energies

Article
Investigation of an Intensified Thermo-Chemical Experimental
Set-Up for Hydrogen Production from Biomass: Gasification
Process Integrated to a Portable Purification System—Part II
Donatella Barisano 1, * , Giuseppe Canneto 1 , Francesco Nanna 1 , Antonio Villone 1 , Emanuele Fanelli 1 ,
Cesare Freda 1 , Massimiliano Grieco 1 , Andrea Lotierzo 1 , Giacinto Cornacchia 1 , Giacobbe Braccio 1 ,
Vera Marcantonio 2, * , Enrico Bocci 3 , Claire Courson 4 , Marco Rep 5 , Tom Oudenhoven 5 ,
Steffen Heidenreich 6 and Pier Ugo Foscolo 7

1 Italian National Agency for New Technologies, Energy and Sustainable Economic Development,
Lungotevere Thaon di Revel, 76, 00196 Rome, Italy; giuseppe.canneto@enea.it (G.C.);
francesco.nanna@enea.it (F.N.); antonio.villone@enea.it (A.V.); emanuele.fanelli@enea.it (E.F.);
cesare.freda@enea.it (C.F.); massimiliano.grieco@enea.it (M.G.); andrea.lotierzo@enea.it (A.L.);
giacinto.cornacchia@enea.it (G.C.); giacobbe.braccio@enea.it (G.B.)
2 Unit of Process Engineering, Department of Engineering, University “Campus Bio-Medico” di Roma,
Via Álvaro Del Portillo 21, 00128 Rome, Italy
3 Department of Engineering Science, Marconi University, 00193 Rome, Italy; e.bocci@unimarconi.it
4 Department of Chemistry and Processes for Energy, Environment and Health, University of Strasbourg,
25 rue Becquerel, CEDEX 2, 67087 Strasbourg, France; claire.courson@unistra.fr
5 HyGear, Westervoortsedijk 73, 6827 AV Arnhem, The Netherlands; marco.rep@hygear.com (M.R.);
t.oudenhoven@hygear.com (T.O.)
6 Pall GmbH, Zur Flügelau 70, D-74564 Crailsheim, Germany; steffen_heidenreich@europe.pall.com
Citation: Barisano, D.; Canneto, G.;
7 Department of Industrial Engineering, University of L’Aquila, Monteluco di Roio, 67100 L’Aquila, Italy;
Nanna, F.; Villone, A.; Fanelli, E.;
Freda, C.; Grieco, M.; Lotierzo, A.; pierugo.foscolo@univaq.it
Cornacchia, G.; Braccio, G.; et al.
* Correspondence: donatella.barisano@enea.it (D.B.); v.marcantonio@unicampus.it (V.M.)
Investigation of an Intensified
Thermo-Chemical Experimental Abstract: Biomass gasification is a versatile thermochemical process that can be used for direct
Set-Up for Hydrogen Production energy applications and the production of advanced liquid and gaseous energy carriers. In the
from Biomass: Gasification Process present work, the results are presented concerning the H2 production at a high purity grade from
Integrated to a Portable Purification biomass feedstocks via steam/oxygen gasification. The data demonstrating such a process chain were
System—Part II. Energies 2022, 15, collected at an innovative gasification prototype plant coupled to a portable purification system (PPS).
4580. https://doi.org/10.3390/ The overall integration was designed for gas conditioning and purification to hydrogen. By using
en15134580
almond shells as the biomass feedstock, from a product gas with an average and stable composition
Academic Editor: Albert Ratner of 40%-v H2 , 21%-v CO, 35%-v CO2 , 2.5%-v CH4 , the PPS unit provided a hydrogen stream, with a
final concentration of 99.99%-v and a gas yield of 66.4%.
Received: 8 May 2022
Accepted: 22 June 2022
Keywords: biomass; gasification; hydrogen; syngas; gas cleaning; gas conditioning; aspen plus;
Published: 23 June 2022
biomass waste; fluidized-bed reactor
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations. 1. Introduction
In this historical period, the struggles against global warming and climate change
united to the necessity for energy security and national independency pointed out the
Copyright: © 2022 by the authors.
importance of finding out a trustworthy alternative to fossil fuels. Biomass is the largest
Licensee MDPI, Basel, Switzerland. source of renewable energy and it is ranked in the fourth place among the energy sources,
This article is an open access article after oil, coal and natural gas; moreover, residual biomass, e.g., from agro-industrial to
distributed under the terms and municipal wastes, is inherently inexpensive [1–3]. These are the reasons why biomass
conditions of the Creative Commons waste is actually considered to be the fuel of renewable origin most suitable to replace the
Attribution (CC BY) license (https:// fossil fuels.
creativecommons.org/licenses/by/
4.0/).

Energies 2022, 15, 4580. https://doi.org/10.3390/en15134580 https://www.mdpi.com/journal/energies

Energies 2022, 15, 4580 2 of 16

In the last decade, the improvement of advanced thermo-chemical technologies has

also encouraged the traditional utilizations of biomass waste in distributed power gener-
ation systems. Nevertheless, appropriate small-scale energy systems must be developed
and optimized, to effectively convert the low-density energy of biomass fuels into heat
and electricity production [2,4,5]. Researchers point to the biomass gasification as one
of the most advantageous thermo-chemical processes, due to its capacity to maintain a
high-rate fuel gas production, along with lower investment costs [6,7]. This process is
promoted at high temperatures, typically 750–1000 ◦ C or higher, depending on the specific
technology of use [8–10], by processing the biomass feedstock with an oxidizing agent
(oxygen, air, steam or a mix of them). The process leads to the production of a fuel gas
commonly called syngas, or product gas, consisting of hydrogen, carbon monoxide, carbon
dioxide, methane and steam, along with several unwanted by-products [11]. Syngas is
considered to be of good quality when it has a low content of nitrogen, a low extent of
contaminants, high heating values (LHV) and, depending on the final application, a high
content of hydrogen [12,13]. Several studies show that the fluidized-bed reactors are the
most indicated for the operation of a gasification process. In fact, due to the possibility of
providing good mixing and gas-solid contact between the gasifying agent and the fuel to
be processed, it ensures high reaction rates and conversion efficiencies [14,15]. Moreover,
compared to other designs, the fluidized-bed reactors have a greater flexibility with respect
to the characteristics of the matrices to be processed and to the range of scalability. All of
this together results in a greater versatility of the gasification technology, based on fluidized
bed reactors with respect to the end uses.
The composition of syngas is affected by several factors, including the physical and
chemical characteristics of the biomass feedstocks, operating conditions (e.g., tempera-
ture and feeding rates), gasifying medium, gasifier design, addition of catalysts and/or
sorbents. [8,9,16–19]. Through composition conditioning and purification of syngas it is
possible to produce high purity hydrogen (higher than 99%-v grade). In view of the climate
targets expected by 2030 and 2050, this gas is gaining more and more interest, with appli-
cations in multiple sectors [20,21]. Hydrogen is, in fact, a very promising energy vector:
it is a “clean” fuel; it can meet all of the energy demands; and it can be utilized in several
applications, such as solid oxide fuel cells, internal combustion engines and gas turbines for
power/CHP production, as well as for the production of substances, such as methanol and
ammonia, which are commodities of high interest in the chemical/biofuel market. Finally,
hydrogen can be used in the so-called «hard to abate» sectors.
The first approach to achieve a high level of hydrogen in the final composition of the
syngas is to use steam and oxygen as the gasifying agents [6]. Then, the purification of the
syngas can be carried out inside the gasifier by means of cracking and steam reforming of
low and high molecular weight hydrocarbons, with the benefits of thermal integrations
and high tar and light hydrocarbons’ conversion [22,23].
The authors, in a previous paper entitled “Investigation of an Intensified Thermo-
Chemical Experimental Set-Up for Hydrogen Production from Biomass: Gasification Pro-
cess Performance-Part I” [24], showed the good results obtained in an intensified gasifier
with the UNIQUE concept [25], which combines the benefit of the process of steam/oxygen
gasification with that of a hot gas-cleaning process, integrated into a single and compact
fluidized-bed reactor. With the aim of producing hydrogen from the biomass feedstocks
through gasification, experimental campaigns were carried out on a prototype intensified
gasification plant coupled to an integrated portable purification system (PPS). The PPS was
designed for gas cleaning and conditioning, for hydrogen separation and production at a
fuel cell vehicle grade (FCV), i.e., grade 4, 99.99%-v of H2 . In the previous paper, quoted
above, the authors only reported the gasification element. The experimental activity was
conducted at a 1 MWth gasification pilot plant and the tests were carried out at 0.25–0.28
Equivalence Ratio (ER), 0.4–0.5 Steam/Biomass (S/B), and 780–850 ◦ C gasification tem-
perature. The biomass feedstock selected was almond shells, a residual biomass ready
for reactor feeding, as well as being characterized by low humidity, high density, low ash
Energies 2022, 15, x FOR PEER REVIEW 3 of 17
Energies 2022, 15, 4580 3 of 16

low ash content, high calorific value and low costs [26]; feeding rates of about 120 and 150
content,
kg high calorific value and low costs [26]; feeding rates of about 120 and 150 kggasi-
dry/h were preliminarily adopted in order to also evaluate the performance of the dry
/h
were preliminarily adopted in order to also evaluate the performance of the
fication reactor after the hardware modifications were implemented to integrate the filtra- gasification re-
actor after the hardware modifications were implemented to integrate the filtration
tion system into the gasifier freeboard. The collected data showed that the filtration sys- system
intoensured
tem the gasifier freeboard.
a dust removalThe collected
efficiency data than
higher showed that the
99%-wt. Thefiltration system
dry syngas finalensured
compo-a
dust removal efficiency higher than 99%-wt. The dry syngas final composition
sition was made up of 27–33%v H2, 23–29%v CO, 31–36%v CO2, 9–11%v CH4; the gas yield was made
up of 27–33%v
calculated H
was 1.2 , 23–29%v CO, 31–36%v CO
2 Nm3dry/kg. A LHV of 10.3–10.9 2 , 9–11%v CH ; the gas yield calculated
MJ/Nm34dry and a cold gas efficiency was
3
1.2 Nmupdry 3
(CGE) to/kg.
75%AwereLHVestimated.
of 10.3–10.9 MJ/Nm dry and a cold gas efficiency (CGE) up to 75%
were estimated.
Starting from the results achieved in [24], in the current work the authors want to
Starting from the results achieved in [24], in the current work the authors want to
present the results of the PPS operation, with the achievement of 99.99%-v of H2. This
present the results of the PPS operation, with the achievement of 99.99%-v of H2 . This
research also includes a whole process simulation, developed via the Chemical Engineer-
research also includes a whole process simulation, developed via the Chemical Engineering
ing commercial software Aspen Plus.
commercial software Aspen Plus.
2.2.Materials
Materialsand
andMethods
Methods
2.1.
2.1.Experimental
ExperimentalSet-Up
Set-Up
The
Theprocess
processof ofbiomass
biomass gasification
gasification waswas carried
carried outout at
at aa 1000
1000 kWkWththpilot
pilotplant
plantlocated
located
at
at the
the ENEA
ENEAResearch
ResearchCentre
Centreof of Trisaia
Trisaia (Rotondella),
(Rotondella), Southern
Southern Italy.Italy. The
The plant
plant isis based
based
on
onaabubbling
bubblingfluidized
fluidizedbedbedreactor
reactordesigned
designed inin
itsits
final configuration
final configuration to host a bundle
to host of
a bundle
sixty, high
of sixty, temperature,
high temperature,ceramic filterfilter
ceramic candles for in-vessel
candles gas filtration.
for in-vessel The candles
gas filtration. were
The candles
arranged in 5 clusters
were arranged of 12 elements
in 5 clusters each and,
of 12 elements each toand,
keeptothe keepcleaning efficiency
the cleaning of such of
efficiency a
filtration system, the
such a filtration dust the
system, cakedust
growing
cake on the candle
growing surface
on the candle was removed
surface wasbyremoved
pulsing of by
N 2; the pulses
pulsing of N2 ;were activated
the pulses were based on feedback
activated based on from the pressure
feedback from the drop at the candles.
pressure drop at the A
candles.
more A more
detailed detailed of
description description of such
such a specific a specific
reactor reactor configuration
configuration is presented in is [24].
presented
With
in [24].
the aim ofWith the aim
producing of producing
FCV-H FCV-H2 ,plant
2, the gasification the gasification
was coupledplant with was coupled
a portable with a
(contain-
portable (containerized) integrated system designed for gas conditioning
erized) integrated system designed for gas conditioning and subsequent purification. In and subsequent
purification.
Figure In Figure
1, a scheme 1, integrated
of the a scheme ofpilot the integrated pilot plant is presented.
plant is presented.

Figure
Figure1.
1. Schematic
Schematic view of the
view of the 11 MW
MWth gasification
gasificationpilot
pilotplant
plantcoupled
coupledwith
withthe
the portable
portable purifica-
purification
th
tion system (PPS).
system (PPS).

To
To evaluate the performance
evaluate the performanceof ofthe
theplant
plantduring
duringitsitsexperimental
experimental operation,
operation, key
key pro-
process
cess parameters,
parameters, suchsuch as flow
as flow rate,rate, pressure
pressure and and temperature,
temperature, werewere monitored
monitored continu-
continuously.
ously. Simultaneously,
Simultaneously, onlineonline and offline
and offline samplings
samplings were carried
were carried out onout
theon the product
product gas atgas
the
Energies
Energies2022,
2022,15,
15,x4580
FOR PEER REVIEW 44of
of17
16

at the gasifier
gasifier and atand
theatPPS
theunit,
PPS unit, to complete
to complete its characterization
its characterization in terms
in terms of composition
of composition and
and contaminants’
contaminants’ loads.
loads.
Regarding
Regarding the portable
portable purification
purificationsystem
system(PPS),
(PPS),the
the unit
unit waswas equipped
equipped withwith a re-
a reactor
actor for water–gas
for water–gas shift (WGS),
shift (WGS), basedbased on catalytic
on catalytic Cu-impregnated
Cu-impregnated foams,foams, and pressure
and pressure swing
adsorption
swing (PSA)(PSA)
adsorption modules for Hfor
modules 2 recovery
H2 recoveryand and
purification. To preserve
purification. To preserve thethe
catalytic
cata-
reactor from a poisoning effect from the hydrogen sulfide (H S), the inorganic
lytic reactor from a poisoning effect from the hydrogen sulfide 2(H2S), the inorganic gase- gaseous
contaminant
ous contaminant evaluated
evaluatedas the most
as the mostcritical, thethe
critical, produced
produced gaseous
gaseousstream
streamwas wassent
senttotoa
asorbent
sorbentguard
guardbedbed(De-H
(De-H22S)
S) before
before entering
entering thethe water–gas
water–gas shift (WGS) reactor. Extra Extra
watervapor
water vaporwaswasadded
addedtotothethe product
product gasgas upstream
upstream fromfrom
thethe
WGS WGS reactor
reactor to increase
to increase the
the hydrogen
hydrogen production.
production. Downstream
Downstream from from
the WGSthe WGS reactor,
reactor, the gasthe
wasgascooled
was cooled and a
and a com-
commercial
mercial syngassyngas compressor
compressor was to
was used used to compress
compress the product
the product gas upgas upbar
to six to six bar
g, to g, to
allow
allow for the proper operation of the pressure swing adsorber. The composition
for the proper operation of the pressure swing adsorber. The composition and flow of and flow of
both the hydrogen-produced gas and the off gas could be quantified to
both the hydrogen-produced gas and the off gas could be quantified to allow for a proper allow for a proper
balance.Figure
balance. Figure22shows
showsaaschematic
schematicviewviewof ofthe
thePPS.
PPS.

Outside
boundaries

H2 storage
vessel
PPS
S H2
H2 mass flow
De-H2S WGS meter
PSA
Product
Gas S
Gas volume
meter

storage vessel
Off gas

Off Gas

Figure 2. Schematic view of the Portable Purification System.

Figure 2. Schematic view of the Portable Purification System.
In
InTables
Tables 11 and
and 2,
2, an
an overview
overview ofof the
the specification
specification for
for the
the measuring
measuringdevices
devicesof
ofthe
the
main process parameters at the gasification plant and the portable purification
main process parameters at the gasification plant and the portable purification systemsystem is
presented.
is presented.
Table 1. Characteristics of the measuring process parameters adopted at the gasification plant.
Table 1. Characteristics of the measuring process parameters adopted at the gasification plant.
Detection Tool Range Accuracy Standard
Temperature Detection
Thermocouples Tool
K Types Range
0 to 1200 °C ClassAccuracy
2 precision ANSIStandard
MC 96.1,
Model Transmitter: IEC 60584-1, Class 2
Temperature Thermocouples K Types 0 to 1200 ◦ C Class 2 precision ANSI MC 96.1,
WT531 and WT532 Honeywell
Model Transmitter: IEC 60584-1, Class 2
Pressure Pressure
WT531Transmitter
and WT532 Honeywell
Honeywell 0 ÷ 3 bar ±0.1% of full scale -
Models WG511
Pressure Pressure
Type Transmitter
316 Stainless Honeywell
Steel Base and 0 ÷ 3 bar ±0.1% of full scale -
Models WG511
Diaphragm
Mass Flow TypeCalibrated
316 Stainless Steel Base and
Flanges - 2% of full-scale ISO 5167:2003 and
Diaphragm
Model Transmitter: ASME MFC-14M-1995
Mass Flow WD520 and WD521 Honeywell
Calibrated Flanges - 2% of full-scale ISO 5167:2003 and
Model Transmitter: ASME MFC-14M-1995
WD520 and WD521 Honeywell
Energies 2022, 15, 4580 5 of 16

Energies 2022, 15, x FOR PEER REVIEW 5 of 17

Table 2. Characteristics of the measuring process parameters adopted at the portable purification
system.

Detection
Table Tool
2. Characteristics Range process parameters
of the measuring Accuracy Standard
adopted at the portable purification
system.
Thermocouples Class 2 precision
Temperature 0 to 350 ◦ C IEC 60584-1, Class 2
TC Type K
Detection Tool Range Accuracy Standard
Pressure Transmitter
Thermocouples
Danfoss Class 2 precision
Temperature 0 to 350 °C IEC 60584-1, Class 2
Pressure ModelTCMBSType K
4701 Full scale = 10 bar ≤±1% -
Pressure
Silicon basedTransmitter
pressure
Danfoss
transducer
Pressure Full scale = 10 bar ≤±1% -
Model MBS 4701
Volume
Silicon flow
based gas meter
pressure transducer
Dresser
Volume flow gas meter MAX volumetric ISO 5167:2003 and
Mass Flow Feed 3 /h ±2%
C-RM-G16
Dresser = 25 m
flowMAX volumetric ASME
ISOMFC-14M-1995
5167:2003 and
Mass Flow Feed RotaryC-RM-G16
gas meter ±2%
flow = 25 m3/h ASME MFC-14M-1995
MassRotary
Flowgas meter
meter
Mass Flow meter
Bürkert Full scale = 500
Mass Flow Product Bürkert Full scale = 500 ±0.3% full scale
Mass Flow Product 2712 (156 262) SL/min ±0.3% full scale
2712
Thermal Mass (156 Controller
Flow 262) SL/min
Thermal Mass Flow Controller

The
Theprocess
processof ofbiomass
biomassgasification
gasificationwas wascarried
carriedoutoutusing
usinga asteam/O
steam/O22 mixture
mixture asas aa
gasification
gasificationagent,
agent,rather
ratherthan
than air,air,
to avoid anyany
to avoid diluting effect
diluting on the
effect onproduct gas and,
the product gasthus,
and,
for it to
thus, forhandle only the
it to handle onlynetthe
stream arising
net stream from the
arising from particular biomass
the particular undergoing
biomass con-
undergoing
version. Air, Air,
conversion. however, was fed
however, wastofed thetoreactor in theinpreliminary
the reactor heating
the preliminary stage.stage.
heating Specifically,
Specif-
the temperature of around 600 ◦ C was achieved by combustion of LPG and, subsequently,
ically, the temperature of around 600 °C was achieved by combustion of LPG and, subse-
of the biomass ◦ C, when the operating conditions were switched to gasifica-
quently, of theuntil 800–850
biomass until 800–850 °C, when the operating conditions were switched to
tion to start the
gasification related
to start the tests.
relatedMore
tests. details
More about
detailsthis preliminary
about producer
this preliminary can be found
producer can be
elsewhere [27].
found elsewhere [27].
As
Asemphasized
emphasizedininFigure Figure 1, of
1, the whole
of the wholeproduced
producedgaseous flux, aflux,
gaseous stream correspond-
a stream corre-
ing to two-fifths was sent to the PPS. In fact, the unit was designed
sponding to two-fifths was sent to the PPS. In fact, the unit was designed for demonstra- for demonstration
purposes and was
tion purposes andtherefore sized sized
was therefore to handle a small
to handle flow rate.
a small flow rate.
In
In Figure 3, a picture of the integrated prototypeplant
Figure 3, a picture of the integrated prototype plantisispresented.
presented.

Figure3.3.Gasifier
Figure Gasifiercoupled
coupledwith
withthe
thecontainerized
containerizedPPS.
PPS.

Inaatypical
In typicalexperimental
experimental run
run of
of the
the biomass
biomass gasification,
gasification, starting
starting from
from room
room temper-
temper-
ature,the
ature, theplant
plantwas
washeated
heated up
upby bycombustion
combustion to
to speed
speed up
up the
the startup
startup step.
step. Specifically,
Specifically,
from room temperature up to 500–600 °C the reactor was heated by feeding biochar to the
1000 kWth reactor, then it was heated up to 800 °C by feeding almond shells. Next, the
operating conditions were switched to the specific gasification operating conditions. The
Energies 2022, 15, 4580 6 of 16

Energies 2022, 15, x FOR PEER REVIEW 6 of 17

from room temperature up to 500–600 ◦ C the reactor was heated by feeding biochar to the
1000 kWth reactor, then it was heated up to 800 ◦ C by feeding almond shells. Next, the
operating conditions were switched to the specific gasification operating conditions. The
approach of
approach of starting
starting to tosupply
supplythe thebiomass
biomassfeedstock
feedstock when when the thereactor
reactortemperature
temperaturewas was
already relatively high was adopted to avoid the risks of clogging
already relatively high was adopted to avoid the risks of clogging the gas filtration system the gas filtration system
andthe
and thepiping
pipingdownstream
downstreamofofthe thegasifier,
gasifier, asas a consequence
a consequence of of
thethe possible
possible condensation
condensation of
of organic compounds during the transient phases. It is,
organic compounds during the transient phases. It is, in fact, known that, even under nom- in fact, known that, even under
nominal
inal burning burning
conditions,conditions, condensable
condensable organicorganicvapors vapors are unavoidably
are unavoidably produced, produced,
namely,
namely, the lower the combustion temperature, the
the lower the combustion temperature, the higher the amount of condensable compounds higher the amount of condensable
compounds
produced. Dueproduced.
to the size Due of to
thethe size overall,
plant, of the plant, overall, the achievement
the achievement of the stable of the stable
gasification
gasificationrequired
conditions conditions aroundrequired
5–6 h.around 5–6 h.
The pre-conditioning procedures
The proceduresof ofthe
thePPSPPSwere were conducted
conducted at the same
at the same timetimeto pre-
to
pare thethe
prepare unit forfor
unit its its
operation
operation withwithrealreal
gas.gas.
During
During thetheheating
heatingup upof the gasifier
of the gasifierboth the
both
De-H2S
the De-H2sorbent
S sorbent and and thetheWGS
WGS catalyst
catalystwere wereheated
heatedup upby byrecirculating
recirculating inert gas over over an an
electrical heater, to prevent water and tar condensation on
electrical heater, to prevent water and tar condensation on the guard bed and WGS catalyst the guard bed and WGS cata-
lyst
as as a result
a result of a cold
of a cold start-up.
start-up. The interconnecting
The interconnecting piping piping
between between the gasifier
the gasifier and PPS andwasPPS
was heated
heated up byup by electrical
electrical tracingtracing (to prevent
(to prevent tar condensation
tar condensation during during the start-up)
the cold cold start-up) and
andgasifier
the the gasifier
output output
stream. stream.
During During the heating
the heating up ofup theofPPS thethis
PPSgas thiswas
gassent
wastosent to a
a flare,
flare,bypassing
thus thus bypassing the PPS. theAfter
PPS. After
reachingreaching the proper
the proper operational
operational temperatures
temperatures of bothof both
the
De-H S sorbent and the WGS catalyst (approx. 300 ◦ C), the interface valve between the
the De-H2S
2 sorbent and the WGS catalyst (approx. 300 °C), the interface valve between
gasifier
the gasifierand and
PPS PPS could be opened
could be openedand theandproduct
the product gas was gas sent to thetoPPS.
was sent the PPS.
The
The integrated experimental
experimentalcampaign,campaign,i.e., i.e.,thethe continuous
continuous operation
operation of both
of both the
the gas-
gasification
ification section sectionandand PPSPPS unit,
unit, waswasthenthen started
started when when thethe product
product gasgas
hadhad a stable,
a stable, drydrygas
gas composition,
composition, based
based onon thethe data
data fromthe
from theonline
onlinechromatographic
chromatographic analysis. The product product
gas
gas was
was monitored
monitored online online by by aa µGC-TCD
µGC-TCD system system from from Agilent
Agilent Technologies
Technologies (see (see [24]
[24] for
for
details).
details).
To
Toavoid
avoidleaks
leaksof ofthe
theproduct
productgas gasthrough
throughthe thefeeding
feedingscrews,screws,thethebiomass
biomassfeedstock
feedstock
was
was supplied to the gasifier under a slight nitrogen stream. The gas analysis concordantly
supplied to the gasifier under a slight nitrogen stream. The gas analysis concordantly
revealed
revealedits itspresence;
presence;the thecontent
contentwaswastypically
typicallylower lowerthan than10%v.10%v.
To
To improve
improve the the characteristics
characteristicsofofthe the produced
produced gasgas in terms
in terms of permanent
of permanent gases’gases’
com-
composition and the organic contaminants’ load, two of the
position and the organic contaminants’ load, two of the five clusters were filled with com- five clusters were filled with
commercial Ni-containing
mercial Ni-containing pellets
pellets (NiO(NiO8.5%wt, 8.5%wt, quadralobe-shaped
quadralobe-shaped pellets)
pellets) for the forgas
thecom-
gas
composition
position upgrading. Each candle was filled with about 1.4–1.5 kg of catalyst pellets. A
upgrading. Each candle was filled with about 1.4–1.5 kg of catalyst pellets. A
zoomed
zoomedview viewof ofsome
someof ofthe
the filled
filled candles
candles before
beforeclosing
closingthe thereactor
reactortoptopcover
coveris is presented
presented
in
inFigure
Figure4.4.

Figure4.4.Detail
Figure Detail of
ofceramic
ceramiccandles
candlesfilled
filledwith
withquadralobe-shaped
quadralobe-shapedpellets
pelletsof
ofcommercial
commercialNi-catalyst
Ni-catalyst
for simultaneous product gas filtration and composition upgrading.
for simultaneous product gas filtration and composition upgrading.

Provided in a non-active form, the catalyst was intended to be activated in situ under
the action of the wet, reducing product gas, in accordance with the technical specification
of the product.
Energies 2022, 15, 4580 7 of 16

Provided in a non-active form, the catalyst was intended to be activated in situ under
the action of the wet, reducing product gas, in accordance with the technical specification
of the product.

2.2. Gasification Test Campaigns

The experimental campaigns focused on in this work refer to a two biomass feeding
rate. The tests were carried out at 0.22–0.25 equivalence ratio (ER), 0.5–0.7 steam/biomass
ratio (S/B), and using Magnolithe GmbH (Hart bei Graz, Austria) [28] sand as the fluidized-
bed inventory. This material was adopted because of its known characteristic of superior
resistance to attrition under fluidized conditions and its property as a primary catalyst
able to promote in situ tar-reforming reactions [29,30]. In Table 3, the most representative
conditions adopted at the gasifier are presented; a summary of the main physical and
chemical characteristics of almond shells, the biomass feedstock adopted, is instead given
in Table 4.

Table 3. Overview of process operating conditions in the gasification campaign at the plan facility
coupled to the PPS.

Operating Parameter Test I Test II

Feeding rate (kgar /h) a 175 135
Steam/Biomass (S/B) b 0.5–0.6 0.65–0.7
Equivalence Ratio (ER) b 0.24–0.25 0.22–0.25
a: ar: as received; humidity content: 10–12%wt; b: during the tests S/B and ER were adjusted in order to control
the temperature inside the reactor.

Table 4. Physical and chemical characteristics of almond shells.

Bulk Density a (kg/m3 ) Humidity a (%wt) Chip Size Range (cm)

450 ± 30 11 ± 2 2–3
a
Proximate Analysis (%wt., dry basis)
Ash Volatile Matter Fixed Carbon b
1.23 ± 0.06 80.6 ± 1.7 18.2 ± 1.8
a
Ultimate Analysis (%wt., dry basis)
C H N Ob Cl S
47.9 ± 0.7 6.3 ± 0.3 0.32 ± 0.02 44.3 ± 1.1 0.012 ± 0.002 0.015 ± 0.002
a
Heating values (kJ/kgdry )
HHV LHV c
19,510 ± 80 18,140 ± 140
a: each measurement was conducted in triplicate and the mean value was used as representative data; b: calculated
as complement to 100; c: LHV(kJ/kg) = HHV(kJ/kg) − 212.2(kJ/kg) × H(%-wt.) − 0.8(kJ/kg) × (O(%-wt.) + N(%-wt.)).

In addition to the ultimate and proximate analysis, to assess in advance the occurrence
of problems with the bed material agglomeration, which could in turn bring problems
to the smooth and continuous plant operation, a study on the thermal behavior of the
ash produced by almond shells was also included. The evaluation was carried out in
accordance with the technical specification CEN/TS 15370-1:2006, a protocol specifically
developed by CEN (Comité Européen de Normalization) for studying the softening and
melting behaviors at high temperatures of ash from solid fuels. The measurements were
carried out using a Heating Microscopes Misura® HSML Mod. 1400-3002 by Expert System
Solutions. Four key temperatures were then acquired, as follows: the “shrinkage starting
temperature” (SST); the “deformation temperature” (DT); the “hemisphere temperature”
(HT); and the “flow temperature” (FT).
Energies 2022, 15, 4580 8 of 16

To complete the measurements, a homogeneous sample of ash from the representative

samples of almond shells was prepared by combustion, in accordance with the UNI EN
14,775 protocol. The thermal behavior study was then performed at a defined heating
rate in a controlled atmosphere; the test specimen made from the ash was heated and
continuously observed, exploring a temperature range between 500 and 1400 ◦ C.
In Table 5, a summary of the four characteristic temperatures is presented, along with
corresponding images of the ash specimen.

Table 5. Characteristic temperatures for the ash-melting behavior of almond shells (CEN/TS 15370-1:2006).

Temperature SST DT HT FT
(◦ C) 915 ± 5 1000 ± 10 1180 ± 10 1210 ± 10

Based on these data, the plant operating conditions were monitored to avoid tem-
perature peaks across the reactor as well as to prevent prolonged overshoots above the
shrinkage starting temperature (SST).

2.3. Simulation Model of the Integrated Plant

The simulation approach adopted in the present work is based on the model previously
developed in [21]. The flow sheet is shown in Figure 5. The block DECOMP is a yield
reactor which converts the biomass input according to the proximate and ultimate analysis
(shown in Table 2). The block RSTOIC is a stoichiometric reactor which simulates the
formation of hydrogen sulfide, ammonia and hydrogen chloride (the nitrogen, chlorine
and sulfur that are in the biomass feedstock are known to produce mainly hydrogen
sulfide, ammonia and hydrogen chloride and a fractional conversion of 1 is in line with
experimental results) [31,32]. The block SEP is a separator which splits the stream S2
into: VOLATILE; CHAR; and INORG, which are made up of the volatile parts, char and
inorganic compounds (hydrogen sulfide, ammonia and hydrogen chloride), respectively.
The VOLATILE stream is then divided into the sub-streams: VOL, which goes to the gasifier
GASIF after mixing with the gasifying agents, and H2 , which occurs in the simulation
of tar production in the TARPROD block, that is a yield reactor. The gasifier model is
an auto-thermal fluidized-bed reactor and it has been simulated according to Gibbs free
energy minimization and with the quasi-equilibrium approach. The bed material of the
gasifier is simulated as sand. The reactions considered in the gasification process are listed
in Table 6. In Figure 5, the streams STEAM, OXYG and AIR are the gasifying agents steam,
oxygen and air, respectively, and they are all shown in the flow sheet since the model is
able to work with all of the combinations of the oxidizing agents [33]; the mass flow of the
stream that was not used was set to zero. Then, stream S6 is the final wet output of the
gasifier. CANDLE is a stoichiometric reactor which simulates the ceramic filter candles at
the freeboard of the gasifier. The stream, DRYSING, is the final dry output of the gasifier,
since the block H2OREMOV is a dryer which removes all of the water. H2SADSOR, which
is an equilibrium reactor, simulates the stage of hydrogen sulfide removal. The sorbent
simulated is zinc oxide. The WGS unit is simulated as an equilibrium reactor while the PSA
unit is simulated as a separator, considering a separation efficiency for hydrogen of 70%
and gas inlet pressure of six bar. Pressurization was achieved with a compressor, before the
PSA unit. A description of the ASPEN Plus flowsheet unit operation is reported in Table 7.
Energies 2022, 15, x FOR PEER REVIEW 9 of 17
Energies 2022, 15, 4580 9 of 16

Figure 5. Flow sheet of the model.

Energies 2022, 15, 4580 10 of 16

Table 6. Gasification reactions [6].

Reaction Reaction Name Heat of Reaction Reaction Number

Heterogeneous reaction
C + 0.5 O2 → CO Char partial combustion (−111 MJ kmol−1 ) (R1)
C + H2 O ↔ CO + H2 Water–gas (+172 MJ kmol−1 ) (R2)
Homogeneous reactions
H2 + 0.5 O2 → H2 O H2 partial combustion (−283 MJ kmol−1 ) (R3)
CO + H2 O ↔ CO2 + H2 Water–gas shift (−41 MJ kmol−1 ) (R4)
CH4 + H2 O → CO + 3H2 Steam-methane reforming (+206 MJ kmol−1 ) (R5)

Table 7. Description of ASPEN Plus flowsheet unit operation presented in Figure 5.

ASPEN Plus Name Block ID Description

Yield reactor—converts the non-conventional stream “BIOMASS” into its
RYIELD DECOMP
conventional components
RSTOIC RSTOIC RStoic reactor—simulates the production of NH3 and H2 S
CANDLE RStoic reactor—simulates the catalyst filter reaction
TARPROD RStoic reactor—simulates the production of toluene and benzene
Separator—separates the biomass into three streams: VOLATILE; CHAR; and
SEP SEP
INORG
SEP SEPH2 Separator—separates 25% of hydrogen to produce tar
H2OREMOV Separator—simulates a dryer which removes all the water
PSA Separator—simulates PSA process and extracts pure hydrogen with 70% efficiency
MIXER MIX Mixer—mixes oxidizing fluid with VOL stream, that represents combustible fluid
MIX2 Mixer—mixes the gas from gasifier with INORG and TAR streams
MIX3 Mixer—mixes the stream S3 and H2
Splitter—splits char unreacted (UNREACT), char to gasifier (TOGASIF) and char
FSPLIT SPLIT
which occurs in tar production (S3)
Gibbs free energy reactor—simulates drying, pyrolysis, partial oxidation and
GASIF gasification and restricts chemical equilibrium of the specified reactions to set the
syngas composition by specifying a temperature approach for individual reactions
REQUIL H2SADSOR REquil reactor—simulates the reaction of ZnO sorbent with H2 S
WGS REquil reactor—simulates water gas shift reaction
COMPRESSOR COMPR Compressor—raises gas pressure upstream of PSA

3. Results and Discussions

3.1. Process Performances
3.1.1. Biomass Gasification Tests with Catalytic Ceramic Candles
The gasification campaign to evaluate the effect of using Ni-pellets catalyst housed in
the filter candles was carried out in the operating conditions summarized in Table 3.
Both of the product gas lines from the gasification reactor, i.e., the one coming from the
clusters containing the catalyst and designed to feed the PPS unit and the other addressed
to the flare, were monitored online via µGC-TCD system.
Figure 6 shows a comparison between the average dry gas composition observed
at the operating conditions corresponding to Test I, after achievement of the gasification
process stabilization (i.e., reactor temperature, ER and S/B), and its operation over several
hours. The data of the dry compositions, relevant to the two gaseous streams produced at
the condition II over time, are presented in Figure 7. In this latter campaign, having run
the biomass gasification at a lower biomass feeding rate, the resulting plant conditions
 Energies 2022, 15, 4580 11 of 16

Energies 2022, 15, x FOR PEER REVIEW 11 of 17

Energies 2022, 15, x FOR PEER REVIEWweremore stable; moreover, the feedstock supply to the gasifier was carried out 11 of 17
without
auxiliary nitrogen to the feeding system, therefore no N2 was detected in the product gas.

Figure 6. Comparison
Figure 6. Comparison of average dry dry
of average composition relevant
composition to thetogas
relevant thestreams exitingexiting
gas streams the catalytic and
the catalytic
Figure 6. Comparison
non-catalytic ceramic of average
filter dry
clusters. composition
Gasification relevantaccording
conditions to the gastostreams
Test I exiting
(refer to the catalytic
Table 1). and
and non-catalytic ceramic filter clusters. Gasification conditions according to Test I (refer to Table 1).
non-catalytic ceramic filter clusters. Gasification conditions according to Test I (refer to Table 1).

Figure 7. Comparison between the dry composition of the gaseous stream at the inlet of the PPS and
Figure 7. Comparison between the dry composition of the gaseous stream at the inlet of the PPS and
addressed
Figure at the flare. Gasification
7. Comparison conditions according to Test II (refer at
tothe
Table 3).
addressed at the flare. between the dry
Gasification composition
conditions of thetogaseous
according stream
Test II (refer to Tableinlet
1). of the PPS and
addressed at the flare. Gasification conditions according to Test II (refer to Table 1).
The comparison of the dry gas composition data indicated, in both of the test cam-
The
paigns comparison
carried out of the dry
under the gas composition
conditions of Testdata indicated,
I and Test II,innoboth of the test
significant cam-
difference
The
paigns comparison
carried out underof the
thedry gas composition
conditions of Testwas data
I and indicated,
Test II, was in both
no significant of the test
difference cam-
between
paignsthe the
carried two gaseous
out under streams. This
the conditions result
of Test Inot not
andwhat what
Testwas
II, no hoped
significantfor; however,
difference itbe-
was
be-
tween
explained twoin gaseous
relation streams.
to the This
effective result was
activation of the loaded hoped
amount for;
of however,
the it
catalyst was
pellets.
tween the in
explained two gaseous
relation streams.
to the
the Thisactivation
effective result was ofnot
the what
loadedwas hopedoffor;
amount thehowever,
catalyst it was
pellets.
Figure
explained in 8 shows
relation to the trend of temperature
effective activation of profiles
the along
loaded the gasifier,
amount of the monitored
catalyst pellets.with
Figure 8 shows
thermocouples the trend
placed in of four
the temperature
most profilesreactor
relevant along the gasifier,
areas, during monitored
the with
gasification
Figure 8 shows
thermocouples placed the trend of temperature profiles
reactor along
areas, the gasifier, monitored cam- with
campaign carried
thermocouples placedoutin
in
the four
under
the themost
four Test relevant
most II conditions.
relevant reactor areas,
during
during
the gasification
the gasification cam-
paign carried
As shown, out under the Test II conditions.
the temperature in the upper part of the gasifier, i.e., next to the ceramic
paign carried out under the Test II conditions.
catalytic candles (T3 in accordance with Figure 8b), at stable conditions ranged around
the value of 600 ◦ C. According to the catalyst provider, the proper temperature is required
to be over 750 ◦ C. Therefore, the discrepancy between the temperature for the proper
pellets’ operation and the temperature achieved in the gasification campaign support the
Energies 2022, 15, 4580 12 of 16

Energies 2022, 15, x FOR PEER REVIEW 12 of 17

hypothesis that the pellets in the candles were not well activated, because the actual process
conditions were not consistent with those from the technical specification.

(a) (b)
Figure8.8.Temperature
Figure Temperature profiles
profiles inside
inside thethe gasification
gasification reactor:
reactor: (a) trends
(a) trends during
during the Test
the Test II gasifica-
II gasification
tion campaign; (b) position of thermocouples for measurement along the gasifier (T1 and
campaign; (b) position of thermocouples for measurement along the gasifier (T1 and T9 temperatures T9 tem-
peratures inside the bed inventory, T2 freeboard area close to the fluidized bed material, T3 temper-
inside the bed inventory, T2 freeboard area close to the fluidized bed material, T3 temperature near
ature near the top of the ceramic candles).
the top of the ceramic candles).
As shown,ofthe
3.1.2. Operation thetemperature
PPS Unit within the
Realupper partGas
Product of the gasifier,
from Biomass i.e.,Gasification
next to the ceramic
catalytic candles (T3 in accordance with Figure 8b), at stable conditions ranged around the
Since the dry composition of the produced gas at the gasifier remained stable during
value of 600 °C. According to the catalyst provider, the proper temperature is required to
the ultimate experimental campaigns, to evaluate the performance of the portable purifi-
be over
cation 750 °C.
system Therefore,
(PPS) towardthethediscrepancy
H2 production between
at FCV thegrade,
temperature for the proper
the designated streampellets’
from
operation
the catalyticand the temperature
candles was send to achieved
the PPS.inDuring
the gasification campaign support
this experimental campaign,thetests
hypoth-
at
esisdifferent
two that the PSA
pellets in the candles
settings, hereafterwere not well
referred to asactivated,
«Condition because
1» andthe actual process
«Condition con-
2», were
ditionsout
carried werebynot consistent
changing with those
the section from the
operation technical
cycle specification.
time. «Condition 1» was set so as to
achieve the goal of producing a H2 stream at the highest purity grade, consistent with the
3.1.2. Operation
application in fuelofcell
thevehicles
PPS Unit with
(i.e., 4.0Real Product Gas
H2 quality). from«Condition
During Biomass Gasification
2», the PSA was
operatedSince
at the dry composition
an increased cycle timeof theto produced
allow for an gasincreased
at the gasifier remained
H2 yield, stable to
eventually during
the
the ultimate experimental campaigns, to evaluate the performance
detriment of its purity grade. The assessments were carried out based on a gas flow rate of the portable purifi-
ofcation system (PPS)
470 NL/min toward
(dry basis) tothe 2 production
theHPPS. This flowatrateFCVwas grade, thepartializing
set by designated stream
the syngasfrom
the catalytic
stream addressedcandles was
to the send
PPS to the PPS.
through During
a control thisThis
valve. experimental
latter wascampaign,
back-adjustedtests at
fromtwo
different
the systemPSA unit settings,
controller hereafter
to allowreferred to as «Condition
for its smooth and stable1» and «Condition
operation. The excess2», were
gas
stream
carriedwas
outsent to a flare for
by changing thedisposal via combustion.
section operation cycle time. «Condition 1» was set so as to
The PSA
achieve pressure
the goal profiles during
of producing a H2 streamthe cycles
at therelevant
highesttopurity
«Condition
grade, 1» runs are with
consistent shown the
inapplication
Figure 9, by way of illustration. In the figure, the syngas feeding
in fuel cell vehicles (i.e., 4.0 H2 quality). During «Condition 2», the PSA wasrate (blue line) and
the H2 flowat(green
operated line) produced
an increased cycle time aretoalso included.
allow Clearly, itH
for an increased can be observed
2 yield, eventuallythattothethe
pressures
detrimentofofthe itsadsorber vessels
purity grade. The cycle between were
assessments 6 bar carried
g and 0out barbased
g, i.e.,on
adsorption
a gas flowand rate
desorption,
of 470 Nl/minrespectively.
(dry basis) to the PPS. This flow rate was set by partializing the syngas
At «Condition
stream addressed 1», the PPS
to the operation
through of the unit was
a control characterized
valve. This latterby wasanback-adjusted
operation of more from
than
the system unit controller to allow for its smooth and stable operation. The excess of
four adsorption cycles (thus, more than one full PSA cycle) within an interval gas
15stream
min. The
wasfeed
sentflowto a allowed
flare for the production
disposal of an average of 101 Nl H2 /min, as deduced
via combustion.
from theThesine
PSAwavepressureof the H2 -produced
profiles during the flow.
cyclesThe gas chromatography
relevant to «Condition 1»measurements
runs are shown
showed that
in Figure 9, the
by wayH2 purity was higher
of illustration. than
In the 99.99%-v.
figure, the syngas feeding rate (blue line) and the
At «Condition
H2 flow (green line)2», an average
produced areofalso125included.
Nl H2 /min was produced,
Clearly, thus confirming
it can be observed the
that the pres-
expected increase in the H yield. Obviously, at these PSA conditions,
sures of the adsorber vessels cycle between 6 bar g and 0 bar g, i.e., adsorption and de-
2 the number of cycles
insorption,
the 15-min reference interval was less than four.
respectively.
At «Condition 1», the operation of the unit was characterized by an operation of more
than four adsorption cycles (thus, more than one full PSA cycle) within an interval of 15
min. The feed flow allowed the production of an average of 101 Nl H2/min, as deduced
Energies 2022, 15, x FOR PEER REVIEW 13 of 17

Energies 2022, 15, 4580 13 of 16

from the sine wave of the H2-produced flow. The gas chromatography measurements
showed that the H2 purity was higher than 99.99%-v.

7 700

6 600

5 500

Flow [Nl/min]
4 400
Pressure [bar(g)]

3 300

2 200

1 100

0 0
0 3 6 9 12 15
Time [minutes]
Pressure PSA vessel 1 Pressure PSA vessel 2
Pressure PSA Vessel 3 Pressure PSA Vessel 4
Syngas feed flow H2 product flow

Figure 9. Representative PSA cycles at «Condition 1»: feed and produced gas flows can be recog-
Figure 9. Representative PSA cycles at «Condition 1»: feed and produced gas flows can be recognized.
nized.
By way of example, in Figure 10, the dry gas compositions of the two main gas streams
At the
exiting «Condition
PSA, i.e.,2»,
H2 an
andaverage
off gas,of 125
are Nl H2/min was produced, thus confirming the
presented.
expected increase in the H2 yield. Obviously, at these PSA conditions, the number of cycles
in the 15-min reference interval was less than four.
By way of example, in Figure 10, the dry gas compositions of the two main gas
streams exiting the PSA, i.e., H2 and off gas, are presented.

Figure 10. Gas chromatographic analysis of the main gaseous streams at the portable purification
Figure 10. Gas chromatographic analysis of the main gaseous streams at the portable purification
system (PPS): (a) stream at the exit of the PSA section (H at 99.99%-v); (b) dry gas composition of
system (PPS): (a) stream at the exit of the PSA section (H22 at 99.99%-v); (b) dry gas composition of
the product gas to the PPS inlet; (c) dry gas composition of the off gas from the PSA.
the product gas to the PPS inlet; (c) dry gas composition of the off gas from the PSA.
The gas measurements of the hydrogen stream, produced under the second conditions,
showed that the H2 purity was still higher than 99.99%-v, i.e., 4.0 H2 quality.
Energies 2022, 15, 4580 14 of 16

3.1.3. Simulation vs. Experimental Results

The simulation was carried out considering 1 MWth as the input and setting 800 ◦ C
during the gasification process, keeping as S/B and ER the average of the experimental
inputs listed in Table 3 for test I and test II, respectively.
The syngas composition before entering the PPS is shown in Table 8, for test I and
test II, and it was evaluated against the experimental results.

Table 8. Experimental results vs. simulative results before entering the PPS unit.

Experimental Results Simulation Results

Test I Test II Test I Test II
S/B 0.5–0.6 0.65–0.7 0.55 0.68
ER 0.24–0.25 0.22–0.25 0.245 0.235
H2 (%v, dry ) 28 39 30.1 42.1
CO (%v, dry ) 30 22 32.2 23.7
CO2 (%v, dry ) 22 35 20.8 31.1
CH4 (%v, dry ) 7 3 5.4 1.9

The comparison between the results coming from the simulation and experimentation
presents values in pretty good agreement. The increasing hydrogen concentration, both
in the simulation and experimental results, due to the increasing of the S/B ratio, is due
to the water–gas reaction, which is more favorable thanks to the higher extent of the
steam. However, the data from the simulative model are higher since the thermodynamic
model overestimates these values. Regarding the methane, the variation in under- or
overproduction in simulative modelling is an ordinary issue, due to neglecting the tar
formation in the equilibrium models [32]. Concerning the concentration of the carbon
monoxide and carbon dioxide, that are lower and higher, respectively, in the experimental
results rather than in the simulation results, this is due to the temperature effect. In fact,
the temperature was kept fixed at 800 ◦ C in the simulation, but in the experimental test it
actually fluttered. The variation of temperature was higher with respect to the variation
of S/B, such that the temperature had the main influence. So, in the simulation results,
the CO concentration increased due to the endothermic reactions R2 (water–gas) and R5
(steam methane reforming), and the CO2 concentration decreased depending on reaction
R4 (water–gas shift), which is exothermic.
At the exit of the WGS block, the concentration of hydrogen is 51%. The PSA unit,
which is simulated to operate at 60 ◦ C and six bar with a separation efficiency for hydrogen
of 70%, allows the achievement of a hydrogen recovery ratio of 48%, calculated as the ratio
of hydrogen obtained out of PSA with respect to the biomass input.

4. Conclusions
An integrated prototype facility based on an intensified gasification process and a
portable purification system (PPS) for gas conditioning and separation was operated to
prove the possibility of producing H2 at FC vehicle grade from biomass feedstocks under
relevant conditions.
The tests were carried out by operating the plant under steam/oxygen conditions and
with the PPS unit in line. The experimental campaigns were successful; thus, proving the
possibility of operating the integrated system in stable conditions, also in the presence of
the innovative system for gas filtration to take place directly into the reactor freeboard. It
was not possible, however, to evaluate the benefits of the presence of the Ni-containing
pellets for gas upgrading. This is probably due to the deviation of the operating conditions
achieved for the pellet-filled candles from the technical specifications required by the
product. As for the specific objective of H2 production, overall, the collected results showed
that it is possible to successfully integrate a low-pressure biomass gasifier, producing low
H2 concentration syngas, with a commercially available PSA system. Based on the flow
Energies 2022, 15, 4580 15 of 16

rate and composition of the gas addressed to the PPS, the experimental data indicated that
a 66.4% hydrogen yield at 4.0 H2 quality (99.99%-v) could be achieved with the system.
A simulative model of the plant was developed by means of the Aspen Plus software.
The results coming from the simulation were validated against the experimental data,
showing that the values were in pretty good agreement, even if the data from the simulative
model were higher since the thermodynamic model overestimates these values.
The production of an off-gas fuel highlights the possibility for overall process im-
provements. In this sense, two major approaches can be envisaged. That is, an adjustment
of the process favoring maximum hydrogen yield or, alternatively, the use of such fuel
for power production, to be used directly at the plant or for grid feeding. Evaluations
of such scenarios require a specific study that was beyond the scope of this paper. This
investigation will be the subject of a future work.

Author Contributions: Conceptualization, methodology, writing—original draft, writing—review

& editing and supervision: D.B.; Conceptualization, methodology, investigation, data curation and
validation: G.C. (Giuseppe Canneto), Investigation, data curation, formal analysis and validation: F.N.
Investigation, data curation, resources and validation: A.V. Methodology, investigation, data curation
and formal analysis: E.F. and C.F. Investigation, data curation and resources: M.G. Investigation,
data curation, formal analysis and validation: A.L. Methodology, investigation, data curation and
supervision: G.C. (Giacinto Cornacchia). Methodology and supervision: G.B. Methodology, software,
formal analysis, writing—original draft, writing—review & editing: V.M. Conceptualization, method-
ology, writing—review & editing and supervision: E.B. Conceptualization and supervision: C.C.
Conceptualization, methodology, writing—review & editing and supervision: M.R. Investigation,
data curation, formal analysis and supervision: T.O. Conceptualization and supervision: S.H. and
P.U.F. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by the Fuel Cells and Hydrogen Joint Undertaking and Horizon
2020 programmes under grant agreements 299732 and 815284, respectively.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: All data are reported in the paper.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature

CHP Combined Heat and Power

DT Deformation Temperature
ER Equivalence Ratio
FT Flow Temperature
HT Hemisphere Temperature
HHV Higher Heating Value
LHV Lower Heating Value
PSA Pressure Swing Adsorption
PPS Portable Purification System
S/B Steam to Biomass ratio
SST Shrinkage Starting Temperature
WGS Water Gas Shift

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