Separation and Purification Technology 210 (2019) 80–92

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Separation and Purification Technology

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

Biogas cleaning: Trace compounds removal with model validation T

a,b,⁎ b a
Davide Papurello , Silvia Silvestri , Andrea Lanzini
a
Department of Energy (DENERG), Politecnico di Torino, Corso Duca degli Abruzzi, 24, 10129 Turin, Italy
b
Fondazione Edmund Mach, Biomass and Renewable Energy Unit, Via E. Mach, 1, 38010 San Michele a/A, Italy

A R T I C LE I N FO A B S T R A C T

Keywords: High energy efficiency SOFCs generators can be adopted for local and distributed micro-generation systems to
Biochar promote the reduction of greenhouse gas emissions with their high fuel flexibility, long-term stability also at
VOCs removal partial load and low noise. One of the main drawbacks for such generators, fed by biogenous gas is the impact of
Biogas trace compounds on the anode compartment. For this reason, a gas clean-up section is mandatory. The effect of
Solid Oxide Fuel Cell (SOFC)
temperature and gas moisture was investigated through experiments on the removal performance of the tested
Carbon
Adsorption modeling
sorbents. An increase in the operating temperature caused lower values of the maximum capacity of the ad-
sorbent. The decrease of removal performance considering a humidified gas is connected to the interference of
water in the pores of activated carbons. Biochar, compared to the other commercial sorbent materials showed
the lowest removal performance, even if with activated biochar the adsorption capacity growth to commercially
available materials. The highest adsorption capacity at 1% of the initial concentration was showed by com-
mercial carbons with 1.75 mg/g for H2S and 20.4 mg/g for HCl. Experimental data were employed in a porous
particle diffusion model to estimate the breakthrough time. Low values of errors validate the model in the first
part of the breakthrough curve, even for competitive adsorption case.

1. Introduction living organisms and conversion to less harmful forms).

The renewable sources coupled to distributed micro-generation
systems could be a plausible scenario for the energy future exploitation
according to the respect of the environment. A plausible ingredient in
this complicated recipe is the exploitation of biomass for the energy
production with high-efficiency generators, such as SOFCs. One of the
main negative aspects of such micro-generators, fed by biogas is the
impact of trace compounds on their performance.
Requirements are related to 1–2 ppm(v) for sulfur compounds
[1–7], 20–50 ppm(v) for chlorines and tars compounds [3,8–14] and as
low as possible for siloxanes concentration [7,15–18]. These limits are
related to the reversible operation for SOFC systems, even if for long
term operation SOFC stack lifetime is shortened accordingly to the
current density, operating temperature and trace compound con-
centration [18].
For this reason, a gas clean-up section is strongly required. Biogas
purification methods can be divided into two broad categories:
• those involving physicochemical phenomena (adsorption or ab-
sorption);
• those involving biological processes (contaminant consumption by
Physisorption deploys weak Van der Walls forces, whereas chemi-
sorption involves the stronger covalent and ionic bonds. Van der Walls
forces require polar or polarizable compounds. Typically, compounds
with no dipole moment (0 D) are classified as non-polar, and else as
polar [19].
Chemical absorption of sulfur in aqueous solutions involves the
oxidation of S2− to S0 and on the capture of S2− through precipitation
of its metallic salts. For example, at the first method belongs the oxi-
dative absorption of H2S and O2 by iron-chelated solutions [20]. A
detailed review of the absorption methods are reported by Abatzoglou
and Boivin [20]. Literature studies have demonstrated how all the ad-
sorption processes exploit semi-batch processes. This is due to the
continuous gas-stream flow and fixed bed of adsorbent which is gra-
dually saturated with the adsorbate. These methods are hardly em-
ployed for large-scale plants mainly due to the lifespan of sorbent
material and regeneration problems [19,21,22]. Despite these issues, a
possible solution could be the lead and lag configuration. This config-
uration ensures the continuity of service [23]. Considering, the material
adopted, iron oxides adsorbents are recognized in literature for their
sulfur removal capacity [20]. Operational experience indicates that

⁎
Corresponding author at: Department of Energy (DENERG), Politecnico di Torino, Corso Duca degli Abruzzi, 24, 10129 Turin, Italy.
E-mail address: davide.papurello@polito.it (D. Papurello).

https://doi.org/10.1016/j.seppur.2018.07.081
Received 23 January 2018; Received in revised form 13 July 2018; Accepted 27 July 2018
Available online 29 July 2018
1383-5866/ © 2018 Elsevier B.V. All rights reserved.
D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

Nomenclature NLDFT non localized density functional theory

PDMS polydimethylsiloxane membrane
1%C/C0 pass-through ratio at 1% PID proportional integrative and derivative controller
10%C/C0 pass-through ratio at 10% Q volumetric flow rate (cm3/min)
C* gas concentration at the equilibrium within the pores qe equilibrium adsorption capacity (mg/gAC)
(ppm(v)) qmax maximum adsorption capacity function of sorbent mate-
C gas bulk concentration (ppm(v)) rial and contaminant (mg/gAC) – when it is reached
C0 initial concentration (ppm(v)) C* = C(x,t)
Carbox activated carbon from Airdep RH relative humidity
co covapors or simulatenuous concentration of H2S and HCl RST3 activated carbon from Norit
cow covapors or simulatenuous concentration of H2S and HCl SEM scanning electron microscopy
and humidified gas SOFC solid oxide fuel cell
D unit of dipole moment (Debye) SSA specific surface area (m2/g)
Dax axial dispersion term T operating temperature (K)
DFT density functional theory tb breakthrough time (min)
EDS energy-dispersive X-ray spectroscopy u gas interstitial velocity (m/s)
H2S hydrogen sulfide VFUEL volumetric flow rate (SNml/min)
HCl hydrogen chloride Vmicro microporous volume (cm3/g)
kfk is the boundary layer mass transfer coefficient VOCs volatile organic compounds
kl langmuir constant function of sorbent material, con- Vtot total volume (cm3/g)
taminant and temperature (m3/mg) w relative humidity 30%
kv overall adsorption rate coefficient (min−1) We equilibrium adsorption capacity (gpollutant/gcoal)
ms sorbent mass (g) x and t are respectively spatial and time coordinates
MSE mean squared error εb bed porosity (or void fraction inter-particle)
MW molecular weight (g/mol) ρb bulk density of the carbon bed (g/cm3)

only about 85% of removal can be achieved (0.56 kgH2S/kgFe2O3), as
reported by Taylor [24]. Hence, iron oxides are mainly used for a first
sulfur abatement section.
VOCs removal by adsorption on activated carbons represents a valid
and economical solution [25]. The main properties of activated carbon
filters for the effective removal of VOCs are high porosity, high super-
ficial area (1500 m2 g−1), high volume, pore distribution [26] and
treatment with metal ions. Impregnated activated carbons, mainly with
caustic bases (NaOH, Na2CO3, NaHCO3, KI), show typical H2S loading
capacities around 0.15 g/g [20]. Barelli et al. showed how the choice of
the impregnating agent is important in the removal of sulphur com-
pounds. In fact, when the carbon is activated with KI and KOH, the role
of water on the adsorption capacity has a positive effect [27]. In Pa-
purello et al. this effect was not highlighted due to the absence of such
agents and the role of water remained negative [28]. The non-im-
pregnated activated carbon show H2S-loading capacities around 0.02 g/
g [20].
Some studies suggest alternative solutions [29], for instance, Yuan
et al. [30] reports that the surface of sludge derived adsorbents can be
used for the desulfurization of digester gas. The removal capacity is
comparable to catalytic activated carbons [30].
Another alternative solution is the use of biomass or waste derived
materials char from pyrolisis or gasification processes [31,32]. In Hervy
et al.[31], two chars were produced by the pyrolysis of used wood
pallets, and a 50/50% mixture of food waste and coagulation-floccu-
lation sludge. The most efficient material was the steam activated char
from food waste and coagulation-flocculation sludge, with a removal
capacity of 65 mgH2S/g under dry syngas [31].
In summary, a first roughing step for the trace compounds limitation
should be followed by at least two guard beds to ensure the SOFC fuel
requirements and continuity of operation. The first step could be cov-
ered by an absorption process or by an iron oxides bed while the ultra-
filtration process can be ensured by solid sorbents, such as activated
carbons or similar [20,33–35].

Mass spectrometer

Blank line
Heated trap
Biogas (CH4/
PDMS filter
CO2)
P-4
+
H2S/HCl
+
H 2O AC filter

Fig. 1. Experimental set-up.

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D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

Table 1 Table 2
Elements identified with SEM-EDS analysis for the samples tested. Surface and volume analysis.
Atomic % Virgin Tested Sample SSA (m2/g) Vtot (cm3/g) Vmicro (cm3/g)

Element Carbox RST3 Biochar Carbox RST3 Biochar Carbox 1237 (Langmuir) 0.407 0.328
RST3 1117 (Langmuir) 0.447 0.300
C 80.9 91.15 98.85 86.96 93.83 99.65 Biochar 75 (Langmuir) 0.04 0.02
O 9.01 5.3 8.37 4.6 Biochar activated 593 (Langmuir) 0.26 0.17
Mg 1.19 0.2 0.1 0.08
Al 1.98 0.68
Si 1.4 1.03
shaker (Fritsch, Germany).
P 0.81
S 0.11 0.57 0.27 0.72 The biochar was activated in temperature to increase the starting
Cl 0.33 0.63 active surface area. The biochar sample was placed in a furnace at
K 0.78 0.78 0.34 0.21 0.37 0.11 750 °C (500 We, C.I.T.T., Milan, Italy), in a quartz tube with id 6 mm
Ca 1.65 0.76 0.8 1.03 0.4 0.24 and od 10 mm, length 60 cm. The sample was fluxed with carbon di-
Mn 0.41
oxide, 100 Sml/min for 1 h.
Fe 1.43 0.72
Zn 1.15 Data from the VOCs removal are used to calculate the adsorption
Total: 100 100 100 100 100 100 capacity for sulfur and chlorine using the following formula:
tt
C0 (H2 S, HCl) . 60 1
It is crucial to predict well the breakthrough time to foresee when
qe =
24.45
·MW ·VFUEL· 6 · ·
10 ms
∫ ⎛1− CC0 ⎞ dt
⎜ ⎟

0 ⎝ ⎠ (1)
the sorbent material needs to be changed. In this article, a porous
particle diffusion model was considered to find the equilibrium con-
2.3. Physicochemical characterization of sorbent materials
centration for two main contaminants contained in the biogas: H2S and
HCl. Experimental tests validate this model.
The physicochemical features of sorbent materials were carried out
in order to individuate the active surface area, the total volume, the
2. Material and methods
microporous volume and the pore distribution. Elemental composition
measurements were performed by scanning electron microscopy (SEM)
2.1. Materials
(FEI Inspect, Philips 525 M, The Netherlands) coupled with EDS ana-
lysis (SW9100 EDAX, The Netherlands). Characteristics of tested sor-
The materials tested are two different commercial activated carbons
bent materials are given in Table 1 and 2.
and a char obtained from the pyrogasification of forestry wood. Norit
The adsorption isotherms for N2 at 77 K were determined using a
RST3 (Cabot corporation, USA) is 3 mm extruded; steam activated
Quantachrome Autosorb 1. Samples were outgassed at 423 K overnight
carbon with catalytic properties, impregnated with calcium hydroxide
before the adsorption measurements. The experimental equipment al-
and potassium hydroxide. Airdep Carbox (Airedepuration plants, Italy)
lows measurement of the relative pressure until 10−6. Langmuir
is an extruded activated carbon with water vapor and impregnated with
equation has calculated specific surface areas for the carbon-based
iron oxide, calcium oxide and potassium oxide. Biochar is obtained
samples in the relative pressure range 0.04–0.1. Micropore volumes
from the pyro-gasification of wood from the waste sorting. The pyro-
were determined by means of the t-plot method in the relative pressure
gasification plant is realized near Turin, (Biesse di Leinì, Italy) with an
range 0.15–0.3. In this method the amount adsorbed is plotted against t,
electrical power of 400 kW and thermal power of 600 kW.
the multilayers thickness calculated from the standard isotherm ob-
tained with a non-porous solid reference. Carbon black was used as
2.2. Experimental apparatus
non-porous reference material for the t-plot.
For carbon-based materials the pore size has been evaluated
The experimental apparatus consists of a teflon tube piping (PTFE)
through the DFT method (Density Functional Theory), using the NLDFT
(i.d. 6 mm), a glass filter with a heated trap and mass spectrometer
equilibrium model for slit/cylindrical pores. The pore distribution for
instrument. Into the glass filter is located the sorbent material, main-
the two different commercial activated carbons, and biochar is reported
taining L/D value constant to 6.6 and a GHSV value constant to
in the following figure. A multimodal distribution is depicted due to the
1636 h−1. This is placed inside an electric oven (500 We, C.I.T.T.,
presence of several families of micropores (below 2 nm). The small
Milan, Italy), where the temperature is controlled at 30 °C by a PID
contribution above 2 nm is ascribed to inter-particles mesopores (see
regulator (Horst, Germany). The sorbent materials were tested with
Fig. 2).
simulated biogas (CH4/CO2 = 1.5) and pollutants such as, H2S con-
centration in the range 10–200 ppm(v), and HCl concentration in the
2.4. Adsorption model theory
range 10–377 ppm(v). Known concentrations of pollutants were avail-
able from certified gas cylinder (Siad spa, Italy). Demineralized water
The following section describes the assumptions and equations used
was co-fed to the mainstream using a liquid mass flow controller and a
for calculating the adsorption of selected contaminants on activated
controlled evaporator mixer (Bronkhorst, The Netherlands). Relative
carbons.
humidity was fixed at 30%, and it was changed from 0 to 100% when
A porous particle diffusion model, which involves the material
the impact of RH was investigated in the gas mixture. The biogas
balance equations in both of the gas-phase and the pore phase, was
mixture was fed to the micro-reactor through mass flow controllers
proposed to simulate the adsorption process [26]. The model adopted is
(Bronkhorst, The Netherlands).
composed by the mass balance equation for the bulk phase in a packed
Fig. 1 depicts the experimental set-up adopted. Red color represents
bed, the mass balance equation within the particle, the isotherm
heated lines at 40 °C with heated strings (isopad Thermocoax, Ger-
equation to describe the adsorption capacity of material and the ideal
many) controlled via a PID regulator (Horst, Germany). A PDMS
adsorption solution theory to consider the competitive adsorption.
(20 μm) membrane was inserted between the filter line and the heated
Several assumptions were made:
trap, to protect the mass spectrometer from the carbon particles. The
mass spectrometer adopted was an HPR 20 (Hiden Ltd., UK). The sor-
1. the adsorption process is isotherm, the temperature of the process is
bent materials were grounded up to 100–180 μm with a vibratory sieve

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9.E-02

8.E-02

7.E-02

Pore size distribution (cc/nm/g)

6.E-02

5.E-02

4.E-02

Carbox
3.E-02 RST3
Biochar
2.E-02

1.E-02

0.E+00
6 9 14 22 35 54 85 134 210 329
Pore width (nm)
Fig. 2. Pore size distribution.

constant and the reaction of adsorption is exothermic meaning that for packed bed [38]. To obtain the rate of adsorption and complete the
the surface is heterogeneous; equation is also necessary to evaluate C*. This term is the gas con-
2. the axial dispersion is considered only longitudinally and not ra- centration at the equilibrium with qmax, or rather the contaminants
dially; quantity adsorbed on porous media. The evaluation of this parameter is
3. the adsorbent particles are spherical and homogeneous in size and obtained using the Langmuir isotherm.
density; The transport phenomenon on porous media can be simplified
4. the external transfer coefficient depicts the mass transfer across the considering two main mechanisms:
boundary layer;
5. the intra-particle mass transport is characterized by the effective • external transport, transport from gas bulk phase to gas film around
pore diffusion coefficient; the particle,
6. the linear velocity of the gas phase is independent of the con- • internal porous transport, it represents the resistance to diffusion of
centration; a contaminant in the intra-particle porosity.
7. a local equilibrium condition is established between the gas con-
centration adsorbed and the solid particle. For activated carbons, the linear adsorption equilibrium cannot be
chosen. The Langmuir isotherm is adapted to describe the non-linear
A similar model was developed by Rosen and by Rasmuson [36,37]. equilibrium behavior of sorbent material [39]. To estimate these
The model adopted is validated with experimental tests. The equation parameters, laboratory tests must be developed. C* is the solution of a
of the model is a partial differential equation in space and time. It is non-linear equation to quantify the rate of material adsorption. The
developed for a vertical dimensional adsorption layer. estimation is performed solving the Langmuir equation (Eq. (4).

∂2C (x , t ) ∂C (x , t ) ∂C (x , t ) 1−εb ∂q (x , t ) kl C ∗
−Dax +u + + =0 qe = qmax
∂x 2 ∂x ∂t εb ∂t (2) 1 + kl C ∗ (4)

The axial dispersion term is an undesirable effect. The aim of To evaluate the adsorption capacity for a mixture the ideal adsorbed
manufacturers and designers is to avoid this phenomenon compared to solution approach (IAS) is followed [40].
the advection term. This contribution can be neglected due to the lower Considering two-compound competitive adsorption the IAS equili-
Peclet number (around 500). This is generally attained by the gas flow brium conditions can be expressed using LeVan and Vermeulen equa-
across the adsorbent media. The accumulation term takes into account tions [41]. The following equation is adopted for the competitive ad-
the mass transfer of the contaminant from gas bulk phase to solid phase. sorption of two compounds.
It represents the rate of adsorption and it contains the transport kinetics
q1, m kl,1 C1 + q2, m kl,2 C2
of the contaminants, but also equilibrium conditions. These conditions qe =
are related to the type of isotherm chosen and related coefficients. The kl,1 C1 + kl,2 C2 (5)
necessity to know porous media characteristics are crucial to develop
The Langmuir equations of two compounds can be expressed with
mass balance within the particle. This term can be written as:
the following equations:
∂q (x , t )
= a (1−εb ) kfk (C −C ∗) qs kl, i Ci
∂t (3) qi = + Δ1,2
1 + ∑i = 1,2 kl, i Ci (6)
Boundary layer mass transfer coefficient (kfk) is calculated using the
empirical formulation of Wakao-Funazkri, as suggested by Xiao et al. where i = 1,2; and Δ1,2 can be expressed using (Eq. (2):

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D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

kl,1 C1 kl,2 C2
Δ1,2 = (q1, m−q2, m ) ln(1 + kl,1 C1 + kl,2 C2)
(kl,1 C1 kl,2 C2 )2 (7)
Another possible model to be considered is based on the Wheeler-
Jonas equation. The Wheeler–Jonas equation allows the estimation of
the breakthrough time of granular activated carbon (GAC) bed [28,42].
This estimation is based solely on measurable and readily available
macroscopic parameters:
We·ms ρb ·We C −C
tb = − ·ln 0
Q·C0 k v·C0 C (8)
This equation is originally based on a continuity equation of the
mass balance. This equation considers the mass balance between the
vapor entering the carbon bed and the sum of the amount adsorbed by
this bed plus the amount penetrating through it.
There are some limitations to this equation:
• the flow pattern has to be a perfect plug flow with axial, but no
radial diffusion;
• the original equation was based on physisorption into micropores;
• the rate constant k has to be of first order concerning the number of
v 3 min for RST3 and 3 min for carbox. Taking into account biochar as a
gas molecules. For pure physisorption, this is usually true in the
first, convex part of the sigmoidal breakthrough curve.
As reported by several authors, this equation is reliable especially
considering the single compound removal. In case of multiple con-
taminants, IAS approach must be adopted [42-46].
3. Results and discussion
3.1. Removal of single compound
To describe the pollutant removal using sorbent materials a pass-
through ratio value (C/C0) is used. C, is the temporal evolution of the
concentration along the filter. This term is evaluated at the end of the
filter. C0, is the starting concentration to be removed from the filter.
This term is evaluated at the beginning of the filter. C/C0 identifies the
concentration state of the gas flow at the output of the filter. The pass-
through ratio at 1% (1%C/C0) concentration corresponds to 0.76 ppm
(v) for H2S (C0 = 76 ppm(v)) and 3.7 ppm(v) for HCl (C0 = 377 ppm
(v)). These values are considered representatives of the reversible pol-
lutant concentration for SOFC applications, as reported elsewhere
[4,9,47]. In the meantime, 10%C/C0 represents the irreversible condi-
tion for SOFC applications. Above this value, the fuel feeding condition
can only generate irreversible issues for SOFCs. Hydrogen sulfide re-
moval with RST3 shows a breakthrough time (tb) with a pass-through
ratio of 1%, around 31 min. For carbox the tb is close to 62 min. At
10%C/C0, the tb is 39 min and 112 min for RST3 and carbox, respec-
tively. With these conditions, the sorbent material should be changed
between 1%C/C0 and 10%C/C0 in 8 min for RST3 and 50 min for
carbox. Carbox shows a more sigmoid behavior compared to RST3.
Taking into account biochar as a sorbent material, the tb is close to
1.5 min and 2 min considering, respectively the 1% and 10% pass-
through ratio. This material without any activation or impregnation
process is useless for H2S removal. Hydrogen chloride removal with
RST3 shows a tb with a pass-through ratio of 1% around 44 min, while
for carbox the tb is close to 34 min. At the 10%C/C0 condition the tb for
RST3 is 47 min and 37 min for carbox. With these conditions, the sor-
bent material should be changed between 1%C/C0 and 10%C/C0 in
sorbent material, the tb is close to 1.6 min and 6.7 min considering,
respectively the 1% and 10% pass-through ratio. This material without
any activation or impregnation process is useless also for HCl removal
(see Fig. 3).
The adsorption capacity evaluated at the starting of the break-
through (C/C0 = 1%) by Eq. (1) is reported in the following table:
The adsorption capacity evaluated with activated biochar show
comparable performance with commercial samples.
The removal performance in case of the single compound shows a
linear correlation with the specific surface area, total volume and mi-
cropore volume. The correlation between adsorption capacity and mi-
cropore volume is stronger with respect to specific surface area and
total pore volume. This is in line with the typology of the adsorbed
molecules, as reported in [48]. In the following figure are reported the
equations for the correlation between adsorption capacity and sorbent
characteristics (see Fig. 4).
There is a strong relationship between the adsorption capacity and

100

90

80

70

60
C/C0 (%)

50

40 RST3 - H2S
carbox - H2S
30 biochar - H2S
RST3 - HCl
carbox - HCl
20
biochar - HCl

10

0
0 50 100 150 200 250 300
Time (min)
Fig. 3. Single compound removal – breakthrough time.

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D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

2
H2S Carbox
1.8
RST3
1.6
1.4

Ads capacity (mg/g)

y = 0.0014x - 0.0347
1.2
Biochar act. R² = 0.9874
1
0.8
0.6
0.4
0.2 Biochar
0
0 200 400 600 800 1,000 1,200 1,400
S BET (m2/g)
2
H2S Carbox
1.8
RST3
1.6
1.4
Ads capacity (mg/g)

1.2 y = 4.1318x - 0.132

Biochar act. R² = 0.9586
1
0.8
0.6
0.4
0.2 Biochar
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50

V tot (cm3/g)
2
H2S Carbox
1.8
RST3
1.6
1.4
Ads capacity (mg/g)

1.2 y = 5.4967x - 0.0641

Biochar act. R² = 0.9941
1
0.8
0.6
0.4
0.2 Biochar
0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

V micro(cm3/g)
Fig. 4. Relationship between adsorption capacity and physical characteristics.

physical characteristics of sorbent materials. Specific surface area and 3.3. Concentration influence on removal performance
pore volumes are directly related with the adsorption capacity of the
sorbent. Two different commercial activated carbons are tested.
Experimental results data for the breakthrough time varying the
starting pollutant concentration for H2S and HCl are reported in Fig. 6.
3.2. Impact of the activation process on the removal performance of biochar Breakthrough time values modeled with Eq. (1) are in agreement with
experimental results, both in case of H2S, HCl and also for two different
Carbon dioxide was selected as activating agent. This selection commercial activated carbon filters. The results confirm a marked de-
wants to simulate an alternative use of a gas exhaust from SOFCs cline in the tb increasing the initial concentration of the contaminant. In
generators. The activation process increased the specific surface area dry condition, RST3 carbon showed better results than carbox sample.
from 75 m2/g to 593 m2/g and also increased the total volume and The biogas with a concentration of H2S around 10 ppm(v), with RST3
micropore volume. This process increased the ability to remove trace
compounds, such as hydrogen sulfide using biochar. The ability to re-
move H2S and HCl was proved according to results reported in Table 3. Table 3
In the following figure activated biochar is compared to the biochar Adsorption capacity for single compound removal.
sample for the removal of H2S (see Fig. 5). GHSV 1636 h−1 H2S (mg/g) HCl (mg/g)
The activated biochar shows comparable results with commercially
RST3 1.53 20.41
available carbons.
Carbox 1.75 12.09
Biochar 0.01 0.27
Activated biochar in Temperature 0.95 8.71

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D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

70

60

50

40
C/C0 (%)

30

20

biochar
10
biochar act

0
0 50 100 150 200 250 300
Time (min)
Fig. 5. Single compound removal – biochar versus activated biochar.

120
H2S Carbox
HCl Carbox
100 H2S RST3
HCl RST3
Breakthrough time (min)

80

60

40

20

0
0 50 100 150 200 250
Initial Concentration (ppmv)
Fig. 6. H2S and HCl removal – concentration dependence.

showed a tb around 60 min and 55 min, respectively in case of model
and experimental condition. Considering the same biogas conditions,
the carbox sample showed a performance (tb) around 54 min and
50 min, respectively in case of model and experimental condition. The
biogas with a concentration of HCl around 10 ppm(v), with RST3,
showed a tb around 103 min and 91 min, respectively in case of model
and experimental condition. Considering the same biogas conditions,
the carbox sample showed a performance (tb) around 99 min and
91 min, respectively in case of model and experimental condition.
Above 50 ppm(v) of H2S the tb was less than 5 min. The breakthrough
time values, in case of HCl were higher compared to H2S for similar
concentrations. This was due to the higher dipole moment of chlorine
compared to sulfur which affected the removal capacity of the sorbent
material. The Wheeler-Jonas equation, adopted as predictive model
worked well with an overestimation of 8% at lower concentrations,
while at higher concentrations there was an overestimation around 1%.
3.4. The impact of moisture and temperature on the removal performance
Fig. 7 depicts the breakthrough time trend for H2S varying the re-
lative humidity and the operating temperature (inlet H2S 10 ppm(v)). It
is highlighted how increasing the operating temperature the break-
through time shows a decreasing rate. The relative humidity content
inside a fuel stream has a negative impact on the H2S removal

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D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

160 160
5°C 5°C
(a) 10°C
(b) 10°C
140 15°C 140 15°C
20°C 20°C
120 25°C 120 25°C
30°C 30°C
Breakthrough time (min)

Breakthrough time (min)

35°C 35°C
100 100 40°C
40°C
45°C 45°C
80 80

60 60

40 40

20 20

0 0
0 10 20 30 40 50 60 70 80 90 0 20 40 60 80 100
Relative Humidity (%) Relative Humidity (%)

Fig. 7. Breakthrough time versus relative humidity content of biogas for H2S and temperature – Norit, RST3 (a), Airdep, Carbox (b).

performance. In fact, contrarily to what reported from Sisani et al. [49] Increasing the operating temperature decreases the adsorption capa-
and from Barelli et al. [27], RST3 shows a continuous decreasing of tb city. Below 20 °C and above RH 50%, a substantial breakthrough time
trend increasing the RH content [49]. In accordance to Sisani et al. decrease is recorded. For RST3, the breakthrough time at RH 0% passes
[49], the higher potassium content in carbox favors the H2S removal from 272 min at 5 °C up to 109 min at 45 °C. Above RH 50% the
with an RH content lower than 10%, in case of RST3. Higher RH values breakthrough time is above zero compared to the removal of H2S. For
instead of favor the H2S removal causes the competition between sulfur carbox, the breakthrough time at RH 0% passes from 266 min at 5 °C up
and water in the absence of the activating agent (KOH). to 104 min at 45 °C. Here, compared to H2S removal case, above RH
For RST3, the breakthrough time at RH 0% passes from 150 min, at 50% the breakthrough time is above zero. The breakthrough time, at
5 °C up to 50 min, at 45 °C while above RH 50% and above 25 °C, the RH 80% shows values above 0 min for all the operating temperature
breakthrough time is around zero. The breakthrough time at RH 80% considered, both for RST3 and carbox sample. At a relative humidity of
shows different values to zero for temperature below 15 °C. Hence the 80% the tb passes from 174 min at 5 °C up to 2.5 min at 45 °C for RST3.
breakthrough time is zero when the operating temperature is above Considering the carbox sample, at a relative humidity of 80% the tb
20 °C. For carbox sample, the breakthrough time at RH 0% passes from passes from 171 min, at 5 °C up to 2.6 min at 45 °C. Considering carbox
135 min at 5 °C up to 41 min at 45 °C, while above RH 50% and above sample, bringing the relative humidity from 0% to 10%, there is an
25 °C, the breakthrough time is around zero. The breakthrough time at increasing trend on the breakthrough time of 6.0% at 5 °C, 6.3% at
RH 80% shows values different to zero for temperature below 15 °C. At 20 °C and 18.1% at 45 °C. When relative humidity is 10% the break-
a relative humidity of 80% the tb passes from 54.7 min at 5 °C up to through time shows a decreasing trend softer compared to RST3 case.
4.3 min at 10 °C. While, still for RST3, above 15 °C the tb is zero. Even if for RST3 sample, changing the operating temperature, the ab-
Considering the carbox sample, at a relative humidity of 80% the tb solute values of tb are higher respect to carbox sample. It results that
passes from 50.7 min at 5 °C up to 5.2 min at 10 °C, while above 15 °C RST3 shows better performance, especially at dry conditions compared
the tb is zero. to carbox sample. The carbox sample shows good performance at RH
Bringing the relative humidity from 0% to 10% there is an in- around 10%. The HCl removal case shows higher breakthrough time
creasing trend on the breakthrough time. values respect to the H2S case. This is due to the higher dipole moment
Fig. 8 depicts the breakthrough time trend for HCl (9 ppm(v)) of HCl (1.08 D) compared to H2S (0.95 D) [50,51]. The dipole moment
varying the relative humidity and the operating temperature. is a measure of the degree of polarity. The phenomenon explained as

300 300
5°C 5°C
(a) 10°C
(b) 10°C
15°C 15°C
250 20°C
250 20°C
25°C 25°C
30°C
Breakthrough time (min)

30°C
Breakthrough time (min)

200 35°C 200 35°C

40°C 40°C
45°C 45°C
150 150

100 100

50 50

0 0
0 20 40 60 80 100 0 20 40 60 80 100
Relative Humidity (%) Relative Humidity (%)

Fig. 8. Breakthrough time versus relative humidity content of biogas and temperature for HCl – Norit, RST3 (a), Airdep, Carbox (b).

87
D. Papurello et al.
follows: the higher the polarity of compounds of interest is the stronger
electron-donating ability become [52].
The combination of the operating temperature and relative hu-
midity on the breakthrough time is reported in Figs. 8 and 9. This aspect
causes the decreasing of the removal performance. Only some salts,
adopted for the impregnation process help the removal performance for
sulfur compounds. This is the case of KOH and KI, which are able to
facilitate the removal of sulfur compounds, as reported in literature
[27,49].
Breakthrough time values modeled with Eq. (3) are in agreement
with experimental results. This data are reported varying the operating
temperature from 5 °C to 45 °C. Breakthrough time for HCl is in general
higher respect to H2S case, both for RST3 and carbox. The results
confirm a marked tb decline increasing the operating temperature. The
maximum breakthrough time value for RST3 at 5 °C is 147 min, for H2S
(RH = 0%) and 278 min for HCl (RH = 0%). The minimum break-
through time value at 45 °C is 52.6 min for H2S (RH = 0%) and 110 min
for HCl (RH = 0%). Considering the carbox sample, the maximum tb is
264 min and 136 min, respectively for HCl and H2S at 5 °C and
RH = 0%. The minimum tb value is 105 min and 45 min, respectively
for HCl and H2S at 45 °C at the same RH condition.
By increasing the operating temperature, the decreasing perfor-
mance of the activated carbon is observed (Fig. 9). As the temperature
rises, the vapor pressure of the adsorbate increases [22,38]. Hence, the
energy level of the H2S and HCl molecules raises to overcome the Van
der Waals attraction and migrate back to the bulk gas phase reducing
the overall breakthrough time [53]. The effect is that the breakthrough
time decreases with increasing adsorbent bed temperature. Thus, an
increase in the operating temperature caused lower values of the
maximum adsorption capacity.
3.5. Removal of multiple compounds and influence of humidified gas
Generally sorbent materials face the contemporary presence of more
than one pollutant (co-vapors removal condition). Fig. 10 shows the
breakthrough time trend for the sorbent materials tested in both single
and multiple compounds configuration (H2S and HCl). The 1%C/C0
ranges from 30 min and 35 min for H2S with RST3, respectively in
single and multiple compounds configuration (H2S + HCl). The
250
200
Breakthrough time (min)
150
100
50
0
275 280 285
Fig. 9. H2S and HCl removal – RST3 and Carbox – Temperature effect.
Separation and Purification Technology 210 (2019) 80–92
removal performance for H2S are similar in single and multiple com-
pounds configuration. When the pass-through ratio is around 10%, the
breakthrough time is 38 min for both configurations (single and mul-
tiple cases). At this point there is the inversion of the curve profile, and
from here forward the removal performance, for RST3 improves in the
single compound configuration. The simultaneous presence decreases
the removal performance due to the competition of HCl for the removal
of H2S. Biochar results are not reported because the pass-through ratio
achieved the saturation value in 10 min.
The 1%C/C0 ranges from 44 min and 47 min for HCl with RST3,
respectively in single and multiple compounds configuration
(H2S + HCl). The removal performance for HCl are similar in single and
multiple compound configuration. When the pass-through ratio is
around 11% the breakthrough time is 49 min for both configurations.
At this point, there is the inversion of the curve profile, and from here
forward the removal performance, for RST3 improves in the single
compound configuration. The simultaneous presence decreases the re-
moval performance due to the competition of H2S for the removal of
HCl.
Results reported in Fig. 11 consider the effect of humidified gas
(RH = 30%) with the simultaneous concentration of H2S and HCl. Here,
the addition of water for all the experimental tests leads to a decrease of
removal performance. Considering the breakthrough at 1% of C/C0, the
time decreases of 77% for RST3 with humid biogas. The reduction of
removal performance adding water to the gas stream is due to the in-
terference of water in the pores of activated carbons.
Biochar results are not reported because the pass-through ratio
achieved the saturation value in 30 min.
The adsorption capacity evaluated by Eq. (1) is reported in the
following table, considering the simultaneous concentration of H2S, HCl
and water:
From single to multiple compounds the adsorption capacity for
RST3 decreases. The influence of water is very important as it can be
seen from the adsorption capacity, table 4.
3.6. Porous particle diffusion model validation – single compound removal
Model validation was accomplished by comparing the experimental
results with data obtained from the model described before. This
H2S Carbox
HCl Carbox
H2S RST3
HCl RST3
290 295 300 305 310 315 320
Temperature (K)
88
D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

100

90

80

70

60
C/C0 (%)

50

40

30
RST3 - H2S RST3 - H2Sco

20
RST3 - HCl RST3 - HClco
10

0
0 50 100 150 200 250
Time (min)
Fig. 10. H2S and HCl removal – (co)-vapors effect.

100

90

80

70

60
C/C0 (%)

50

40

30
RST3 - H2Sco RST3 - H2Sco w

20

10 RST3 - Hclco RST3 - HClco w

0
0 50 100 150 200 250
Time (min)
Fig. 11. H2S and HCl removal – co-vapors effect – water influence.

Table 4 validation is necessary to understand the real ability to predict packed

Adsorption capacity for multiple compound removal and water influence. bed breakthrough. The model must be precise especially at an ultra-low
GHSV 1636 h−1 H2Sco (mg/ HClco (mg/ H2Sco-w HClco-w (mg/ concentration to be suitable for SOFC feeding requirements. In this
g) g) (mg/g) g) case, the focus is just on the first part of the breakthrough curve:
0–0.4% on the y-axis (C/C0). It is interesting to investigate the com-
RST3 1.48 11.19 0.42 0.06 petitive adsorption of H2S and HCl [6,54,55]. H2S single compound
Biochar 0.01 0.54 0.005 0.46
Activated biochar 1.09 6.4 0.47 0.08
removal appears closer to the experimental case.
Fig. 12 describe the breakthrough time for two different activated
carbons to remove 55 ppm(v) of H2S.
Porous particle diffusion model fits the experimental data very well,
espcially around the breakthrough point (0–0.4% C/C0). In fact, for

89
D. Papurello et al. Separation and Purification Technology 210 (2019) 80–92

Fig. 12. Breakthrough time – H2S 55 ppm(v) - fitting evaluation for Norit RST3 (orange) and Airdep Carbox (blue). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

RST3 the value of mean squared error (MSE) is equal to 0.029%. The
breakthrough point is predicted by the model around 47 min and by the
experimental data at 48 min.
The breakthrough point is predicted after 60 min, for carbox carbon
while experiments underline a breakthrough after around 80 min of
operation. Despite this discrepancy between these values, the MSE
value is fixed around 0.071%.
Fig. 13 depicts the simultaneous removal of two trace compounds:
H2S and HCl detected in biogas from organic waste. Results achieved
from the model and compared to experimental points shows a C/C0
trend accurate for H2S (35.1 min against 35.22 min), while under-
estimate the HCl removal performance (breakthrough point expected
10 min later). Here the percentage error for the breakthrough point
estimation is 0.34% for H2S and 23% for HCl, Fig. 13.
In summary, low values of MSE validate the model in the first part
of the breakthrough curve, even for competitive adsorption. The prin-
cipal result achieved from the porous particle diffusion model is the
excellent capacity to estimate the breakthrough time. This estimation is
the most important point for SOFC feeding with biogas produced from
organic waste.
4. Conclusions
The removal of selected trace compounds considering the covapor
condition, the operating temperature and also humid biogas conditions
were studied on commercially available sorbents and waste-derived
material (biochar). The best removal performance, in single compound
removal condition (H2S or HCl) was achieved by RST3. Biochar, com-
pared to the other sorbent materials showed the lowest removal per-
formance, both for H2S and HCl. Activated biochar with carbon dioxide
at 750 °C, showed interesting results comparable with commercially
available sorbents. This was due the increasing of specific surface area
and porous volume.
Operating temperature affects the removal performance for all the
sorbents considered. The vapor pressure of the adsorbate increases with
the temperature. This favors the energy level rising for the trace com-
pounds to overcome the van der walls attraction bonds. This causes the
migration to the bulk gas phase reducing the breakthrough time. Thus,
an increase in the operating temperature caused lower values of the
maximum capacity of the adsorbent. The humidity contained in the
biogas affects negatively the removal performance. This is connected to
the interference of water with trace compounds on the pores of

0.25

H2S
H2S model
0.20 HCl
HCl model

0.15
C/C0

0.10

0.05

0.00
0 10 20 30 40 50 60
Time (min)
Fig. 13. Breakthrough time – H2S 64 ppm(v) and HCl 307 ppm(v) - fitting evaluation for Norit RST3.

90
D. Papurello et al.
activated carbons. It was found that the commercially available sor-
bents and waste-derived material tested are negatively affected by
water inside biogas.
Experimental data were employed in a porous particle diffusion
model to estimate the breakthrough time. Low mean squared errors
were achieved in the first part of the breakthrough curve, even for
competitive adsorption for SOFC feeding requirements.
Future works will involve experiments on various methods of acti-
vation for biochar samples and on the model validation for the con-
temporary pollutants removal.
Acknowledgements
This work is a part of the work for the demosofc project which is
carried out by Politecnico di Torino and other European partners (FCH-
JU). In addition, this research is part of the BWS project (Biowaste for
SOFCs), project funded by the Fondazione Cassa di Risparmio di Trento
e Rovereto. A special thanks to Ph.D. Fiorilli Sonia for her important
and fundamental work and a special thanks to our technician Bressan
Maurizio.
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