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Sustainable hydrogen production options from

food wastes

Gozde Duman a, Koray Akarsu b, Alper Yilmazer a,

Tugba Keskin Gundogdu c, Nuri Azbar b,c, Jale Yanik a,b,*
a
Faculty of Science, Department of Chemistry, Ege University, 35100, Bornova, Izmir, Turkey
b
Center for Environmental Studies, Ege University, 35100, Bornova, Izmir, Turkey
c
Engineering Faculty, Bioengineering Department, Ege University, 35100, Bornova, Izmir, Turkey

article info abstract

Article history: In this study, two thermochemical processes, namely steam gasification and supercritical
Received 20 August 2017 water gasification (SCWG), were comparatively studied to produce hydrogen from food
Received in revised form wastes containing about 90% water. The SCWG experiments were performed at 400 and
19 December 2017 450
C in presence of catalyst (Trona, K2CO3 and seaweed ash). The maximum hydrogen
Accepted 23 December 2017 yield was obtained at 450
C in presence of K2CO3 catalyst. In second process, hydrothermal
Available online xxx carbonization was used to convert food wastes into a high-quality solid fuel (hydrochar)
that was further gasified in a dual-bed reactor in presence of steam. The steam gasification
Keywords: of hydrochar was carried out with and without catalysts (ironceria catalyst and dolomite).
Supercritical water gasification The maximum hydrogen yield obtained from steam gasification process was 28.08 mmol/g
Steam gasification dry waste, about 7.7 times of that from SCWG. This study proposed a new concept for
Hydrogen production hydrogen production from wet biomass, combination of hydrothermal carbonization
Biomass following steam gasification.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

produces H2 and CH4 in higher amounts. But the main prob-

Introduction
Biomass gasification is one of the green hydrogen production
methods as the biomass is CO2 neutral, environmentally clean
and well spread all over the world. A number of studies have
been published regarding hydrogen production from biomass
via different processes. Biomass based hydrogen production
technologies can be divided into two general categories:
thermochemical and biochemical processes. Biological pro-
cesses are the steam reforming of gas produced by fermen-
tation, and the direct biological production of hydrogen via the
coupled dark and photo fermentation [1]. In thermochemical
process, steam gasification is a promising technology, which
lem of conventional steam gasification is the impurities like
char and tar. Therefore, purification operations are needed to
achieve the required quality standard. Extensive studies have
been reported on the tar elimination in steam gasification of
biomass. In order to enhance hydrogen production by tar
elimination, many catalysts have been studied for steam
gasification of biomass [2]. Moreover, the most important
drawback of steam gasification is that it becomes very ineffi-
cient for a high moisture biomass, due to the necessity of
energy intensive drying process. So, for the biomass with high
moisture content (up to 90%), biochemical processes or su-
percritical water gasification are preferable. A major

_
* Corresponding author. Faculty of Science, Department of Chemistry, Ege University, 35100, Bornova, Izmir, Turkey.
E-mail address: jale.yanik@ege.edu.tr (J. Yanik).
https://doi.org/10.1016/j.ijhydene.2017.12.146
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2017.12.146
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0

limitation of biochemical processes is that they are very slow direct steam gasification of sewage sludge. In another study,
with a relatively low efficiency and often the case, an addi- 
Alvarez-Murillo reported that hydrochar of olive stone pro-
tional step for steam reforming of methane is required. On the vided improved gasification characteristics [29].
other hand, gasification in supercritical water media (above The huge amount of food wastes are being generated over
374
C and 22.1 MPa) is a novel method for conversion of the world and it is an important issue, directly linked with
biomass into gaseous product, consisting of mainly CO2, H2 environmental, economic and social impacts. However, they
and CH4. The main advantage of supercritical water gasifica- can be considered as a plentiful resource for hydrogen pro-
tion is the high gasification efficiency and low levels of char duction. In this study, hydrogen production from food wastes
and tars [3]. Above the critical point, water exhibited unique was studied. Because food waste is a wet feedstock, hydro-
properties such as low viscosity, high diffusivity and low thermal processes were chosen as gasification and pretreat-
dielectric constant. Due to lower the dielectric constant and ment methods. Differently from the studies in the literature,
the number of hydrogen bonds than those of ambient water, the objective of this study was to investigate the two pro-
supercritical water acts as organic solvent which is effective in cesses, comparatively, for hydrogen production: (1) super-
dissolving many organic compounds and gases and thus critical water gasification and (2) conventional steam
providing the homogeneity in reaction media [4]. Moreover, gasification of the hydrochar derived from food wastes. To the
water does not only behave like solvent, it is also a reactant best of the authors' known, the gasification processes have not
producing H2 in SCWG conditions, the conversion of CO with been investigated with food wastes so far.
water into H2 and CO2 [5].
Supercritical water gasification (SCWG) has received
extensive worldwide attention, many studies on SCWG of Materials and methods
both model compounds such as cellulose and lignin [6], humic
acid [7], glucose [8] and lactose [9] and real biomass such as Material
black liquor [10], horse manure [11], fruit wastes [12], chicken
manure [13], algae [5,14] or sewage sludge [15] etc. were con- Food wastes (containing 88.6 wt % water) were collected from
ducted. There are some recent reviews [16e18] about the main hall of Izmir Municipality and then smashed into slurry
research studies carried out in the last decades. There are two in a blender. The slurry was stored at 30
C until use. The
approaches for SCWG of biomass in terms of operating tem- hydrochar was obtained by hydrothermal carbonization (HTC)
perature; low temperature SCWG (between 374
C 550
C) of food wastes. A 150 g slurry of food wastes was loaded into
and high temperature SCWG (between 550
C 700
C) [19]. the reactor (V ¼ 500 mL) and sealed. The reactor was heated to
Due to high activation energy of gasification reactions pro- 200
C and kept for 1 h. Resulting hydrochars and aqueous
ducing H2, catalysis is necessary for future development of phases were separated by filtration and were oven dried at
low temperature SCWG technology [18]. The various catalysts 105
C for 24 h. For HTC, process conditions were selected
have been evaluated to increase H2 yield with high gasification taking into account the mass yield (43.0 wt %) and energy yield
efficiency. Both homogenous alkali catalysts such as K2CO3, (55.9%). The dried hydrochar was ground and passed through
NaOH, KOH, CaCO3, Na2CO3, KHCO3 and heterogeneous tran- a 0.20-mm mesh for steam gasification experiments. The
sition metal catalysts mainly as Ni, Pd, Co, Mo and Zn have properties of food wastes and their hydrochar are given in
been tested in previous studies [20e22]. Among them, alkali Table 1.
salts are cost-effective catalysts and enhance water gas shift In supercritical water gasification experiments, Trona
reaction, providing high H2 yields [5,18]. (Na2CO3$NaCO3$2H2O), K2CO3 and seaweed ash were used as
Besides SCWG, steam gasification of the hydrochar derived catalyst. Seaweed ash was obtained by burning seaweed at
from biomass via hydrothermal carbonization as a pretreat-
ment process may be another option for hydrogen production
from the biomass with high moisture content. Hydrothermal Table 1 e Properties of food waste.
carbonization (HTC) occurs in aqueous medium at low tem-
Food waste Hydrochar
peratures ranging from 160 to 270
C under autogenic pres-
sure. Because of this, HTC is an especially promising Solid content (as received, wt%) 11.4 e
pH 3.6 e
technology for conversion of feedstock having high water
Proximate analysis (dry, wt%)
content (up to 80%) into a coal-like product, called hydrochar. Volatile matter 61.1 46.1
A number of studies have been performed on hydrothermal Fixed carbon 33.1 50.7
carbonization covering a wide range of wastes with high water Ash 5.8 3.2
content, such as grape pomace [23], orange pomace [24], Elemental Analysis (dry, wt%)
poultry litter [25], sewage sludge [26], olive mill wastewater C 46.7 62.1
H 5.2 5.1
[27], digestate [28], etc.
N 2.2 2.5
Despite the great interest arisen by HTC processes, a few
S 0.2 <0.1
study has been concerned the suitability of HTC as upgrading GCV (MJ/kg) 19.0 24.7
pretreatment for subsequent biomass steam gasification Inorganic content (dry, wt%)
[15,29]. Gai et al. [15] investigated the steam gasification of Na 0.01 0.01
hydrochar derived from HTC of sewage sludge. They observed K 2.67 1.43
that steam gasification of sewage sludge derived hydrochar Ca 0.63 0.99
Fe 0.05 0.11
resulted in a higher hydrogen yield and energy efficiency than

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0
850
C for 5 h. It contains mainly Ca (15.6%), Mg (9.2%), Na
(7.8%) and K (7.1%). Trona was used as received. Dolomite
(CaMg(CO3)2) was calcined at 850
C for 5 h before use. K2CO3
(purity: 99.99%, powder) was purchased from SigmaeAldrich.
Steam gasification experiments
Gasification of biomass was conducted in a two-stage fixed
bed reactor heated by two different furnaces (Fig. 1). The
reactor is constructed of stainless steel with an inner diameter
of 60 mm and of a total length of 100 mm and have two
different baskets, placed at 15 mm away from top and bottom
of the reactor. This heating rate and the final temperature of
two furnaces were adjusted by a temperature PID controller.
The top (biomass) bed temperature was monitored by type K
thermocouple. In a typical run, 3 g of hydrochar or 10%
seaweed added 3 g of hydrochar were placed in the top bed
and the same amount of catalyst was placed in bottom bed.
Thermal steam gasification experiments were also performed
without catalyst loading in bottom basket. The reactor system
was continuously purged with N2 flow (50 ml/min) from the
vertical line at the top of the reactor. The bottom bed was
heated to the desired temperature (700e850
C) at rate of
10
C/min in N2 flow. After the bottom bed temperature
reached steady state conditions, heating of top bed to the
850
C was commenced at a heating rate of 8
C/min and hold
at 850
C for 60 min to complete char gasification. Once the
biomass reactor was 200
C, steam was introduced from the
horizontal line with the help of N2 flow (50 mL/min) at a flow
rate of 0.6 mL H2O/min.
Gas products passed through condenser and two ice cold
traps cold traps, where tar compounds and also unreacted
water were condensed.
Fig. 1 e Scheme of steam gasification.
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3
The non-condensable gases were collected using a Tedlar
gas sample bag. After the experiment, the gases were
analyzed using gas chromatography. The quantity of gas was
determined by the known amount of N2 which was used as
sweeping gas with the known flow rates and duration of
collected in gas sample bag. The steam gasification experi-
ments were carried out in duplicate.
Supercritical gasification experiments
Supercritical gasification experiments were carried out in an
autoclave (Buchi Glassuster Limbo model). The reactor had a
volume capacity of 450 mL designed to a maximum temper-
ature and pressure of 500
C (internal temperature) and
600 MPa, respectively. Buchi btc model PID controller was used
to ensure accurate temperatures and efficient heating cooling
of the reactor and jacket. The reactor was equipped with a
pressure release valve, safety valve, pressure gauge and an
external magnetic stirrer. After loading 150 g of the food
wastes, the reactor was sealed by using torque. In case of
catalytic studies, adequate amount of catalyst was added and
mixed in the reactor. N2 line was connected to the reactor and
flushed with nitrogen to remove the air inside the reactor.
Then, reactor was pressurized with N2 to 10 bar as initial
pressure. Then the reactor was heated to desired temperature
at a rate of 5
C/min and held at this temperature for 1 h. Once
the reaction time was completed, the reactor was rapidly
cooled to room temperature by integrated water cooling sys-
tem with maximum capacity. Gas product was collected from
the vent line using a Tedlar bag and the volume of gas was
measured by using water replacement method. The solid
residue (char) was separated from the liquid by filtration
under vacuum; dried at 105
C and then weighted. In case of
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0
liquid product containing two different phase (aqueous and oil
phase), aqueous phase was taken out by using the pipette and
oil was recovered by washing with dichloromethane (DCM).
After DCM solution was dried with Na2SO4, DCM was evapo-
rated to recover the oil. The aqueous phase and oil were
weighted and then stored at þ4
C in sealed bottles for further
analysis. The oil and char yields were calculated based on
solid content of food waste. TOC analyzer (HachLange IL550-
TOC-TN) was used to determine the residual total organic
carbon (TOC) content in the aqueous phase.
The product gas analysis was carried out by Agilent 7890A
gas chromatograph (Refinery Gas Analyzer). The hydrocarbon
gases were analyzed in FID channel. The first TCD channel
(reference gas He) was configured to detect permanent gases,
which include CO2, CO and N2. The second TCD Channel (third
detector, with reference gas N2) was dedicated to analyze
hydrogen only. The gasification experiments were carried out
in duplicate and standard deviations were found less than 5%.
Results
Supercritical water gasification
Product yields
In the SCWG of carbonaceous materials, the yield and
composition of gases depend on the gasification conditions,
such as temperature, the ratio of biomass to water, heating
rate and reaction time as well as the type of feedstock. In this
study, heating rate and reaction time were chosen as based on
previously studies related to supercritical water gasification of
biomass model components [30]. Food wastes (~11 wt% dry
solids) were used as received because the 5e10 wt % of solid in
the suspension has been used in most of SCWG experiments
in literature. Nanda et al. [11] reported that high feed con-
centration led to compromised carbon conversion efficiency
and gas yields due to the decline in water molecules. They [12]
also reported a sharp decrease in H2 selectivity from 32.2% to
19.7% upon an increase in feedstock (orange peel) concentra-
tion from 10% to 20%.
In our study, we investigated the effect of temperature and
type of catalyst on the yield and composition of product gases
and other products. Table 2 gives the gasification results from
different conditions. The weight percent of the gases was
calculated on the basis of total gas yields (i.e. H2, CO, CO2, CH4
and C2eC5 gases).
Table 2 e Product distribution of HTG (wt%, on solid matter).
400
C
Thermal Thermal
Catalyst amount e e 1%
Pressure, bara 320 470 470
Gas 30.0 33.0 38.9
Coke 31.2 23.4 23.4
Tar e e e 14.0
TOC in aq., ppm 9167 ± 149 3429 ± 114 5472 ± 32
a
Observed maximum temperature during HTG.
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As expected, the highest amount coke was obtained at low
temperature without catalyst. Similar results have been re-
ported for SCWG of cellulose [31] pinewood and wheat straw
[22]. The coke may have originated from not completed the
solvolysis or hydrolysis reactions. The increase of tempera-
ture led to decrease in coke amount to some extent. The in-
crease in temperature also led to a decreased in TOC content
in the liquid phase implying that it promoted the degradation
of water soluble products, which are intermediates in the
formation of gas and tarry compounds. To enhance the gasi-
fication, alkali catalysts, namely Trona, K2CO3 and seaweed
ash were employed. The advantages of alkali catalysts over
metallic heterogeneous catalysts are low cost, higher con-
version rates with improving total gas yields and carbon
gasification efficiency [12]. In contrast to heterogeneous cat-
alysts, supplementary steps for recovery and reuse are not
needed. In addition, there is no catalyst poisoning problem in
case alkali catalysts.
The use of catalysts decreased the coke amount, while it
increased the formation gas and tarry compounds which is
unwanted by-product. In order to investigate the effect of
catalyst amount on gas composition, SCWG of food waste at
450
C was conducted by using Trona as catalyst. By increasing
the amount of Trona, the formation of solid product was
decreased while gas and tar yields were increased. The in-
crease in tar formation in the presence of sufficient amount of
catalyst indicated that the catalysts promoted the char
decomposition leading to the tarry compound formation be-
sides catalyzing the gasification reactions. The increase in
TOC seems to be the consequence of the increase in solid
carbon conversion.
After determining the optimal temperature (450
C) and
catalyst amount (5%), food wastes were gasified in presence of
K2CO3 and seaweed ash to investigate the effect of alkali
catalyst type on SCWG. The gas yields were similar for all
catalysts. The K2CO3 showed similar activity as Trona, in
terms of char decomposition and tar formation. But highest
coke and tar yields were obtained in case of seaweed ash. In
catalytic runs, some approximations were needed in coke
calculations depending on the solubility of catalysts. When
using Trona and seaweed ash, 10% and 52.5% of catalysts,
respectively, were assumed to remain in the solid phase.
Thus, the yield of coke was corrected by excluding the
remaining catalyst amount from the weight of solid residues.
However, seaweed ash (containing high CaO) may adsorb CO2
during the gasification process [31] and form calcium
450
C
Trona K2CO3 Seaweed ash
2.5% 5% 10% 5% 5%
480 490 500 480 485
46.2 44.9 46.4 44.7 43.9
5.3 1.6 0.6 3.25 11.4
16.0 18.8 15.6 21.2
6734 ± 160 8244 ± 372 7025 ± 71 8416 ± 178 4387 ± 150
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0
carbonate having low solubility which would contribute to a
weight increase in the solid product.
Gas composition
Under all gasification conditions, the gas product was
composed of carbon dioxide, hydrogen, and methane as major
components and C2eC4 gases were as minors (Fig. 2). The very
low yields of carbon monoxide (0e0.05 mmol/g dry food
waste) were obtained even at low temperature and absence of
catalyst. The gasification of biomass under supercritical water
conditions occurs through following reactions [30];
C6H12O6 þ 6H2O / 6CO2 þ 14H2
C6H12O6 / 3CH4 þ 3CO2
The H2 formation reaction is endothermic while CH4 pro-
duction is exothermic. According to per Le Chatelier's princi-
ple, the elevated temperatures favor the H2 formation,
whereas CH4 would be favorable at high pressures. Higher
temperatures lead to higher conversion but reduce SCWG's
energy efficiency.
In addition to above reactions, it has been reported by
many authors [3,16,18] that water gas shift (WGS) (Eq. 3) and
methanation (Eq.4) reactions also take place in SCWG.
CO þ H2O / CO2 þ H2
CO þ 3H2 / CH4 þ H2O
It is desirable to achieve gasification at lower temperatures
with the help of catalysts. The presence of a catalyst changes
Fig. 2 e Product gas distribution from SCWG of food wastes.
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5
the reaction pathway of the biomass gasification, resulting in
an increase in the H2 and CH4 yields.
The addition of alkali salts strongly affected the gas
composition, as demonstrated by using various model sub-
stances [32,33] and different kinds of biomass feedstocks
[34,35].
The alkali catalysts, for instance, NaOH, KOH, LiOH,
Na2CO3, K2CO3 or Ca(OH)2 are active reactants for high
hydrogen yields via the water-gas shift reaction. Sinag et al.
[33] proposed a reaction pathway for hydrogen formation in
presence of K2CO3 as follows;
(1) K2CO3þH2O / KHCO3 þ KOH (5)
(2) KOH þ CO / HCOOK (6)
HCOOK þ H2O / KHCO3 þ H2 (7)
2 KHCO3 / H2O þ K2CO3 þ CO2 (8)
H2O þ CO 4 HCOOH 4 H2 þ CO2 (9)
In absence of catalyst, the amounts of H2, CH4 and hydro-
carbon gases produced at 400
C were lower than that at 450
C
while CO2 amount (6.26 and 6.10 mmol/g dry matter, respec-
tively) was nearly same. H2 amount was increased by 133%
(3) with the rise in the temperature from 400
C to 450
C (Fig. 3). It
should be also noted that in experiments at 400
C, H2 amount
(4) was higher than that of CH4 while SCWG at 450
C produced
more CH4 than H2. This result indicated that the increase in
temperature might promote thermal degradation of biomass
(Eq. 2). The use of catalyst extremely promoted hydrogen
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0

Fig. 3 e H2 and CH4 yields from SCWG of food wastes.

production and hydrogen yield increased with the increase of
catalyst concentration. However, CH4 formation was not
increased at the same extent. Watanabe et al. [36] studied the
reformation of CH4 with alkali catalysts in near-critical and
supercritical water. They found that alkali catalysts promote
the following reaction;
yield varied between 6.10 and 8.11 mmol gas/g dry matter.
This result might be associated with the dissolution of CO2 in
aqueous medium forming carbonate salts and/or carbonic
acids.
Steam gasification

CH4 þ 2H2O / CO2 þ H2 (10) The principal reactions in steam gasification of hydrochar in
dual-bed system used as following pathways [37,38];
With a catalyst concentration of 5 wt%, Trona gave satis- At top bed:
factory results in term of both H2 and unwanted tar yield.
Considering the advantage of gasification with a lower quan- Hydrochar/H2 þCO þ CO2 þCH4
tity of catalyst usage and tar formation, catalyst concentration þ Cn Hm þtar Pyrolysis ðbetween 200e500
CÞ (11)
of 5 wt% was assumed as base case for gasification with other


C þ H2 O/CO þ H2
Steam reforming of char ðbetween 500e850
CÞ (12)
C þ 2H2 O/CO2 þ2H2

catalysts. The highest hydrogen yield (3.64 mmol/g dry mat-

ter) was obtained in the presence of K2CO3. The similar At bottom bed:
hydrogen yields were obtained both in the presence of Trona
(2.78 mmol/g dry matter) and seaweed ash (2.73 mmol/g dry Cm Hn þmH2 O/mCO þ ðm þ 1=2nÞH2 O steam reforming of tar
matter). (13)
According to the postulated reactions above (Eq. 8 and 9),
CO þ H2 O/CO2 þ H2 water  gas shift reaction (14)
the considerable increase in CO2 production are expected by
both temperature and the addition of catalyst. However, CO2

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0 7

Table 3 e Hydrogen yields from steam gasification based

Cn Hm þ 2n H2 O/nCO2 þ ð2n þ m=2 H2 Þ on dry food waste, mmol/g dry food waste.
(15)
steam reforming hydrocarbons H2 CH4
where CnHm represents light gases such CH4, C2H4, C2H6, C3H8, H-850-T 28.39 ± 1.94 1.59 ± 0.03
C3H6, etc. HA-850-T 27.57 ± 5.44 1.52 ± 0.04
The use of catalyst enhanced the reactions in bottom bed, H-700-T 23.04 ± 1.17 1.27 ± 0.02
HA-700-T 27.28 ± 0.02 0.88 ± 0.04
providing H2 formation (Fig. 4). In literature, both manufac-
H-700-Dolomite 26.44 ± 1.07 1.26 ± 0.01
tured catalysts and naturally occurring minerals have been
H-700-Fe-Ce 26.46 ± 0.36 1.22 ± 0.01
widely used as tar reforming catalyst. Dolomite has been HA-700-Dolomite 28.08 ± 1.46 1.08 ± 0.06
widely tested because they are inexpensive and abundant and
can reduce the tar content of the product gas. Besides dolo-
mite, the iron based catalysts are another important group of
ash. And they suggested that wood ash was a suitable catalyst
catalysts and have been tested in biomass gasification studies
for the gasification reaction. Yip et al. [45] studied steam
[37,39]. It was reported that iron oxide catalyst affected the
gasification of both the raw and acid-treated biochar samples
composition of the gaseous products by catalyzing the WGS
and found the presence of the inherent AAEMs in biochars
reaction as well as it has the tar destruction effect. In order to
play an important role in the biochar gasification reactions.
increase the catalyst activity, CeO2 can be considered as a
Fig. 4 shows the gas yields from steam gasification of hydro-
promoter. Ceria shows promising catalytic activities and
char under different conditions. In this study, the effects of
selectivity in partial oxidation because of its redox properties
seaweed ash addition to hydrochar and the catalyst type and
[40]. It has also the ability to promote metaleceria interaction
catalyst bed temperature on the hydrogen production were
and metal dispersion [41]. In our previous studies [38,40,41],
investigated. In these group experiments, the temperature of
CeO2eFe2O3 catalyst exhibited the excellent performance for
the top bed was maintained at 850
C. In Fig. 4, the gasification
both hydrogen production and tar decomposition in steam
runs were named as following the ‘‘Feedstock at top bed-
gasification of lignocellulosic and algal biomasses. In this
Bottom bed (catalyst bed) temperature e Catalyst type’’
study, we used dolomite and CeO2eFe2O3 as catalyst in bot-
sequence (e.g., H- 700- dolomite stands for gasification of
tom bed to produce hydrogen via steam gasification of
hydrochar over dolomite (bottom bed temperature: 700
C),
hydrochar. Additionally, seaweed ash, as catalyst, was added
whereas HA- 850-T stands for thermal gasification of ash
to hydrochar at 10 wt %. Recent published reports showed that
added hydrochar (bottom bed temperature: 850
C).
the presence of inherent alkali and alkaline earth metallic
In thermal runs (H-850-T and H-700-T), the yield of both
species (AAEMs) in biomass enhanced the production of H2
hydrogen and total main gaseous products decreased with the
and CO2 in biomass gasification [42,43]. Hauserman [44]
decrease in bottom bed temperature. This indicated that
studied the catalytic effect of added AAEMs in gasification of
higher temperature promoted thermal cracking of tar and
biomass and coal. They observed that the gasification reac-
wateregas shift reaction. On the other hand, the addition of
tivity of both coal and biomass increased by adding of wood

Fig. 4 e Gas yields from steam gasification of hydrochar derived from food wastes.

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8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0

Table 4 e Hydrogen yields from the hydrothermal gasification and steam gasification of different biomass.
Biomass Gasification method Operating conditions H2 yield, mmol/g dry biomass Reference
Pinewood SCWG 550
C Dolomite KOH 0.99 [31]
5.55
Coconut shell SCWG 600
C K2CO3 4.78 [12]
Sugarcane bagasse 4.36
Aloe vera rind 3.59
Canola meal SCWG 650
C K2CO3 3.36 [6]
Wheat straw 2.08


Timothy grass 550 C K2CO3 1.83


Horse manure SCWG 600 C Na2CO3 5.31 [11]


Diosgenin solid waste SCWG 550 C K2CO3 0.01 [47]


Macroalgae SCWG 500 C NaOH 0.03 [45]


Almond shell SCWG 460 C hydrochar 11.63 [48]


Sunflower stalk SCWG 500 C K2CO3 Trona 9.68 [39]
9.39
Corncob 500
C K2CO3 Trona 7.96
11.88
Fucus serratus SCWG 500
C no catalyst 7.17 [5]
Laminaria digitata 6.42
Rice husk Steam gasification 900
C 9.75 [42]
Rice straw 10.09
Safflower seed cake Steam gasification 850e700
C, CeO2eFe2O3 66.61 [41]
Fucus serratus Steam gasification 850e700
C, CeO2eFe2O3 46.25 [38]
Laminaria digitata 18.43
Walnut shell Steam gasification 850e700
C, CeO2eFe2O3 72.68 [40]
Almond shell 71.61

seaweed to hydrochar had no effect on hydrogen yield in case
bottom bed temperature was 850
C. This shows that the
bottom bed temperature of 850
C was enough thermal
cracking of tar and wateregas shift reaction. One interesting
observation can be noted on the effect of seaweed ash addi-
tion in case bottom bed temperature 700
C. One can expect
that alkali species only enhance the steam reforming of char
(Eq. 12) and the reactions at bottom bed are independent of the
seaweed ash. Because of this, hydrogen yields should be
similar for H -700 eT and HA -700 eT. However, hydrogen
yield from HA -700 eT (63.44 mmol/g hydrochar) was higher
than from H -700 eT (53.58 mmol/g hydrochar). Promoting
effect of seaweed in top bed on the homogeneous reactions in
bottom bed (Eq. 13e15) might be attributed to gaseous AAEMs
(in seaweed ash) vapored from top bed [42,46]. Zolin et al. [46]
investigated the volatilization of AAEMs during thermal
degradation of biomass. They reported that some parts of
AAEMs released in the form of gaseous and involved in the
steam reforming reactions.
Since a high temperature is unfavorable in terms of the
energy efficiency, the bottom bed temperature of 700
C was
chosen in catalytic steam gasification experiments. The use of
dolomite and Fe2O3eCeO2 led to increase in the H2 and CO2
production whereas the other gases remained nearly con-
stant. Hydrogen yields were 61.48 and 61.54 mmol/g hydro-
char for Dolomite and Fe2O3eCeO2, respectively. These results
showed that the catalysts used had considerable activity for
both the steam reforming of tar (Eq.13) and wateregas shift
reaction (Eq. 14). On the other hand, hydrogen yield from
catalytic gasification of ash added hydrochar in presence of
dolomite was 65.30 mmol/g hydrochar, was slightly higher
than that from other catalytic runs.
Comparison of hydrogen yields
The hydrogen yields obtained from food wastes are quite
comparable with hydrogen yields obtained from different
biomasses via steam reforming and SCWG (Table 4).
From the comparison of Fig. 3 and Table 3, it is clearly seen
that steam gasification produces more hydrogen than SCWG.
This result is well agreed with previous reports [5,38]. The
steam gasification of dried Fucus serratus and Laminaria digitata
[38] produced more hydrogen gas than that of SCWG of Fucus
serratus and Laminaria digitata (Table 4). Possible reason is that
food wastes are converted into not only gases, also it is con-
verted into tar, solid and water soluble compounds (Table 2).
Conclusion
In this study, hydrogen production from food wastes was
investigated by thermochemical methods, namely supercrit-
ical water gasification (SCWG) and steam gasification. In
SCWG, the alkaline catalysts significantly increased the
hydrogen yield. Alkaline species enhanced the wateregas
shift reaction and reformation of methane leading to H2 pro-
duction rather than methanation. The highest hydrogen yield
(3.64 mmol/g dry waste) was obtained in the presence of
K2CO3 catalyst. In steam gasification of hydrochar derived
from food waste in a dual-bed gasifier, the use of catalysts
(Fe2O3eCeO2 and dolomite) enhanced both tar degradation
and hydrogen production via water-shift reaction. Most
interesting finding was that the addition of seaweed ash to
hydrochar showed promoting effect in both steam reforming
of char and the homogeneous reactions in catalyst bed. It is

Please cite this article in press as: Duman G, et al., Sustainable hydrogen production options from food wastes, International Journal of
Hydrogen Energy (2018), https://doi.org/10.1016/j.ijhydene.2017.12.146
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 0
clear statement that the steam gasification produces more
hydrogen (28.08 mmol/g dry waste) than SCWG.
As conclusion, the results obtained in this study showed
that the steam gasification of the hydrochar derived from
biomass via hydrothermal carbonization pretreatment is a
promising method for hydrogen production from wet biomass
(containing up to 90% water).
Acknowledgements
The financial support from TUBITAK-MAG under contract
2015-M-314 and Ege University under contract 16-FEN-046 are
gratefully acknowledged.
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