Waste Management: I. Iraola-Arregui, P. Van Der Gryp, J.F. Görgens

Waste Management 79 (2018) 667–688
Contents lists available at ScienceDirect
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: [email protected] (I. Iraola-Arregui), [email protected] (P. Van Der Gryp), [email protected] (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 for reducing waste volume, to conserve landfill space while allow-
ing energy recovery. It consist on the thermal decomposition of a
We live in a consumer society where due to the fast way of life, material in the absence of oxygen (inert atmosphere) to produce
products have a very short service life. The world population is gas (non-condensable low-molecular-volatiles including C1-C6
increasing together with the lifestyle development and urbanisa- hydrocarbons, hydrogen, CO, CO2 etc.), oil (hydrocarbon liquid con-
tion. Urban area dwellers produce higher waste levels than rural taining water) and char (pyrolytic solid) fractions (Wampler,
area inhabitants, who tend to reuse and recycle more (Hoornweg 1995). Yields and composition of pyrolysis products are affected
and Perinaz, 2012). Therefore, the waste production rate is increas- by the conversion conditions and the chemico-physical properties
ing and will continue doing so in the future. of the raw material, type of reactor, residence time, etc. (Williams,
As a case in point, due to the high amount of cars required 2013). For example, fast pyrolysis (high heating rates and short
nowadays, >1.5 billion tyres are produced per year in the world vapour residence times) is preferred to maximise the oil yield
(ETRMA, 2014; JATMA, 2016; RMA, 2015), which sooner or later (Bridgwater, 2012a), opposed to slow pyrolysis which enhances
they will become a waste (Karakurt, 2014). Although tyres do not char production (Hodgson et al., 2016).
present a danger to the health on their own, the inappropriate dis- For pyrolysis to be an attractive process from a commercial
posal and mismanagement of big amounts can cause serious prob- point of view, all the products obtained should have a market.
lems not only to the environment but also to human beings. The gas fraction can be used as a fuel in industrial combustion pro-
Tyres are thermoset materials that cannot be melted and repro- cesses. For instance, it can be used to partially fulfil the energy
cessed and are infusible, insoluble and have very high strength and requirements of the pyrolysis process itself. The liquid fraction
resistance to abrasion, heat, chemicals and degradation. These can also be used as fuel (due to its high calorific value) or as a
properties make waste tyres highly difficult to recycle. Therefore, potential source for valuable chemical such as: benzene, toluene,
the handling of used tyres is gaining a lot of attention (Torretta xylene or limonene (Antoniou and Zabaniotou, 2013). These chem-
et al., 2015). Due to the waste management legislation becoming icals can be used as precursors for the manufacture of chemicals
more and more severe, landfilling of waste tyres is getting banned with more complex structure, as solvents in laboratory and indus-
in numerous countries (EEA, 2009). There are several alternatives trial applications or in the case of limonene even as cleaning or fra-
for tyre recycling such as reclaiming and retreading, but they have grance agent (Danon et al., 2015b). The gas and liquid fractions
limited applicability. Recycling cannot address the full problem, as have a potential market however, the solid product has to be
it is a very high cost process resulting in products with question- upgraded and valorised so it can be used for more demanding
able characteristics (Antoniou et al., 2014). applications, for example as reinforcing filler or activated carbon.
Feeding a society that does not stop growing is also a challenge In its raw form, char consist of a carbon matrix containing most
from the point of view of waste as crop residues are the main of the inorganic compounds present in the raw material (ash)
source of inedible phytomass (Smil, 1999). and some condensed organic by-products generated during sec-
Biomass is a non-fossil biogenic solid product generated by nat- ondary reactions in the reactor.
ural and anthropogenic processes. Biomass varieties can be classi- There are different waste materials; thermoplastics, tyres and
fied according to their biological diversity, source and origin in: biomass that are appropriate for undergoing pyrolysis, due to their
wood and woody biomass, herbaceous and agricultural, aquatic, combustible properties and high volatile matter content and
animal and human wastes, contaminated biomass and industrial because they are rich in long polymer chains that can be easily
wastes (semi-biomass) and mixtures (Vassilev et al., 2010). Waste cracked into smaller molecules (hydrocarbon gas and pyrolysis
biomass is derived from several processing methods applied to oil) (Bernardo, 2011).
obtain biomass products (Easterly and Burnham, 1996). Biomass Thermoplastics pyrolysis char yields are so low that so far no
wastes have been used all over the world since the old times in work has been published (according to our knowledge) on polymer
several applications, such as farmyard manure, basketing, mat demineralisation, thus it will not be further analysed in this
making, and so on. In modern times, the development of synthetic review.
fibres, chemical fertilisers, etc. have replaced the use of this residue During pyrolysis of waste tyres, the chemical additives in the
(Prasad and Power, 1991), increasing the amount of biomass left in sample evaporate first and then rubber fraction devolatilises by
the fields. depolymerisation/condensation, leaving only the carbon black
Aside from the waste disposal matter, an additional global con- and minerals (Danon et al., 2015a). The gas and TDO (tyre derived
cern is the energy crisis. The energy content of waste can be recov- oil) originate from the volatiles fraction emerging from the process,
ered by means of either biological processes (e.g. anaerobic while the char consists of the solid fraction (Martinez et al., 2013).
digestion) or thermo-chemical processes (combustion, pyrolysis The solid obtained (commonly known as pyrolytic char) is a
or gasification). Owing to its simplicity and environmental bene- heterogeneous, porous structure with a low surface area, mainly
fits, pyrolysis is proving to be a promising form of waste recycling, made of carbon black added during processing. The char is much
with the production of potentially valuable products (Collard and coarser than the carbon black added to the tyre during processing,
Blin, 2014; Danon et al., 2015b). Pyrolysis is an attractive solution due to the fact that volatile products formed during pyrolysis tend
I. Iraola-Arregui et al. / Waste Management 79 (2018) 667–688 669
to get absorbed on the surface of the char as carbonaceous materi- into the internal pores. If the char is intended to be used as a car-
als increasing its size (Senneca et al., 2000). Char consists of many bon black substitute, the high amount of minerals can hinder its
undesired elements [<15 wt% is ash, resulting from the additives use (Chaala et al., 1996). Demineralisation through leaching is
used for tyres manufacturing (Helleur et al., 2001)] that reduce the most popular technique used regarding the complete removal
its commercial value. Tyre derived char must be upgraded by or minimisation of the quantity of metals present in the chars and
removing contaminants such as TDO, sulphur, metals and silicon, raw materials.
from the carbon structure (Lee et al., 1999), so it can be used in In this context, demineralisation performed on waste tyres and
more demanding applications. For example, the high ash, sulphur lignocellulosic biowaste before and after pyrolysis is the focus of
and zinc concentrations of the raw char impedes its utilisation as this comprehensive review. Demineralisation is defined, followed
carbon black in the conservative tyre industry. by the conditions and parameters that can be modified (paying
Biomass is an abundant renewable carbon source that might be special attention to the chemistry and solvent choice) for adjusting
used for bio-based energy, chemicals and materials production, the procedure to the material to be treated. The literature regard-
due to its potential to alleviate the emission of greenhouse gases ing the demineralisation of waste materials (biomass and tyres)
(Patel et al., 2016). Regarding biomass wastes, the focus will be and its effect on the final products are exhaustively reviewed and
on lignocellulose materials including: grasses and woody materi- the convenience of performing demineralisation on waste materi-
als, agricultural wastes and forestry residues. The demand for lig- als before or after pyrolysis is discussed.
nocellulosic materials is increasing rapidly due to an increasing
range of applications in renewable energy, chemicals and materials 2. Demineralisation
production that are relatively unaffected by feedstock prices.
Besides that, the use of biomass as an alternative energy source Demineralisation of solid materials is performed via leaching of
also reduces the poverty in emerging and developing countries act- the undesired phase. Leaching is a type of liquid-solid extraction
ing as a stimulus for economic growth (Bildirici, 2013). whereby a soluble fraction (leachant or solute) is partially or
The minerals present in the raw biomass during pyrolysis can totally removed from an insoluble, permeable solid phase by use
cause operational problems linked to the slagging of metals and of a liquid lixiviant (Richardson et al., 2002). First, the solvent
clogging of the equipment (Bazargan et al., 2015), poisoning and has to be brought into contact with the surface of the solid phase.
deactivation of catalyst used in pyrolysis (Yildiz et al., 2015) and Once there is intimate interaction, the solvent invades the solid
reduce the quality of the products. and penetrates the pores through diffusion, dissolving the lea-
It is evident that one of the main challenges of the 21st century chant. Finally, the solute will diffuse to the surface so it is trans-
is the generation of energy and valuable products from waste, ferred to the bulk solution, resulting in separation of the
while minimising the use of natural resources. In this regard, the components originally in the solid (Newton, 1959). A schematic
valorisation of carbonaceous solid waste for the production of diagram of the demineralisation procedure is given in Fig. 1.
higher valued goods, seem to fit perfectly in the objective men- This technique of extracting a solid using a solvent has been
tioned before. However, the presence of residual elements in char used since ancient times and it is known by many names: lixivia-
products represents limitations in further applications of these tion, leaching, solid-liquid extraction, percolation, etc. It has been
materials (Asadieraghi and Wan Daud, 2014). The inorganic matter widely used for the extraction of minerals from their ores
present in the raw material can modify the activity and selectivity (hydrometallurgy) or to obtain valuable chemicals present in
of both primary and secondary decomposition reactions that occur plants. It can also occur naturally due to the rain, causing the dis-
during pyrolysis (Di Blasi et al., 2009), hence the possibility of placement of wastes towards the rivers and oceans (Yadav and
changing the product yield and composition by pretreating the Yadav, 2014).
material to be pyrolised (Aho et al., 2013). The demineralisation The material to be treated will influence the conditions applied
of the feedstock can also help reducing the corrosion and formation for demineralisation since it will depend on the surface chemistry,
of toxic species during thermal processes (Yu et al., 2014). roughness, volume, soluble solid distribution, etc.
The inorganic species in the feedstock primarily end up in the
solid fraction, making the char highly polluted and can affect their 2.1. Conditions of demineralisation
possible applications; for instance, in the case of using char as acti-
vated carbon sorbent precursors, minerals can affect the porosity The major process parameters for demineralisation that must
of the char, as they might block the access of the activating agent be selected/determined, to obtain the most cost and energy
Fig. 1. Schematic diagram of demineralisation mechanism.

efficient method, are discussed below. These parameters are not 2.1.5. Operation mode
straight-forward to establish, as there may be several opposing fac- The choice will depend on the stage of the study; batch is the
tors (Sharma, 2007). best option for preliminary lab scale work since it is cheaper and
more convenient (Newton, 1959), while continuous processing is
2.1.1. Surface area the best at industrial scale (Green and Perry, 2008). There is plenty
The higher the surface area and the easier the accessibility to of work published on demineralisation in small-scale (Deng et al.,
the pollutants via high porosity, the more favoured the demineral- 2013; Liu and Bi, 2011; Yu et al., 2014), as the design of a leaching
isation will be. The surface area of the feedstock is determined by process is based on laboratory results. Nevertheless, when these
the particles size and shape. results have to be scaled up, this has to be carried out empirically.
For example, penetrating tyre rubber surface can be practically
impossible due to its chemical structure and physical properties 2.1.6. Agitation/mixing/mass transfer
(Martinez et al., 2013). The release of volatile organic components, There are mainly two methods of contacting the solid and liquid
during pyrolysis, increases the development of a porosity network phases: percolation and dispersing the solid into a liquid phase and
and surface area of char making it more easily accessible to sol- then separating from it (Green and Perry, 2008). The design of the
vents. In the case of tyre, the values reported in literature range reactors changes from column to horizontal and it also varies the
from 0.059 to 3.5 m2/g (Selbes, 2009) in the case of crumb (rubber method of agitating from impellers such as, turbines, paddles or
before pyrolysis) and 56.5–85 m2/g in the case of char (after pyrol- propellers to air agitation such as, Pachuca tanks or autoclaves.
ysis) (Shah et al., 2006; Ucar et al., 2005). Regarding biomass, raw Whatever the contact method, leaching will be favoured by
material before undergoing pyrolysis ranges from 1.188 105 of increasing the surface per unit volume of solid to be extracted.
empty fruit bunches to 1.46 m2/g of waste wood, and 1.6 m2/g of Stirring of the solvent is important as it increases the transfer of
sawdust (pyrolysed at 500 °C) (Messina et al., 2016) to 299 m2/g material from the surface of the particles to the mass of the
of coconut coir (pyrolysed at 600 °C) (Shen et al., 2012). The con- solution.
centration of ash is also higher in the char (Hadi et al., 2016) and
more reachable to be removed. 2.1.7. Method of operation
If leaching equipment is to be fully defined four categories must
2.1.2. Particle size be assigned: operating cycles (Liaw and Wu, 2013) (batch, semi-
Smaller particle size is generally desired due to an increase in continuous or continuous), method of contacting (Wadsworth
the contact area between the solid and the liquid, thus increasing and Schwartzberg, 1987) (percolation or solid dispersion), direc-
the mass transfer rate. In addition, the distance that the solute tion of streams (King, 1980) (concurrent, countercurrent or hybrid
must travel through the interior of the solid is smaller, which flow) and by staging (single stage or multiple stages). Taking all
assists with the leaching. Crushing and grinding some solid parti- these factors into account there are several types of reactors that
cles can make the soluble portion more accessible to the solvent are based on different geometries and features: Bollman type, Ken-
accelerating the leaching (Treybal, 1955). However, for wastes nedy, Bonotto, Rotocell, Screw-conveyor extractors, column type,
such as tyres, the processing cost of generating fine particles is pro- etc. (Green and Perry, 2008). These reactors are mainly used in
hibitive, as it may require grinding to be done under cryogenic con- industrial scale processes such as metals extraction from ores by
ditions (Karger-Kocsis et al., 2013). In biomass, the smaller hydrometallurgy (Newton, 1959). In laboratory experiments the
fractions contain higher ash content (Arvelakis and Koukios, majority of tests are performed using more simplistic approaches
2002) making the larger fraction a better choice for further upgrad- like a single stage batch reactor, consisting of a temperature con-
ing. In any case, extremely small particles are not desired as they trolled vessel with or without stirring (Chaala et al., 1996;
entail problems in the separation steps. Ravichandran et al., 2013).
2.1.3. Temperature 2.1.8. Solvent and pH

In general, it is desirable to use as high leaching temperature as Leaching can be performed using many different solvents at
possible, due to the higher solubility of the solute in the solvent, several pH values. In the case of the organic volatiles (hydrophobic
thus achieving higher solute concentrations in the liquid product. aromatic compounds) trapped on the pores of the chars after
The lower viscosity of the lixiviant at high temperature, also pyrolysis, organic solvents such as acetone, toluene or dichlorome-
favours mass transfer. The temperature chosen will depend on tane are used due to their nature (Dutta et al., 2017). The choice of
the material to be treated (Yu et al., 2014). When natural products the solvent and pH used, will depend on the sample nature and the
are leached, too high temperatures can lead to the deterioration of chemicals targeted during the demineralisation process, and there-
the solid. Therefore, most of the pre-treatment of lignocellulosic fore the choice of solvent will be analysed more in depth together
biomass is performed at room temperature (Mourant et al., 2011). with the chemistry of the process in Section 2.2.
The increased energy requirements and processing costs associ- Although the use of organic solvents might help increasing the
ated with higher temperatures should also be taken into account to accessibility to the minerals present in the solids they will not be
decide the most suitable value. analysed in this review as they cannot be considered demineralisa-
tion agent per se.
2.1.4. Contact time and leaching rate Demineralisation has to be analysed case by case as changing
Leachability is a function of time and it typically changes in the some parameter might change the optimum conditions to carry
long term. Time depends on the reaction kinetics. Generally, at the out leaching.
beginning, leaching is very fast but after a while, the leaching rate
decreases. There are two main reasons for the high initial rate of 2.2. Chemistry
dissolution; the concentration of the solvent is usually at maxi-
mum and the greatest possible surface of soluble mineral is The chemical composition of the elements present in the mate-
exposed. As dissolution proceeds, the rate slows down due to: rials to be pyrolised or after pyrolysis, vary strongly from sample to
the decrease in contact surface because most minerals will already sample, thus the treatment that should be applied to remove them,
be dissolved and the depletion of the solvent strength (Newton, will also differ greatly. Due to the availability, low cost and other
1959). concerns (this will be analysed more in depth in Sections 3 and
4), the materials that will act as carbon feedstocks to the pyrolysis 2.2.1. Water
process are mainly waste biomass and tyres (Kaminsky and Water leaching is the most preferred solution. Besides its low
Zorriqueta, 2007; Kan et al., 2016; Martinez et al., 2013). These cost, it also has a low environmental impact given the possibility
materials are usually contaminated by several chemicals which of disposing the leachate back into the field in some biomass sam-
come for instance, from the inorganic matter added to biomass ple cases. This practise allows the retention of nutrients on site,
during harvesting (Vassilev et al., 2010) and processing and the avoiding the depletion of inorganic nutrients in the soil and there-
chemicals used to vulcanise and give the tyres their desired prop- fore the use of fertilisers (Sochacki et al., 2013). In the case of more
erties (Kreider et al., 2010). The major inorganic elements, macro contaminant species, such as heavy metals from waste tyres, the
components, found in these materials are (Jenkins et al., 1998): water is recovered by distillation or reverse osmosis.
Al, Ca, Fe, K, Mg, Na, P, S, Si and Zn. In some cases traces of other Water leaching is one of the most common natural occurrences.
elements such as Cl, Cr, Cu, Mn and Ti may also be present. The Rain drops act as finely dispersed solvent, and are brought into
chemical compositions of the materials addressed in this work contact with natural and/or synthetic surfaces, leaching some ele-
are detailed in Sections 3 and 4. These elements can appear in their ments to the soil or rivers. This has to be taken into account when
elemental form or either forming oxides, carbonates, sulphates or choosing materials for outdoor applications, for example waste
salts (Alexandre-Franco et al., 2010; Vassilev et al., 2012). Some tyres in artificial reefs (Collins et al., 2002), playground swings,
of their possible compositions are given in Table 1. etc. (Wik and Dave, 2009), as the polluted leachate might be diffi-
In general, the mineral matter present in the raw material cult to control and dispose of.
before undergoing pyrolysis stays in the char. The biggest differ- Water leaching provides the removal of water-soluble inorganic
ence lies in the higher concentration of these elements in the char elements, such as Ca, K, Mg and Na. Inorganic salts also get dis-
due to the decrease of the organic phase (Yargicoglu et al., 2015). solved in water. Some examples of the chemical reactions
Inorganics can get trapped by new organic compounds gener- (Miller, 1960; Pan and Zhao, 2015) taking place during water dem-
ated during the thermal conversion. ineralisation are given below:
It is highly difficult to choose the most suitable solvent for a
demineralisation process as there are many criteria that must be CaO + H2 O ! Ca(OH)2
satisfied. The solvent selected should offer the best balance of a
number of desirable characteristics (Mogensen, 1982), such as: MgO + H2 O ! Mg(OH)2
Na and K also form soluble hydroxides.
Solubility: the solvent and the carrier must be largely insoluble
Hydrogen peroxide as a solvent will be considered together
in each other, to ensure that no carrier (inert solid phase) will
with water, due to the low acidity and different method of action
dissolve in the demineralising agent.
compared to the other solvents. H2O2 is slightly acidic but it will
Chemical reactivity: the solvent should not enter into undesired
act in different ways depending on the pH of the solution
reactions with the solute and must be chemically stable under
(Aydogan, 2006). It is frequently used in acidic media due to the
process conditions, for example to avoid oxidation. A low pH
high oxidation potential. However, it can also act as a reducing
value means more H+ ions available to react with metals, and
agent. Hydrogen peroxide is known to be a relatively unstable
high redox potentials are desired to extract soluble metals from
compound, whose decomposition can be catalysed by Fe3+ ion.
the solid.
The products generated at decomposition are oxygen and water
Viscosity: high viscosity values reduce mass transfer and heat
(Antonijević et al., 1997):
transfer rates, and in general, solvents of low or medium viscos-
ity are thus preferred. H2 O2 ! O2 + 2H2 O
There are also a number of additional solvent properties that

must be taken into account because they affect the overall cost 2.2.2. Acidic
of the entire operation: corrosiveness, flammability, toxicity, Non water-soluble elements need acid solutions to be removed.
recoverability, etc. The specifics of each application will determine Low pH values are generally favourable for metal ion solubilisation.
the interaction and relative significance of the factor mentioned Most metals and metal ions are basic and only react with an acid,
above. thus, acids have the leading role in leaching (Meshram et al., 2015).
Depending on the pH, solvents can be classified in three groups: These reactions occur generally through reduction-oxidation
Water, acidic and alkaline. (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
Table 1
Possible composition of minerals present cheap and abundantly available. Their leaching reactions take
in carbonaceous materials. 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
Elements Possible composition
the sample with the strong acids, contaminating the final product.
Al Al2O3
On the other hand, HNO3 and HF are weaker acids, but they can act
Ca CaCO3, CaO, CaSO4
Cu CuO as oxidising agents. Nitric acid can act both as oxidising and nitrat-
Fe Fe2O3, FeS2, FeCO3 ing agent. Hydrofluoric acid, is a relatively weak acid because it
K K2O, KCl forms strong interactions with hydronium ions in solution (Lai
Mg MgO et al., 2016). However, fluoride (F) ion is a strong oxidising agent
Na Na2O, NaCl
P P2O5
and it is highly reactive towards metals, inorganic salts, and sili-
S SO3 cates. HF is even able to dissolve SiO2, not due to its acidic nature
Si SiO2 but rather through the oxidising effect of its anion (Steel and
Ti TiO2 Patrick, 2003). The rest of the acids are unable to dissolve SiO2 even
Zn ZnS, ZnO, ZnCO3
at very severe conditions (Shi et al., 2012).
Analysing the literature, (Goodman et al., 2000; Kim et al., 2009; residue) organic fraction consist of the primary cell wall compo-
Reddy et al., 1999; Underwood et al., 2001; Yang et al., 1985; Zhu nents [cellulose, hemicelluloses and lignin (Eom et al., 2013)].
et al., 2016), the following possible chemical reactions (schematic) The energy that can be used is stored in the organic part. Generally,
can be hypothesized: the inorganic matter is physically or chemically bound to biomass
structure in the form of oxides, silicates, carbonates, sulfates, chlo-
Al2 O3 + 3HX Ac ! Al2 (Ac)3 + 3H2 O
rides, and phosphates (Raveendran et al., 1995). The amount of
minerals depend on the growing season and environmental condi-
Fe2 O3 + 3HX Ac ! Fe2 (Ac)3 + 3H2 O tions. Some elements are naturally present in plants as macro
nutrients (i.e. Na and K) and other nutrients such as Mg, S, Ca
ZnS + HX Ac ! ZnAc + H2 S and P. Table 2 brings together the chemical composition of several
biomass samples.
TiO2 + 2HCl ! TiOCl2 + H2 O In the same plant, the distribution of metals present is different,
as a consequence of the plant’s biology: The stem needs lignin to
Fe2 O3 + 6HNO3 ! 2Fe(NO3 )3 + 3H2 O provide the mechanical strength needed, while leaves are richer
in metals since they accumulate metals through transpiration
SiO2 + 6HF ! H2 SiF6 + 2H2 O and photosynthesis (Fahmi et al., 2007). Analysing the table in
detail a great dispersion in the elements can be observed even
Fe2 O3 + 10HF ! 2H2 FeF5 + 3H2 O 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
FeS2 + 2HNO3 ! Fe(NO3 )2 + H2 S + S
products, the minerals present vary greatly depending on the land.
There are more than only natural occurrences modifying the com-
MY O + H2 Ac ! YMAc + H2 O
position of the biomass samples. The low amount of inherent inor-
where X = 1 or 2 depending on the acid; Ac = SO4 for sulphuric, NO3 ganic elements existing in most forest land woods is increased by
for nitric and Cl for hydrochloric acid; M = Ca, Cu, K, Na Mg and Zn; fertilization and irrigation of agricultural and herbaceous and
and Y = 2 for Na K and Zn. short-rotation energy crop plants (Dayton et al., 1999). Due to
Weak inorganic acids (e.g. H3PO4) (Hassan et al., 2009) and anthropogenic soil pollution, the metal concentration in plants
organic acids such as acetic (Stefanidis et al., 2015), citric, lactic can be several magnitudes higher than the metal levels of plants
and formic acid have also been used in leaching processes, but with cultivated in non-contaminated soil (Mayer et al., 2012). Regard-
limited reports on these investigations. less, the alkali elements amount in biomass is much higher than
in other carbonaceous precursors.
2.2.3. Alkaline Dissimilar biomass materials consist of various quantities of
The most well-known alkali solvents for demineralisation are; mineral matter, e.g. coconut shells contain <1 wt%, whereas straw
NaOH, Ca(OH)2, KOH, Na2CO3 and NH+4, with NaOH having the contains up to 25 wt%. Straws and husks contain 90–95 wt% of Si in
strongest leaching capacity. Sodium carbonate is actually a salt, their ashes (Deiana et al., 2008), while wood ash, the ash of
but it acts as a weak alkali after dissolving in water. Alkali are more bagasse, corn cob and corn stalks are constituted by high Ca, Mg
selective towards dissolving some elements than acids (Gupta and and K contents. Rice husk contains 100 times as much Zn as other
Mukherjee, 1990). Alkali can dissolve silica (at elevated tempera- biomass types (Raveendran et al., 1995).
ture), alumina and also remove different forms of sulphur Pyrolysis is the most frequently used method to prepare bio-
(Mukherjee and Borthakur, 2003). The reactions can be repre- fuel as it can give as high liquid yield as 75 wt% with appropriate
sented in a simplified way as (Miki et al., 2016; Mukherjee, 2003): operating conditions (Jahirul et al., 2012). Pyrolysis is a thermal
process in which biomass polymers are fragmented into light com-
Al2 O3 + 2MOH ! MAlO2 + H2 O pounds that are able to volatise, thereby producing a liquid pro-
duct referred to as bio-oil (Collard and Blin, 2014). The solid
FeS2 + 2MOH ! M2 S + Fe(OH)2 + S leftover called biochar consist mainly of the inorganic residues pre-
sent in the biomass and carbon compounds formed during pyroly-
SiO2 + 2MOH ! M2 SiO3 + H2 O sis and accounts for 10–35 wt%.
From the inorganic components present in biomass, alkali met-
ZnO + NH4 Cl ! Zn(NH3 )2 Cl2 + H2 O als are thought to be the elements giving rise to more disadvan-
tages during high temperature treatments (Wigley et al., 2016).
where M = Na or K. Potassium can lower the average apparent first-order activation
Compared with the acid leaching, alkaline leaching has advan- energy for pyrolysis by up to 50 kJ/mol (Nowakowski et al.,
tages of faster kinetics as well as a simpler impurity removal pro- 2007). Potassium also influences the product distribution, as it
cess. Nevertheless, the higher price of caustic soda makes the catalyses the gasification reaction. In the presence of potassium
alkaline leaching method less competitive than acidic leaching. CO2 and H2O react with the char formed during pyrolysis to form
Therefore, although alkaline solvents show reasonable metals CO and H2, decreasing hence the char yield (Raveendran et al.,
extraction capacity, they are generally combined with acid leach- 1995). Na has similar but weaker effect than K. Both elements lose
ing to decrease the overall cost of the process (Chaala et al., 1996). their catalytic activity in the presence of silica or sulphur as they
react to form alkali silicates or alkali sulfates. The alkaline earth
3. Demineralisation of (lignocellulosic) biomass waste and its metals Mg and Ca seem to be bound to the biomass structure in
pyrolysis char the form of carboxylates and act as crosslinks, joining different
parts of biomass together. Removing them by means of acid solu-
3.1. Mineral content of lignocellulosic biomass tions will relax the biomass structure and this would increase the
yield of sugars or other oligomeric compounds in the produced
Biomass consist of organic and inorganic fractions. Lignocellulosic bio-oil and decrease the chance of reactions to form water
biomass (woody biomass, herbaceous biomass and agricultural (Mourant et al., 2011). Ca also reacts with sulphur to give sulfates
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)

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 et al. (2011) stated that the removal of alkali and alkaline earth ele-
to sustained furnace operations. Ca can promote the activity of ments did not result in significant changes in the yields of bio-oil
Ni but can act as a poison to Fe. Khelfa et al. (2013) found that and bio-char. Nonetheless, they affirmed that the bio-oil proper-
MgCl2 and also NiCl2 but to a lesser extend, increased the char resi- ties, e.g. viscosity, were drastically affected. Bio-oil produced
due while decreasing the maximum pyrolysis temperature and through pyrolysis cannot be used as an alternative to petroleum
changed the composition of the gas fraction. These mean that it transportation due to its high viscosity, high water and ash con-
was catalysing the primary dehydration of cellulose. On the other tents, low heating value, instability and high corrosiveness (Xiu
hand, ligning was not affected by the metals. and Shahbazi, 2012). Some problems such as the viscosity, high
Patwardhan et al. (2010) studied the yield of levoglucosan dur- water content or low heating value might be partially mitigated
ing biomass pyrolysis and found the strongest influence changed in by pre-treating the biomass (Corton et al., 2016; Oudenhoven
this order for the cations analysed: K+ > Na+ > Ca2+ > Mg2+. Among et al., 2013). Due to the fact that, during storage the metals present
the calcium salts used in the study, levoglucosan yield decreased in the oil which have been transferred to the vapours from the
in the following order Cl > NO–3 OH– > CO2– 3
3 PO4 . The inor- char, catalyse polymerization resulting in an increase in viscosity
ganic constituents of biomass also contribute to adverse impacts with time (Das et al., 2004). Biomass pretreatment using acid solu-
on reactors, furnaces, heat exchangers, turbines, emission control tion could avoid an additional fractionation step, simplifying the
devices and other equipment. The issues associated to the presence process and large scale bio-oil production (Leijenhorst et al.,
of the inorganic compounds include equipment corrosion, fouling 2016). The energy consumption and total cost of the process will
of surfaces, catalysts deactivation, and bed agglomeration in reac- be extensively reduced (Yang et al., 2010).
tors (Carpenter et al., 2014; Leijenhorst et al., 2016). In the gas, Another reason for demineralisation before pyrolysis, besides
high concentration of HCl and KCl, lead to corrosion of the equip- the increased in quality and bio-oil yield at the expense of gas, char
ment used (Wang et al., 2010). Silicon is relatively inert in pyrolysis and water, is the mitigation of catalyst poisoning when catalyst are
reactions, however, Si can react with alkali oxides and salts to form added to the pyrolysis process. Bridgwater (2012b) resolved that
eutectics which have lower melting points (<800 °C) and depend- the limiting ash content in biomass to reduce or avoid its catalytic
ing on the pyrolysis temperature, they may end up in the volatile effect should be around 2.5 wt%, although this can vary with the
fraction (Bazargan et al., 2015). chemical composition of the ash and other process parameters.
Different studies show that a metal can simultaneously catalyse Jiang et al. (2013) studied the impact that demineralisation had
and enhance depolymerisation reactions. Thus, depending on in rice straw samples regarding physicochemical structure and
desired products the choice of the metal added or their removal pyrolysis characteristics. They discovered that the majority of K
will vary. and Na were present in the form of water-soluble salts and not
In general, K, Na, Ca, Mg, Si, S and Cl (in this order) are the ele- physiologically bound to the plant tissue whereas most of Ca and
ments to be removed to have an optimum control of the pyrolysis Mg was present in the form of water-insoluble salts and therefore
reaction. to remove the latter, cell walls had to be disrupted (Carpenter et al.,
Most of the inorganic elements present in the biomass end up in 2014). Strong acids such as H2SO4 or HCl could remove strongly
the biochar as they do not volatilise at pyrolysis temperatures bonded elements but they will have negative effect on the fibre
(Al-Wabel et al., 2013). structure of biomass due to the fact that, it dissolved hemicellulose
and cellulose. The fibre erosion led to the creation of a large num-
3.2. Demineralisation of lignocellulosic biomass ber of micropores and mesopores, resulting in increasing of total
pore volume and BET surface area of the samples. A further advan-
The demineralisation of the material can be performed before or tage of the pretreatmet is the potential removal of hemicelluloses
after the pyrolysis process. An overview of the results of the from which aldehydes and related degradation products are
research activities carried out in this field are presented in Table 3. derived which give the bio-oil a peculiar smell and contribute to
Pretreatment of feedstocks prior to pyrolysis provides an oppor- the aging effect (Bridgwater, 2012b). However, the demineralisa-
tunity to produce bio-oils with diverse chemical composition and tion treatment using H2SO4 and HCl can add residual sulphur and
physical properties for specific applications (Hassan et al., 2009). chlorine amounts to the treated sample and can cause the
According to Reichel et al. (2013) and Stefanidis et al. (2015) the volatilization of alkali metals that may contribute to acid gas and
demineralised biomass samples gave higher liquid yield, while aerosol (Yu et al., 2014). Baxter et al. (1998) found out that Cl
decreasing the solid and gas fractions. On the contrary, Mourant 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% HNO3 69.9
Miscanthus 4 H2O 23.0
2 1 wt% HNO3 38.6
675
676
Table 3 (continued)
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

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

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
677
678
Table 3 (continued)
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.

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.
during pyrolysis but that it also depends on the other elements (Bell and Worrall, 2011). Its high porosity could also improve soil
present in the samples. Alkali react with sulphur to form alkali sul- water holding capacity reducing the soil degradation.
fates while chlorine appears to play a shuttle role, facilitating the Some general behaviours are extracted from the findings of the
transport of alkali from the fuel to surfaces, where the alkali forms authors analysed in this review paper.
sulfates. These compounds form deposits on the equipment used, Commonly biomass materials have low ash content with a max-
reducing the facility efficiency, capacity, and availability. imum value of 18.4 wt% for herbaceous biomass (Vassilev et al.,
The vaporization of alkali metals as chlorides can potentially 2010), although the amounts vary greatly from sample to sample
lead to the formation of toxic compounds (Dayton et al., 1999). depending on: plant species, growing conditions, fertilizer and pes-
Scott et al. (2001) analysed the rate of cation removal during the ticide used, harvesting time, etc. The major elements present are
column leaching of poplar wood samples to evaluate the economic Na, Cl, K, Ca and Mg although some other trace elements can also
feasibility of performing the process in an industrial scale. It was be found in varying quantities. Some inorganic components are
concluded that hot water washing alone was able to remove a in water soluble forms (chlorides, nitrates, carbonates and phos-
major amount of the alkaline cations from wood, been potassium phates) while most of the Ca and Mg are in water insoluble forms.
more easily removed than calcium. The exchange process was con- When demineralisation is performed as a pre-treatment on lig-
sidered to be fast and relatively cheap. nocellulosic biomass before pyrolysis, water washing cannot fully
One main downsides of the pretreatment is the need of a subse- remove inorganics i.e. maximum removal value at room tempera-
quent drying process of wet biomass prior to been pyrolysed to ture was 67.7 wt% (Jenkins et al., 1996). Increasing the temperature
reduce the moisture content. The dewatering can be performed of the water additional ash can be removed by increasing the met-
by mechanical means or by thermal drying. A new process for als solubility in the leaching agent. Increasing the leaching temper-
energy-efficient liquid/solids separation has been studied by ther- ature from 30 °C to 90 °C the ash removal of candlenut wood
mally assisted mechanical dewatering (Mahmoud et al., 2011). The improved a 22.9 wt% (Deng et al., 2013). Hot water treatment
mechanical method consisting in pressure-assisted dewatering, may open up the biomass structure, allowing the washing medium
can reduce the moisture content to 50% (Turn et al., 1997) but to penetrate deeper within the biomass particles removing more
also removes superficial liquid and hence additional soluble inor- inorganic matter. Washing time affects the demineralisation beha-
ganic constituents (Yu et al., 2014). The most common way is to viour; at the beginning (short period) there is a rapid leaching step
air dry the pre-treated samples at relatively low temperatures followed by a slow leaching step for a relatively long period. There-
(<105 °C) in small ovens or under vacuum conditions in a desicca- fore, once the fast leaching step is over, the effect of time decreases
tor. The drying times vary from 12 h (Mayer et al., 2012) to 24 h noticeably. Distilled or deionised water gave generally better
(Asadieraghi and Wan Daud, 2014) or in some cases until the results compared to tap water; 6.2 wt% improvement for wheat
weight is constant (Messina et al., 2016). The cost of the process straw and only 0.5 wt% for rice straw due to the different nature
should be borne entirely by the fuel/products obtained through of the inorganics present (Jenkins et al., 1996) mainly due to the
the pyrolysis. mineral dissolved in tap water being adsorbed on the biomass
There is also an added cost associated with the recovery and sample.
disposal of the liquor used for demineralising (Liu et al., 2017). In In lignocellulosic biomass, some inorganics are in cationic form
order to avoid the cost associated problem, Oudenhoven et al. bounded to reactive sites in the structure of biomass therefore,
(2013) reused the liquid fraction obtained during the pyrolysis of water is not enough to remove all these elements. Those metals
biomass as leaching agent, effectively removing the alkali ions ini- will only be able to be removed by ion exchange from an acid.
tially present in the feedstock. The acid washing was concluded to be the most effective technique
The post-treatment for demineralisation of biochar originating for ash removal, reaching 99% removal in some cases (Mayer et al.,
from the pyrolysis of biomass is widely used (Shen et al., 2012), 2012). The treatments with weak organic acids are not as efficient
mainly when producing activated carbon (Aygün et al., 2003; in mineral removal as the ones carried out with inorganic acids;
Sharma et al., 2009). However, most of the authors that use this 48 wt% for acetic acid treated switchgrass against 72 wt% when
technique do not analyse the demineralisation after pyrolysis in treating it with HCl (Liu and Bi, 2011). Despite that, inorganic acids
depth, they only apply it to their material without studying its (even in mild concentrations) may destroy by opening or loosening
effects. the structure of the biomass macropolymer leaving the metals
Deiana et al. (2008) compared the textural parameters of sev- more exposed for leaching the internal structure of biomass,
eral activated carbons produced from the leaching and activation hydrolysing hemicellulose and pectic materials whereas organic
of biochar derived from rice husk. When acid leaching was applied acid do not change significantly the surface of biomass samples.
to the samples the BET values improved enormously. In the case of When strong acids such as HCl and H2SO4 are used, special atten-
untreated AC BET increased from 290 m2/g to 750–1000 m2/g if tion has to be put in order to avoid residual elements such as Cl and
leaching was performed. Nevertheless, there was a big difference S from the acids as they can affect pyrolysis negatively. The extra
between treating the sample before the activation step of after. rinses required to remove the residual ions are a major drawback
The results suggest that when the leaching step is performed that could limit the large-scale application. Regarding thermal sta-
before the activation, the inorganic salts are removed, allowing bility, the temperature of initial weight loss shifted to higher val-
the penetration of water vapour on the pores created during the ues for acid treated samples. Demineralisation shifted the
removal of the elements generating a more developed pore maximum degradation rate temperature of wood sawdust from
network. 350 °C to 370 °C (Messina et al., 2016). This indicates a higher ther-
Rice straw char was treated with HCl and HCl-HF and the sur- mal stability against oxygen and nitrogen.
face characteristics and pentachlorophenol adsorption capacity Treating biomass to remove the unwanted metallic constituents
before and after the treatment were evaluated. The demineralisa- prior to pyrolysis has the potential to affect not only the ash but all
tion increased the surface area and the pore volume increasing the products of the process. Bio-oil yield increased 22.6% after pre-
the adsorption although the new acidic functional groups created treating palm fruit bunches with water for 24 h (Abdullah and
on the surface had a weak hindering effect (Lou et al., 2011). Gerhauser, 2008). The pretreatment has the advantage of improv-
The biochar produced during the pyrolysis of biomass can also ing the quality of crude bio-oil because it avoids the polymerisa-
be used on the agricultural land to capture and store carbon, as a tion during storage reducing the viscosity and water amount
fertiliser or to improve soil quality to increase food production present in the oil.
The need to remove minerals from waste biomass prior to formed during pyrolysis and becoming inaccessible-insoluble in
pyrolysis represents a somewhat costly step both economically water.
and in terms of energy, since the volume of material to be treated Demineralisation is performed onto pyrolysis solid products
is much bigger in the pretreatment than in the case of post- mainly when the chars are physically or chemically activated to
treatment due to the low amount of char present when biomass produce adsorbents. Acid treatment is an efficient way to deminer-
samples are pyrolysed. Therefore, the volume of solvent employed alise and increase the surface area of the carbon before or after
during the treatment will be notably higher. Not only that, but a activation. The demineralisation step increased the BET of all the
drying step that will increase the cost of the entire process should chars treated although, in some cases, that did not translate into
also be added. a better adsorption capacity. The change in polarity associate to
There are many less published works that study the demineral- the deashing might be the reason for the decrease in adsorption.
isation after the process of pyrolysis [the technology started to be The recommended method to treat waste biomass is sum-
studied in the early 1990s (Liu et al., 2017)] by which it can be con- marised in Fig. 2.
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- 4. Demineralisation of waste tyres and its pyrolysis char
treatment only acids are used. It might be that during pyrolysis
some of the elements that were present in a water-soluble form 4.1. Metal content of waste tyres
change their formula due to the high temperatures encounter dur-
ing the process, becoming trapped in the new organic structure 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
Fig. 2. Proposed process diagram for biomass waste demineralisation. 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
structure that shapes the tyre. These metals are also found in the on the surface of the tyre. Fields studies carried out by Edeskar
case of using pieces of tyre in which the casing is not removed. (2006) also monitored the pollution of tyres used in 3 different civil
When using crumb the elements that are part of steel such as Fe engineering applications as lightweight fill in a noise barrier, in a
and Mg are drastically reduced. capping layer in a road construction and in an embankment fill
The chemical composition of the tyres is also altered due to the material in a driving range in fields. The author concluded that only
different nature (car or truck) and brand that produces them. As some Zn and Fe were found in higher concentrations when tyre
tyres are separated only by their use (car or truck, at best) and shreds were used. Nevertheless, these values were too low so tyres
not by their manufacturer, the difference that exists between the were classified as inert waste by the EC landfill directive.
chemical compositions is mitigated by the intermingling of all Solano et al. (2012) studied the use of recycled-tyre crumb rub-
types of materials. ber, as a lightweight material for amending green roof media.
These contaminants originate from the compounds added to the Despite its advantages as a recycled product, crumb leaches Zn in
tyre in order to meet specific tyre performance requirements. In potentially toxic quantities for green roof plants and the overall
the char, the carbon content is very high (>80 wt%), but sulphur ecosystem. They observed a large sample to sample variation,
content is about half of the amount initially present in the tyre which reflects the variability of Zn in the crumb samples. During
(<3 wt%) where it is performing as the crosslinking agent between the first 12 h significantly more Zn was released from the acid
elastomer chains (Mark et al., 2005). The most common metals water treatment than the neutral pH one, but thereafter no signif-
found in the crumb and char are Zn, S, Si, Fe, Mg, Al and Ca. Those icant differences were found in the cumulative Zn leached.
metals appear mainly in their elemental form or in their corre- Char can be used in several application provided that it is pre-
sponding oxide or sulphide. Zn derives from the zinc oxide added treated to reach the minimum requisites. It needs further upgrad-
to the rubber to control vulcanization and enhance the physical ing to be used in different applications such as: adsorbent and
properties (Williams and Besler, 1995). To reduce the cost and additive. The char can also be used as feedstock for activated car-
for ecological reasons, some tyre manufactures replace some carbon production.
bon black with silicon or SiO2 thus the high amount of Si present Activated carbon is very efficient in waste water treating appli-
in the crumb or char. Due to the high boiling point of SiO2, it does cation, but the commercial adsorbents are still very expensive.
not leave the sample with the volatiles during pyrolysis therefore it Therefore, using a cheap starting material such as waste tyres will
stays in the solid residue. CaCO3 is also used for replacing CB thus reduce the price and make it more attractive. Activation of char
the presence of the element in the char. Fe and Mg might be related obtained from pyrolysis of waste tyres has gained a lot of attention
to some small steel wire pieces that were not removed from the (Gupta et al., 2011b; Manocha et al., 2013; Mui et al., 2010a). The
tyre before pyrolysis. surface area of the char is low (SBET < 100 m2/g) and thus, it has a
low adsorption capacity. However, they are mainly mesoporous
4.2. Demineralisation of waste tyres (Tanthapanichakoon et al., 2005) (around 90% of pores) and this
might help the adsorption of pollutants on that range of sizes. The
Several demineralisation works performed on waste tyres char has to be activated either by physical or chemical activation
crumb and waste tyre derived chars have been summarised in processes to create new porosity and/or to enhance the one present
Table 5. in the sample. The demineralisation step can be performed before
Both, waste tyre crumb and the char obtained by pyrolysis have (Chan et al., 2012) or after (Gupta et al., 2012, 2014) the activation
several applications. Crumb can be used as a filler in rubber phase. Ariyadejwanich et al. (2003) found that treating the char in
(Karger-Kocsis et al., 2013) and concrete (Atahan and Yücel, an acidic solution before the steam activation step, increased the
2012), or as lightweight aggregate for flowable fill (Pierce and mesopore volume and microporosity of the activated carbon, due
Blackwell, 2003). While char can be used to replace carbon black to the creation of new active sites that were subsequently devel-
(Martínez et al., 2013) in pigments (Pilusa and Muzenda, 2013) oped during the activation step. While, comparing the performance
or bitumen (Feng et al., 2016) or activate it and use it to remove of the demineralisation treatment after activation, the main
organic (Gupta et al., 2011a) and inorganic (Helleur et al., 2001) improvement was related only to the minerals removal.
pollutants. Nevertheless, the minerals present in their composition Shah et al. (2006) demineralised waste tyre pyrolytic char using
can pose some problems to their applicability. HCl or H2SO4 before the activation step. The surface area of the
The leaching of tyre constituents may pose environmental con- adsorbent increased from 85 m2/g to 870 and 800 m2/g (HCl and
cerns when using them in civil/environmental applications. Selbes H2SO4 respectively) before the activation step. Further improve-
et al. (2015) studied the leaching of organic and inorganic compo- ment was observed after the activation step, reaching values of
nents from waste tyres crumb and chips under different pH condi- 940 and 910 m2/g (HCl and H2SO4 respectively) that are in the
tions, similar to the ones encountered in natural environments. same range of the commercially available activated carbons which
They observed that for smaller size tyre chips, the leaching of specific surface area values range between 800 and 1100 m2/g.
organics was higher however, the leaching of inorganic con- Before the activation, a demineralisation step to get rid of the
stituents was independent of the size. At basic pH conditions the maximum amount of contaminant metals is desired. Removing
leaching of organics increased, whereas acidic pH conditions led the minerals present in the surface before the activating step can
to elevated concentrations of metals. Leaching was minimal lead to a better development of the porosity as the activating agent
around the neutral pH values. Nelson et al. (1994) focused their will have easier accessibility through the new created pores. How-
study on the toxicity of artificial reefs made of waste tyres. They ever, the reactivity of the activated carbon can decrease due to the
found out that Zn, Cd, Cu and Pb where leached from the tyres in removal of some elements such as Ca and Zn as they might have
the laboratory experiments in high enough amounts to be toxic some kind of catalytic effect during activation (Antoniou et al.,
to some fish species. Nevertheless, due to the big volume of water 2014). Chlorinating activated carbons produced from tyres also
encountered in natural environments where artificial reefs are cre- increased the toluene adsorption (Zhu et al., 2009) corroborating
ated it is unlikely that the zinc concentrations leached from the the possible catalytic effect of Cl.
tyres used in artificial reefs would ever cause acute or even chronic Although there is a lot of work done using the demineralisation
toxicity. Collins et al. (2002) also reached similar conclusions and of waste tyre char for obtaining cheap adsorbents, the effect of the
suggested that the leaching only occurred in the few microns deep 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.

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

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
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.
If the demineralisation is performed before pyrolysis, undesired Antonijević, M.M., Dimitrijević, M., Janković, Z., 1997. Leaching of pyrite with
hydrogen peroxide in sulphuric acid. Hydrometallurgy 46, 71–83. https://doi.
reactions derived from the presence of minerals during pyrolysis
org/10.1016/S0304-386X(96)00096-5.
could be avoided, and the quality and yield of all the final products Antoniou, N., Stavropoulos, G., Zabaniotou, A., 2014. Activation of end of life tyres
will be improved. The biggest drawback for this practise is the big pyrolytic char for enhancing viability of pyrolysis – critical review, analysis and
volume of sample to be treated. Pre-treatment is not performed in recommendations for a hybrid dual system. Renew. Sustain. Energy Rev. 39,
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Waste Management: I. Iraola-Arregui, P. Van Der Gryp, J.F. Görgens

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Waste Management 79 (2018) 667–688

Contents lists available at ScienceDirect

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

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

Fig. 1. Schematic diagram of demineralisation mechanism.

2.1.3. Temperature 2.1.8. Solvent and pH

There are also a number of additional solvent properties that

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

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

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

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

D-H2O: Distilled water.

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

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

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