to partially fulfil the energy
requirements of the pyrolysis process itself. The liquid fraction
can also be used as fuel (due to its high calorific value) or as a
potential source for valuable chemical such as: benzene, toluene,
xylene or limonene (Antoniou and Zabaniotou, 2013). These chem-
icals can be used as precursors for the manufacture of chemicals
with more complex structure, as solvents in laboratory and indus-
trial applications or in the case of limonene even as cleaning or fra-
grance agent (Danon et al., 2015b). The gas and liquid fractions
have a potential market however, the solid product has to be
upgraded and valorised so it can be used for more demanding
applications, for example as reinforcing filler or activated carbon.
In its raw form, char consist of a carbon matrix containing most
of the inorganic compounds present in the raw material (ash)
and some condensed organic by-products generated during sec-
ondary reactions in the reactor.
There are different waste materials; thermoplastics, tyres and
biomass that are appropriate for undergoing pyrolysis, due to their
combustible properties and high volatile matter content and
because they are rich in long polymer chains that can be easily
cracked into smaller molecules (hydrocarbon gas and pyrolysis
oil) (Bernardo, 2011).
Thermoplastics pyrolysis char yields are so low that so far no
work has been published (according to our knowledge) on polymer
demineralisation, thus it will not be further analysed in this
review.
During pyrolysis of waste tyres, the chemical additives in the
sample evaporate first and then rubber fraction devolatilises by
depolymerisation/condensation, leaving only the carbon black
and minerals (Danon et al., 2015a). The gas and TDO (tyre derived
oil) originate from the volatiles fraction emerging from the process,
while the char consists of the solid fraction (Martinez et al., 2013).
The solid obtained (commonly known as pyrolytic char) is a
heterogeneous, porous structure with a low surface area, mainly
made of carbon black added during processing. The char is much
coarser than the carbon black added to the tyre during processing,
due to the fact that volatile products formed during pyrolysis tend
 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
to get absorbed on the surface of the char as carbonaceous materi-
als increasing its size (Senneca et al., 2000). Char consists of many
undesired elements [<15 wt% is ash, resulting from the additives
used for tyres manufacturing (Helleur et al., 2001)] that reduce
its commercial value. Tyre derived char must be upgraded by
removing contaminants such as TDO, sulphur, metals and silicon,
from the carbon structure (Lee et al., 1999), so it can be used in
more demanding applications. For example, the high ash, sulphur
and zinc concentrations of the raw char impedes its utilisation as
carbon black in the conservative tyre industry.
Biomass is an abundant renewable carbon source that might be
used for bio-based energy, chemicals and materials production,
due to its potential to alleviate the emission of greenhouse gases
(Patel et al., 2016). Regarding biomass wastes, the focus will be
on lignocellulose materials including: grasses and woody materi-
als, agricultural wastes and forestry residues. The demand for lig-
nocellulosic materials is increasing rapidly due to an increasing
range of applications in renewable energy, chemicals and materials
production that are relatively unaffected by feedstock prices.
Besides that, the use of biomass as an alternative energy source
also reduces the poverty in emerging and developing countries act-
ing as a stimulus for economic growth (Bildirici, 2013).
The minerals present in the raw biomass during pyrolysis can
cause operational problems linked to the slagging of metals and
clogging of the equipment (Bazargan et al., 2015), poisoning and
deactivation of catalyst used in pyrolysis (Yildiz et al., 2015) and
reduce the quality of the products.
It is evident that one of the main challenges of the 21st century
is the generation of energy and valuable products from waste,
while minimising the use of natural resources. In this regard, the
valorisation of carbonaceous solid waste for the production of
higher valued goods, seem to fit perfectly in the objective men-
tioned before. However, the presence of residual elements in char
products represents limitations in further applications of these
materials (Asadieraghi and Wan Daud, 2014). The inorganic matter
present in the raw material can modify the activity and selectivity
of both primary and secondary decomposition reactions that occur
during pyrolysis (Di Blasi et al., 2009), hence the possibility of
changing the product yield and composition by pretreating the
material to be pyrolised (Aho et al., 2013). The demineralisation
of the feedstock can also help reducing the corrosion and formation
of toxic species during thermal processes (Yu et al., 2014).
The inorganic species in the feedstock primarily end up in the
solid fraction, making the char highly polluted and can affect their
possible applications; for instance, in the case of using char as acti-
vated carbon sorbent precursors, minerals can affect the porosity
of the char, as they might block the access of the activating agent
Fig. 1. Schematic diagram of demineralisation mechanism.
669
into the internal pores. If the char is intended to be used as a car-
bon black substitute, the high amount of minerals can hinder its
use (Chaala et al., 1996). Demineralisation through leaching is
the most popular technique used regarding the complete removal
or minimisation of the quantity of metals present in the chars and
raw materials.
In this context, demineralisation performed on waste tyres and
lignocellulosic biowaste before and after pyrolysis is the focus of
this comprehensive review. Demineralisation is defined, followed
by the conditions and parameters that can be modified (paying
special attention to the chemistry and solvent choice) for adjusting
the procedure to the material to be treated. The literature regard-
ing the demineralisation of waste materials (biomass and tyres)
and its effect on the final products are exhaustively reviewed and
the convenience of performing demineralisation on waste materi-
als before or after pyrolysis is discussed.
2. Demineralisation
Demineralisation of solid materials is performed via leaching of
the undesired phase. Leaching is a type of liquid-solid extraction
whereby a soluble fraction (leachant or solute) is partially or
totally removed from an insoluble, permeable solid phase by use
of a liquid lixiviant (Richardson et al., 2002). First, the solvent
has to be brought into contact with the surface of the solid phase.
Once there is intimate interaction, the solvent invades the solid
and penetrates the pores through diffusion, dissolving the lea-
chant. Finally, the solute will diffuse to the surface so it is trans-
ferred to the bulk solution, resulting in separation of the
components originally in the solid (Newton, 1959). A schematic
diagram of the demineralisation procedure is given in Fig. 1.
This technique of extracting a solid using a solvent has been
used since ancient times and it is known by many names: lixivia-
tion, leaching, solid-liquid extraction, percolation, etc. It has been
widely used for the extraction of minerals from their ores
(hydrometallurgy) or to obtain valuable chemicals present in
plants. It can also occur naturally due to the rain, causing the dis-
placement of wastes towards the rivers and oceans (Yadav and
Yadav, 2014).
The material to be treated will influence the conditions applied
for demineralisation since it will depend on the surface chemistry,
roughness, volume, soluble solid distribution, etc.
2.1. Conditions of demineralisation
The major process parameters for demineralisation that must
be selected/determined, to obtain the most cost and energy
670 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
efficient method, are discussed below. These parameters are not
straight-forward to establish, as there may be several opposing fac-
tors (Sharma, 2007).
2.1.1. Surface area
The higher the surface area and the easier the accessibility to
the pollutants via high porosity, the more favoured the demineral-
isation will be. The surface area of the feedstock is determined by
the particles size and shape.
For example, penetrating tyre rubber surface can be practically
impossible due to its chemical structure and physical properties
(Martinez et al., 2013). The release of volatile organic components,
during pyrolysis, increases the development of a porosity network
and surface area of char making it more easily accessible to sol-
vents. In the case of tyre, the values reported in literature range
from 0.059 to 3.5 m2/g (Selbes, 2009) in the case of crumb (rubber
before pyrolysis) and 56.5–85 m2/g in the case of char (after pyrol-
ysis) (Shah et al., 2006; Ucar et al., 2005). Regarding biomass, raw
material before undergoing pyrolysis ranges from 1.188
105 of
empty fruit bunches to 1.46 m2/g of waste wood, and 1.6 m2/g of
sawdust (pyrolysed at 500 °C) (Messina et al., 2016) to 299 m2/g
of coconut coir (pyrolysed at 600 °C) (Shen et al., 2012). The con-
centration of ash is also higher in the char (Hadi et al., 2016) and
more reachable to be removed.
2.1.2. Particle size
Smaller particle size is generally desired due to an increase in
the contact area between the solid and the liquid, thus increasing
the mass transfer rate. In addition, the distance that the solute
must travel through the interior of the solid is smaller, which
assists with the leaching. Crushing and grinding some solid parti-
cles can make the soluble portion more accessible to the solvent
accelerating the leaching (Treybal, 1955). However, for wastes
such as tyres, the processing cost of generating fine particles is pro-
hibitive, as it may require grinding to be done under cryogenic con-
ditions (Karger-Kocsis et al., 2013). In biomass, the smaller
fractions contain higher ash content (Arvelakis and Koukios,
2002) making the larger fraction a better choice for further upgrad-
ing. In any case, extremely small particles are not desired as they
entail problems in the separation steps.
2.1.3. Temperature
In general, it is desirable to use as high leaching temperature as
possible, due to the higher solubility of the solute in the solvent,
thus achieving higher solute concentrations in the liquid product.
The lower viscosity of the lixiviant at high temperature, also
favours mass transfer. The temperature chosen will depend on
the material to be treated (Yu et al., 2014). When natural products
are leached, too high temperatures can lead to the deterioration of
the solid. Therefore, most of the pre-treatment of lignocellulosic
biomass is performed at room temperature (Mourant et al., 2011).
The increased energy requirements and processing costs associ-
ated with higher temperatures should also be taken into account to
decide the most suitable value.
2.1.4. Contact time and leaching rate
Leachability is a function of time and it typically changes in the
long term. Time depends on the reaction kinetics. Generally, at the
beginning, leaching is very fast but after a while, the leaching rate
decreases. There are two main reasons for the high initial rate of
dissolution; the concentration of the solvent is usually at maxi-
mum and the greatest possible surface of soluble mineral is
exposed. As dissolution proceeds, the rate slows down due to:
the decrease in contact surface because most minerals will already
be dissolved and the depletion of the solvent strength (Newton,
1959).
2.1.5. Operation mode
The choice will depend on the stage of the study; batch is the
best option for preliminary lab scale work since it is cheaper and
more convenient (Newton, 1959), while continuous processing is
the best at industrial scale (Green and Perry, 2008). There is plenty
of work published on demineralisation in small-scale (Deng et al.,
2013; Liu and Bi, 2011; Yu et al., 2014), as the design of a leaching
process is based on laboratory results. Nevertheless, when these
results have to be scaled up, this has to be carried out empirically.
2.1.6. Agitation/mixing/mass transfer
There are mainly two methods of contacting the solid and liquid
phases: percolation and dispersing the solid into a liquid phase and
then separating from it (Green and Perry, 2008). The design of the
reactors changes from column to horizontal and it also varies the
method of agitating from impellers such as, turbines, paddles or
propellers to air agitation such as, Pachuca tanks or autoclaves.
Whatever the contact method, leaching will be favoured by
increasing the surface per unit volume of solid to be extracted.
Stirring of the solvent is important as it increases the transfer of
material from the surface of the particles to the mass of the
solution.
2.1.7. Method of operation
If leaching equipment is to be fully defined four categories must
be assigned: operating cycles (Liaw and Wu, 2013) (batch, semi-
continuous or continuous), method of contacting (Wadsworth
and Schwartzberg, 1987) (percolation or solid dispersion), direc-
tion of streams (King, 1980) (concurrent, countercurrent or hybrid
flow) and by staging (single stage or multiple stages). Taking all
these factors into account there are several types of reactors that
are based on different geometries and features: Bollman type, Ken-
nedy, Bonotto, Rotocell, Screw-conveyor extractors, column type,
etc. (Green and Perry, 2008). These reactors are mainly used in
industrial scale processes such as metals extraction from ores by
hydrometallurgy (Newton, 1959). In laboratory experiments the
majority of tests are performed using more simplistic approaches
like a single stage batch reactor, consisting of a temperature con-
trolled vessel with or without stirring (Chaala et al., 1996;
Ravichandran et al., 2013).
2.1.8. Solvent and pH
Leaching can be performed using many different solvents at
several pH values. In the case of the organic volatiles (hydrophobic
aromatic compounds) trapped on the pores of the chars after
pyrolysis, organic solvents such as acetone, toluene or dichlorome-
tane are used due to their nature (Dutta et al., 2017). The choice of
the solvent and pH used, will depend on the sample nature and the
chemicals targeted during the demineralisation process, and there-
fore the choice of solvent will be analysed more in depth together
with the chemistry of the process in Section 2.2.
Although the use of organic solvents might help increasing the
accessibility to the minerals present in the solids they will not be
analysed in this review as they cannot be considered demineralisa-
tion agent per se.
Demineralisation has to be analysed case by case as changing
some parameter might change the optimum conditions to carry
out leaching.
2.2. Chemistry
The chemical composition of the elements present in the mate-
rials to be pyrolised or after pyrolysis, vary strongly from sample to
sample, thus the treatment that should be applied to remove them,
will also differ greatly. Due to the availability, low cost and other
concerns (this will be analysed more in depth in Sections 3 and
 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
4), the materials that will act as carbon feedstocks to the pyrolysis
process are mainly waste biomass and tyres (Kaminsky and
Zorriqueta, 2007; Kan et al., 2016; Martinez et al., 2013). These
materials are usually contaminated by several chemicals which
come for instance, from the inorganic matter added to biomass
during harvesting (Vassilev et al., 2010) and processing and the
chemicals used to vulcanise and give the tyres their desired prop-
erties (Kreider et al., 2010). The major inorganic elements, macro
components, found in these materials are (Jenkins et al., 1998):
Al, Ca, Fe, K, Mg, Na, P, S, Si and Zn. In some cases traces of other
elements such as Cl, Cr, Cu, Mn and Ti may also be present. The
chemical compositions of the materials addressed in this work
are detailed in Sections 3 and 4. These elements can appear in their
elemental form or either forming oxides, carbonates, sulphates or
salts (Alexandre-Franco et al., 2010; Vassilev et al., 2012). Some
of their possible compositions are given in Table 1.
In general, the mineral matter present in the raw material
before undergoing pyrolysis stays in the char. The biggest differ-
ence lies in the higher concentration of these elements in the char
due to the decrease of the organic phase (Yargicoglu et al., 2015).
Inorganics can get trapped by new organic compounds gener-
ated during the thermal conversion.
It is highly difficult to choose the most suitable solvent for a
demineralisation process as there are many criteria that must be
satisfied. The solvent selected should offer the best balance of a
number of desirable characteristics (Mogensen, 1982), such as:
 Solubility: the solvent and the carrier must be largely insoluble
in each other, to ensure that no carrier (inert solid phase) will
dissolve in the demineralising agent.
 Chemical reactivity: the solvent should not enter into undesired
reactions with the solute and must be chemically stable under
process conditions, for example to avoid oxidation. A low pH
value means more H+ ions available to react with metals, and
high redox potentials are desired to extract soluble metals from
the solid.
 Viscosity: high viscosity values reduce mass transfer and heat
transfer rates, and in general, solvents of low or medium viscos-
ity are thus preferred.
There are also a number of additional solvent properties that
must be taken into account because they affect the overall cost
of the entire operation: corrosiveness, flammability, toxicity,
recoverability, etc. The specifics of each application will determine
the interaction and relative significance of the factor mentioned
above.
Depending on the pH, solvents can be classified in three groups:
Water, acidic and alkaline.
Table 1
Possible composition of minerals present
in carbonaceous materials.
Elements Possible composition
Al Al2O3
Ca CaCO3, CaO, CaSO4
Cu CuO
Fe Fe2O3, FeS2, FeCO3
K K2O, KCl
Mg MgO
Na Na2O, NaCl
P P2O5
S SO3
Si SiO2
Ti TiO2
Zn ZnS, ZnO, ZnCO3
671
2.2.1. Water
Water leaching is the most preferred solution. Besides its low
cost, it also has a low environmental impact given the possibility
of disposing the leachate back into the field in some biomass sam-
ple cases. This practise allows the retention of nutrients on site,
avoiding the depletion of inorganic nutrients in the soil and there-
fore the use of fertilisers (Sochacki et al., 2013). In the case of more
contaminant species, such as heavy metals from waste tyres, the
water is recovered by distillation or reverse osmosis.
Water leaching is one of the most common natural occurrences.
Rain drops act as finely dispersed solvent, and are brought into
contact with natural and/or synthetic surfaces, leaching some ele-
ments to the soil or rivers. This has to be taken into account when
choosing materials for outdoor applications, for example waste
tyres in artificial reefs (Collins et al., 2002), playground swings,
etc. (Wik and Dave, 2009), as the polluted leachate might be diffi-
cult to control and dispose of.
Water leaching provides the removal of water-soluble inorganic
elements, such as Ca, K, Mg and Na. Inorganic salts also get dis-
solved in water. Some examples of the chemical reactions
(Miller, 1960; Pan and Zhao, 2015) taking place during water dem-
ineralisation are given below:
CaO + H2 O ! Ca(OH)2
MgO + H2 O ! Mg(OH)2
Na and K also form soluble hydroxides.
Hydrogen peroxide as a solvent will be considered together
with water, due to the low acidity and different method of action
compared to the other solvents. H2O2 is slightly acidic but it will
act in different ways depending on the pH of the solution
(Aydogan, 2006). It is frequently used in acidic media due to the
high oxidation potential. However, it can also act as a reducing
agent. Hydrogen peroxide is known to be a relatively unstable
compound, whose decomposition can be catalysed by Fe3+ ion.
The products generated at decomposition are oxygen and water
(Antonijević et al., 1997):
H2 O2 ! O2 + 2H2 O
2.2.2. Acidic
Non water-soluble elements need acid solutions to be removed.
Low pH values are generally favourable for metal ion solubilisation.
Most metals and metal ions are basic and only react with an acid,
thus, acids have the leading role in leaching (Meshram et al., 2015).
These reactions occur generally through reduction-oxidation
(REDOX) reactions. The reactivity of the elements depend on their
capacities as reducing agents. Metals from group 1 in the periodic
table are highly reactive and thus they even react with water.
The most commonly used acids in leaching are H2SO4 and HCl
(Gupta and Mukherjee, 1990). They are both very strong, relatively
cheap and abundantly available. Their leaching reactions take
place by replacing the H+ ion with metal cations (Tian et al.,
2016). In some cases, the problem is that undesirable Cl and S enter
the sample with the strong acids, contaminating the final product.
On the other hand, HNO3 and HF are weaker acids, but they can act
as oxidising agents. Nitric acid can act both as oxidising and nitrat-
ing agent. Hydrofluoric acid, is a relatively weak acid because it
forms strong interactions with hydronium ions in solution (Lai
et al., 2016). However, fluoride (F) ion is a strong oxidising agent
and it is highly reactive towards metals, inorganic salts, and sili-
cates. HF is even able to dissolve SiO2, not due to its acidic nature
but rather through the oxidising effect of its anion (Steel and
Patrick, 2003). The rest of the acids are unable to dissolve SiO2 even
at very severe conditions (Shi et al., 2012).
672 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
Analysing the literature, (Goodman et al., 2000; Kim et al., 2009;
Reddy et al., 1999; Underwood et al., 2001; Yang et al., 1985; Zhu
et al., 2016), the following possible chemical reactions (schematic)
can be hypothesized:
Al2 O3 + 3HX Ac ! Al2 (Ac)3 + 3H2 O
Fe2 O3 + 3HX Ac ! Fe2 (Ac)3 + 3H2 O
ZnS + HX Ac ! ZnAc + H2 S
TiO2 + 2HCl ! TiOCl2 + H2 O
Fe2 O3 + 6HNO3 ! 2Fe(NO3 )3 + 3H2 O
SiO2 + 6HF ! H2 SiF6 + 2H2 O
Fe2 O3 + 10HF ! 2H2 FeF5 + 3H2 O
FeS2 + 2HNO3 ! Fe(NO3 )2 + H2 S + S
MY O + H2 Ac ! YMAc + H2 O
where X = 1 or 2 depending on the acid; Ac = SO4 for sulphuric, NO3
for nitric and Cl for hydrochloric acid; M = Ca, Cu, K, Na Mg and Zn;
and Y = 2 for Na K and Zn.
Weak inorganic acids (e.g. H3PO4) (Hassan et al., 2009) and
organic acids such as acetic (Stefanidis et al., 2015), citric, lactic
and formic acid have also been used in leaching processes, but with
limited reports on these investigations.
2.2.3. Alkaline
The most well-known alkali solvents for demineralisation are;
NaOH, Ca(OH)2, KOH, Na2CO3 and NH+4, with NaOH having the
strongest leaching capacity. Sodium carbonate is actually a salt,
but it acts as a weak alkali after dissolving in water. Alkali are more
selective towards dissolving some elements than acids (Gupta and
Mukherjee, 1990). Alkali can dissolve silica (at elevated tempera-
ture), alumina and also remove different forms of sulphur
(Mukherjee and Borthakur, 2003). The reactions can be repre-
sented in a simplified way as (Miki et al., 2016; Mukherjee, 2003):
Al2 O3 + 2MOH ! MAlO2 + H2 O
FeS2 + 2MOH ! M2 S + Fe(OH)2 + S
SiO2 + 2MOH ! M2 SiO3 + H2 O
ZnO + NH4 Cl ! Zn(NH3 )2 Cl2 + H2 O
where M = Na or K.
Compared with the acid leaching, alkaline leaching has advan-
tages of faster kinetics as well as a simpler impurity removal pro-
cess. Nevertheless, the higher price of caustic soda makes the
alkaline leaching method less competitive than acidic leaching.
Therefore, although alkaline solvents show reasonable metals
extraction capacity, they are generally combined with acid leach-
ing to decrease the overall cost of the process (Chaala et al., 1996).
3. Demineralisation of (lignocellulosic) biomass waste and its
pyrolysis char
3.1. Mineral content of lignocellulosic biomass
Biomass consist of organic and inorganic fractions. Lignocellulosic
biomass (woody biomass, herbaceous biomass and agricultural
residue) organic fraction consist of the primary cell wall compo-
nents [cellulose, hemicelluloses and lignin (Eom et al., 2013)].
The energy that can be used is stored in the organic part. Generally,
the inorganic matter is physically or chemically bound to biomass
structure in the form of oxides, silicates, carbonates, sulfates, chlo-
rides, and phosphates (Raveendran et al., 1995). The amount of
minerals depend on the growing season and environmental condi-
tions. Some elements are naturally present in plants as macro
nutrients (i.e. Na and K) and other nutrients such as Mg, S, Ca
and P. Table 2 brings together the chemical composition of several
biomass samples.
In the same plant, the distribution of metals present is different,
as a consequence of the plant’s biology: The stem needs lignin to
provide the mechanical strength needed, while leaves are richer
in metals since they accumulate metals through transpiration
and photosynthesis (Fahmi et al., 2007). Analysing the table in
detail a great dispersion in the elements can be observed even
for the same species depending on the origin of the sample and
moment of collection. It must be taken into account that these
products are collected in different locations and being natural
products, the minerals present vary greatly depending on the land.
There are more than only natural occurrences modifying the com-
position of the biomass samples. The low amount of inherent inor-
ganic elements existing in most forest land woods is increased by
fertilization and irrigation of agricultural and herbaceous and
short-rotation energy crop plants (Dayton et al., 1999). Due to
anthropogenic soil pollution, the metal concentration in plants
can be several magnitudes higher than the metal levels of plants
cultivated in non-contaminated soil (Mayer et al., 2012). Regard-
less, the alkali elements amount in biomass is much higher than
in other carbonaceous precursors.
Dissimilar biomass materials consist of various quantities of
mineral matter, e.g. coconut shells contain <1 wt%, whereas straw
contains up to 25 wt%. Straws and husks contain 90–95 wt% of Si in
their ashes (Deiana et al., 2008), while wood ash, the ash of
bagasse, corn cob and corn stalks are constituted by high Ca, Mg
and K contents. Rice husk contains 100 times as much Zn as other
biomass types (Raveendran et al., 1995).
Pyrolysis is the most frequently used method to prepare bio-
fuel as it can give as high liquid yield as 75 wt% with appropriate
operating conditions (Jahirul et al., 2012). Pyrolysis is a thermal
process in which biomass polymers are fragmented into light com-
pounds that are able to volatise, thereby producing a liquid pro-
duct referred to as bio-oil (Collard and Blin, 2014). The solid
leftover called biochar consist mainly of the inorganic residues pre-
sent in the biomass and carbon compounds formed during pyroly-
sis and accounts for 10–35 wt%.
From the inorganic components present in biomass, alkali met-
als are thought to be the elements giving rise to more disadvan-
tages during high temperature treatments (Wigley et al., 2016).
Potassium can lower the average apparent first-order activation
energy for pyrolysis by up to 50 kJ/mol (Nowakowski et al.,
2007). Potassium also influences the product distribution, as it
catalyses the gasification reaction. In the presence of potassium
CO2 and H2O react with the char formed during pyrolysis to form
CO and H2, decreasing hence the char yield (Raveendran et al.,
1995). Na has similar but weaker effect than K. Both elements lose
their catalytic activity in the presence of silica or sulphur as they
react to form alkali silicates or alkali sulfates. The alkaline earth
metals Mg and Ca seem to be bound to the biomass structure in
the form of carboxylates and act as crosslinks, joining different
parts of biomass together. Removing them by means of acid solu-
tions will relax the biomass structure and this would increase the
yield of sugars or other oligomeric compounds in the produced
bio-oil and decrease the chance of reactions to form water
(Mourant et al., 2011). Ca also reacts with sulphur to give sulfates
 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688 673

Table 2
Main inorganic elemental composition of the ashes of several biomass samples on a dry base, given in ppm.

Al Ca Fe K Mg Na P S Si Others REF
Wood
Albizia sawdust 188.4 3387.8 331.2 2703.2 171.5 22.9 20.1 Azeez et al. (2010)
Beech – 1620 120 452 365 130 – Stefanidis et al. (2015)
Beech 16.7 1683.1 110.8 1207.8 355.3 67.7 175.7 Azeez et al. (2010)
Iroko sawdust 209.0 8507.3 379.6 3879.8 790.5 32.1 35.3 Azeez et al. (2010)
Mallee (Eucalyptus) 1376 689 355 246 115 200 244 Liaw and Wu (2013)
Oak 27 1485 66 1190 423 47 242 3 Stefanidis et al. (2015)
Oak bark 78 11,670 109 3282 601 40 408 2400 1706.2 Jin et al. (2013)
Oak sapwood 14 450 107 1875 536 18 127 1800 315.8 Jin et al. (2013)
Oak heartwood 5 63 54 684 241 58 <60 1600 101.1 Jin et al. (2013)
Parkinsonia aculeata 14,300 236,600 6900 53,200 57,300 106,900 118,800 Messina et al. (2016)
Pine 167 1732 287 1049 425 36 151 3 Stefanidis et al. (2015)
Pine wood 4961 150,621 52,365 34,297 27,244 100 8906 Naik et al. (2010)
Pine bark 470 7510 120 640 890 50 80 Liu and Bi (2011)
Pine chips 23.4 246 36.4 65.9 25.7 7.9 5.5 15.1 Eberhardt and Pan (2012)
Poplar 19.3 782.8 12.0 769.0 282.0 15.1 117.0 14.0 13.5 Eom et al. (2011)
P. radiata 70.9 756 81.5 524.9 204 60.3 146.6 63 61.3 Wigley et al. (2015)
Spruce 4.6 867.2 9.0 380.5 101.3 25.9 187.8 Azeez et al. (2010)
Spruce chips 100 4100 100 1300 400 0 200 1100 400 400 Reichel et al. (2013)
Subabul – 6025 614 614 1170 92 100 66 195 44 Raveendran et al. (1995)
Willow 60 3133 74 1957 385 58 804 301 36 Fahmi et al. (2007)
Willow 11,500 5900 1600 100 1900 Corton et al. (2016)
Yellow poplar bark 248 8530 105 1977 668 23 257 1800 1433.6 Jin et al. (2013)
Yellow poplar sapwood 22 482 56 798 319 34 <60 2100 279.1 Jin et al. (2013)
Yellow poplar 19 1016 51 826 429 19 <60 2100 370.6 Jin et al. (2013)
heartwood
Herbaceous-agricultural
Grass
Dactylis glomerata 4505 26,710 1100 2821 Fahmi et al. (2008)
Eucalyptus 80 9734 158 1007 550 242 684 2 Stefanidis et al. (2015)
Festuca leaves 87.8 3004 70.4 26960.4 1501.5 241.7 2754.1 2194.8 52 Fahmi et al. (2007)
Festuca stem 98 2181.5 48 18,227 1058 147.5 2396 1121 71 Fahmi et al. (2007)
Lolium leaves 81.2 6161.2 89.2 30713.5 1520.8 622.2 3253.5 3405 61.2 Fahmi et al. (2007)
Lolium stem 35 1688.5 23.5 15637.5 880 613 2300.5 1017 51.5 Fahmi et al. (2007)
Miscanthus 230 2361 178 2670 371 101 151 4 Stefanidis et al. (2015)
Miscanthus 1800 12,000 1500 700 Corton et al. (2016)
Reed canary 2784 1456 598 74 Fahmi et al. (2008)
Reed canary 100 2800 100 1400 600 100 800 600 – Greenhalf et al. (2012)
Switchgrass 102 6173 113 717 542 158 494 615 43 Fahmi et al. (2007)
Switchgrass 4.4– 1800– 5.5– 3600– 1800– 210– 360– Liu and Bi (2011)
8.7 2900 7.9 4000 2400 250 370
Switchgrass 200 5000 200 5700 700 100 400 900 – Greenhalf et al. (2012)
Timothy grass 585 – 1041 20,479 22,796 1500 1187 Naik et al. (2010)
Straw
Barley straw 153 4879 87 17,562 1298 2039 931 5 Stefanidis et al. (2015)
Barley straw 2583 – 2690 – 16,490 17,768 100 746 Naik et al. (2010)
Danish cereal straw 50 4000 100 10,000 700 500 800 1500 8000 Sander (1997)
Flax straw 637 47,385 1904 64,006 21,780 900 2313 Naik et al. (2010)
Rape straw 300 16,500 300 9000 900 200 2000 3200 100 Greenhalf et al. (2012)
Rice straw 4884.8 461.3 27147.7 2721.7 333.9 1600 Jiang et al. (2013)
Rice straw 98.9 2306.2 268.9 16104.9 913.2 291.9 1300.1 265.4 25.8 Eom et al. (2013)
Rice straw – 4772 205 5402 6283 5106 752 221 174,510 555 Raveendran et al. (1995)
Rice straw 2100 17,500 2100 2600 2200 900 7400 Jenkins et al. (1996)
Rice straw 2128 8200 2072 1418 800 Liu et al. (2013)
Wheat straw 2455 7666 132 28,930 4329 7861 214 787 44,440 75 Raveendran et al. (1995)
Wheat straw 41 2383 36 11,826 575 786 314 6 Stefanidis et al. (2015)
Wheat straw 5332 9622 902 101 Fahmi et al. (2008)
Wheat straw 800 3800 100 17,500 2300 – 300 2000 14,600 1700 Reichel et al. (2013)
Wheat straw 4300 19,500 1900 1000 800 3900 20,200 Jenkins et al. (1996)
Wheat straw 11,613 – 5820 – 22,534 14,381 600 1000 Naik et al. (2010)
Wheat straw 100 5100 200 5700 700 100 400 900 100 Greenhalf et al. (2012)
Stalk
Corn stalk 1911 4686 518 32 5924 6463 2127 564 13,400 108 Raveendran et al. (1995)
Corn stalk 9490 140 34,800 1090 3720 2900 11,800 16,440 Yanik et al. (2007)
Cotton stalk 7380 70 29,000 1430 910 3900 300 10,870 Yanik et al. (2007)
Oreganum stalk 13,600 180 52,400 1660 1910 2900 2250 11,500 Yanik et al. (2007)
Sunflower stalk 1110 49,100 1960 79,100 2360 2250 5900 11,500 30,230 Yanik et al. (2007)
Tobacco stalk 1210 33,700 1420 74,800 840 1290 4900 2640 11,370 Yanik et al. (2007)
Husk
Coconut shell 73 1501 115 1965 389 1243 94 35 256 27.8 Raveendran et al. (1995)
Ground nut shell 3642 12,970 1092 17,690 3547 467 278 299 10,960 126.3 Raveendran et al. (1995)
Millet husk – 6255 1020 3860 11,140 1427 1267 317 150,840 181 Raveendran et al. (1995)

(continued on next page)

674 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

Table 2 (continued)

Al Ca Fe K Mg Na P S Si Others REF
Peanut shell 4680 13,040 2310 6620 47,880 5350 700 Wang et al. (2012)
Rice husk – 1793 533 9061 1612 132 337 163 220,690 1405 Raveendran et al. (1995)
Rice husk 2529 1252 2086 4227 4023 1037 1300 65 Cai and Liu (2016)
Other residues
Arundo donax cane 487 10,620 245 108 663 Giudicianni et al. (2014)
Sugar cane bagasse – 1518 125 2682 6261 93 284 60 17,340 59 Raveendran et al. (1995)
Sugar cane bagasse 30 870 40 1750 4370 120 140 420 9110 1470 Das et al. (2004)
Coconut coir 148 477 187 2438 532 1758 47 64 2990 101.6 Raveendran et al. (1995)
Coir pith 1653 3126 837 26,283 8095 10,564 1170 476 13,050 1331.4 Raveendran et al. (1995)
Corn cob – 182 24 9366 1693 141 445 15 9857 36 Raveendran et al. (1995)
Corn cob 162.1 249.3 144.1 5408.4 404.7 29.3 72.5 Azeez et al. (2010)
Corn cob – 1170 – 24,000 – – 3880 2900 2340 12,110 Yanik et al. (2007)
Cotton gin waste – 3737 746 7094 4924 1298 736 58 13,000 70 Raveendran et al. (1995)
Maize silage 800 2300 900 7000 1200 200 2200 1800 8100 500 Reichel et al. (2013)
Mallee (Eucalyptus) leaf 7876 3057 1699 5927 1165 1200 1949 Liaw and Wu (2013)
Sargassum spp. 414.6 8000 21,870 1800 400 11,600 1700 164.5 Diaz-Vazquez et al.
(2015)

like potassium does but the deposits formed are more favourable
to sustained furnace operations. Ca can promote the activity of
Ni but can act as a poison to Fe. Khelfa et al. (2013) found that
MgCl2 and also NiCl2 but to a lesser extend, increased the char resi-
due while decreasing the maximum pyrolysis temperature and
changed the composition of the gas fraction. These mean that it
was catalysing the primary dehydration of cellulose. On the other
hand, ligning was not affected by the metals.
Patwardhan et al. (2010) studied the yield of levoglucosan dur-
ing biomass pyrolysis and found the strongest influence changed in
this order for the cations analysed: K+ > Na+ > Ca2+ > Mg2+. Among
the calcium salts used in the study, levoglucosan yield decreased
in the following order Cl > NO–3  OH– > CO2– 3
3  PO4 . The inor-
ganic constituents of biomass also contribute to adverse impacts
on reactors, furnaces, heat exchangers, turbines, emission control
devices and other equipment. The issues associated to the presence
of the inorganic compounds include equipment corrosion, fouling
of surfaces, catalysts deactivation, and bed agglomeration in reac-
tors (Carpenter et al., 2014; Leijenhorst et al., 2016). In the gas,
high concentration of HCl and KCl, lead to corrosion of the equip-
ment used (Wang et al., 2010). Silicon is relatively inert in pyrolysis
reactions, however, Si can react with alkali oxides and salts to form
eutectics which have lower melting points (<800 °C) and depend-
ing on the pyrolysis temperature, they may end up in the volatile
fraction (Bazargan et al., 2015).
Different studies show that a metal can simultaneously catalyse
and enhance depolymerisation reactions. Thus, depending on
desired products the choice of the metal added or their removal
will vary.
In general, K, Na, Ca, Mg, Si, S and Cl (in this order) are the ele-
ments to be removed to have an optimum control of the pyrolysis
reaction.
Most of the inorganic elements present in the biomass end up in
the biochar as they do not volatilise at pyrolysis temperatures
(Al-Wabel et al., 2013).
3.2. Demineralisation of lignocellulosic biomass
The demineralisation of the material can be performed before or
after the pyrolysis process. An overview of the results of the
research activities carried out in this field are presented in Table 3.
Pretreatment of feedstocks prior to pyrolysis provides an oppor-
tunity to produce bio-oils with diverse chemical composition and
physical properties for specific applications (Hassan et al., 2009).
According to Reichel et al. (2013) and Stefanidis et al. (2015) the
demineralised biomass samples gave higher liquid yield, while
decreasing the solid and gas fractions. On the contrary, Mourant
et al. (2011) stated that the removal of alkali and alkaline earth ele-
ments did not result in significant changes in the yields of bio-oil
and bio-char. Nonetheless, they affirmed that the bio-oil proper-
ties, e.g. viscosity, were drastically affected. Bio-oil produced
through pyrolysis cannot be used as an alternative to petroleum
transportation due to its high viscosity, high water and ash con-
tents, low heating value, instability and high corrosiveness (Xiu
and Shahbazi, 2012). Some problems such as the viscosity, high
water content or low heating value might be partially mitigated
by pre-treating the biomass (Corton et al., 2016; Oudenhoven
et al., 2013). Due to the fact that, during storage the metals present
in the oil which have been transferred to the vapours from the
char, catalyse polymerization resulting in an increase in viscosity
with time (Das et al., 2004). Biomass pretreatment using acid solu-
tion could avoid an additional fractionation step, simplifying the
process and large scale bio-oil production (Leijenhorst et al.,
2016). The energy consumption and total cost of the process will
be extensively reduced (Yang et al., 2010).
Another reason for demineralisation before pyrolysis, besides
the increased in quality and bio-oil yield at the expense of gas, char
and water, is the mitigation of catalyst poisoning when catalyst are
added to the pyrolysis process. Bridgwater (2012b) resolved that
the limiting ash content in biomass to reduce or avoid its catalytic
effect should be around 2.5 wt%, although this can vary with the
chemical composition of the ash and other process parameters.
Jiang et al. (2013) studied the impact that demineralisation had
in rice straw samples regarding physicochemical structure and
pyrolysis characteristics. They discovered that the majority of K
and Na were present in the form of water-soluble salts and not
physiologically bound to the plant tissue whereas most of Ca and
Mg was present in the form of water-insoluble salts and therefore
to remove the latter, cell walls had to be disrupted (Carpenter et al.,
2014). Strong acids such as H2SO4 or HCl could remove strongly
bonded elements but they will have negative effect on the fibre
structure of biomass due to the fact that, it dissolved hemicellulose
and cellulose. The fibre erosion led to the creation of a large num-
ber of micropores and mesopores, resulting in increasing of total
pore volume and BET surface area of the samples. A further advan-
tage of the pretreatmet is the potential removal of hemicelluloses
from which aldehydes and related degradation products are
derived which give the bio-oil a peculiar smell and contribute to
the aging effect (Bridgwater, 2012b). However, the demineralisa-
tion treatment using H2SO4 and HCl can add residual sulphur and
chlorine amounts to the treated sample and can cause the
volatilization of alkali metals that may contribute to acid gas and
aerosol (Yu et al., 2014). Baxter et al. (1998) found out that Cl
and S are not the only responsible for giving adverse reactions
Table 3
Summary of leaching conditions used in different biomass samples demineralisation.

Material Temp. [°C] Time Demineralisation Sample to Removed Observation and comments Ref.
[h] agent Demineralisation ash [wt.%]
agent ratio
Demineralisation before pyrolysis (pre-treatment)
Sugarcane bagasse 25 ± 2 1 H2O 12.5 g/150 ml 32.8 Water leached showed highest sugar content. Das et al. (2004)
24 H2O 12.5 g/150 ml 46
24 H2O 25 g/150 ml 42.3
1 5 M HCl 12.5 g/150 ml 12.2 Acid demineralisation hydrolyses the
increase hemicellulose and cellulose and increased the
1 0.5% HF 73.5 bio oil viscosity.
1 1% HF 84.7
1 2% HF 95.8
1 3% HF 98.4
Poplar wood 60 12 2 M HCl 20 g/100 ml 84.3 After pyrolysis levoglucosan amount was Eom et al. (2011)
Room 1 3% HF 25 g/300 ml 82.9 increased and the amount of C6-type phenols
Temp. decreased in the demineralised biomasses.
90 2 D-H2O – 28.6

I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

2 Tap H2O – 30.0 Some inorganics were increased due to being
present in the demineralising agent.
Rice straw 25 ± 3 2 DI-H2O 1 g/10 ml 33.3 Most of Ca and Mg are in water insoluble Jiang et al. (2013)
forms.
5 wt% CH3COOH 47.1
5 wt% HCl 50.7 Negative impact on the physicochemical
5 wt% HNO3 54.7 structure of the sample.
5 wt% H2SO4 46.0
5 wt% H3PO4 47.7
Cassava stalk 28 24 H2O soaking 7 g/500 ml 31.6 Increasing the washing time decreased the ash Pattiya et al. (2013)
28 H2O stirring 33.7 content. The increase on temperature was only
80 H2O soaking 37.9 noticed after 24 h treatment, decreasing the
28 1 0.05 wt% HCl 59.1 ash content. The acid wash in both cases was
3 61.5 the most effective treatment to remove
Cassava rhizome 28 24 H2O soaking 28.5 elements.
H2O stirring 35.5
80 H2O soaking 45.5
28 1 0.05 wt% HCl 52.3
3 54.7
Rice straw Room 1 3 wt% HF 80 g/1150 g 93.1 No structural or compositional changes. Eom et al. (2013)
Temp.
Pine 50 4 H2O 4 g/80 ml 43.1 The temperature is an important factor Stefanidis et al. (2015)
2 1 wt% CH3COOH 77.3 regarding demineralisation. At low
2 1 wt% HNO3 87.8 temperature (room Temp.) the ash removal
Oak 4 H2O 59.3 increased with time whereas at high
2 1 wt% CH3COOH 76.7 temperature, the duration did not significantly
2 1 wt% HNO3 89.8 affect the ash removal.
Wheat straw 4 H2O 17.2 Nitric acid proved to be more effective than
2 1 wt% CH3COOH 18.5 acetic acid as demineralising agent.
2 1 wt% HNO3 21.8 Demineralised samples pyrolysis gave higher
Barley straw 4 H2O 42.4 liquid yield and less gas and char.
2 1 wt% CH3COOH 49.4
2 1 wt% HNO3 54.0
Eucalyptus 4 H2O 29.8
2 1 wt% CH3COOH 19.8
2 1 wt% HNO3 69.9
Miscanthus 4 H2O 23.0
2 1 wt% CH3COOH 31.5
2 1 wt% HNO3 38.6

675
(continued on next page)
 676
Table 3 (continued)

Material Temp. [°C] Time Demineralisation Sample to Removed Observation and comments Ref.
[h] agent Demineralisation ash [wt.%]
agent ratio
Palm kernel shell Room 48 2 M HCl 20 g/300 ml 72 Degradation temperature increased due to the Asadieraghi and Wan Daud
Temp. 2 M HF 33 catalytic effect of minerals removed. The (2014)
2 M HNO3 71 biomass structure was damaged (mainly in the
2 M H2SO4 66 case of HCl) although main framework was
2 M HClO4 69 unchanged.
Empty fruit bunches 2 M HCl 63
2 M HF 94
2 M HNO3 59
2 M H2SO4 58
2 M HClO4 54
Palm mesocarp fibre 2 M HCl 26
2 M HF 84
2 M HNO3 21
2 M H2SO4 24
2 M HClO4 26

I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

Sargassum spp. (S. fluitans, S. Natans, S. 28 12 Nanopure milli-Q H2O 8 g/10 ml 54.5 Total biomass is reduced average 36%. Soluble Diaz-Vazquez et al. (2015)
Filipendula 10% v/v H2SO4 62.1 carbohydrates and proteins decreased due to
10% v/v HNO3 74.5 the polysaccharides dissolution.
10% v/v CH3COOH 96.4
10% v/v C6H8O7 67.2
Wood Room 4 0.1 M HCl 1 g/20 ml 24.2 Removed metals had a small effect on the Vamvuka et al. (2006)
Temp. 0.1 M CH3COOH 18.2 reactivity of biomass pyrolysis.
Cotton 0.1 M HCl 67.7
0.1 M CH3COOH 58.1
Arundo Donax 30 – D-H2O 6 g/120 ml 49.0 After pyrolysis the demineralised samples Giudicianni et al. (2014)
0.1 M HCl 51.0 chars are capable to improve only soil physical
3.5 M HCl 29.4 properties given its reduced nutrient content.
Parkinsonia aculeata 80 1 10 wt% HCl 1 g/20 ml 85.7 Biochar from the demineralised sample has Messina et al. (2016)
potential as environmentally friendly solid bio-
fuel, inexpensive rough adsorbent, soil
enhancer, and CO2 capture agent in soil.
Switchgrass 25 2 DI-H2O 1 g/10 ml 20.9 Ash in comparison to lignin has the most Fahmi et al. (2008)
Festuca arundinacea 39.7 dominant effect on pyrolysis yields.
Willow 60 6 2 M HCl 10 g/50 ml >99.5 – Mayer et al. (2012)
Rice straw Room 1 min Tap H2O sprayed 100 g 2.6 Less effective due to short contact time and bad Jenkins et al. (1996)
Temp. wetting.
– Tap H2O flushed 100 g/20L 6.6 Extraction is complete after application of 4 1
– D-H2O flushed 7.1 per 100 g.
– D-H2O flushed 50 g (milled)/7L 8.7
24 D-H2O 100 g/7L 10.2 –
Wheat straw Room 1 min Tap H2O sprayed 100 g 26.9 Less effective due to short contact time and bad
Temp. wetting.
– Tap H2O flushed 100 g/20L 61.5 Extraction is complete after application of 4 1
– D-H2O flushed 67.7 per 100 g.
– D-H2O flushed 50 g (milled) /7L 60.0
24 D-H2O 100 g/7L 52.3 –
Swtichgrass leaves 80 2 Double D-H2O 1 g/20 ml 65.9 K, P, S and Cl present in the ashes were Vamvuka and Sfakiotakis
Giant reed leaves 62.5 incorporated in soluble forms of the original (2011)
Cardoon leaves 27.0 minerals but Si was associated like stable
minerals such as quartz.
Wheat straw 30 3 D-H2O 12.5 g/1L 56.8 As water temperature rises, the relative energy Deng et al. (2013)
60 60.4 loss increases. A possible reason is that more
90 69.7 organic matter will enter water as the
Rice straw 30 8.2 temperature increases. The amorphous silica is
60 17.6 bound to the polysaccharide part of the hull,
90 30.1 cellulose and hemicellulose, rather than lignin
Corn stalk 30 38.9 thus, when temperature is increased a sudden
60 47.5 increase in removal efficiency of SiO2 is
90 57.5 observed.
Rice hull 30 2.1 –
60 2.2
90 6.8
Candlenut wood 30 6.4 –
60 28.6
90 29.3
Cotton stalk 30 61.5 The increment of the moisture content is larger
60 60.1 than the decrement of the ash content after
90 63.8 washing, thus, its higher heating value
decreases.
Willow 60 2 H2O – 46.8 – Sebestyén et al. (2013)
Spruce 65.6
Hemp 67.8
Wheat straw 20.1

I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

Sweet sorghum bagasse 28.6
Rice straw – 2x24 DI-H2O 1 kg/40L 14.3 – Dayton et al. (1999)
Wheat straw – D-H2O 1 kg/120L 49.5
Switchgrass 13.8
Wood fuel 10.2
Swithcgrass (0.3–0.4 mm) 20 0.25 D- H2O 1 g sample/30 g 22.5 First part of the work consisted in an Liu and Bi (2011)
solution orthogonal experiment design in order to study
0.5 1 g sample/40 g 27.0 the leaching time, the ratio of water to samples
solution and particle size so as to identify the optimal
1 1 g sample/20 g 20.1 leaching conditions. They concluded that
solution particle size has the most significant impact on
48 1 g sample/40 g 42.8 the leaching performance followed by the
solution water-to-sample ratio and the leaching time
and that water leaching is ineffective for
inorganic constituents’ removal from pine bark
samples.
0.01 HNO3 1 g sample/20 g 36.5 The three samples were treated under the
0.01 HCl solution 35.6 same pH (CH3COOH acidity is lower so it needs
3 M CH3COOH 36.5 higher concentration) and the results were
similar but HNO3 and HCl lead to mass loss.
Pine bark (0.3–0.4 mm) 48 D-H2O 1 g sample/20 g 8.6 Acetic acid removed more inorganic
0.01 M HNO3 solution 35.5 constituents than hydrochloric acid and nitric
0.5 M HNO3 84.6 acid at the same pH level. Using higher acid
0.01 M HCl 14.3 concentrations, the removal was greater been
0.05 M HCl 67.4 the sulphuric acid the one with the best
0.1 M HCl 72.4 removal efficiency. But using inorganic acids,
0.5 M HCl 86.0 undesired elements such as N, Cl and S will
0.5 M H2SO4 89.6 enter the sample than later can give rise to
3 M CH3COOH 38.4 sulphur dioxide or chlorinated organic
5 M CH3COOH 48.4 compounds during the thermochemical
process.
P. radiate wood chips 30 4 DI- H2O 70 g/700 ml 34.1 It removed the soluble salts (around 40%of the Wigley et al. (2015)
sample).
1% CH3COOH 61.0 The reduction of inorganics was slightly better

(continued on next page)

677
 678
Table 3 (continued)

Material Temp. [°C] Time Demineralisation Sample to Removed Observation and comments Ref.
[h] agent Demineralisation ash [wt.%]
agent ratio
1% HCOOH 65.8 for mineral acids compared to the organic
1% H2SO4 73.2 acids.
1% HCl 73.2
1% HNO3 70.7
90 DI_ H2O 29.3 Mass yields did not change, water soluble
1% CH3COOH 70.7 extractives were removed and minimal
1% HCOOH 73.2 carbohydrate degradation occurred, when
water and organic acids were used for
treatment.
1% H2SO4 75.6 Mineral acids all reduced the biomass yield
1% HCl 75.6 significantly during leaching. HCl is very
1% HNO3 68.3 severe, hydrolysing hemicellulose and H2SO4
treated samples increased their S amount
substantially.

I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

Demineralisation after pyrolysis (post treatment)
Cow manure Pyro at 600 °C 6 h Repeated rinsing 1 M HCl 2 g/10 ml 91.2 Adsorption increased greatly for Li et al. (2017)
Cow manure Pyro at 700 °C 6 h 1:1M HCl HF mix 85.6 oxytetracycline but decreased slightly for
D-H2O carbaryl after demineralisation.
Rice pyro at 450 °C 1 h 40 120 1 M HCl and 10% (v/v) HF 1:5 solid/liquid 72.5 Bulk C and O contents, as well as the bulk Sun et al. (2013)
Rice pyro at 600 °C 1 h 73.1 polarity of biochars increased after deashing,
Wheat pyro at 450 °C 1 h 45.9 due to the fact that the minerals present in
Wheat pyro at 600 °C 1 h 46.3 biochars affected the spatial distribution of
Maize pyro at 450 °C 1 h 71.4 polar groups
Maize pyro at 600 °C 1 h 40.0
Rice straw pyro at 400 °C 3 h Twice 4 1 M HCl and 1 M HF 1:10 solid/liquid 78.7 – Qu et al. (2016)
Bamboo shaves pyro at 400 °C 3 h treated mix neutralized with 1 M 77.9
NaOH
Rice husk flash pyro at 500 °C 100 1 M HCl 3 h + 15% Na2CO3 4 h – 87.7 The BET of the char increased from 25.6 to Alvarez et al. (2015)
227 m2/g.
Rice husk pyro 500 °C 2 h – 0.5 25% w/w HF 2.5:1 liquid/solid 98.1 Leaching the char using HF produce solids with Deiana et al. (2008)
50% w/w HF 100 higher ssa and VT; they are respectively 10-fold
and twice those of the char.
AC Wat.Act 850 °C 105 min 25% w/w HF 100 Leaching of the activated samples produce
50% w/w HF 98.5 solids that present the highest values of
textural parameters.

D-H2O: Distilled water.

DI-H2O: Deionised water.
Pyro: pyrolised at.
 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
during pyrolysis but that it also depends on the other elements
present in the samples. Alkali react with sulphur to form alkali sul-
fates while chlorine appears to play a shuttle role, facilitating the
transport of alkali from the fuel to surfaces, where the alkali forms
sulfates. These compounds form deposits on the equipment used,
reducing the facility efficiency, capacity, and availability.
The vaporization of alkali metals as chlorides can potentially
lead to the formation of toxic compounds (Dayton et al., 1999).
Scott et al. (2001) analysed the rate of cation removal during the
column leaching of poplar wood samples to evaluate the economic
feasibility of performing the process in an industrial scale. It was
concluded that hot water washing alone was able to remove a
major amount of the alkaline cations from wood, been potassium
more easily removed than calcium. The exchange process was con-
sidered to be fast and relatively cheap.
One main downsides of the pretreatment is the need of a subse-
quent drying process of wet biomass prior to been pyrolysed to
reduce the moisture content. The dewatering can be performed
by mechanical means or by thermal drying. A new process for
energy-efficient liquid/solids separation has been studied by ther-
mally assisted mechanical dewatering (Mahmoud et al., 2011). The
mechanical method consisting in pressure-assisted dewatering,
can reduce the moisture content to 50% (Turn et al., 1997) but
also removes superficial liquid and hence additional soluble inor-
ganic constituents (Yu et al., 2014). The most common way is to
air dry the pre-treated samples at relatively low temperatures
(<105 °C) in small ovens or under vacuum conditions in a desicca-
tor. The drying times vary from 12 h (Mayer et al., 2012) to 24 h
(Asadieraghi and Wan Daud, 2014) or in some cases until the
weight is constant (Messina et al., 2016). The cost of the process
should be borne entirely by the fuel/products obtained through
the pyrolysis.
There is also an added cost associated with the recovery and
disposal of the liquor used for demineralising (Liu et al., 2017). In
order to avoid the cost associated problem, Oudenhoven et al.
(2013) reused the liquid fraction obtained during the pyrolysis of
biomass as leaching agent, effectively removing the alkali ions ini-
tially present in the feedstock.
The post-treatment for demineralisation of biochar originating
from the pyrolysis of biomass is widely used (Shen et al., 2012),
mainly when producing activated carbon (Aygün et al., 2003;
Sharma et al., 2009). However, most of the authors that use this
technique do not analyse the demineralisation after pyrolysis in
depth, they only apply it to their material without studying its
effects.
Deiana et al. (2008) compared the textural parameters of sev-
eral activated carbons produced from the leaching and activation
of biochar derived from rice husk. When acid leaching was applied
to the samples the BET values improved enormously. In the case of
untreated AC BET increased from 290 m2/g to 750–1000 m2/g if
leaching was performed. Nevertheless, there was a big difference
between treating the sample before the activation step of after.
The results suggest that when the leaching step is performed
before the activation, the inorganic salts are removed, allowing
the penetration of water vapour on the pores created during the
removal of the elements generating a more developed pore
network.
Rice straw char was treated with HCl and HCl-HF and the sur-
face characteristics and pentachlorophenol adsorption capacity
before and after the treatment were evaluated. The demineralisa-
tion increased the surface area and the pore volume increasing
the adsorption although the new acidic functional groups created
on the surface had a weak hindering effect (Lou et al., 2011).
The biochar produced during the pyrolysis of biomass can also
be used on the agricultural land to capture and store carbon, as a
fertiliser or to improve soil quality to increase food production
679
(Bell and Worrall, 2011). Its high porosity could also improve soil
water holding capacity reducing the soil degradation.
Some general behaviours are extracted from the findings of the
authors analysed in this review paper.
Commonly biomass materials have low ash content with a max-
imum value of 18.4 wt% for herbaceous biomass (Vassilev et al.,
2010), although the amounts vary greatly from sample to sample
depending on: plant species, growing conditions, fertilizer and pes-
ticide used, harvesting time, etc. The major elements present are
Na, Cl, K, Ca and Mg although some other trace elements can also
be found in varying quantities. Some inorganic components are
in water soluble forms (chlorides, nitrates, carbonates and phos-
phates) while most of the Ca and Mg are in water insoluble forms.
When demineralisation is performed as a pre-treatment on lig-
nocellulosic biomass before pyrolysis, water washing cannot fully
remove inorganics i.e. maximum removal value at room tempera-
ture was 67.7 wt% (Jenkins et al., 1996). Increasing the temperature
of the water additional ash can be removed by increasing the met-
als solubility in the leaching agent. Increasing the leaching temper-
ature from 30 °C to 90 °C the ash removal of candlenut wood
improved a 22.9 wt% (Deng et al., 2013). Hot water treatment
may open up the biomass structure, allowing the washing medium
to penetrate deeper within the biomass particles removing more
inorganic matter. Washing time affects the demineralisation beha-
viour; at the beginning (short period) there is a rapid leaching step
followed by a slow leaching step for a relatively long period. There-
fore, once the fast leaching step is over, the effect of time decreases
noticeably. Distilled or deionised water gave generally better
results compared to tap water; 6.2 wt% improvement for wheat
straw and only 0.5 wt% for rice straw due to the different nature
of the inorganics present (Jenkins et al., 1996) mainly due to the
mineral dissolved in tap water being adsorbed on the biomass
sample.
In lignocellulosic biomass, some inorganics are in cationic form
bounded to reactive sites in the structure of biomass therefore,
water is not enough to remove all these elements. Those metals
will only be able to be removed by ion exchange from an acid.
The acid washing was concluded to be the most effective technique
for ash removal, reaching 99% removal in some cases (Mayer et al.,
2012). The treatments with weak organic acids are not as efficient
in mineral removal as the ones carried out with inorganic acids;
48 wt% for acetic acid treated switchgrass against 72 wt% when
treating it with HCl (Liu and Bi, 2011). Despite that, inorganic acids
(even in mild concentrations) may destroy by opening or loosening
the structure of the biomass macropolymer leaving the metals
more exposed for leaching the internal structure of biomass,
hydrolysing hemicellulose and pectic materials whereas organic
acid do not change significantly the surface of biomass samples.
When strong acids such as HCl and H2SO4 are used, special atten-
tion has to be put in order to avoid residual elements such as Cl and
S from the acids as they can affect pyrolysis negatively. The extra
rinses required to remove the residual ions are a major drawback
that could limit the large-scale application. Regarding thermal sta-
bility, the temperature of initial weight loss shifted to higher val-
ues for acid treated samples. Demineralisation shifted the
maximum degradation rate temperature of wood sawdust from
350 °C to 370 °C (Messina et al., 2016). This indicates a higher ther-
mal stability against oxygen and nitrogen.
Treating biomass to remove the unwanted metallic constituents
prior to pyrolysis has the potential to affect not only the ash but all
the products of the process. Bio-oil yield increased 22.6% after pre-
treating palm fruit bunches with water for 24 h (Abdullah and
Gerhauser, 2008). The pretreatment has the advantage of improv-
ing the quality of crude bio-oil because it avoids the polymerisa-
tion during storage reducing the viscosity and water amount
present in the oil.
680 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

The need to remove minerals from waste biomass prior to
pyrolysis represents a somewhat costly step both economically
and in terms of energy, since the volume of material to be treated
is much bigger in the pretreatment than in the case of post-
treatment due to the low amount of char present when biomass
samples are pyrolysed. Therefore, the volume of solvent employed
during the treatment will be notably higher. Not only that, but a
drying step that will increase the cost of the entire process should
also be added.
There are many less published works that study the demineral-
isation after the process of pyrolysis [the technology started to be
studied in the early 1990s (Liu et al., 2017)] by which it can be con-
cluded that in relation to this material, the pre-treatment is more
widespread. Although in the pre-treatment step water is used as
the most popular demineralising agent when it comes to post-
treatment only acids are used. It might be that during pyrolysis
some of the elements that were present in a water-soluble form
change their formula due to the high temperatures encounter dur-
ing the process, becoming trapped in the new organic structure
Fig. 2. Proposed process diagram for biomass waste demineralisation.
formed during pyrolysis and becoming inaccessible-insoluble in
water.
Demineralisation is performed onto pyrolysis solid products
mainly when the chars are physically or chemically activated to
produce adsorbents. Acid treatment is an efficient way to deminer-
alise and increase the surface area of the carbon before or after
activation. The demineralisation step increased the BET of all the
chars treated although, in some cases, that did not translate into
a better adsorption capacity. The change in polarity associate to
the deashing might be the reason for the decrease in adsorption.
The recommended method to treat waste biomass is sum-
marised in Fig. 2.
4. Demineralisation of waste tyres and its pyrolysis char
4.1. Metal content of waste tyres
Tyre industry uses a wide variety of different compositions in
order to obtain highly durable and trustable products. To obtain
tyre, the untreated weak and soft rubber must be vulcanised. This
process consists of heating the rubber in the presence of sulphur
and initiators in order to get cross links between the polymer
chains, thus creating a three dimensional chemical network
(Mark et al., 2005).
Tyres are composed of several constituents: 60–65 wt% rubber
[generally consist of blends of styrene butadiene rubber (SBR),
polybutadiene (PBD), and natural rubber (NR)], 25–35 wt% rein-
forcing agent or filler [mainly carbon black (CB) but it can also be
a mixture of CB and silicon dioxide], chemical additives [vulcanis-
ing system comprising sulphur, peroxides, accelerators and activa-
tors (ZnO) and antidegradation agents] steel and textile (Wik and
Dave, 2009). A wide variety of rubber compositions are used in
the tyre industry. Their chemical composition is proprietary and
change from brand to brand and model to model. The elements
found in the waste tyres and waste tyre pyrolysis char are gathered
in Table 4.
The chemical composition of the tyres varies greatly depending
on the type of sample used. The entire tyre that has not been torn
apart contains a large amount of metals associated with the metal

Table 4
Metal content of waste tyres and waste tyres pyrolysis char in ppm.

Ref San Quek and Undri Selbes et al. San Quek and Chan Mui Shah Undri et al. López
Miguel Balasubramanian, et al. (2015) Miguel Balasubramanian et al. et al. et al. (2013) et al.,
et al. (2011) (2013) et al. (2011) (2011) (2010a) (2006) (2013)
(2002) (2002)
Tyre Char
Crumb Chips
Al 956 680 - 2220 520 1988 1300 1380 - - - - 2040
Ba – – 34 – – – – 70 – – 5 5 –
Ca 1544 38,900 – 1720 540 5755 3680 0.3 5894 24,000 – – 4527
Co 38.7 – 1 – – 86.3 – 130 – – 144 13 –
Cr 49.4 – 4 3 41 119 – 100 – – 25 8 –
Cu 68.5 50 6 40 310 119 80 340 – – 144 360 44
Fe 28,188 300 453 1400 110,000 4895 890 3820 1329 – 23,370 15,080 760
K – 990 – 420 590 – 1420 800 937 – – – 800
Mg 444 400 – 290 150 970 860 740 – – – – 747
Mn 13.9 – 11 20 660 642 – 60 – – 164 110 –
Ni 5.9 – 4 10 50 10.5 – 60 – – 27 13 –
P – – – 160 170 – – – – – – – 300
Pb 59 – 130 50 40 120 – 110 – – 77 113 –
S 16,200 – 18,000 1440 1160 18,690 – 16,000 – 26,000 23,000 20,000 33,000
Si – 5630 – – – – 26,620 – – 16,000 – – 33,472
Ti 105 – – – – 135 – – – – – – 330
Zn 12,700 10,240 1299 15,900 11,500 30,950 25,250 20,260 58,539 42,000 58,280 45,130 28,482
Others 16.9 400 8 524 312 67.9 4500 850 – – 26 22 8786
 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
structure that shapes the tyre. These metals are also found in the
case of using pieces of tyre in which the casing is not removed.
When using crumb the elements that are part of steel such as Fe
and Mg are drastically reduced.
The chemical composition of the tyres is also altered due to the
different nature (car or truck) and brand that produces them. As
tyres are separated only by their use (car or truck, at best) and
not by their manufacturer, the difference that exists between the
chemical compositions is mitigated by the intermingling of all
types of materials.
These contaminants originate from the compounds added to the
tyre in order to meet specific tyre performance requirements. In
the char, the carbon content is very high (>80 wt%), but sulphur
content is about half of the amount initially present in the tyre
(<3 wt%) where it is performing as the crosslinking agent between
elastomer chains (Mark et al., 2005). The most common metals
found in the crumb and char are Zn, S, Si, Fe, Mg, Al and Ca. Those
metals appear mainly in their elemental form or in their corre-
sponding oxide or sulphide. Zn derives from the zinc oxide added
to the rubber to control vulcanization and enhance the physical
properties (Williams and Besler, 1995). To reduce the cost and
for ecological reasons, some tyre manufactures replace some car-
bon black with silicon or SiO2 thus the high amount of Si present
in the crumb or char. Due to the high boiling point of SiO2, it does
not leave the sample with the volatiles during pyrolysis therefore it
stays in the solid residue. CaCO3 is also used for replacing CB thus
the presence of the element in the char. Fe and Mg might be related
to some small steel wire pieces that were not removed from the
tyre before pyrolysis.
4.2. Demineralisation of waste tyres
Several demineralisation works performed on waste tyres
crumb and waste tyre derived chars have been summarised in
Table 5.
Both, waste tyre crumb and the char obtained by pyrolysis have
several applications. Crumb can be used as a filler in rubber
(Karger-Kocsis et al., 2013) and concrete (Atahan and Yücel,
2012), or as lightweight aggregate for flowable fill (Pierce and
Blackwell, 2003). While char can be used to replace carbon black
(Martínez et al., 2013) in pigments (Pilusa and Muzenda, 2013)
or bitumen (Feng et al., 2016) or activate it and use it to remove
organic (Gupta et al., 2011a) and inorganic (Helleur et al., 2001)
pollutants. Nevertheless, the minerals present in their composition
can pose some problems to their applicability.
The leaching of tyre constituents may pose environmental con-
cerns when using them in civil/environmental applications. Selbes
et al. (2015) studied the leaching of organic and inorganic compo-
nents from waste tyres crumb and chips under different pH condi-
tions, similar to the ones encountered in natural environments.
They observed that for smaller size tyre chips, the leaching of
organics was higher however, the leaching of inorganic con-
stituents was independent of the size. At basic pH conditions the
leaching of organics increased, whereas acidic pH conditions led
to elevated concentrations of metals. Leaching was minimal
around the neutral pH values. Nelson et al. (1994) focused their
study on the toxicity of artificial reefs made of waste tyres. They
found out that Zn, Cd, Cu and Pb where leached from the tyres in
the laboratory experiments in high enough amounts to be toxic
to some fish species. Nevertheless, due to the big volume of water
encountered in natural environments where artificial reefs are cre-
ated it is unlikely that the zinc concentrations leached from the
tyres used in artificial reefs would ever cause acute or even chronic
toxicity. Collins et al. (2002) also reached similar conclusions and
suggested that the leaching only occurred in the few microns deep
681
on the surface of the tyre. Fields studies carried out by Edeskar
(2006) also monitored the pollution of tyres used in 3 different civil
engineering applications as lightweight fill in a noise barrier, in a
capping layer in a road construction and in an embankment fill
material in a driving range in fields. The author concluded that only
some Zn and Fe were found in higher concentrations when tyre
shreds were used. Nevertheless, these values were too low so tyres
were classified as inert waste by the EC landfill directive.
Solano et al. (2012) studied the use of recycled-tyre crumb rub-
ber, as a lightweight material for amending green roof media.
Despite its advantages as a recycled product, crumb leaches Zn in
potentially toxic quantities for green roof plants and the overall
ecosystem. They observed a large sample to sample variation,
which reflects the variability of Zn in the crumb samples. During
the first 12 h significantly more Zn was released from the acid
water treatment than the neutral pH one, but thereafter no signif-
icant differences were found in the cumulative Zn leached.
Char can be used in several application provided that it is pre-
treated to reach the minimum requisites. It needs further upgrad-
ing to be used in different applications such as: adsorbent and
additive. The char can also be used as feedstock for activated car-
bon production.
Activated carbon is very efficient in waste water treating appli-
cation, but the commercial adsorbents are still very expensive.
Therefore, using a cheap starting material such as waste tyres will
reduce the price and make it more attractive. Activation of char
obtained from pyrolysis of waste tyres has gained a lot of attention
(Gupta et al., 2011b; Manocha et al., 2013; Mui et al., 2010a). The
surface area of the char is low (SBET < 100 m2/g) and thus, it has a
low adsorption capacity. However, they are mainly mesoporous
(Tanthapanichakoon et al., 2005) (around 90% of pores) and this
might help the adsorption of pollutants on that range of sizes. The
char has to be activated either by physical or chemical activation
processes to create new porosity and/or to enhance the one present
in the sample. The demineralisation step can be performed before
(Chan et al., 2012) or after (Gupta et al., 2012, 2014) the activation
phase. Ariyadejwanich et al. (2003) found that treating the char in
an acidic solution before the steam activation step, increased the
mesopore volume and microporosity of the activated carbon, due
to the creation of new active sites that were subsequently devel-
oped during the activation step. While, comparing the performance
of the demineralisation treatment after activation, the main
improvement was related only to the minerals removal.
Shah et al. (2006) demineralised waste tyre pyrolytic char using
HCl or H2SO4 before the activation step. The surface area of the
adsorbent increased from 85 m2/g to 870 and 800 m2/g (HCl and
H2SO4 respectively) before the activation step. Further improve-
ment was observed after the activation step, reaching values of
940 and 910 m2/g (HCl and H2SO4 respectively) that are in the
same range of the commercially available activated carbons which
specific surface area values range between 800 and 1100 m2/g.
Before the activation, a demineralisation step to get rid of the
maximum amount of contaminant metals is desired. Removing
the minerals present in the surface before the activating step can
lead to a better development of the porosity as the activating agent
will have easier accessibility through the new created pores. How-
ever, the reactivity of the activated carbon can decrease due to the
removal of some elements such as Ca and Zn as they might have
some kind of catalytic effect during activation (Antoniou et al.,
2014). Chlorinating activated carbons produced from tyres also
increased the toluene adsorption (Zhu et al., 2009) corroborating
the possible catalytic effect of Cl.
Although there is a lot of work done using the demineralisation
of waste tyre char for obtaining cheap adsorbents, the effect of the
demineralisation itself is not analysed in depth.
Table 5

682
Summary of leaching conditions used in different chars derived from pyrolysis of waste tyres demineralisation.

Material Temp. Time Demineralisation Sample to Removed Observation and comments Ref.
[°C] [h] agent Demineralisation agent ash [wt.%]
ratio
Demineralisation before pyrolysis (pre-treatment)
Tyre plugs (ø = 10.2 cm) – 31 days Lake water 2900 g/16L – Zn was the higher concentrated element in the leachate Nelson et al.
followed by Ca, Pb, Cu and Cd. (1994)
Tyre crumb (<3 mm) – 18 Water 2 g/40 ml – Zn, Se, Pb and Cd (trace amounts) were on the leachates. Mattina et al.
pH 4.2 water Decreasing the pH, all the elements dissolved in the (2007)
solution increased.
Tyre debris (10–80 lm) – 24 pH 3–7 ultra pure 50 and 100 g/L – These leachates contain a much higher quantity of Zn Gualtieri et al.
water than scrap leachates. Acid rains influence the elution (2005)
process.
Tyre chips (car and truck) – 3x7 5, 15, and 25‰ 140 g/2.8L – At higher salinity level there was less leaching of metals. Hartwell et al.
days salinity water Salinity may affects either the leachability of toxic (1998)
constituents or the interaction of salts and the toxic
chemicals.
Truck tyre (0.4–3.3 mm) Room 6–96 Tap water 25 g/500 ml – Studied the zinc leaching from the crumb. The zinc Rhodes et al.

I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

Temp. DI- H2O leaching decreases with increasing tyre particle radius (2012)
but increased linearly with the time.
Tyre (90% car + 10% truck) crumb Room 28 days pH 4 water (HCl) 100 g solid/2L solution 73.0 Zn, Al, Ca, Mg, K and S leached more from crumb Selbes et al.
Temp. pH 7 water 34.7 rubbers, as they are associated with the rubbery portion (2015)
pH 10 (NaOH) 9.0 of the tyre
Tyre (90% car + 10% truck) chips (2.5x2.5 mm) pH 4 water (HCl) 12.8 Big amount of Fe and Mn leached due to the wires
pH 7 water 0.2 present in the sample. More Fe and Mn present in the
pH 10 (NaOH) 0.5 leachate than the solubility limits, thus there must be
chelating between the leaching organics and those
metals.
Demineralisation after pyrolysis (post-treatment)
Char pyrolised at 500 °C – 24 1 M H2SO4 10 g/1L >90 Chars pre-treated prior to activation have higher yield, Mui et al. (2010a)
surface area and micropore volume.
1 M HNO3 1 g/100 ml >90 It might be possible to prepare carbons having different Mui et al. (2010b)
pore size distribution via acid leaching.
Tyre char 60 1.5 70 wt% H2SO4 – 91.7 – Pilusa and
Muzenda (2013)
Char pyrolised at 450 °C 105 1.5 5 M HCl – 86.3 The reactivity of the demineralized char was on average Cunliffe and
Char pyrolised at 475 °C 81.9 22% less than untreated char. After demineralisation, the Williams (1999)
Char pyrolised at 500 °C 87.4 surface area increased slightly, reaching a value of
Char pyrolised at 525 °C 83.9 75 m2/g.
Char pyrolised at 560 °C 91.0
Char pyrolised at 600 °C 78.5
Tyre char Room 24 1 N HCl – 82.4 Acid treatment and activation increased the surface Shah et al. (2006)
Temp. 1 N H2SO4 34.2 areas and decreased the concentration of contaminants.
Char pyrolised at 350 °C (catalysed with CaC2) Room 24 1 N HCl – – The surface area increased from 80 m2/g to 800 m2/g Shah et al. (2007)
Temp.
Char treated with 69% HNO3 24 h Room 2 1 N H2SO4 20 g/L 69.6 Dem. treatments increased the BET surface from 37 m2/g López et al. (2013)
Temp. D- H2O 73.2 in the untreated char to 38 m2/g in the case of HNO3/
H2SO4 system and 57 m2/g in the case of HNO3/ H2O
Char pyrolysed at 500 °C Room 24 Conc. HF – 52.4 Activated carbon from acid treated char has higher pore Zhu et al. (2009,
Temp. volumes and surface areas than the one derived from the 2011)
untreated char.
Passenger car tyre char 100 2 10 wt% HCl – 5 The high amount of ash is due to the high Si amount Ucar et al. (2005)
(38 wt%) that is not possible to remove with acids.
Truck tyre char 64–73 This is more suitable for activation due to low ash
content.
Char pyrolysed at 500 °C Room 24 1 M HCl 2–3 g/100 ml 57.3 Acid treatment improved the porous properties of the Ariyadejwanich
Temp. activated carbon. et al. (2003)
Char pyrolysed at 550–600 °C – 336 3 N NaOH – 25.2 – Manocha et al.
3 N HNO3 19.2 (2013)
3 N H2SO4 15.6
3 N HCl 22.2
Tyre char – – H2SO4 3 ml/g 15.8 The extent of demineralisation increased with increasing Chaala et al.
4 ml/g 37.0 acid to char ratio and the optimal ratio (10 ml/g) was (1996)
8 ml/g 48.6 determined when the extracted ash reached a plateau.
10 ml/g 53.4
12 ml/g 56.2
– – 0.1 N H2SO4 10 ml/g 4.1 Using an acid concentration higher than 1 N appeared to
0.9 N H2SO4 39.7 have a minor effect on the residual ash content of the
9.8 N H2SO4 55.5 char, thus, the optimal concentration was fixed at 1 N
20 – 1 N H2SO4 10 ml/g 30.8 The optimal value for the heating temperature was
40 50.0 found to be 60 °C.
60 53.4
60 0.17 1 N H2SO4 10 ml/g 37.7 Increasing the reaction time provided a char with a
0.33 46.6 lower ash content. The optimal time at this temperature
0.5 53.4 was found to be 30 min.
0.67 55.5
0.83 56.8

I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

1 56.8
60 0.5 Once reused 1 N 10 ml/g 52.0 When the recovered acid is used once the values are
H2SO4 similar to the fresh acid but using it more times, the
Twice reused 1 N 46.6 removal efficiency is lower and lower.
H2SO4
3 times reused 1 N 32.2
H2SO4
Waste tyres char pretreated with 1 N H2SO4 at 60 °C, 60 0.5 1 N NaOH 10 ml/g 60.2 The optimal concentration of NaOH was found to be 5 N.
30 min, 10 ml/g acid to char ratio 2 N NaOH 67.2 After acid/alkali combined treatment, the resulting salts
3 N NaOH 69.5 essentially consisted of sulphates (in solution) and
4 N NaOH 71.9 hydroxides (deposits).
5 N NaOH 79.0
10 N NaOH 79.4
Char pyro 500 °C 70 3 2 N HCl – 75.7 The acid treatment used has removed inorganics such as Choi et al. (2014)
Char pyro 600 °C 77.5 zinc oxides that might play a catalytic role during
Char pyro 700 °C 75.8 activation to remove volatiles and develop the pore
Char pyro 800 °C 76.5 structure of activated char.
%30 pine+%30 tyre+ %40 plastic mixture char 60 1 1 M HCl 1 g/100 ml 70 – Bernardo et al.
%50 tyre+ %50 plastic mixture char 64 (2012)
Truck tyre derived char from South African industry 20 24 5M HNO3 10 g char/ 100 g solvent 68.3 HCl and HNO3 show the highest ash removal but non- Henry (2015)
5M HCl 69.5 ash products found in the char are also extracted. H2SO4
5M H2SO4 65.8 results were a bit confusing due to its high dehydrating
5M CH3COOH 45.1 effect (acid remnants uptaking humidity).
5M H2O2 43.9
5M NaOH 20.7
Char treated with HCl 80 1 1M NaOH 10 g char/ 100 g solvent 82.9 Sequential extraction removed more minerals than a
Char treated with H2SO4 48.2 single demineralisation procedure.
Char treated with HNO3 75.0

683
684 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688

Upgrading used tyres char to carbon black has not been broadly
studied, as it is much easier to produce activated carbon. Comparing
to activated carbon, carbon black has many more applications
(Harber and Young, 2001): it is largely used as reinforcement in
rubber, as a pigment in inks and as coating due to its electrical con-
ductive properties (Huang, 2002). It is used in polymer filler appli-
cations due to its stabiliser effect enhancing the thermal (Wen et al.,
2012) and ultraviolet radiation (Wu et al., 1995) stability. Although
it is used in less demanding applications such as in conveyor belts,
footwear or reinforcement in road bitumen (Feng et al., 2016), the
main use of CB is as filler in tyres. They exist many grades (tyre
industry alone uses about 40 different) depending on the applica-
tion. In order to use pyrolysis-derived char as a reinforcing material,
size reduction together with purification have to be achieved.
During milling or pulverisation processes to obtain small parti-
cles, undesired metals were also removed (Pilusa and Muzenda,
2013). Since the bond work index of silica is higher than that of
carbon black it make it possible to separate them by physical
methods. Regardless of the minerals removed by physical methods,
the char samples should undergo a more exhaustive demineralisa-
tion to fulfil the CB specifications: low ash [<0.5 wt% (De Marco
Rodriguez et al., 2001)] and sulphur contents.
Akyildiz et al. (2010) performed demineralisation experiments
to reduce the sulphur and ash content of the char derived from
Fig. 3. Proposed process diagram for waste tyres demineralisation.
waste tyres. A HCl and HNO3 mixture resulted in the highest
degree of demineralisation (60.5%) and desulphurisation (95.3%),
but was not enough for reaching the commercial carbon black val-
ues. Therefore, they used acid digestion to reduce the S value to
When demineralisation was performed as a post-treatment on
<0.5% attaining the value of N330 commercial carbon black.
the char derived from waste tyre rubber pyrolysis, the use of strong
Taking into account the information analysed in Section 4.2 and
acid proved to be effective in the removal of a big amount of inor-
gathered in Table 5, regarding the demineralisation of waste tyres
ganic minerals (Zn, Ca, K, Fe) and some organic phase. The ash con-
and the char derived from pyrolysis, the following principles were
tent was reduced >90% (Mui et al., 2010a; Pilusa and Muzenda,
drawn.
2013). Alkali solvents also remove metals and metal oxides in
The chemical composition of the tyres varies greatly depending
some cases, even more than acids reaching 25.2% removal for
on the type of sample analysed from passenger car having 18.5 wt%
NaOH against 22.2% of HCl (Manocha et al., 2013). NaOH seems
ash to truck with 5 wt% ash (Ucar et al., 2005), whole tyres, chips,
to be the most effective solvent removing Si compounds. Sequen-
strips or crumb. If the metal casing is removed, the amount of Fe
tial extraction using different acids or acid and alkali remove
and Mg is significantly reduced, from 1.1 wt% and 0.07 wt% respec-
higher amounts of minerals. The ash content was reduced to
tively in chips containing metal wires to 0.14 wt% Fe and 0.0002 wt%
3 wt% (Chaala et al., 1996) because their combination creates salts
Mn when wires were removed (Selbes et al., 2015). The mayor ele-
that are soluble in water based solutions.
ments present are Zn, S, Si, Fe, Mg, Al and Ca. They originate from
Demineralisation lead to higher fixed carbon contents and
the compounds added to the tyre during processing. S will be part
higher calorific values of the chars, increasing their value as energy
of the structure of the vulcanized rubber because it is the linking
source. The acid or acid/alkali leaching, increases the surface area
agent between the polymer chains, while other chemicals
values of char. Shah et al. (2006) increased the surface area of
(i.e. ZnO or SiO2) will only be physically attached to the rubber,
the tyre pyrolysis char up to 870 m2/g by demineralising with
therefore being more easily accessible to be removed.
HCl. Demineralisation also increases micro- and mesopore vol-
There are no papers (to the best of our knowledge) that analyse
umes not only after activation step but also in pyrolysis derived
the effect of the demineralisation using chemicals performed on
chars and in activated carbons treated after activation process,
waste tyre (whole, pieces or crumb) prior to pyrolysis. The diffi-
although in this case to a lower extent. Activated carbons coming
culty of penetrating the surface of this very resistant material
from demineralised chars show lower reactivity when activated.
together with the large amount of solvent necessary to treat such
This phenomenon might be attributed to the removal of inorganic
volume of product make this practice expensive and at the same
compounds (Ca, Zn, etc.), which appear to allow the thorough dif-
time difficult to execute. The study of the demineralisation of
fusion of steam into inner carbon matrix generating more active
waste tyres focuses on the leaching of elements during their use
sites. Higher yields obtained for treated chars are also linked to
in civil engineering applications, such as noise barriers and artifi-
the lower reactivity.
cial reefs. The biggest concern of reusing scrap tyres in those appli-
The recommended method to treat scrap tyres is summarised in
cations is the leaching of tyre constituents with time and their
Fig. 3.
potential harmful impact in the environment. As those uses are
usually performed outdoors, the leaching agent studied has always
been water. The more reactive strong acids might result in rubber 5. Conclusions
degradation. The element that causes more concern because it rep-
resents 1–2 wt% of the tyre and has been analysed more in depth is Waste tyres and lignocellulosic biowastes are easily available
Zn. Zn leaches from tyres in all cases studied: lake water, deionised and relatively cheap renewable energy resources, making them
water and different pH water. Although this element can be toxic good candidates to undergo pyrolysis. In this review, some dem-
for some organisms, in general, the small amount leached and ineralisation treatments applied to waste materials for their valori-
the big surfaces affected make its utilisation safe. sation have been overviewed.
 I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688
If the demineralisation is performed before pyrolysis, undesired
reactions derived from the presence of minerals during pyrolysis
could be avoided, and the quality and yield of all the final products
will be improved. The biggest drawback for this practise is the big
volume of sample to be treated. Pre-treatment is not performed in
tyres as the raw material is highly unreactive, but it the most pop-
ular choice when it comes to biowaste.
On the other hand, if the demineralisation is carried out after
pyrolysis only the char will be affected. The lower volume needed
to treat the char will reduce the price of the treatment signifi-
cantly. The higher porosity of the chars compared to the feedstocks
makes post-treatment the preferred option when the main objec-
tive is to improve the quality of the solid fraction.
The choice of one or the other system will depend on the final
use of the products. In any case, it is necessary to carry out the
demineralisation in as optimal manner as possible to minimize
the cost of chemicals, as well as to minimize capital costs.
The current literature is lacking a deep study on the economic
feasibility of the demineralisation process. In this respect, we sug-
gest to focus the future work on the following direction:
 The energy demands and cost associated to all the steps
involved in demineralisation (stirring, drying, produced waste
management, etc.) should be taken into account.
 The study of the disposal and recovery of the leachate (acid or
base) from an economic and ecological point of view has to be
addressed.
 The drying step must be analysed from an industrial perspective
as small batch drying does not pose the same problems as large
scale continuous processes do.
 More work regarding the large-scale demineralisation of waste
materials is necessary as an implemented industrial method
might affect the whole process commercial value.
Acknowledgments
Financial assistance of REDISA and NRF towards this research is
hereby acknowledged. Opinions expressed and conclusions arrived
at are those of the authors and are not necessarily to be attributed
to the funding bodies.
Conflict of interest
There are no known conflicts of interest associated with this
publication.
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