Fuel 206 (2017) 155–161

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Full Length Article

Municipal waste leachate conversion via catalytic supercritical water

gasification process
Antonio Molino a,⇑, Massimo Migliori b, Alessandro Blasi c, Mariano Davoli d, Tiziana Marino e,
Simeone Chianese f, Enrico Catizzone b, Girolamo Giordano b
a
ENEA Portici Research Centre, P. Enrico Fermi 1, I-80055 Portici (NA), Italy
b
University of Calabria, Dept. of Environmental and Chemical Engineering, Via P. Bucci cubo 44a, Rende (CS), Italy
c
ENEA Trisaia Research Centre, SS 106 Ionica, I-75026 Rotondella (MT), Italy
d
University of Calabria, Dept. of Biology, Ecology and Earth Science, Via P. Bucci cubo 15a, Rende (CS), Italy
e
Institute on Membrane Technology (ITM-CNR), Via P. Bucci 17/c, I-87030 Rende (CS), Italy
f
Università degli Studi della Campania ‘‘L.Vanvitelli”, Dept. of Civil and Building Engineering, Design and Environment, Via Roma 9, 81031 Aversa (CE) Italy

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

Article history: The aim of the paper is to investigate the thermal conversion of Municipal Waste Leachate (MWL) to
Received 12 April 2017 Synthetic Natural Gas (SNG), based on two step process: gasification with water in supercritical condi-
Received in revised form 26 May 2017 tions (SCWG) followed by a catalytic upgrading of the resulting gas phase. The proposed combination
Accepted 30 May 2017
showed advantages in terms of biomass conversion efficiency with respect to the conventional
approaches. As the initial biomass liquid phase includes some carboxylic acids, which are the usual inter-
mediate of biomass decomposition process in SCWG, it is expected that the combined effect of catalysis
Keywords:
and SCW leads to an increase of syngas yield, together with an enrichment in hydrogen. Experimental
Leachate treatment
Gasification
tests, carried out by varying MWL flow rate, showed that SCWG technology allows to produce a syngas
Supercritical water with a Higher Heating Value (HHV) of about 15–17 MJ/kg. Hydrogen and methane compositions of the
Synthetic Natural Gas produced syngas varied in the range 25–47%v/v and 11–18%v/v, respectively. Syngas upgrading experi-
Catalytic conversion mental tests were carried out by using a Nickel based catalyst increasing methane SNG fraction up to
Syngas upgrading 50%v/v.
Ó 2017 Published by Elsevier Ltd.

1. Introduction
Municipal Waste Leachate (MWL) treatment represents one of
the most relevant problem in the field of waste treatment as this
liquid watery fraction -diluted an rich of organic content- comes-
up from any of the waste treatment processes: from sanitary land-
filling to any of the energy valorisation techniques (anaerobic
digestion, composting etc.) [1]. Leachate contains inorganic and
organic elements, xenobiotic organic compounds and heavy met-
als, generally classified as hazardous substances occurring in lea-
chate. In fact, MWL exhibits acute and chronic toxicity and if not
appropriately treated, it can permeate ground water increasing
the pollution of soil, ground and surface water [2]. Moreover, lea-
chate is a product of landfills, wherein excess water percolates
through landfill waste layers, freeing organic compounds from
the waste and carrying them away concentrated in leachate. Fur-
thermore, the presence of leachate may cause malodorous and
⇑ Corresponding author.
E-mail address: antonio.molino@enea.it (A. Molino).
aerosols [3,4], increasing distrust of the people toward this liquid
fraction.
Biological and chemical treatment have been proposed to over-
come leachate processing problem [5,6]: flocculation/precipitation
techniques have been studied by Amokrane et al. and Tatsi et al.
[7,8], whilst Copa and Medil proposed activated carbon adsorption
of organic fraction to treat this leachate flows [9]. Recently, chemical
oxidation method [10,11] and membrane processes such as reverse
osmosis [12] and nanofiltration [13] have been also investigated.
In addition, due to the high available volume, a more effective
energy valorisation of this substrate would be a profitable way to
recover the organic fraction of MWL, even though the high water
dilution represents a difficult task to be overcome. On the other
hand, gasification in supercritical water condition (SCWG) is a
promising technology to more profitably treat and promote wet
biomass and organic wet substances [14] such as digestate, munic-
ipal solid organic wastes etc., compared to the traditional methods
used to produce synthetic natural gas or liquid biofuels [15–21]. In
fact, the SCWG technology is suitable for treatment of biomasses
containing large amount of water (up to 90%) and this is due to

http://dx.doi.org/10.1016/j.fuel.2017.05.091
0016-2361/Ó 2017 Published by Elsevier Ltd.
156 A. Molino et al. / Fuel 206 (2017) 155–161

the possibility to recover the energy contents from the outstream at the SCWG operative conditions [22]. Another advantage of this
thanks to the vaporization of feed stream. This configuration is process is related to the high vapour content in the gas phase that
similar to a steam cycle but with the advantage that it is possible promotes the water gas shift reaction, in order to increase the
to recover the organics from the gasification reactions taking place hydrogen content in the syngas and helps the methanation stoi-
chiometry reaction [23,24]. At last but not least, is the overcoming
of the Achille’s heel of the gasification processes, that is the tar for-
Table 1 mation [25–27]. Water in supercritical conditions changes its
Waste Leachate composition.
polarity and more tars can be solubilized in the liquid phase with
Raw leachate sample [%w/w] Dry basis composition [%w/w] the main effect to obtain a tar-free syngas.
Water 86 ± 3 Volatiles 80 ± 2 The Renewable Energy Directive (2009/28/EC) establishes an
Total solid content 9.5 ± 0.8 Ashes 20 ± 2 overall policy for the production and promotion of energy from
Lactic acid 8.8 ± 0.07 HHV / LHV [MJ/kg] 20 ± 2/ 11.8 ± 1 renewable sources in the EU. In this direction, in the biofuel sector,
Acetic Acid 0.9 ± 0.007 C 33 ± 1
it is provided that all EU countries must also ensure that at least
Ethanol 0.2 ± 0.002 H 3.5 ± 0.4
N 2.1 ± 0.1 10% of their transport fuels come from renewable sources by
2020. Furthermore, on 30 November 2016, the Commission

Fig. 1. Combined SCGW + Catalytic SNG converter experimental apparatus.

 A. Molino et al. / Fuel 206 (2017) 155–161
published a proposal for a revised Renewable Energy Directive to
make the EU a global leader in renewable energy and ensure that
the target of at least 27% renewables in the final energy consump-
tion in the EU by 2030 is met.
By this way, SNG production via SCW gasification could help to
achieve these targets with the production of Synthetic Natural Gas
(SNG) as an effective candidate for ready-to-use applications such
as automotive of in-grid injection [28].
In this paper, a preliminary investigation of a combined SCWG
and catalytic conversion system to convert the MWL to SNG is pre-
sented. Experimental activity was carried out by using a bench
scale experimental apparatus. Conditions milder than SCWG and
a commercial Nickel based catalyst, aiming to maximize the bio-
methane fraction from the SCWG process outstream, were used.
The effect of the MWL flow rate variation on syngas and SNG com-
positions and SNG productivity was studied.
2. Experimental section
2.1. Leachate characteristics
Leachate from municipal solid urban waste was obtained from a
Calabrian waste treatment company (CalabraMaceri S.p.A., Italy). It
was sifted before using it in the SCWG reactor with a mesh of 100 mm
in order to separate the solids from the liquids phase. The main char-
acteristics of the leached are listed in Table 1. As shown, leachate is a
C-rich biomass with a relevant composition of carboxylic acids. This
suggest that this raw material is suitable for energy recovery pur-
poses and since acids are intermediate of any biomass gasification
[29], a significant bio-syngas yield can be expected.
2.2. Catalytic test apparatus
The experimental set-up used for leachate treatment is showed
in Fig. 1. Chemical installation consists of two different process
steps: the supercritical water gasification treatment, followed by a
catalytic post treatment of the produced syngas. The SCWG process
was carried out in a 450 mL tubular reactor (Parr Instrument Co)
with an internal diameter of 25 mm, external diameter of 48 mm
and total length of 1120 [30]. The outlet process stream from the
reactor was fed to a room temperature condenser in order to sepa-
rate an aqueous dilute solution from the pressurized gas stream sent
to the catalytic converter. Catalyst investigations were carried out
by using a metallic cylinder reactor ad of AISI 304 with a volume
of 50 ml filled with 10 g of catalyst and glass beads. Preliminary tests
were carried out only on the SCWG process by varying the feed flow
in the reactor from 10 ml/min to 40 ml/min, while the operative
conditions of temperature and pressure were kept constant at
550 °C and 250 bar, respectively. For each test, in order to achieve
the steady state condition, the process time was reduced from 60
to 20 min when increasing the flow rate from 10 to 40 ml/min.
Before its used, Nickel catalysts was fluxed in H2/N2 at 300 °C and
20 bar in order to reduce the Nickel oxide to metallic Nickel. In this
phase outstream it was analyzed by using GC-FID and monitoring
the oxygen till to zero concentration that corresponding to the total
reduction of nickel oxide. The produced syngas before and after
methanation stage was separated from water in a condense, quanti-
fied by using a GILMONT Instruments flow meter and analyzed in
terms of composition every 3 min, through the on-line gas chro-
matograph HP 6890 equipped with a conductivity detector.
2.3. Catalyst properties
A commercial Ni catalyst supported on Alumina (BASF, G1-85),
suitable for the methanation of CO2 or CO/CO2 mixtures from off-
157
gases process, was used for the post SCWG treatment. Surface
properties were studied via Scanning Electron Microscopy (SEM)
(ESEM FEG QUANTA 200). Monolithic catalysts were dried at
40 °C for 24 h and successively coated with a thin carbon film by
using a high-resolution sputtering and high vacuum carbon coater
(Q150T ES, QUORUM Technologies) prior to SEM observation. The
surface chemical composition was determined via EDX analysis
by using a specific Energy Dispersive Spectroscopy (EDS) X-ray sys-
tem toll, with a crystal detector Si/Li, (EDAX GENESIS 4000). Textu-
ral properties were studied by performing nitrogen adsorption-
desorption isotherms at
196 °C with an ASAP 2020 Micromeritics
instrument. The specific surface area and micropore volume were
estimated by adopting BET and t-plot models. Pore size distribu-
tion was obtained by using BJH methods from the desorption
branches [31–33]. Catalyst properties are listed in Table 2.
3. Results and discussion
3.1. Leachate SCWG process
The MWL was tested in the SCWG process, aiming to assess the
performance of this technology to treat this substrate. The effect of
the residence time was investigated by varying the MWL feed flow
rate in the range 10–40 ml/min. Mass balance of the stream leaving
the SCWG reactor was carried out and it was expressed in terms of
solid, liquid and gaseous fractions, on weight basis as reported in
Fig. 2.
As shown, when increasing the MWL flow rate in the SCWG
reactor, an increase of the liquid phase from 25%w/w to 51%w/w
was observed whilst both solid and gaseous fractions decreased
from 64%w/w to 45%w/w and from 11%w/w to 5%w/w, respec-
tively. Otherwise, when the residence time is lowered, a decrease
in gasification efficiency is observed, being the gas phase the
end-product of the SCWG process. This observed effect does not
agree with the experimental results of gasification of some model
species (such as glucose) that are intermediate of SCWG process.
Table 2
BASF G1-85 catalyst properties.
Chemical Physical
Ni [wt%] 54 Geometry (tablets) [mm] 55
Al2O3 [wt%] 20 Crus Strength (side wall) [N] >80
Attrition [wt%] Max 2
Bulk Density [g/cm3] 1.05
B.E.T. Specific Area [m2/g] 192
BJH Desorption cumulative volume [cm3/g] 0.364
Fig. 2. SCWG phase distribution as a function of the feed flow rate.
158 A. Molino et al. / Fuel 206 (2017) 155–161

As highlighted by several studies in case of real substrates, due to
the solid content of the stream feed to the reactor, plugging prob-
lems may arise. In fact, in the Fig. 2 is shown that the sum of solid
and liquid phases covers the 80% of the total balance and this is
according to other papers [34] especially when the process tem-
perature is lower than 500 °C. In particular, the liquid phase outlet
SCWG process has a great interest in terms of biomolecules that
could be extracted, such as furfurals and acetic acid mostly used
in the green chemistry sector as green solvents or biobased for bio-
plastics [30]. Respect to the literature data [28,34], low syngas pro-
duction could be due to the high complexity of the molecules in
the leachate.
Therefore, an increase of the solid fraction is observed when
increasing the feed flow rate [29,30,35,36]. Syngas composition
as a function of the residence time is reported in Fig. 3 and exper-
imental tests confirmed that SCWG process allows the production
of a performing syngas, with a higher heating value in the range of
15–17 MJ/kg calculated by using Dulong formula as showed below:
X
HHV syngas ¼ HHV i  yi ð1Þ

Fig. 3. Syngas composition as a function of the feed flow rate.

Fig. 4. Carbon gasification efficiency (CGE) and gas yield (GY) as a function of the MWL flow rate.
 A. Molino et al. / Fuel 206 (2017) 155–161 159

where HHVi is the higher heating value of each combustible specie dry syngas moles
GY ¼ ð2Þ
and yi is the volume fraction for each one. dry MWL mass
Data reveal the effect of the feed flow rate increase on the gas
composition: carbon dioxide and methane fractions are improved, carbon mass in the gas phase
from 35%v/v to 45%v/v and from 11%v/v to 18%v/v respectively, CGE ¼  100 ð3Þ
carbon mass feed
whilst hydrogen content drops down from 47%v/v to 25%v/v. Minor
compounds of the syngas (such as carbon monoxide and C+2 spe-
massout SNG process

massins
SNG Productiv ity ¼
CH4 CH4
cies) followed the same trend of carbon dioxide.  100 ð4Þ
Experimental findings agree with those from several research mass of syngasin
TOT
activities, especially for the tests carried out at lower residence Results of GY and CGE reported in Fig. 4 highlight that both
time [31]. parameters follow the same trend: the higher the MWL flow rate
In order to quantify the performances of SCWG in the case of the lower the GY and the lower the CGE, in agreement with litera-
leachate treatment, the following technological parameters were ture data [29,31–33,35,36]. This effect can be explained by consid-
assessed: Gas Yield (GY), Carbon Gasification Efficiency (CGE) and ering the decrease of the reaction time, corresponding to the
Syntetic Natural Gas (SNG) productivity increase of feed flow rate, for the gasification of the carbon derived
from a complex matrix such as leachate.

3.2. Catalytic SNG production

Syngas upgrading experiments to SNG were performed by using

a commercial catalyst from BASF named G1-85. Results of upgrad-
ing treatment are shown in Fig. 5, in which volumetric composition
of the processed syngas is reported as a function of the MWL flow
rate.
Fig. 5 shows that the upgraded syngas was mainly composed of
a mixture of methane and carbon dioxide whilst the hydrogen and
carbon monoxide concentrations were always lower than 3%v/v, in
agreement with experimental findings published by several
research centres that are working on the Synthetic Natural Gas
production via Sabatier & Senders reactions [24].
The effect of the residence time on the syngas composition was
also highlighted: when the feed flow rate increased, the methane
composition decreased from 50%v/v to 31%v/v while CO2 fraction
increased from 50%v/v to 64%v/v. Furthermore, the effect of the
feed flow rate on SNG productivity (from SCWG) and on H2/(CO
+ CO2) molar ratio was simultaneously evaluated. As sketched in
Fig. 6, both SNG productivity, in the SCWG step, and H2/(CO
+ CO2) molar ratio, in the catalytic step, decreased with respect
Fig. 5. Upgraded syngas composition as a function of the MWL flow rate.

Fig. 6. SNG productivity and H2/(CO + CO2) molar ratio as a function of the MWL flow rate.
160 A. Molino et al. / Fuel 206 (2017) 155–161

to feed flow rate increase from 11% to 2% and from 1.12 to 0.45, 3.3. Catalyst physical properties evaluation
respectively. In particular, H2/(CO + CO2) molar ratio values were
far away from the stoichiometric theoretical condition of the over- In order to assess the catalyst stability and gain some insight
all reaction for SNG production from syngas, which is characterized about, deactivation and solid deposition, scanning electron micro-
by H2/(CO + CO2) of 4: scope (SEM) was carried out on the catalyst after a catalytic run of
140 min. External, side and top surface, as well as the cross section,
CO þ 3H2 $ CH4 þ H2 O ð5Þ
were observed (Magnification 450) and images are reported in
CO2 þ H2 $ CO þ H2 O ð6Þ Fig. 7. The thick wrinkled layer present on the G1-85 BASF catalyst
was mainly composed of char and ashes originating from leachate
while the total reaction is: catalytic treatment. In fact, according with Francis diagram [23],
CO2 þ 4H2 $ CH4 þ 2H2 O ð7Þ char formation is favoured at temperature lower than 350 °C. such
as in the case of SNG synthesis.

Fig. 7. SEM images of catalysts after 140 min of SNG process. (a) Side view; (b) Cross Section; (c) top view.

Fig. 8. BSE SEM images of catalysts after 140 min of SNG process. (a) Side view; (b) Cross Section; (c) top view.
 A. Molino et al. / Fuel 206 (2017) 155–161
Table 3
EDX analysis of catalyst and deposit Municipal.
Chemical species Fresh Catalyst Regenerated Catalyst
[%wt] [%wt]
C – – 21
Na – 0,4
Mg – 0,2
Al2O3 22 21,5
P 1 0.9
S – – 0.3
Cl 0.5 – 0.4
K 1 0.9
Ca 3 3
Ni 53 53
Backscattered electron images were carried obtained in order to
further investigate the catalyst structure after its use, as reported
in Fig. 8. No char and ashes are present in the catalyst cross section,
evidencing as the organic layer only affected the external surface.
Exhausted samples were regenerated with a double step: (i)
overnight treatment at 500 °C under N2 flow (10 ml/min and tem-
perature ramp 2 °C/min) and (ii) calcination in air (10 ml/min) at
350 °C (temperature decrease 10 °C(min) for 3 h. EDX analysis
was performed, in order to evaluate the catalyst stability after its
use and the deposit composition. Data of Table 3 clearly indicates
that deposit is mainly composed by carbon, whilst no difference
in chemical composition are observed after regeneration.
4. Conclusions
In this paper a promising double step route for the municipal
waste leachate conversion has been presented. Composition anal-
ysis of leachate revealed the presence of carboxylic acids, interme-
diate of any gasification process, which makes this substrate an
eligible candidate for the supercritical water gasification treat-
ment. In this concern the use of double step process based on pri-
mary supercritical water gasification process, followed by a
catalytic treatment to produce Synthetic Natural Gas was revealed
as a valuable option to the energetic valorisation of the leachate.
The SCWG step allows to produce, from a real substrate, a bio-
syngas phase with interesting composition and HHV, according
to an optimized residence time. In addition, the resulting gas phase
undergoes through a catalytic process (Catalyst G1-85 BASF) aim-
ing to upgrade the syngas to Synthetic Natural Gas with a CH4 con-
tent up to 50%v/v. In particular, by decreasing MWL flow rate an
increase of H2/(CO + CO2) molar ratio from 0.45 to 1.12 was
observed, which corresponds to an increase of SNG productivity
of about the 80%, passing from 2% to 11%. Catalyst stability was
assessed after 140 min of processing of a real biomass, and the
regeneration process confirmed a good recovery of structural and
physical and chemical characteristics.
Acknowledgements
Authors gratefully acknowledge CalabraMaceri S.p.A (Rende,
Italy) for supplying leachate for experimental tests.
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