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Fuel Processing Technology 137 (2015) 259268

Contents lists available at ScienceDirect

Fuel Processing Technology


journal homepage: www.elsevier.com/locate/fuproc

Reforming of tars and organic sulphur compounds in a plasma-assisted


process for waste gasication
Massimiliano Materazzi a,b, Paola Lettieri a,, Luca Mazzei a, Richard Taylor b, Chris Chapman b,
a
b

Department of Chemical Engineering, University College London, Torrington Place, London WC1E 7JE, UK
Advanced Plasma Power, South Marston Business Park, Swindon, SN3 4DE, UK

a r t i c l e

i n f o

Article history:
Received 21 November 2014
Received in revised form 9 March 2015
Accepted 10 March 2015
Available online 7 April 2015
Keywords:
Waste gasication
Fluidized bed
Plasma
Tar
Sulphur

a b s t r a c t
Waste gasication is considered a valuable and sustainable solution to the production of clean energy (via gas
turbines or gas engines) and bio-fuels, such as synthetic natural gas and bio-hydrogen, provided that the syngas
produced in the gasier is free of condensable tars and organic sulphur contaminants that cause equipment fouling and deactivation of catalytic stages downstream. In particular, catalytic reaction stages are highly sensitive to
specic trace contaminants (e.g. PAHs, thiophenes, etc.), necessitating the use of additional cleaning operations
to remove these residues to levels where the catalyst degradation is acceptable. In this work, the use of thermal
plasma (coupled with primary waste treatment) to completely reform tars and organic sulphur compounds to
simple gaseous products (predominantly H2 and CO) is assessed. To this end, a 20-hour waste gasication run
was performed on a two-stage uid bed-plasma demonstration plant to investigate the tar evolution in the
syngas, with special attention on the chemistry of generic and sulphur-substituted aromatics within the plasma
stage. The organic fraction in the gas phase was found to be completely reformed under plasma conditions,
leaving essentially CO, H2 and H2S as ultimate products. In particular, reduction efciencies typically exceeded
96%v/v for complex organics (e.g. PAH) and thiophenes were observed. The syngas, after a tertiary simplied
gas cleaning process, is suitable for high efciency power generation, or conversion to a fuel gas capable of injection into national or industrial supply grids.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The major technical obstacle faced by conventional waste gasiers/
pyrolysers is the high level of tars and organosulphur contamination
in the syngas, which can cause fouling and corrosion problems in the
power island, as well as the inactivation of the catalysts used in conversion processes by poisoning and carbon deposition. This has been the
primary cause of waste gasication developments failing over the last
30 years and has prevented their commercial adoption with efcient
technologies for power generation (e.g. gas engines, fuel cells, etc.)
and catalytic transformation to generate either hydrogen or alternative
fuels [15].
The level of tars and contaminants in the syngas is equally
determined by the gasier design, feedstock nature and process conditions [5]. Fluid bed systems are currently the most employed in waste
gasication [6]. They include a range of different designs, such as bubbling uid bed (BFB), circulated uid bed (CFB) and dual uid bed [6].
Fluid bed gasiers (FBG) have been shown to be very exible in their
Corresponding author. Tel.: +44 207 6707867; fax: +44 207 3832348.
Corresponding author. Tel.: +44 1793 238523; fax: +44 1793 828 287.
E-mail addresses: p.lettieri@ucl.ac.uk (P. Lettieri), chris.chapman@app-uk.com
(C. Chapman).

http://dx.doi.org/10.1016/j.fuproc.2015.03.007
0378-3820/ 2015 Elsevier B.V. All rights reserved.

ability to handle a range of wastes, without the need for additional fossil
fuels or woody biomass to be added to the process. The expanded bed of
inert particles creates a large mass of hot material that is able to absorb
and mitigate uctuations in fuel conditions with little-to-no change in
performance. This ywheel effect is better suited to minimise spikes
in emissions due to the wide fuel variability when working with
waste-based materials, where small differences in fractions of certain
key components, plastics in particular, may cause disproportionate
changes in the gasication product yields. However, with high volatility
(more than 60%) and low ignition temperature (250350 C), waste
material is prone to devolatise immediately after the injection into the
reactor [7], making it more susceptible to tar formation and sulphur
contaminants release when compared to other fuels, such as biomass
or coal. The assumption is often made that tars and organosulphur compounds are progressively converted to CO, H2, and H2S with increasing
reaction severity, which is a function of oxygen content, temperature
and time. This is true with primary tar products, characterised by primary vapours and mixed oxygenates, such as phenols, acetaldehyde, cresol
and sulfones, which are very reactive in high temperature conditions.
However, the relative proportion of aromatic and longer chain polycyclic aromatic hydrocarbons (PAH) increases with increasing temperature, and a more refractory tar is left in the producer gas [8].
Naphthalene and thiophene, for example, do not thermally react in

260

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

the gas phase up to temperatures as high as 950 C. So, once formed, it is


unlikely that they will decompose at the normal gasication conditions
used [8].
Furthermore, waste materials are likely to contain substances in
varying quantities in the ash-forming fraction (i.e. soda, potash, sulphates, phosphates, chlorides etc.) which can form low melting point
eutectics in the uid bed. The maximum temperature of operation of
the FBG is therefore limited to around 800-850 C, to avoid the melting
danger of the various mineral phases in the system, which would promote coalescence of solid particles and deuidisation of the bed [7]. At
these temperatures, a certain range of problematic components is still
stably present, or newly generated. The literature reports an average tar
loading of FBG reactors of about 10 g/Nm3 (mainly PAHs) [8], while the
total sulphur content is in the order of 100 ppm (142 mg S/m3) [9]. Cui
et al. [10] analysed the producer gas of a uid bed gasier at 800 C fuelled
with wood chips, and identied principally tar species with an average
concentration of 15.5 gm3 (dry gas basis) and several organosulphur
contaminants such as thiophene (5.58 mg S/m3), benzo[b]thiophene
(0.85 mg S/m3) and an unknown (0.9 mg S/m3) compound. Although
PAHs and thiophenic sulphur compounds in low concentration are
often not adequately evaluated, they are more persistent than other
contaminants in gas cleaning processes, and require specialised unit operations. There has therefore been a signicant effort to develop technologies that can remove these contaminants in a technically robust and
economical way.
One possible approach is to condense the tars from the gas stream
using either water or oil washing, and attempt to recover the signicant
energy contained in the tar condensate by recycling it to the thermal
treatment stage [11]. An example of such approach has been developed
at the Energy Research Centre of the Netherlands (ECN) with a multiple
stage scrubber in which the gas is cleaned by special scrubbing oil [12].
However, particularly in the treatment of wastes, contaminants including sulphur, chlorine, heavy metals and particulates are then inevitably
concentrated in the recycle stream. This may limit or even preclude the
possibility of tar recycling, leaving a problematic waste for disposal and/
or clean-up which is not only highly toxic but typically embodies
around 10% of the energy value of the input fuel [13]. This stream
could be incinerated or combusted separately for energy recovery, but
this introduces further technical and economic challenges given the
high concentration of pollutants (primarily sulphur and chlorine
based) both in the solid residue and in the emissions from the combustor. The removed organics may also be partially water-soluble and so
may be present at elevated levels in the water scrubbing/efuent
clean-up system. Moreover, although such removal systems have been
designed and operated on fuel gases generated from low tar/sulphur
biomass feedstocks (such as hard wood), their application to waste
fuels, where the complex spectrum of contaminants generated is very
different, has not been reliably tested.
The other approach reported in the literature is the addition of
catalysts and transition metal oxides within the gasier to reduce the
tar loading and promote hydrogenation and/or steam reforming of the
organics [8,14]. Analogously, organic sulphur compounds can be converted into hydrogen sulphide and similar compounds [15]. However,
the results have not been promising due to a combination of coking
and friability of the added catalyst [8]. Furthermore, waste streams contain high levels of ash and inerts, which dilute and reduce the efcacy of
the added materials, so that the extent of tar and organosulphur reduction that can be attained by this method is limited. These catalysts also
add to the operating cost of the plant, especially if we consider that
they are often used in separate hydrodesulphurisation units downstream of the gasier [16]. The ongoing research is then moving towards
developing inexpensive catalysts which are active in the presence of
both hydrocarbons and sulphur compounds, and can be commercially
operated at relatively mild conditions [16].
A further technical issue that is frequently associated with conventional waste gasiers/pyrolysers is that they may produce a solid ash/

deposit residue that can contain high levels of carbon, residual tars
and sulphates. This not only represents a loss in energy conversion in
the process but, more importantly, represents a large volume of waste
(typically 1060% of the ash mass) that must be sent to a hazardous
landll facility [17].
To avoid all these problems, the use of thermal plasma (coupled with
primary waste treatment) has recently been applied for its ability to
completely reform/crack the tars to simple gaseous products (predominantly H2 and CO), which contribute to the net caloric value (NCV) of
the cleaned gas. Simultaneously, inorganic particulate and ash-type
components are converted into a stable vitried product. The hydrogen
rich syngas from the two-stage process contains very low residual levels
of tars and, in addition to potential use for high efciency power generation, is suitable for the production of liquid fuels, renewable hydrogen
and/or substitute natural gas [1820].
Thermal plasma arcs are characterised by their high temperature
and intense UV radiation. The energy density of the plasma arc is typically two orders of magnitude higher than a combustion ame [21].
The energy input from plasma is readily controllable and (unlike combustion systems) is independent of the process chemistry, generating
low off-gas volumes, reducing the size, complexity and the associated
capital and operating cost of the downstream gas cleaning equipment
and rendering the process exible to changes in the fuel characteristics,
typical of waste materials.
The main advantage of coupling the two technologies is that the
oxidant addition rate and power input in the two-stage process can be
controlled independently while, unlike single stage processes, the
gasication stability is not dependent on the gas evolved from the fuel
itself. Critically, the heat input to the units and emission control are
not dependent on the ability to combust residues such as char and
tars that are generated in the process and whose composition and quantity cannot be readily controlled [22]. This is an especially important
consideration in treating waste feedstocks, which are heterogeneous
in nature and contain much higher levels of ash and volatile matter
than conventional biomass.
This study is concerned principally with the thermal treatment of
sulphur-rich refuse derived fuel (RDF) prepared from municipal solid
waste (MSW), commercial and industrial (C&I) and automotive
shredded residue (ASR) wastes. A 20-hour waste gasication run was
performed on a moderately large scale demonstration plant which
incorporates a plasma processing stage (i.e. plasma converter, or PC)
for conditioning the gas generated from a uid bed gasier (FBG). An
experimental program was dened to investigate tar evolution in the
hot syngas, focusing on the chemistry of generic and sulphursubstituted aromatics within the plasma stage. This provides a clearer
understanding of the mechanism as to how these contaminants evolve
and provides a basis for assessing the role of plasma chemistry on the
reforming process.
2. Experimental
2.1. Materials
The prepared RDF comes from a number of waste treatment facilities
in oc form of size ranging from 5 to 40 mm. Key raw materials arising
in the original waste were food (37%), paper and card (1530%), plastics (1015%), wood (510%) and textiles (510%). Other combustibles
(~ 2-5%) and other non-combustibles (510%) were also prominent.
Although not specied, anecdotal evidence would suggest that the
other combustibles would include materials such as rubber, underlay
and foam (used in upholstery and bedding, for example). Similarly,
the non-combustible fraction would contain materials such as construction and demolition waste (C&D), rubble and ceramics. Once received,
the RDF was bagged into individual exible intermediate bulk containers (FIBC) containing ca. 70150 kg each. These bags were then
sampled, using a cone and quartering technique, and a weighted

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

Styrene
1%

Polyethylene
4%

Lignin
20%

Other (PET,
LDPE, PVC,
etc.)
5%

Cellulose
47%

Hemicellulose
23%

S/ mg g-1

average sample was prepared. This sample was then sent to an independent, United Kingdom Accreditation Service (UKAS)-certied testing
laboratory for ultimate and proximate analysis, along with caloric
value (CV) measurement. The results of this analysis are summarised
in Table 1.
The wide range of component materials associated with the original
wastes, and sulphur content therein, makes the exact organic groups
speciation very challenging. Nonetheless, the organic RDF matrix can
be viewed as a combination of different complex macromolecular structures (e.g. cellulose, hemicellulose, lignin, polyethylene, etc.) reecting
the parent materials composition. Organic sulphur is bound in these
functional groups, and can be categorised into one of the functionalities
such as thiols (SH), sulphide bonds (S), thiophenes, thiopyrones,
etc. [16,23]. Sulphur is also present in elemental form (S) and two inorganic forms, being pyritic sulphur (FeS2), and sulphates (Na2SO4, CaSO4,
FeSO4), largely found in car-tyre scrap and demolition wood [23].
The relative distribution of the different forms of sulphur in the main
four RDF organic structures (i.e. lignin, hemicelluloses, cellulose and
plastic polymers) is reported in the literature [2427] and shown in
Fig. 1. Thus, in the studied RDF sample the inorganic sulphate is about
3035% of the total sulphur, the elemental sulphur is about 12% and
the rest of the sulphur, approximately 6070%, is either tightly adsorbed
polysulphide and/or covalently bounded to the organic matrix as thiols
or sulphides. However, given the high variability of RDF composition,
this apportioning of sulphur between organic and inorganic is not
certain, and remains only a reasonable approximation.

261

18

Organically bound S (-SH,


-S, -S-S)

16
14

Inorganic S (SO4)

12
10

Elemental S

8
6
4
2
0

2.2. Process equipment

Lignin

Data reported and discussed in this paper are generated from a specic set of test work performed with the Advanced Plasma Power plant
in Swindon (UK), which is a reduced capacity version of a commercial
uid bed-plasma plant. It comprises a FBG designed for steam/oxygen
gasication closely coupled to a single carbon electrode plasma converter, as shown in Fig. 2.
The waste feed is metered into the FBG under controlled conditions,
using a variable speed screw feeder at rates of up to 100 kg/h, and a
crude syngas is produced. The FBG is specically congured to handle
a broad range of feeds, from the relatively simple (e.g. biomass) to
those usually considered more problematic (such as RDF). The FBG contains a bed of nominally 1 mm mullite particles, whose particle size has
been selected to match the hydrodynamic conditions within the bed enabling efcient uidisation whilst avoiding high rate of elutriation.
Mullite is also chosen on account of its low cost, high availability, and
good resistance to thermal shock and attrition. The uid bed is maintained at a temperature of between 700 and 850 C, with the actual

Table 1
Proximate and ultimate analysis of the RDF used.
RDF (as received)
Mechanical characteristics
Mean particle size, mm
Bulk density, kg/m3

30
70

Proximate analysis, % (w/w)


Fixed carbon
Volatile matter
Ash
Moisture

6.4
59.6
16.18
13.08

Ultimate analysis, % (w/w)


C
H
O
N
S
Cl
NCV, MJ/kg (dry basis)

41.84
5.01
21.65
1.58
0.4
0.25
19.47

Hemicellulose

Cellulose

Mixed plastic

Fig. 1. (Top) Estimated RDF organic matrix composition in its principal basic constituents
(values given in weight %, dry-ash free); (Bottom) Rough estimation of the relative contribution from sulphur species in RDF constituents derived from literature [2427].

operating condition depending on fuel characteristics and desired reaction proles. The ows of steam and oxygen are nely controlled to
maintain the bed temperature, ensure good uidisation of the gasier
bed and achieve the required syngas quality. Bottom ash is drawn
down to the bottom of the FBG and then screened at 2 mm to separate
out the oversize material. The undersized material is returned to the
uid bed unit, while the rest is fed into the PC. The crude syngas produced exits from the top of the gasier and is then passed by way of a
refractory lined duct to the PC. The PC is a transferred arc plasma furnace
with a molten pool of slag and metals at the base, formed from the melting of the inorganic fraction of the fuel feed. The slag melt also ensures
that an effective electrical path is maintained with the conductive
hearth/anode return electrodes which are built into the converter
hearth. The syngas enters the side of the converter chamber above the
slag level and circulates around the periphery of the cylindrical chamber
allowing the gas to increase in temperature (~1200 C) while receiving
maximum exposure to the intense ultra violet light from the plasma arc,
aiding cracking of tar substances. Separation of small particulates (y
ash, entrained bed particles, char fragments) from the syngas is promoted by the cyclonic action, which forces particles in the range of 101000
micron to impact the wall, lose momentum and fall in the slag melt. This
vortex produced by the swirling gas ensures efcient recovery of particles in the PC and converts these into slag, which is tapped periodically
from the base of the furnace. Downstream of the PC, the syngas is cooled
down to below 200 C in a steam boiler prior to a very basic treatment to
remove any residual particulates and acid gas contaminants (mostly,
HCl and H2S). This includes a dry lter (incorporating a ceramic lter
unit with sodium bicarbonate dosing and activated carbon) followed
by a wet scrubber. Water condenses from the syngas as it is cooled
below the dew point when entering the scrubber. The water mixed
with the scrubbing alkaline liquor dissolves almost all the nitrogenous
compounds, chloride, uoride, and sulphur gases present as well as

262

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

Wet
scrubber
unit

Fuel addition
system

Fig. 2. Schematic of the Gasplasma process and gas sampling points (Gi).

lesser amounts of CO2. Before the cleaned gas leaves the top of the
scrubber, it passes through a demister to reduce any entrained water
droplets and is then discharged through the gas outlet at the top of
the scrubber. The liquor collects in the sump of the scrubber from
where it is pumped by the centrifugal pump back to the top of the
tower. Slightly negative pressure (510 mbar) is maintained within
the process using an induced draft (ID) fan located after the wet scrubber. In the demonstration plant, the rened gas (LHV = 10-14 MJ/Nm3)
is directed to a gas engine for production of power before the oxidised
gases are released to atmosphere.
The major difference that affects gas composition between this plant
and the full-scale plant is the much greater relative quantities of inerting
gas (i.e. Argon) that are used to provide both purge and gas seals in the
Swindon plant as compared to those used in the full-scale plant. The
reason for this is that the requirement for sealing and purging gas
does not scale proportionally with the size of the plant. Nevertheless,
the information from the demonstration plant is sufciently reliable to
understand the behaviour of organics in a two-stage process and assess
the capacity of plasma to crack and reform problematic components,
such as tars and thiophenes, without excessive boundary layer effects.
A full and more detailed description of the apparatus and plant operation is available in the literature and not reported in this paper [28,29].
2.3. System monitoring and analysis
The plant was specically instrumented with direct and continuous
measurements of ows, gas composition, temperatures and pressures,
to study the reforming of tars at high temperatures [29]. The on-line
syngas composition was monitored at different locations of the plant
using a Gasmet Fourier Transform Infrared (FTIR) Spectroscopy gas
analyser. The FTIR samples the gas stream ten times per second
and can be set to average these samples over varying time periods
(1060 seconds). Specic gas species analysed included: CO, CO2, H2O,
NH3, NOx, SOx, COS, HF, HCl and a number of key volatile organic species
(i.e. CH4, C2H2, C2H4, C6H6, C7H8, C6H5OH and C10H8). A K1550R Hydrogen Gas Analyser supplied by HiTech Instruments (with compensation
from an IR600 CO2 analyser) is also used for the direct monitoring of
hydrogen. Additional CO/CO2 IR monitoring using is undertaken
utilising a XEntra 4210 analyser. The caloric value of the gas and its
Wobbe index are monitored using a CWD 2005 Calorimeter.
A Biogas 5000 electro-chemical analyser is used to allow for the continuous monitoring of hydrogen sulphide (0500 ppm). The unit simultaneously allows the measurement of CH4, CO2, O2 and H2S. For safety

reasons, the oxygen concentration of the syngas is also monitored


using a paramagnetic sensor which is incorporated in the Xentra 4210
Servomex analyser. A Michell XTP-601 paramagnetic oxygen sensor is
also used as a redundant system to the Servomex unit. If, when gasifying, the concentration of O2 in the syngas exceeds 1%, then the system
is automatically shut down.
Tar species and organosulphur compounds are identied using gas
bag sampling. Gas samples from different locations are drawn into
Tedlar bags and sent for off-line measurement. An aliquot of sample is
withdrawn from each bag using a glass syringe and subsequently
injected into a modied purge & trap (P/T) concentrator. The volatile organic species are thermally desorbed from the trap, separated by GC and
analysed by a very sensitive positive ion electron impact MS.
Before starting the plant, a total of 100 kg (50:50 w/w) of iron pig
and stimulant-ushing slag (33.7% SiO2, 28.8% CaO, 3.2% Al2O3, 34.3%
Fe2O3) was charged to the PC to act as a return path for the DC plasma
circuit. In normal, steady state operation, the slag slowly accumulates
in the base of the converter over time, giving a more uniform temperature, avoiding excessive temperatures in the plasma arc impingement
zone and more rapid melting of the ashes from the FBG. At the completion of the trials, a slag sample was extracted from the plasma converter
and prepared to less than 4 mm grain-size by crushing and sieving.
Chemical analysis was carried out by an independent, UKAS accredited
laboratory (Environmental Scientics Groups Ltd.) with the required
suite of tests for detecting sulphates and the organic content in the
solid residue, including total dissolved solids (TDS), dissolved organic
carbon (DOC), total organic carbon (TOC), loss on ignition (LOI) and
trace organic parameters including benzene, toluene, ethylbenzene,
and xylenes (BTEX), polychlorinated biphenyls (PCBs) and PAHs.
X-ray uorescence (XRF) analysis was also employed to obtain quantitative compositional data on the bulk oxides after sample fusion into a
glass bead using lithium tetraborate. Trace element analysis was carried
out by inductively coupled plasma optical emission spectroscopy (ICPOES).
3. Results and discussion
The most important ranges of the operational parameters used in
the demonstration plant for the test to be discussed here are listed in
Table 2.
The RDF was fed with an addition rate of 3550 kg/h. The oxidants
rates were adjusted to maintain a bed uidisation velocity of between
0.6 and 0.8 m/s. The plasma power was controlled to provide a syngas

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268


Table 2
Test conditions in the APP demonstration plant.
Operating parameters

Values

RDF feed rate (kg/h)


FBG temperature (C)
FBG supercial gas velocity (m/s)
Oxygen to fuel ratio (w/w)
Steam to O2 (mole) ratio
Plasma converter exit temperature (C)
Energy at the electrode (kW)

3550
750
0.75
0.280.33
2.53
11001200
100130

temperature of 11001200 C from the plasma converter and keep the


slag in liquid form. Gas measurements were performed as discussed in
the previous section.

3.1. Syngas composition


The average data for the most prominent syngas constituents recorded during the FTIR monitoring periods at several locations of the
plant are presented in Table 3. To allow for comparison, the change of
syngas GHV is also given.
The syngas composition varies considerably depending upon the location of the sampling point. The cleaned syngas (G3) mainly consists of
H2 and CO (40.4% and 26.8% respectively), but also contains CO2 (15.7%),
small amounts of N2 and residual water vapor. Note that all values are
for a gas generated in the pilot plant unit which contains relatively
higher levels of inerting gas (Argon) than would occur in a commercial
system. The level of nitrogen in all samples is of uncertain origin - the
most likely explanation for most of this N2 is the ingress of some quantities of air into the fuel addition system (i.e. FBG feeder), due to the low
pressure at which the whole pilot plant is operated. When the effect of
the inert gases is accounted for, the projected GHV of the syngas is
above 10 MJ/Nm3.
The raw producer gas exiting the FBG (G1) is still shown to be highly
affected by the devolatilised RDF input. In addition to CO and H2, it contains a myriad of hydrocarbon species from methane through to long
chain and aromatic tar components (e.g. naphthalene), resulting in a
relatively poor quality of the syngas. Of relevance, the steam, CO2 and
SO2 content is also very high.
The reason for this can be reasonably linked with the feedstock nature and composition, and the complex gasication dynamic within

Table 3
Average gas composition measured by FTIR at different location of the plant. *Diatomic
molecules are derived by K1550R Hydrogen Gas Analyser and cross-checking calculations.
Description:
Sampling point

Units

Syngas:
CO
H2*
CO2
H2O
Ar
N2 *
NH3
SO2

vol %
vol %
vol %
vol %
vol %
vol %
ppmv
ppmv

Hydrocarbons:
Methane
Acetylene
Ethylene
Benzene
Toluene
Naphthalene
Phenol
GHV (tar free)

vol %
ppmv
ppmv
ppmv
ppmv
ppmv
ppmv
MJ/Nm3

Downstream
FBG

Downstream
PC

Downstream gas
cleaning

G1

G2

G3

8.1
20.8
21.4
35.6
3
2.1
45
171

21.4
32.1
11.4
25.1
6.8
2.2
45
75.4

26.8
40.4
15.7
3.4
8.7
4.0
3
2.91

9
1759
38480
8446
2646
1243
252
7.25

1
56.8
914
37.7
27.6
42
10.4
7.19

1.2
46.7
878
36
25.4
25
5.3
8.98

263

the uid bed gasier. The FBG system is autothermal, in the sense that
it usually relies on a fraction of the input char, being xed carbon,
that reacts with the oxygen through the bed and provides sufcient
heat to sustain the endothermic reactions that produce H2 and CO.
The strong turbulence and mixing in the bed distribute the char and
the devolatilising fuel particles throughout the bed, establishing a gas
environment where these solids are converted [30]. However, reactor
operations resulting in lack of contact between char/oxygen and an
unfavorable consumption of oxygen by the devolatilisation gases are
frequently observed in large scale FBGs [30]. These issues are exacerbated when operating on RDF, due to the much lower xed carbon content
(ca 5%) and much higher volatile content (50-60%) compared to other
fuels, such as biomass or coal. Crucially, the higher levels of volatiles reduce the delivery of fuel char into the bed, and more devolatilised
products, in which tar is the less reactive, react with oxygen producing
CO2, H2O and SO2. This effect is even more evident when high quantities
of moisture and ash are present in the feedstock material and the oxidant supply rate must be enhanced to generate sufcient heat to sustain
the gasication reaction. Eventually, this leads to a syngas with higher
content of combustion gases and lower GHV.
In comparison, the syngas from the plasma converter (G2) appears
to be much richer in the primary syngas constituents (i.e. H2 and CO),
with the CO/CO2 and H2/H2O ratios considerably higher than those measured in G1. Furthermore, an examination of the gasier exit gas composition revealed that up to ~10% methane and other volatile organics
were present in the measured data, while almost no organic carbon
(NC1) presence was detected downstream of the PC (methane is
about 1%). Such shift in gas composition is strongly indicative of increasingly favourable conditions for hydrocarbons cracking and reformation
routes, both catalysed by the plasma action [29,31], where the residual
carbon monoxide and hydrogen contents of the syngas are strongly enhanced by the destruction of organic species, such as:
C n H x nH2 O n x=2H 2 nCO

C n H x nCO2 x=2H 2 2nCO

At the high temperatures observed in the plasma converter, the


water gas shift (WGS) equilibrium also plays a crucial role. The equilibrium describes the relative concentration of the main syngas constituents in the following:
CO H2 OCO2 H2

The reaction is reversible and the main reacting direction is evidently dictated by the process temperature. Since the WGS is equilibrium
controlled, it is not surprising that WGS dominates the gas-phase
composition at the plasma converter, where equilibrium conditions
are always achieved [22]. This is due to the combined effect of high
operating temperature - given by the high arcing frequency - and long
residence time of gas in the reaction chamber (N2 seconds). These results can be very interesting for applications of synthesis gas in second
generation biofuel that require tar concentration below 0.1 mg m 3
and a specic H2/CO ratio. In particular, the hydrogen to carbon monoxide ratio of the syngas can be controlled via a modication of the
external energy into the plasma converter, with or without the use of
additives such as steam or CO2 [32].
Fig. 3 gives the changes of the WGS constituents ratios measured
downstream the PC over time. It can be noted that the concentrations
were fairly stable during the trial, although a general upward trend in
CO/CO2 ratio was observed.
The increase in CO/CO2 ratio cannot be attributed to the WGS reaction, which depends only upon the temperature of the system. In fact,
the WGS reaction should also result in an increase in H2/CO ratio,

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

CO/CO2 ratio

264

4.5
4
3.5
3
2.5
2
1.5
1
0.5
0
00:00:00 02:00:00 04:00:00 06:00:00 08:00:00 10:00:00 12:00:00 14:00:00 16:00:00

Test duration [hh:mm:ss]


3

H2/CO ratio

2.5
2
1.5
1
0.5
0
00:00:00 02:00:00 04:00:00 06:00:00 08:00:00 10:00:00 12:00:00 14:00:00 16:00:00

Test duration [hh:mm:ss]


Fig. 3. Dynamic CO/CO2 (top) and H2/CO (bottom) ratio proles downstream the plasma converter.

which instead remained stable over the duration of the run. This shift
in simultaneous H2 and CO production could possibly have been
accelerated during the test due to the accumulation of catalytically
active elements in the slag. Several studies proved that, at the same temperature, the gasication reaction rate with slag is higher than that
without slag, so the furnace slag can accelerate slow reaction of tar
and carbon with steam and CO2 to produce more H2 and CO [32,33].
The slag accumulation was signicant with a rate of ca. 4.5 kg/h in a furnace of 100 kg of starting material. The high contents of Mg and Ca of
molten ashes (see Table 6, Section 4.2.1) could be, therefore, the reason

that made slag act as a catalyst for hydrocarbons gasication. Analogous


observations are reported in the literature [3335].
3.2. Tar and organosulphur conversion
The chromatographic analyses of the raw FBG syngas extracts conducted herein conrmed their contamination with condensable organic
compounds, PAHs in particular. It was found that, due to the high levels
of tarry/sooty products prior to plasma treatment, it was only possible
to sample the gas stream exiting the FBG for a relatively short period

Table 4
Composition and concentration for main tar components by gas chromatographer analysis of off-gas bag samples. Boiling points (b.p.) are given at 25 C and 1 bar.
Description:

Downstream FBG

Downstream PC

Downstream gas cleaning

Sampling point

G1

G2

G3

b.p (C)

Volatile organic carbons:


Benzene
Toluene
Ethylbenzene
m + p Xylene
o-Xylene
Styrene
Indane
Indene

mg/m3
mg/m3
mg/m3
mg/m3
mg/m3
mg/m3
mg/m3
mg/m3

2000
1489
1165
221
115
290
250
100

222
5
0.21
0.22
0.15
3
8
0.5

15.66
4.4
1.1
-

80.01
110.6
136.6
138.4
144
145
176.5
182.4

Tars:
Naphthalene
1-Methyl-naphtalene
2-Methyl-naphtalene
Acenaphthylene
Acenaphtene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene

g/m3
g/m3
g/m3
g/m3
g/m3
g/m3
g/m3
g/m3
g/m3
g/m3

1350
500
278
700
60
180
120
82
22
12

182
40
12
60
5
1
5
1
1
1

18
-

218
240
241
279
279
295
340
340
375
404

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

Tar concentration in gas sample


(g/m3)

VOC concentration in gas sample


(mg/m3)

(maximum 15 minutes) before blocking of the sampling line occurred.


This also resulted in a quite relevant analysis error (20%). By contrast,
sampling of the off-gas downstream of the plasma converter could be
conducted indenitely.
Table 4 shows the concentrations of hydrocarbons compounds
assayed in the syngas before and after plasma treatment, along with
the respective boiling points.
As mentioned above, the groups of organic contaminants assayed in
the syngas directly from the FBG contained primarily VOCs and PAHs.
Gas samples revealed eight different VOC species (boiling point below
200 C): toluene, benzene, ethylbenzene, m + p xylene, o-xylene, styrene, indene, indane, at high concentrations (e.g. toluene above
1000 mg/Nm3). Of interest, the plasma downstream product spectrum
shows the complete destruction of these compounds except for a trace
of benzene (~200 mg/Nm3) (Fig. 4).
Polynuclear aromatics are also present in the FBG sample, with high
levels of naphthalene, acenaphthylene, 1-methyl-naphtalene,
acenaphtene, uorine, phenanthrene, anthracene, uoranthene and
pyrene, with cumulative levels of up to ca. 3000 g/Nm3. These are reduced to below 250 g/Nm3 after plasma treatment. Key compounds
in the ultimate products are the olens, such as ethylene (~900 ppmv,
Table 3), which are likely intermediates in aromatic hydrocarbons
reforming, and are often used for tracing the tar reforming and
evolution chemistry [29,36]. Under a high temperature environment
with a gas composition as indicated in Table 3, naphthalene reduction
was observed to be 96.6%, which was higher than that of generic
steam/dry-reforming conditions, where the presence of H2 can act as inhibitor during the reforming of tars [3739]. As shown later in
Section 4.2.2, the reason for the higher conversion may be due to the
presence of CO, O and OH radicals in the gas mixture produced by the
2500

Pre plasma
2000

Post plasma

1500

1000

500

1400

Pre plasma

1200

Post plasma

1000
800

plasma arc. These species tend to oxidise aromatic and aliphatic intermediates, preventing them from re-combining with other radicals to
form tertiary tars and soot [29].
From the examined samples, it is evident how the complex chemical
structure of the parent RDF substrate is seemingly reected in the FBG
products, which maintain a large portion of the original organic functional groups. For example, lignin in RDF represents a potential precursor for PAH formation, due to the aromatic nature of this polymer [40].
Analogously, sulphur is released as hydrogen sulphide (H2S) and a myriad of compact and relatively stable molecules such as methanthiole,
COS, carbon disulphide (CS2), thiophene, and benzothiophene
(Table 5). As for the other tars, the organosulphur decomposition in
the plasma converter occurs due to destabilisation of the hydrocarbon,
which leads to fragmentation of the molecule by breakage of S-C
bonds. These fragments undergo different reactions forming gaseous
products, such as H2S and COS (Table 4).
As a result, the level of organic sulphur in the gas phase after the
plasma treatment alone (i.e. before the gas cleaning) is less than 500
ppbv, i.e. 93% less than that of a single stage FBG. Fig. 5 shows the effect
of thermal cracking on thiols and thiophenes. It was observed that the
concentration of sulphur-substituted aromatics in the FBG sample was
very high with peak levels of up to 3000 ppb; this was reduced to
extremely low levels (average of 30 ppb) after plasma treatment.
There was also a marked reduction in the level of methanthiole from
an average of 750 ppb, before, to around 70 ppb, after the plasma converter. These very low levels of organic sulphur in the gas stream
would support the operation of the downstream gas cleaning units
and catalytic stages in a commercial plant.
Unlike other solid fuels, interaction between gas sulphur species and
char, to form char-bound sulphur in the FBG bed, was not recorded in
this test, due to low quantity of xed carbon in RDF (residual carbon
in FBG sand sampled at the end of the trial is considerably below 1% in
weight). Thus, almost the totality of the organic sulphur, quantied as
the 6065% of the initial sulphur measured in the feedstock, reported
to the FBG gas phase, and subsequently reformed in the plasma converter (Fig. 6). Further release of gaseous sulphur, initially as SO2, may occur
in the plasma converter as a result of evaporation and/or dissociation of
inorganic sulphur, i.e. sulphates, in the ashes [41]. In fact, although
sulphates (e.g. CaSO4, K2SO4) are stable at up to more than 1000 C in
their pure form, thermodynamic calculations have indicated that the
presence of silicon and aluminium in the ashes lowers the thermal stability, and K and Ca are preferably incorporated into alumina-silicate
structures above 800900 C [41]. These conditions are largely met in
the PC, were the ash fraction, which is relatively rich in silica and alumina, is captured and melted in the slag pool at 15001600 C. As a result,
the sulphur release in the PC increases from 65% to nearly 91%, which
suggests that the majority of inorganic sulphur initially present in the

Table 5
Composition and concentration for main sulphur component in off-gas bag samples. Boiling points (b.p.) are given at 25 C and 1 bar.
Description:

Downstream Downstream Downstream


FBG
PC
gas cleaning

600

Sampling point

400

Gas sulphur:
H2S
SO2

ppmv
ppmv

Organic sulphur:
COS
CS2
Methanthiole
Thiophene
2-Methylthiophene
3-Methythiophene
Benzothiophene

200
0

Fig. 4. Tars and VOC distribution measured pre and post plasma.

265

G1

G2

G3

b.p. (C)

210
170

356
71

53
5

- 60
- 10

ppmv
16
ppbv 1170
ppbv
750
ppbv 2800
ppbv
300
ppbv
350
ppbv
610

32
360
70
34
b5
b5
b3

8
74
25
18
-

- 50.2
46.24
5.95
84.2
113.3
114
221

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

Organic sulfur concentration in gas


sample (ppbv)

266

3500

Table 6
Slag bulk and trace analysis.

Pre plasma

3000

Post plasma

Trace Metals by ICP (dry)

2500
2000
1500
1000
500
0

Fig. 5. Thiols and thiophenes distribution measured pre and post plasma.

feedstock (~35% w/w) has dissociated in the slag phase. The remaining
amount of sulphur (less than 10%) was not measured and was possibly
bound in the y ashes as sulphate or sulphide species.
There also appears to be a direct relationship in the PC (sampling
point G2), with H2S and COS trending upwards as the SO2 content
decreases. This suggests that the SO2 produced in the FBG and newly
generated in the PC is subsequently converted to reduced sulphur
species (i.e. H2S, COS), indicating that the high temperature and long
residence time in the PC are such that equilibrium conditions are always
attained.

700
600

100

G1

G2

G3

90
80

500

70
60

400

50

300

40
30

200

20

100

10

S in gas phase / initial S (%)

H2S, COS and SO2 concentration


(ppmv)

3.2.1. Slag analysis


The analytical results for the slag sample are summarised in Table 6,
where the primary components are silica and alumina.
Table 6 shows also a reasonable retention of more volatile components such as calcium and magnesium, which are known to promote
slow carbon-steam reactions.
As anticipated in the previous section, the very low level of measurable sulphur concentrations in the slag indicates that sulphur is not
retained as simple sulde salts. The majority of the inorganic and tar sulphur initially present in RDF is recovered in the gas cleaning section
(third column in Table 5), indicating that it is released during plasma
reforming as a volatile component, mainly H2S.
Testing of the slag samples against other organic parameters showed
also near zero values (Table 7).
Total Organic Carbon (TOC) was below 1% in weight, and levels of
PCBs and PAHs were cumulatively less than 7 g/kg and 2.0 g/kg, respectively. Levels of BTEX were also less than 0.6 mg/kg. These very

H2S

COS

SO2

Total gas S

Fig. 6. Gas sulphur species distribution after FBG (G1), PC (G2), and gas cleaning units
(G3).

Oxides in RDF slag

Metal

mg/kg

Metal

mg/kg

Oxide

% w/w

Aluminum
Calcium
Iron
Magnesium
Phosphorus
Silicon
Potassium
Sodium
Titanium
Thallium
SO4

218438
122073
49357
14165
446.6
141825
2593
5291
12385
0.1
126

Chromium
Copper
Nickel
Vanadium
Zinc
Cobalt
Manganese
Lead
Antimony
Arsenic

124.7
62.2
15.2
48.2
46.4
3.3
12754
10.0
4.1
1.7

SiO2
Al2O3
Fe2O3
TiO2
CaO
MgO
Na2O
K2O
Mn3O4
P2O5
SO3

32.5
35.6
5.9
1.4
19
2.1
0.7
0.3
2.1
0.1
0.3

low values are due to the combination of high temperature, turbulence


and residence time attained in the plasma converter, which results in
the conversion of residual carbon and tars to gas-phase carboncontaining species, e.g. CO and CO2.
Testing of different samples against inorganic (i.e. heavy metals)
parameters has also showed compliance with waste acceptance criteria
WAC for inert wastes [42]. As non-hazardous wastes (European Waste
Catalogue/List of Waste Regulations code 19 04 01 vitried wastes)
this material is suitable for landlling at an inert waste landll, or capable of further materials processing to fabricate enhanced quality ceramic glass products.
3.2.2. The effect of plasma
It is well known that the plasma arc formed at a high temperature to
a stream of gas and dust is effective due to the large amount of thermal
energy involved leading to tar and char reforming. At the same time,
many studies report that the plasma generates a large fraction of radicals, ions, electrons and excited molecules that together with the
high-energy radiation make the environment within the PC highly reactive [1822,44]. All these factors coexist and interact with each other,
making the exact understanding of chemical role of the plasma
challenging.
In order to better assess the role of plasma in tar conversion against
thermal effects, the plasma arc was subject to a short planned disruption. The duration of the disruption (less than ve minutes) was short
enough to not signicantly affect the reactor temperature, which
remained above 1000 C. This was possible thanks to the high mitigation effect produced by the refractory walls and the large hot mass of
slag at the base of the converter working as thermal reservoir. As a consequence, the test had minimal-to-no impact on syngas characteristics,
which maintain a stable trend over the whole duration of the test (see
Fig. 3). Nevertheless, this operational decision led to sudden rises in
the presence of benzene and naphthalene, both known to be highly
refractory compounds, as shown in Fig. 7.
Naphthalene levels are seemingly the most sensitive to plasma
power input rate. The disruption quickly leads to a stepwise rise in residual naphthalene levels to values above 350 ppm. However, when
normal operation is restored, this additional load is quickly reduced
below 15 ppm.
A similar observation is made for benzene levels. During normal
operation, the levels observed are below 1000 ppm, and progressively
reduce as the PC refractory reaches thermal stability and more slag

Table 7
Residual organics analysis for slag sample.
Parameter

Slag sample

DOC

TDS

PCB

PAH

BTEX

TOC

LOI

mg/kg

mg/kg

g/kg

g/kg

mg/kg

w/w%

3.7

45

b7.0

b2.0

b0.6

b0.96

b0.2

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

Disrupted Power-6 kW
Outlet Temperature-1005 C
Feed rate -98 kg/h

Naphtalene [ppmv]

350
300
250
200

5000
4500
4000
3500

Mean Power-120 kW
Outlet Temperature-1150 C
Feed rate-102 kg/h

3000
Naphtalene

150

Benzene

100

2500
2000
1500

Benzene [ppmv]

400

267

1000

50

500

0
0
00:00:00 02:00:00 04:00:00 06:00:00 08:00:00 10:00:00 12:00:00 14:00:00 16:00:00

Test duration [hh:mm:ss]


Fig. 7. Variation of plasma conditions during benzene and naphthalene monitoring (G2 sampling).

accumulates in the system. However, the disruption in plasma application leads to a short term spike as observed with naphthalene. Furthermore, the benzene levels were seemingly slower to restore under
common values when compared to naphthalene. The reason for this
may be attributed to the different nature of the contaminants and to
the mechanism of tar conversion in a plasma reactive environment, as
already discussed by the authors in a previous paper [26]. In a high
thermal environment (above 900 C), the tar decomposition proceeds
by thermal cleavage and hydrogenation of double bonds that break
the aromatic structure into smaller intermediates (e.g. phenyl radicals,
acetylene, etc.), which become the main decomposition products [43].
In absence of plasma activated species, the primary tar radicals would
naturally tend to combine together into aromatic (benzene) and polycyclic aromatic (naphthalene) hydrocarbons, eventually leading to
soot formation. This would explain the sudden increase in these contaminants in the gas phase when the plasma is interrupted, even at
above 1000 C. The intermediate step of phenyl hydrogenation during
naphthalene reforming, however, tends to have a buffering effect on
benzene content, since, if more phenyl radicals are produced, more
phenyl hydrogenation is likely to occur, releasing benzene as a product.
This results in a slower decrease in total benzene concentration over
time. These effects could be offset by injecting small quantities of oxidants (e.g. O2 or H2O) into the PC, assisting in the oxidative degradation
of aromatic intermediates [26,44].
A very similar behavior can be assumed for sulphur substituted aromatics. Thiophene, for example, is a very stable compound and does not
thermally decompose in gas up to temperatures as high as 1100 C. So,
once formed, it is unlikely that it will decompose at the thermal
conditions that were achieved in the PC. These properties have been attributed to its aromatic nature which allows the free electron to be
largely delocalised [45]. In the presence of plasma, however, catalytic
destabilisation of the aromatic ring may occur even at temperatures
lower than 1100 C, as also reported by Mohammedi at al. [46]. The
high activity of plasma causes the thiophene ring to fragment through
the impact of energetic electrons, and form radicals such as R, SH,
S and so on. The interaction of these radicals with O, OH and H can produce some small hydrocarbons (mainly acetylene), H2S, H2 and oxygen
bearing compounds such as CO and COS [45,46].
As a result, most of the organosulphur constituents consisting largely of thiophenes are reformed under active plasma conditions, leaving
essentially CO, H2 and H2S as ultimate products.

uid bed-plasma plant was conducted over 20 hours of operation


with sulphur-rich RDF prepared from municipal solid waste (MSW),
commercial and industrial (C&I) and automotive shredded residue
(ASR) wastes. The efcacy of the plasma treatment is well illustrated
in the investigative testwork campaign which shows measurements
from sampling the syngas before and after the plasma converter from
a demonstration plant for the main organic, volatile and condensable
compounds. It is seen that both tars and organic sulphur species are
present in the crude syngas exiting from the FBG stage at elevated
levels. When exposed to the inuence of the plasma arc converter
they are reduced to very low levels. Reduction efciencies typically
exceeded 96%v/v for complex organics (e.g. PAH) and thiophenes
were observed.
The data suggests that the percentage of sulphur in the RDF converted to H2S and organosulphur compounds in the FBG ranged between
50% and 60%, which is similar to that initially measured for the organically bound sulphur in RDF. The organic fraction in the gas phase is
then reformed under plasma conditions, leaving essentially CO, H2 and
H2S as ultimate products. The second dominant sulphur species under
the plasma experimental condition was SO2, which equated to around
90% conversion of the initial RDF sulphates content, and is subsequently
converted to H2S and COS. There was no detectable organic sulphur
observed in the outlet gas, nor in the slag by-product off the PC.
The test has also highlighted the importance of the plasma chemistry
as opposed to thermal activation mechanism in contaminants reforming.
It was observed that aromatics behaviour is much more affected by
plasma generation than by the actual thermal regime. An abrupt
decrease of the plasma power input quickly leads to a stepwise rise in
residual naphthalene and benzene levels to values above 350 and
3500 ppm, respectively. This occurs despite the temperature being
maintained above 1000 C. Only when normal operation is restored,
does this additional load quickly reduce back to normal values.
In summary, it was evident that the plasma converter stage was essential to the overall process in terms of generating a syngas of predictable and consistent composition which was free from tars and organic
sulphur contaminants. For commercial applications the syngas would
be suitable for use in catalytic stages for bio-fuel production, as a source
of hydrogen for use in energy systems and in SOFC for power generation, after removal of H2S and SO2 in conventional gas cleaning units.

References
4. Conclusions
In the present work, the evolution of tars and sulphur containing
compounds in the syngas generated from a waste uid bed gasier
and subsequently reformed in a plasma converter was investigated.
An experimental test mimicking the normal commercial operation of a

[1] R. lvarez-Rodrguez, C. Clemente-Jul, Hot gas desulphurisation with dolomite


sorbent in coal gasication, Fuel 87 (2008) 35133521.
[2] H. Kuramochi, W. Wu, K. Kawamoto, Prediction of the behaviours of H2S and HCl
during gasication of selected residual biomass fuels by equilibrium calculation,
Fuel 84 (2005) 377387.
[3] P. Boldrin, M. Millan-Agorio, N.P. Brandon, Effect of sulfur- and tar-contaminated
syngas on solid oxide fuel cell anode materials, Energy Fuel 29 (2015) 442446.

268

M. Materazzi et al. / Fuel Processing Technology 137 (2015) 259268

[4] T. Nakazato, Y.B. Lin, M. Kusumoto, N. Nakagawa, K. Kato, H2S removal by ne limestone particles in a powder-particle uidized Bed, Ind. Eng. Chem. Res. 42 (2003)
34133419.
[5] X. Meng, Biomass gasication: the understanding of sulfur, tar, and char reaction in
uidized bed gasiers, Doctoral Thesis, Delft University of Technology, 2012.
[6] U. Arena, Process and technological aspects of municipal solid waste gasication. A
review, Waste Manag. 32 (4) (2012) 625639.
[7] W.A.W.A.K. Ghani, A.B. Alias, K.R. Cliffe, Co-combustion of refuse derived fuel with
coal in a uidised bed combustor, J. Eng. Sci. Technol. 4 (1) (2009) 122131.
[8] T.A. Milne, R.J. Evans, Biomass gasication tars: their nature, formation and conversion, NREL, Golden, CO, USA, Report no. NREL/TP-570-25357, 1998.
[9] M. Jazbec, K. Sendt, B.S. Haynes, Kinetic and thermodynamic analysis of the fate of
sulphur compounds in gasication products, Fuel 83 (16) (2004) 21332138.
[10] H. Cui, S.Q. Turn, V. Keffer, D. Evans, T. Tran, M. Foley, Contaminant estimates and
removal in product gas from biomass steam gasication, Energy Fuel 24 (2)
(2010) 12221233.
[11] Y. Neubauer, Strategies for Tar reduction in fuel-gases and synthesis-gases from biomass gasication, J. Sustainable Energy Environ. Spec. Issue (2011) 6771.
[12] J.W. Knemann, Technical information paper OLGA tar removal from gasication
product gas, dahlman, 2010.
[13] R.W.R. Zwart, A. Van der Drift, A. Bos, H.J.M. Visser, M.K. Cieplik, H.W.J. Konemann,
Oil-based Gas washing exible Tar removal for high-efcient production, Wiley
InterScience, 2009.http://dx.doi.org/10.1002/ep.10383.
[14] M.M. Yung, W.S. Jablonski, K.A. Magrini Bair, Review of catalytic conditioning of
biomass-derived syngas, Energy Fuel 23 (4) (2009) 18741887.
[15] W.F. Elseviers, H. Verelst, Transition metal oxides for hot gas desulphurisation, Fuel
78 (1999) 601612.
[16] M.D. Kaufman Rechulski, T.J. Schildhauer, S.M.A. Biollaz, Ch. Ludwig, Sulfur containing organic compounds in the raw producer gas of wood and grass gasication, Fuel
128 (2014) 330339.
[17] Barea A. Gomez, L.F. Vilches, C. Leiva, M. Campoy, C. Fernandez-Pereira, Plant
optimization and ash recycling in uidised bed waste gasication, Chem. Eng. J.
146 (2009) 227236.
[18] L. Helsen, A. Bosmans, Waste-to-energy through thermochemical processes
matching waste with process, First international symposium on enhanced landll
mining, Houthalen-Helchteren, Belgium, 2010.
[19] A. Fourcault, F. Marias, U. Michon, Modelling of thermal removal of tars in a high
temperature stage fed by a plasma torch, Biomass Bioenergy 34 (9) (2010)
13631374.
[20] L. Bromberg, D.R. Cohn, A. Rabinovich, J.E. Surma, J. Virden, Compact plasmatronboosted hydrogen generation technology for vehicular applications, Int. J. Hydrogen
Energy 24 (4) (1999) 341350.
[21] A.M. Fridman, Plasma Chemistry, Cambridge University Press, New York, 2008.
[22] M. Materazzi, P. Lettieri, L. Mazzei, R. Taylor, C. Chapman, Thermodynamic modelling and evaluation of a two-stage thermal process for waste gasication, Fuel 108
(2013) 356369.
[23] R. Zevenhoven, P. Kilpinen, Control of pollutants in ue gases and fuel gases,
Chapter 3, Sulphur. For the Helsinki University of Technology course ENE-47.153,
Helsinki University of Technology Espoo, Finland, 2004, ISBN 951-22-5527-8.
(Available at: http://users.abo./rzevenho/gasbook.html).
[24] E. Sjstrm, Wood chemistry, Fundamentals and application2nd edition, Academic
Press Inc., San Diego, USA, 1993.
[25] Marton J. Lignins, Occurrence, formation, structure and reactions, in: K.V. Sarkanen,
C.H. Ludwig (Eds.), Wiley- Interscience, USA, 1971.

[26] J. Knudsen, P. Jensen, W. Lin, F.J. Frandsen, K. Dam-Johansen, Sulfur transformation


during Thermal conversion of herbaceous Biomass, Energy Fuel 2004 (18) (2004)
810819.
[27] D.T. Strohbeen, An investigation of the reactions leading to volatilization of inorganic sulfur during pyrolysis with vanillic acid and sodium gluconate, PhD-thesis, The
Institute of Paper Chemistry, Appleton Wisconsin, 1981.
[28] R. Taylor, R. Ray, C. Chapman, Advanced thermal treatment of auto shredder residue
and refuse derived fuel, Fuel 106 (2013) 401409.
[29] M. Materazzi, P. Lettieri, L. Mazzei, R. Taylor, C. Chapman, Tar evolution in a two
stage uid bed-plasma gasication process for waste valorization, Fuel Process.
Technol. 128 (2014) 146157.
[30] A. Gmez-Barea, B. Leckner, Modeling of biomass gasication in uidized bed, Prog.
Energy Combust. Sci. 36 (4) (2010) 444509.
[31] M.J. Gallagher, et al., On-board plasma-assisted conversion of heavy hydrocarbons
into synthesis gas, Fuel 89 (6) (2010) 11871192.
[32] P. Li, Q. Yu, Q. Qin, W. Lei, Kinetics of CO2/coal gasication in molten blast furnace
slag, Ind. Eng. Chem. Res. 51 (49) (2012) 1587215883.
[33] M.F. Irfan, M.R. Usman, K. Kusakabe, Coal gasication in CO2 atmosphere and its kinetics since 1948: A brief review, Energy 36 (1) (2011) 1240.
[34] C.L. Spiro, D.W. McKee, P.G. Kosky, E.J. Lamby, D.H. Maylotte, Signicant parameters
in the catalysed CO2 gasication of coal chars, Fuel 62 (3) (1983) 323330.
[35] D. Erincin, A. Sina , Z. Misirlio lu, M. Canel, Characterization of burning and CO2 gasication of chars from mixtures of zonguldak (turkey) and australian bituminous
coals, Energy Convers. Manag. 46 (17) (2005) 27482761.
[36] D.H. Lee, K.-. Kim, Y.-. Song, W.S. Kang, S. Jo, Mapping plasma chemistry in hydrocarbon fuel processing processes, Plasma Chem. Plasma Process. 33 (1) (2013)
249269.
[37] A. Jess, Mechanisms and kinetics of thermal reactions of aromatic hydrocarbons
from pyrolysis of solid fuels, Fuel 75 (12) (1996) 14411448.
[38] P. Simell, O. Jouko, A. Outi Hepola, I. Krause, Effects of gasication gas components
on tar and ammonia decomposition over hot gas cleanup catalysts, Fuel 76 (12)
(1997) 11171127.
[39] D.J. Draelants, Y. Zhang, H. Zhao, G.V. Baron, Preparation of nickel-modied ceramic
lters by the urea precipitation method for tar removal from biomass gasication
gas, Studies in Surface Science and Catalysis, vol. 143, Elsevier, 2000, pp. 159165.
[40] A. Fraga, A.F. Gaines, R. Kandiyoti, Characterization of biomass pyrolysis tars produced in the relative absence of extraparticle secondary reactions, Fuel 70 (7)
(1991) 803809.
[41] J. Knudsen, P. Jensen, K. Dam-Johansen, Transformation and release to the Gas phase
of Cl, K, and S during combustion of annual biomass, Energy Fuel 2004 (18) (2004)
13851399.
[42] Environment Agency, Guidance on sampling and testing of wastes to meet landll
waste acceptance procedures, 2005.
[43] B.J. Vreugdenhil, R.W.R. Zwart, Tar formation in pyrolysis and gasication, Publication: ECN-E--08-087Available at www.ecn.nl2009.
[44] D.H. Lee, K. Kim, M.S. Cha, Y.-. Song, Plasma-controlled chemistry in plasma
reforming of methane, Int. J. Hydrog. Energy 35 (20) (2010) 1096710976.
[45] M. Xing, J. Kong, J. Dong, H. Jiao, F. Li, Thiophenic sulfur compounds released during
coal pyrolysis, Environ. Eng. Sci. 30 (6) (2013).
[46] M.N. Mohammedi, J.L. Leuenberger, J. Amouroux, Desulfurization Study of Hydrocarbon Molecules by Plasma Process for Gas/Oil Applications. Preprints of PapersAmerican Chemical Society Division Fuel Chemistry, 41, 1, 503509. 211th National
meeting, 1996.