A Review of Catalytic Aqueous-Phase Reforming of

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 6 ) 1 e3 0
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Review Article
A review of catalytic aqueous-phase reforming of

oxygenated hydrocarbons derived from biorefinery
water fractions
I. Coronado a,*, M. Stekrova b, M. Reinikainen a, P. Simell a, L. Lefferts c,

J. Lehtonen b
a
VTT Research Centre of Finland Ltd., Finland
b
Department of Biotechnology and Chemical Technology, School of Chemical Technology, Aalto University, Helsinki,
Finland
c
MESAþ Institute for Nanotechnology, University of Twente, Enschede, The Netherlands
article info abstract
Article history: Aqueous-phase reforming (APR) of oxygenated hydrocarbons is a process for the produc-
Received 23 February 2016 tion of hydrogen and light alkanes. The reactants of APR remain in liquid phase during the
Received in revised form reaction avoiding an energetically demanding vaporization-step compared to processes
30 April 2016 such as steam reforming (SR). Furthermore, low reaction temperatures thermodynamically
Accepted 5 May 2016 favour the formation of hydrogen with low carbon monoxide content. Therefore, APR has
Available online xxx been recently considered as a promising route to upgrade organic compounds found in
biorefinery water fractions.
Keywords: Aqueous oxygenated hydrocarbons are reformed at low temperatures (200e250 C) and
Aqueous-phase reforming high pressures (15e50 bar), typically with platinum- and nickel-based catalyst. In addition,
Oxygenated hydrocarbons metal combinations of these and other metals have been applied to enhance the catalyst
Hydrogen performance. Alumina has been extensively used as catalyst support in APR. Nonetheless,
Alkanes other oxides and carbonaceous materials have been applied to improve the stability of
Metal catalyst catalysts.
Hydrothermal conditions and high pressure present operational challenges that hinder
the development of aqueous-phase reforming. However, low yields of desired products and
fast catalyst deactivation constitute the main barriers. To maximize the APR effectiveness,
the optimization of operation conditions and more active and durable catalysts are
required.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
* Corresponding author. Tel.: þ358 40 668 2831.

E-mail address: irene.coronado@vtt.fi (I. Coronado).
http://dx.doi.org/10.1016/j.ijhydene.2016.05.032
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Coronado I, et al., A review of catalytic aqueous-phase reforming of oxygenated hydrocarbons derived
from biorefinery water fractions, International Journal of Hydrogen Energy (2016), http://dx.doi.org/10.1016/j.ijhydene.2016.05.032
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 6 ) 1 e3 0
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Aqueous-phase reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. Evaluation of APR performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.2. Feedstock and products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3. Effect of reaction conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3.1. Feedstock concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3.2. Temperature and pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3.3. Residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3.4. Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.3.5. Effect of nitrogen co-feeding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.4. Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.4.1. Hydrogen formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.4.2. Alkanes and carbohydrates formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.5. Reactor types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
APR performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
addition, hydrogen is utilized in the hydrotreatment of sus-

Introduction tainable biomass resources for biofuel production. The envi-
ronmental advantages of producing non-fossil hydrogen are
The transition from the fossil-based to a bio-based economy well known. Accordingly, hydrogen is commonly considered
demands the replacement of conventional, unsustainable as the main product of APR.
processes. Biorefineries represent an alternative to produce Oxygenated hydrocarbons such as sugars and alcohols
chemicals, fuels, power and heat from renewable lignocellu- were the feedstock first proposed in 2002 by the group of
losic biomass. Representative examples of biorefineries Dumesic to produce hydrogen applying platinum catalysed
include thermochemical processes such as gasification and aqueous-phase reforming. Cortright et al. [5] studied the per-
pyrolysis [1]. The target products of these processes are formance of platinum-based catalysts to convert aqueous
frequently accompanied by an aqueous fraction with organic C:O ¼ 1:1 oxygenated hydrocarbons into hydrogen. Few years
compounds, for instance oxygenated hydrocarbons. The after this first publication, Virent Energy Systems, Inc., with
disposal of these water fractions entails costly conditioning Cortright as Executive Vice President, claimed to be
treatments. Additionally, misusing the organic compounds commercializing the Aqueous Phase Reforming process for
contained in the water fractions decreases the feedstock- the production of hydrogen and gaseous alkanes from glycerol
usage efficiency compared to the case in which these and sorbitol [6]. Today, Virent, Inc. [7] pursues to scale up its
organic compounds were upgraded to valuable products. The patented technologies which apply aqueous-phase reforming
value of all the product streams should be maximized to in- to plant-based sugars to produce hydrocarbon products,
crease the production efficiency of biorefineries. including gasoline, diesel, jet fuel, and chemicals.
Hydrothermal processes have been applied to convert During the past years, the amount of studies focused on
lignocellulosic biomass or intermediate products from APR to produce hydrogen and alkanes has increased. Re-
biomass processing with high water content into bio- searchers have examined feedstock components and con-
chemicals and biofuels. These processes are conducted in centrations, catalysts with different active metals, promoters
liquid phase applying temperatures in the range of 100e600 C and supports, variations in reaction conditions, and a few
and pressures between 1 and 400 bar [2,3]. An advantage reactor designs. However, the aqueous-phase reforming pro-
derived from these conditions is the suppression of an ener- cess still remains in laboratory scale. Further research is
getically demanding vaporization-step. Hydrothermal pro- needed to optimize the process productivity and launch APR
cesses can be classified into two categories, sub- and to scales closer to commercialization.
supercritical technologies, based on the critical point of water This work reviews the state of catalytic aqueous-phase
[2]. Water reaches the critical point at 374.2 C and 221.2 bar. reforming of oxygenated hydrocarbons. First, aqueous-
Among the processes that apply subcritical conditions [4], this phase reforming is introduced and compared with other
work focuses on aqueous-phase reforming (APR). In this type reforming technologies. Second, various parameters to
of reforming, hydrogen and carbon dioxide are produced evaluate the APR performance are presented, and discussed.
among other gaseous and liquid products from organic com- Third, the performance of APR is evaluated considering
ponents in aqueous phase. Hydrogen is a renewable energy different feedstock, reaction conditions, and catalysts.
carrier that can be converted to electricity and heat. In Additionally, this paper analyses the reactor technologies
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 6 ) 1 e3 0 3
conventionally applied in aqueous-phase reforming. perfor- Tropsch (Eqs. (5) and (6)) are side reactions that consume
mance parameters and reactor types applied in APR are novel hydrogen to produce alkanes. The selectivity of hydrogen is
topics introduced in this study. Furthermore, a broader scope additionally affected by mass transfer limitations which re-
of subjects such as feedstock applied in APR and expected sults in H2 consumption in the side reactions of the liquid
products has been considered in comparison to other review phase. For instance, aqueous-phase dehydration (Eq. (7)) and
works [8]. hydrogenation (Eq. (8)) reactions produce alkanes and carbo-
hydrates at the expense of hydrogen [15].
Cn H2nþ2 On þ nH2 O4nCO þ ð2n þ 1ÞH2 DH > 0 (1)

Aqueous-phase reforming
CO þ H2 O4CO2 þ H2 DH < 0 (2)
Autothermal reforming, partial oxidation, and to a larger
extend steam reforming (SR) have been traditionally applied
CO þ 3H2 4CH4 þ H2 O DH < 0 (3)
to produce hydrogen from natural gas and hydrocarbon feeds
[9]. Steam reforming occurs at high temperatures and mild
CO2 þ 4H2 4CH4 þ 2H2 O DH < 0 (4)
pressures, and high reaction rates are obtained [10]. High
temperatures affect the stability of the catalyst due to thermal
ð2n þ 1ÞH2 þ nCO/Cn H2nþ2 þ nH2 O DH < 0 (5)
cracking of the feedstock leading to coke formation, and
compromise the energy efficiency of the process. Moreover,
hydrogen production by the parallel wateregas shift (WGS) ð2nÞH2 þ nCO/Cn H2n þ nH2 O DH < 0 (6)
reaction is unfavourable at high temperatures [11]. In
contrast, aqueous-phase reforming is conducted at low tem- carbohydrate
Cn H2nþ2 On þ H2 4 þ H2 O DH < 0 (7)
peratures at which reforming of oxygenated hydrocarbons alkane
and the WGS reaction are favoured [12]. Fig. 1 shows the en-
Cn H2nþ2 On þ H2 4carbohydrates DH < 0 (8)
ergy balance of autothermal, steam and aqueous-phase
reforming. APR has been proven to be more energetically Aqueous-phase reforming of oxygenated hydrocarbons
efficient than the other technologies [13]. Higher efficiency (Eq. (1)) is conventionally conducted at low temperatures
derives from lower energy requirements by the suppression of (200e250 C), and at pressures close to the bubble point of the
water evaporation [10]. Therefore, APR offers a promising feedstock (15e50 bar) to produce hydrogen and carbon mon-
route to process the biorefinery water fractions with organic oxide. Although reforming of carbohydrates is thermody-
compounds to obtain more valuable products such as namically favourable at lower temperatures than for alkanes
hydrogen and alkanes. [10,16], this reaction is kinetically and thermodynamically
Eqs. (1)e(8) describe the reactions involved in aqueous- promoted at higher temperatures. Nevertheless, lower tem-
phase reforming of oxygenated hydrocarbons, with for peratures decrease the number of decomposition reactions
instance C:O ¼ 1:1 ratio, and side reactions in gas and liquid and facilitates the exothermic conversion of carbon monoxide
phases. Reforming of carbohydrates (Eq. (1)) and wateregas through the WGS reaction (Eq. (2)), which results in gas mix-
shift (Eq. (2)) are desired reactions to produce hydrogen. tures of H2 and CO2 with low CO concentration [17]. The side
Conversely, methanation (Eqs. (3) and (4)) and Fischer- reactions (Eqs. (3)e(8)) are also exothermic and favoured at
low temperature. These reactions produce short-chain al-
kanes (C1eC6) and carbohydrates compromising the hydrogen
selectivity in APR [16].
Fig. 2 shows an example of bond scissions and reaction
pathways in aqueous-phase reforming of ethylene glycol.
Hydrogen and carbon monoxide are produced in aqueous-
phase reforming by CeC as well as CeH and/or OeH bond
scission of oxygenated compounds (I). Further reaction of
carbon monoxide with H2O in the water shift reaction pro-
duces H2 and CO2 (III). Consecutive reactions in the gas phase
(IV (a) and (b)) consume hydrogen to produce methane. On the
other hand, CeO bond cleavage (II) leads to the formation of
side products such as alkanes, alcohols and organic acids in
detriment of hydrogen production.
As an alternative to hydrogen production, aqueous-phase
dehydration/hydrogenation (APD/H) of oxygenated hydrocar-
bons have been considered for the production of C1eC6 al-
kanes [13]. The high volatility of hexane and lighter
hydrocarbons reduces their value as liquid fuel blending-
compounds. Therefore, some authors propose the produc-
Fig. 1 e Operation conditions, and cooling and energy tion of heavier alkanes (C7eC15) by APD/H and subsequent
needs (thermal and electrical) for hydrogen production by aldol condensation to form CeC bonds [18].
reforming of glycerol [14].
Fig. 2 e Reaction pathways of aqueous-phase reforming of ethylene glycol [13].
Evaluation of APR performance feedstock (Table 1, Item 3). This can be easily calculated for the
experiments run in batch mode. The value thereby obtained
The products of aqueous-phase reforming consist of two defines the tendency of feedstock to be converted into a spe-
phases, gas and liquid, collected from two different streams. cific product among all the products both in liquid and gas
The composition and flow rate of gaseous products can be phase. Conversely, to calculate a reliable value of converted
accurately measured. Among the produced gases, hydrogen is feedstock is difficult in continuously operated processes when
regarded as the main product of aqueous-phase reforming. the outlet flow rate of the liquid stream is inaccurately
Accordingly, the production of hydrogen is considered in the measured. Therefore, many authors solely consider the gas
majority of performance parameters applied to evaluate APR production to define hydrogen selectivity, neglecting thus the
(Table 1, items 2e5). On the other hand, the liquid products liquid products (Table 1, Items 4 and 5). Hydrogen selectivity
often comprise a complex mixture of hydrocarbons and calculated by the formulas in Items 3 and 4 (Table 1) are
oxygenated hydrocarbons, in some cases difficult to identify. comparable if the feedstock is converted only to gaseous
Nonetheless, quantifying the outlet flow rate of the liquid products. In contrast, the values of selectivity obtained with
stream constitute a more significant challenge in continuous Items 3 and 4 significantly differ when the liquid products
processes. constitute a considerable part of the total production and are
Table 1 shows formulas frequently applied to evaluate the disregarded in the calculation. The results obtained with the
performance of aqueous-phase reforming. Traditional evalu- formulas in Items 4 and 5 are comparable if the experimental
ation parameters such as conversion and yield (Table 1, Items reforming ratio is equal to the stoichiometric reforming ratio.
1 and 2) are applied in the performance evaluation of aqueous- These ratios are equal when the feedstock is totally reformed
phase reforming. The traditional formula to determine the to CO and H2, and carbon monoxide entirely reacts in the WGS
hydrogen selectivity requires the calculation of converted reaction to produce CO2 and H2. However, the reforming ratio
Table 1 e Parameters and formulas conventionally applied to evaluate APR performance.

Item Parameter Formula
1 Conversion molout
Xð%Þ ¼ 100 molinmolin
2 Hydrogen yield Yð%Þ ¼ 100 molmol out H2

R1a
in feedstock
3 Hydrogen selectivity (I) molout H2

SI H2 ð%Þ ¼ 100 ðmolin mol R1a
out Þfeedstock
4 Hydrogen selectivity (II) SII H2 ð%Þ ¼ 100 C atHin2 produced

gas products Ra
1
5 Hydrogen selectivity (III) SIII H2 ð%Þ ¼ 100 P molmolout H2

gas products
out
6 Hydrogen formation rate mmolðH2 Þ=min

gðcatalystÞb
7 Carbon selectivity Si ð%Þ ¼ 100 CC at
ati in gas product
in gas products
8 Carbon yield CtoGc ð%Þ ¼ 100 CCatatgas product
feedstock
CtoLd ð%Þ ¼ 100 C at liquid product

C at feedstock
a
R ¼ H2/CO2 (stoichiometric reforming ratio).
b
Some authors use grams of active metal.
c
Carbon to gases.
d
Carbon to liquids.
at ¼ atoms.
varies in practice due to incomplete reforming and WGS re- feedstock [16]. C:O ¼ 1:1 molecules are frequently selected as
action, as well as because of side reactions. Hydrogen for- model compounds due to favoured scission of CeC bonds and
mation rate (Table 1, Item 6) is also commonly applied to subsequent hydrogen formation [10]. Glucose, with carbon-
evaluate the hydrogen production in APR. This parameter is oxygen ratio equal to 1, constitutes a promising candidate
defined as the production rate of hydrogen in either mol, for H2 production in APR. This compound is highly available as
weigh or volume units per unit of time, per either weight or energy reserve, and needs little upstream treatment, which
volume of either catalyst or active metal depending on the minimize operating costs. However, glucose participates in
study. homogeneous reactions to form organic acids, aldehydes and
Carbon selectivity (Table 1, Item 7) also regards exclusively carbonaceous deposits that reduces the H2 selectivity, and
the gaseous products. Therefore, the selectivity values ob- promote catalyst deactivation [10,42]. Alternatively, APR of
tained with this formula are representative when the liquid more reduced C:O ¼ 1:1 compounds such as sorbitol, glycerol,
products can be neglected. Furthermore, carbon conversion to ethylene glycol and methanol result in higher hydrogen
liquids (Table 1, Item 8) constitutes a reliable evaluation selectivity and yield (Fig. 3) [5,16].
parameter exclusively when the collection and quantification Glycerol is the main by-product derived from the produc-
of liquid products are accurate. tion of first generation biodiesel. Consequently, the utilization
The Appendix included in this study summarizes the re- of this by-product has been extensively reviewed [46] to pro-
sults reported in literature for the aqueous-phase reforming duce hydrogen [8,47], and fuels and chemicals [48,49].
of different compounds. The results are presented in terms Hydrogen production by aqueous-phase reforming of glycerol
of conversion, and selectivity and production rate of has been broadly investigated [22,50e54]. The majority of
hydrogen and methane at specified reaction conditions. studies evaluate the product selectivity and yield at various
These evaluation parameters are commonly applied in operation conditions [35], and applying different catalysts [55]
literature. However, different units and formulas to define to maximize hydrogen production.
the same parameters hinder the direct comparison of results. Acetaldehyde, ethanol, propylene glycol, and ethylene
To consult the original publications referenced in Tables glycol can be found among the liquid products of aqueous
A1eA5 is recommended to obtain more accurate informa- glycerol reforming [56]. These components have been there-
tion regarding the calculation methods applied in every fore applied as model compounds to achieve a better under-
study. standing of the reaction mechanism of glycerol reforming. In
particular, ethylene glycol has been frequently used as model
Feedstock and products compound [57e61] because of the high conversion to gas and
hydrogen yield obtained in APR (Fig. 4).
Biorefinery water fractions with dissolved organic compounds Aqueous-phase reforming of oxygenated hydrocarbons
are the target feedstock of aqueous-phase reforming. Mix- derived from thermochemical processing of lignocellulosic
tures of oxygenated hydrocarbons in low concentration biomass, such as Fischer Tropsch (FT) and pyrolysis processes
(1e10 wt-%) are usually found in water streams derived from are considered to a lesser extent in literature. The water
biomass processing. These organic mixtures which composi- fraction derived from FT reaction includes components such
tion might not be entirely defined are complex to process. In as alcohols, acids, and hydrocarbons [63]. On the other hand,
spite of the complexity, hydrogen and hydrocarbons can be components such as acetic acid, sugars, hydroxyacetone,
produced by APR of cellulose [19] wastepaper [20] and the methanol, furfural and acetaldehyde can be found in the
aqueous phase of pyrolysis bio-oil. Nonetheless, aqueous- aqueous fraction of pyrolysis oils [64]. Acetic acid has been
phase reforming of model compounds that represent real occasionally utilized as model compound in APR. However,
biorefinery water compositions or intermediate products reforming of aqueous acetic acid is characterized by the for-
typically formed in the APR process is recommendable to mation of intermediates [42,65], and catalyst deactivation
achieve a better understanding of the reaction mechanism [66].
[21]. Model compounds commonly applied in APR include
oxygenated hydrocarbons such as glycerol [22], ethylene gly- Effect of reaction conditions
col, ethanol, methanol, acetic acid, acetaldehyde [23], acetol
[24], butanol [25], cellulose [19], fructose, sucrose [26], furfural Feedstock concentration
[27], glucose, sorbitol [5], galactitol [28], cyclic compounds [29], Water fractions derived from biorefineries are highly diluted.
and xylitol [30]. Similarly, the model-compound solutions applied in APR
Aqueous-phase reforming of oxygenated hydrocarbons include 1e10 wt-% of oxygenated hydrocarbons. Considering
generates gas and liquid streams. The gas product may the low concentration of the organic phase, significant
contain hydrogen, carbon dioxide, carbon monoxide, amount of water has to be processed through APR. Therefore,
methane and C2eC6 alkanes. The composition of the liquid the effect of feedstock concentration on the performance of
product obtained from APR varies depending on the feedstock APR has been evaluated to optimize the process. As shown in
(Table 2). Alcohols, acids and other carbohydrates are Fig. 5, aqueous-phase reforming exhibited higher carbon to
frequently found in the liquid stream. gas conversion and hydrogen yield when more diluted feed-
Among the gaseous products derived from APR, re- stocks were applied [10,22].
searchers aim to maximize the hydrogen production. Selec- Reforming of more concentrated feedstocks resulted in
tivity to H2 increases in APR of lighter [44], more reduced [45] higher carbon content in the liquid than in the gaseous
oxygenated hydrocarbons, and with less concentrated products [41]. Furthermore, different liquid product
Table 2 e Liquid products from aqueous-phase reforming of different model compounds.

Model compound Liquid products Ref.
Glycerol Glyceraldehyde; hydroxyacetone; ethylene glycol; propylene glycol; 1,2- [31e36]
ethanodiol; acetaldehyde; propanal; 1-propanal; 2-propanol; 1-propanol;
ethanol; methanol; 2-methyl propylene; butane; pentane; acetic acid;
propanoic acid; lactic acid
Ethylene glycol Butane, glycolic acid, glycol aldehyde, methanol, acetic acid, ethanol, [37e39]
methanol, acetone, 2-propanol
Xylitol, sorbitol, galactitol Ketones, alcohols, furans, cyclic ethers, acids, aromatics, sugars, polyols, [28,40,41]
carbonyl compounds
Acetic acid Ethylene glycol, methanol, acetaldehyde [23]
Methanol, ethanol Acetaldehyde, acetic acid, ethyl acetate [42,43]
Glucose Aromatic ethers, C5eC6 ester groups [26]
Fig. 5 e Effect of feedstock concentration on glycerol APR

Fig. 3 e Hydrogen (circles) and alkanes (squares) performance at 220 C, 25 bar and 0.1 ml/min over 0.6 wt-%
selectivities from aqueous-phase reforming of 1 wt-% Pt-catalyst [22].
oxygenated hydrocarbons over 3 wt-% Pt/Al2O3 at 225 C
(open symbols and dashed curves) and 265 C (filled
symbols and solid curves) [10]. Temperature and pressure
Thermodynamically, aqueous-phase reforming of oxygenated
compounds is favoured at low temperatures between 200 and
250 C. The side reactions introduced in Section Aqueous-
phase reforming are also promoted within this range of tem-
peratures. Moreover, the pressure in the system has to be
above the bubble point of the feedstock, typically 20e50 bar, to
maintain liquid state.
The effect of temperature and pressure on aqueous-phase
reforming, and on the extent of reactions such as WGS,
methanation and carbon formation was theoretically evalu-
ated in a thermodynamic study. Methanol, acetic acid and
ethylene glycol were used as model compounds. Hydrogen
selectivity was considerably low when methanation and solid
carbon formation were considered in the simulations. In
contrast, methane selectivity achieved close to stoichiometric
values [68]. Carbon formation and subsequent catalyst deac-
Fig. 4 e Performance of aqueous-phase reforming of
tivation are usually limited at low temperatures. However,
polyols over 7 wt-% Pt/CMK-9 catalyst at 250 C and 45 bar.
carbon deposition has been reported [5] at mild temperature
Edited from Ref. [62].
and above 39 bar [69]. Deactivation by other mechanisms such
distribution was also observed by variations in the feedstock as leaching and sintering may also occur due to hydrothermal
concentration [67]. This effect can be attributed to the reaction conditions and/or acid medium [70], and high pressure [71].
order variation of reforming and parallel reactions with Experimentally, total conversion and conversion to gases
different feedstock concentrations [10,57]. increased at high temperatures and pressures [72e74]. The
carbon concentration in the liquid products decreased at

higher temperatures [75] due to the promotion of CeC and
CeO bond cleavage [41]. Additionally, hydrogen yield is fav-
oured at high temperature and low pressure [72,76]. The for-
mation of methane and other alkanes showed opposite
tendency [73,77]. Figs. 6 and 7 illustrate the effect of temper-
ature and pressure on the APR performance.
The partial pressure of hydrogen was considered to eval-
uate the performance of APR. Hydrogen production decreased
with higher partial pressure of hydrogen. This effect was
attributed to a reduction of the reforming reaction order due
to lower availability of catalytic active sites. As a result, in-
termediate species derived from dehydrogenation reactions
may undergo dehydration and hydrogenation at the expense
of hydrogen, instead of further reforming to produce
hydrogen [13,57]. The production of hydrogen might addi-
tionally decrease by the equilibrium-shift of the WGS reaction
[10]. Therefore, some research groups have utilized hydrogen
Fig. 7 e Effect of pressure on the production rate of H2 (a),
co-feeing to promote the hydrogenation of oxygenated hy-
CO2 (b), and CH4 (c) for the APR of 5 wt-% ethylene glycol at
drocarbons to produce alkanes [79].
225 C over Ni20SnAl7 catalysts [76].
Fig. 8 shows the effect of pressure on the performance of
steam reforming and aqueous-phase reforming at constant
temperature. In terms of conversion rate, the performance of
APR was poorer. Nevertheless, the hydrogen and carbon dioxide
selectivity were higher at the aqueous-phase conditions. Ulti- and the flow regime of the liquid reactants and gaseous
mately, the APR performance improved at higher temperature products has therefore an important effect on the process
and lower pressure. The authors suggested higher desorption performance. Consequently, the residence time of different
rate of gaseous products at lower pressure which may increase types of reactor, such as batch, semi-batch, and continuously
the availability of active metals on the catalyst surface, and fed, significantly affects the process results.
consequently the activation energies decreased [77]. Focusing on continuously fed reactors, weight (WHSV) and
liquid (LHSV) hourly space velocity typically applied in
Residence time aqueous-phase reforming ranges from 1 to 10 h1. Longer
Multiphase reactions such as APR commonly suffer from residence time resulted in higher total conversion [70,80,81],
mass transfer limitations. The contact time with the catalyst and carbon conversion to liquids. In contrast, shorter resi-
dence time improved the carbon conversion to gases and
hydrogen selectivity [16,82]. Fig. 9 shows the performance of
xylitol and sorbitol APR with different values of space velocity.
Additives
Acidifying the reaction medium facilitates dehydration re-
actions. Subsequently, hydrogenation and alkane formation
may occur increasing the alkane selectivity (Fig. 10) [10].
Addition of acids including HCl or solid acids such as
SiO2eAl2O3 supported catalysts have been therefore consid-
ered to increase alkane production [40].
The APR performance can be enhanced reducing the pH of
the reaction medium, for instance by adding CaO powders.
More basic medium increased the glycerol conversion by
promoting the CeC bond scissions, and improved the hydro-
thermal stability of the catalyst [84]. Additives such as KOH
also enhanced the stability of the catalyst by minimizing the
particle growth [85]. Furthermore, the hydrogen yield was
increased in the presence of KOH and NaOH (Fig. 11) [86,87].
Effect of nitrogen co-feeding

The mass transfer resistance existing at the gaseliquid
interface, as well as the inter- and intra-particle resistance are
Fig. 6 e The effect of temperature and pressure on the the main barriers to improve hydrogen selectivity in APR.
performance of 1 wt-% ethylene glycol APR over 3Pt/3CeAl Nitrogen co-feeding was proposed to promote the transfer of
catalyst [78]. hydrogen molecules from the catalyst surface to the gas bulk,
Fig. 8 e Effect of pressure, and SR to APR transition on butanol (BuOH) conversion at 185 and 215 C (left); and effect of
pressure, and SR to APR transition on hydrogen and carbon dioxide selectivity [77].
Fig. 9 e Effect of WHSV on conversion of xylitol (a) and sorbitol (b), and on hydrogen selectivity (left); and effect on hydrogen
yield (upper right) and alkane selectivity (lower right) of 10 wt-% polyols APR at 225 C and 29.3 bar. Adapted from Ref. [83].
Fig. 10 e Carbon selectivities for aqueous-phase reforming of 5 wt-% sorbitol at 538 K and 57.6 bar. A) Addition of mineral
acid (HCl) in feed over 3 wt-% Pt/Al2O3 [pHfeed ¼ 7 (white), pHfeed ¼ 3 (grey), and pHfeed ¼ 2 (black)] and B) addition of solid acid
(SiO2eAl2O3) to 3 wt-% Pt/Al2O3 (white), mixture 2: Pt/Al2O3 (3.30 g) and SiO2eAl2O3 (0.83 g) (grey), and mixture 1: Pt/Al2O3
(1.45 g) and SiO2eAl2O3 (1.11 g) (black) [13].
Fig. 11 e Effect of modifiers on the APR of 5 wt-% ethylene

glycol over Ni catalysts at 225 C, 25.8 bar, and
Fig. 12 e Effect of hydrogen stripping with nitrogen on the
WHSV ¼ 0.36 h¡1 [87].
ethylene glycol conversion and hydrogen selectivity of APR
at 220 C and 35 bar [82].
reducing the participation of hydrogen in secondary reactions.

Fig. 12 shows the improvement achieved on the conversion
catalyst has been selected by many authors due to high carbon
and selectivity of aqueous ethylene glycol reforming by ni-
conversions and selectivity towards hydrogen, and low pro-
trogen co-feeding [82].
duction of alkanes [5,10,12,57]. Moreover, the activity of
platinum-based catalysts can be improved to promote dehy-
Catalysts drogenation of oxygenated compounds, for instance, by
increasing the availability of metal active-sites. An inexpen-
Hydrogen formation sive alternative to platinum are nickel-based catalysts. These
To produce hydrogen, aqueous-phase reforming of oxygen- catalysts have proven to favour the CeC bond cleavages and
ated hydrocarbons requires catalysts that promote CeC bond the WGS reaction. Therefore, more research has been focus on
cleavage and wateregas shift (WGS) reaction. In addition, the nickel-based catalyst in the recent years to improve the ac-
cleavage of CeO bonds and hydrogenation of CO and CO2 tivity and durability of this type of catalysts [88].
should be minimized. Platinum, nickel, ruthenium, and in Davda et al. [10] conducted a comparative study of the
general metals from Group VIII exhibit high activity for CeC activities and selectivity of metals such as Ni, Pd, Pt, Ru, Rh
bond scission. Conversion of CO and water to H2 and CO2 by and Ir in reforming reactions (Fig. 13). The catalytic activity of
WGS is favoured by metals including copper, cobalt and the metals decreased in the following order:
ruthenium [10]. Nevertheless, the catalyst most commonly Pt ~ Ni > Ru > Rh ~ Pd > Ir. Platinum catalysts exhibit the
used for APR is platinum supported on g-alumina. This highest catalytic activity in APR reaction, comparable to the
observed over Pt supported on CeO2eAl2O3. Pt supported on a-

Al2O3 modified with both CeO2 and ZrO2 was also tested [72].
The redox properties of the support favoured the WGS reac-
tion increasing the H2 yield. Pt/Al2O3eCeO2eZrO2 showed
higher APR activity, and higher hydrogen selectivity and yield
than Pt supported on silica or a-alumina. In contrast, this
catalyst deactivated by fast sintering [72]. A different type of
mixed oxide such as FeeCr enhanced the dispersion of Pt
particles which resulted in higher catalytic activity and
hydrogen production [94].
Platinum supported on carbon (Pt/C) was tested in APR of
cellulose, glucose, sorbitol and lignocellulosic biomass [19,95].
Hydrogen yield was significantly lower over Pt/C than Pt/g-
Al2O3. Additionally, slight deactivation was observed with the
carbon support. The stability of carbonaceous materials in the
hydrothermal conditions of APR has promoted the use of
Fig. 13 e Selectivity of alkanes and hydrogen, and carbon
activated carbon, and other carbon-based structures.
dioxide turn over frequency of ethylene glycol aqueous-
Different types of ordered mesoporous carbon, namely rod
phase reforming at 210 C and 22 bar [10].
type- CMK-3 and hollow types- CMK-5 and CMK-9, were tested
as Pt supports [58,61,62]. Ordered mesoporous carbon exhibi-
ted high hydrothermal stability, and the ordered structure and
activity of nickel catalysts. Additionally, Pt and Pd catalysts high dispersion of Pt remained undisturbed. Moreover, Pt/
exhibit high selectivity to H2 production. In contrast, Rh, Ru CMK-3 showed twice as high hydrogen production as Pt/C
and Ni supported on silica favoured alkane production [10]. and Pt/g-Al2O3. Nevertheless, Pt/CMK-5 achieved higher H2
yield than Pt/CMK-3 due to the open structure of the support
Platinum based catalyst. Platinum catalysts have been tested and higher dispersion of Pt in Pt/CMK-5 [62].
using different supports (Table 3). Basic supports lead to In order to improve the catalytic properties, combinations
higher catalytic activity and higher H2 yield. On the other of platinum with other metals have been tested (Table 4).
hand, alkane formation was favoured by acidic or neutral Dumesic et al. discussed in detail the utilization of bimetallic
supports [55]. Wateregas shift reaction plays a key role in the catalyst applied in the upgrading process of lignocellulosic
production of hydrogen. Therefore, catalysts with basic sites biomass by APR, hydrogenolysis, hydrogenation or oxidation,
that promote the WGS reaction are considered to improve APR to high-value products [96]. Huber et al. compared the cata-
activity and selectivity. Accordingly, APR over Pt supported on lytic activity of bimetallic catalysts including PtePd, PteNi,
solid basic oxides achieve superior performance [89]. PteCo, PteFe and PdeFe in APR. Bimetallic catalysts generally
Most of publications in aqueous-phase reforming focus on showed higher activity than the monometallic version. The
Pt supported on g-Al2O3 [22,41,56,57,90e92]. The performance activity of Pt-based catalysts was more significantly enhanced
of Pt supported on g-alumina was described by Shabaker et al., by addition of Ni, Co or Fe. In the same study, the activity of
in 2003. Pt/g-Al2O3 showed nearly 100% selectivity to hydrogen Pd-based catalysts was also favoured by addition of Fe, which
formation in aqueous-phase reforming of ethylene glycol and worked as a WGS promoter [97]. Furthermore, Pt based cata-
methanol [57]. This catalyst shows high initial APR activity. lysts were promoted with metals such as Mn, Re, Cs, Ba, Ga, Ag
However, undesired transformation of g-alumina into and Mo. An increase in carbon to gas conversion was observed
boehmite (AlO(OH)) accompanied by sintering of the sup- especially with the PteRe catalyst. On the other hand, the
ported metal particles, and carbonaceous deposits on the strong interaction between Pt and Mn formed PteMn alloys.
catalyst surface result in catalyst deactivation. Moreover, the The addition of Mn considerably enhanced H2 yield in com-
hydrated boehmite phase increases the surface acidity of the parison with monometallic Pt catalyst and other bimetallic
catalyst which increases the formation of undesired products. combinations [98].
This reduces the potential industrial application of Pt/g-Al2O3 The addition of Fe, Co and Ni to Pt supported on g-Al2O3
catalyst [93]. On the other hand, APR over Pt supported on was tested in APR reactions [99]. The highest catalytic activity
boehmite has showed stable, higher activity than Pt/g-Al2O3 in was achieved over PteNi/g-Al2O3. Various characterization
some studies. Consequently, boehmite can be chosen as an techniques confirmed high Pt and Ni dispersions, and the
efficient support of Pt with high activity for H2 formation due promoting effect between both elements. Ni-containing cat-
to the extensively hydroxylated surface of boehmite and alysts exhibited higher conversion in comparison to mono-
effective oxidation of platinum [33,60]. metallic Pt/g-Al2O3. However, nickel-alumina suffered
Cerium and alumina mixed oxides (CeO2eAl2O3) were considerable initial deactivation during the stabilization
tested as potential supports for reforming of glycerol [78]. period until the steady state was reached [99]. Moreover,
Doping the alumina support with CeO2 significantly improved combination of Pt and Ni supported on alumina doped with
APR activity because of higher metal dispersion and active ceria-doped (CeO2eAl2O3) allowed the reduction of Pt content
metal surface area. Furthermore, no production of CO was from 3 to 1 wt-%, and resulted in a slight increase of the
Table 3 e Supported platinum catalysts for hydrogen production.

Support Type of support Metal loading (wt.%) Preparation Feedstock Feedstock T ( C) Pressure (bar) Reactor Ref.
method concentration (wt.%) type
Al2O3 Catapal B g-Al2O3 0.16 Incipient wetness Methanol 1 210 22.4 Fixed-bed [57]
(Grace) 0.59 impregnation Ethylene glycol 10 225 22.9 flow system
3.43
g-Al2O3 0.3 Incipient wetness Glycerol 5 180 11.4 Fixed-bed [22]
0.6 impregnation 10 200 17.1 flow system
0.9 220 25
1.2
Commercial catalyst 5 Commercial catalyst Sorbitol 10 210 Autogenous Fixed-bed [41]
(Degussa, F 214 XSP) 20 217 (4 bar above flow system
30 221 critical pressure)
225
Catapal B g-Al2O3 3 Incipient wetness Ethylene glycol 5 210 1 Fixed-bed [90]
(Grace) impregnation 63 flow system
100
Commercial catalyst 5 Commercial catalyst Glycerol 1 200 16 Autoclave [56]
(Precious Metals 10 220 23.5
Corporation PMC) 240 33.5
g-Al2O3 1.5 Incipient wetness Ethylene glycol 5 270 90 Fixed-bed [60]
Boehmite (AlO(OH)) impregnation flow system
Mixed oxides Hematite (a-Fe2O3) 0.5 FeeCr mixed oxides- Ethylene glycol 10 225 29.5 Fixed-bed [94]
FeeCr mixed oxides solid thermal flow system
decomposition
reaction using citric
acid
Pt cat. by incipient
wetness
impregnation
Al2O3 Pt (1 or 3 wt.%) Incipient wetness Glycerol 1e5 240 40 Fixed-bed [78]
CeO2/Al2O3 Ce (1, 3, 6 and 9 wt.%) impregnation flow system
SiO2 Pt (1 and 2 wt.%) Ion exchange Glycerol 10 200 16 Autoclave [72]
a-Al2O3 Pt/Ce4Zr1a (1 wt.% Pt, 1 wt.% Incipient wetness 225 24
CeO2eZrO2/a-Al2O3 ZrO2, 4 wt.% CeO2) impregnation 250 44
(Ce4Zr1a)
Carbon Activated carbon 5 Commercial (Sigma Glucose 150 Autogenous Autoclave [95]
Aldrich) Kenaf hydrolysates 250
Kenaf (herbaceous plant)
biomass ¼ lignocellulosic
biomass
Nano- and micro- 7 Incipient wetness Ethylene glycol 10 250 45 Fixed-bed [61]
sized ordered impregnation Glycerol flow system
mesoporous carbon
(OMC)
CMK-3 and CMK-5
Ordered mesoporous 1e10 Incipient wetness Ethylene glycol 10 250 45 Fixed-bed [58]
carbon (CMK-3) impregnation flow system
11
12
Table 4 e Supported bimetallic platinum catalysts for hydrogen production.

Metal combination Support Metal loading (wt.%) Preparation Feedstock Feedstock T Pressure Reactor type Ref.
method concentration ( C) (bar)
(wt.%)
PteM (M ¼ Pd, Ni, Co, Fe) Al2O3 (Catapal B-g- Pt (3 wt.%) Incipient wetness Ethylene glycol 10 210 25.4 Fixed-bed flow [97]
PdeFe Al2O3, Grace) Pt: M ¼ (1:1e1:9) impregnation 225 29.3 system
Fe2O3 (Nanocat)
Silica (Cab-O-Sil
fumed silica)
Pt Ordered mesoporous Pt (1 wt.%) Incipient wetness Ethylene glycol 10 250 45 Fixed-bed flow [98]
PteM (Pt:M ¼ 1:0.5e1:3)
M carbon (CMK-3) impregnation system
PteM (M ¼ Mn, Re, Fe, Activated carbon
Cs, Ba, Ga, Ag, Mo) g-Al2O3
Pt g-Al2O3 Pt (3 wt.%) Solegel Glycerol 10 230 30 Fixed-bed flow [99]
Ni Ni, Co, Fe (10 wt.%) 250 50 system
PteFe
PteCo
PteNi
Pt CeO2eAl2O3 Ce (3 wt.%) CeO2eAl2O3- Glycerol 1 240 40 Fixed-bed flow [53]
Ni Pt (1 or 3 wt.%) prepared by system
PteNi Ni (3, 6, 12 and 18 wt.%) impregnation of g-
Al2O3
Sequential or
simultaneous
incipient wetness
impregnation
Pt Activated carbon 5 wt.% Incipient wetness Glycerol 30 230 30 Fixed-bed flow [101]
PteMo Pt:Mo ¼ 1:1 impregnation system
Pt Multiwalled carbon Monometallic: Monometallic: Glycerol 30 230 32 Fixed-bed flow [100]
PteMo nanotubes Pt (5 wt.%) Incipient wetness system
PteCo (MWCNTs) Co (5 wt.%) impregnation
Bimetallic: Bimetallic:
Pt (5 wt.%) Sequential incipient
Pt:Co or Pt:Mo ¼ 1:1 or Co wetness
(1.6 wt.%) impregnation
Mo (2.6 wt.%)
Pt Multiwalled carbon Monometallic: Monometallic: Glycerol 30 230 32 Fixed-bed flow [103]
PteCo nanotubes Pt (5 wt.%) Incipient wetness system
(MWCNTs) Co (5 wt.%) impregnation
Bimetallic: Bimetallic:
Pt (5 wt.%) Sequential incipient
Co (0.8, 1.6 or 7.8 wt.%) wetness
Pt:Co ¼ 1:0.5, 1:1, 1:5 impregnation
Pt Multiwalled carbon Pt (5 wt.%) 10 230 32 [84]
PteNi nanotubes (MWCNT) Pt:M ¼ 1:1 atomic ratio:
Ni (1.5 wt.%)
Co (1.5 wt.%)
Cu (1.6 wt.%)
Pd (2.7 wt.%)
Ru (2.6 wt.%)
Pt:Ni ¼ 2:1 and 1:2 atomic
ratio:
Ni (0.75 and 3 wt.%)
Pt Single walled carbon Pt (8 wt.%) Incipient wetness Ethylene glycol 10 225 26 Fixed-bed flow [102]
PteCo nanotubes (SWNT) Pt:Co ¼ 0.3 impregnation system
Pt AlOOH layer 2 Washcoating Sorbitol 1 220e240 35e40 Washcoated [82]
Ru (microchannels) 1.6 AlOOH layer was microchannel
PteRu deposited on the reactor
inner walls
Active metals were
immobilized on
AlOOH by
impregnation
Pt Activated carbon Pt (3 wt.%) Incipient wetness Glycerol 10 225 29 Single-channel [86]
PteRe Re (1 and 3 wt.%) impregnation microreactor
Pt Activated carbon Pt (3 wt.%) Incipient wetness Glycerol 10 225 29 Single-channel [105]
PteRe Re (1e4.5 wt.%) impregnation microreactor
Re (3 wt.%)
Pt g-Al2O3 Pt (4 and 5 wt.%) Pt/TiO2-incipient Xylitol 10 225 29.3 Fixed-bed flow [106]
PteRe TiO2 PteRe (4e4 wt.%) wetness system
impregnation
PteRe/TiO2-
sequential incipient
wetness
impregnation
Pt/Al2O3-Sigma
eAldrich
Pt Activated carbon Rh:Re ¼ Pt:Re ¼ 2 Monometallic: Glycerol 10 225 25 Autoclave [107]
PteRe Incipient wetness
Re impregnation
Rh Bimetallic:
RheRe Sequential incipient
wetness
impregnation
13
hydrogen production. In addition, no substantial catalyst hydrogen production (Table 5). Supported nickel catalysts
deactivation was observed [53]. generally show high conversion and H2 selectivity, and low
Higher glycerol conversion and H2 formation rates were methane selectivity [32]. However, metallic nickel frequently
achieved over carbon modified by PteCo and PteMo than with oxidizes under hydrothermal conditions which results in
monometallic platinum catalysts. The hydrogen selectivity catalyst deactivation. Additionally, leaching of the active
remained constant for PteCo and Pt catalysts while decreased metal and sintering of the metal particles are common causes
for PteMo [100]. Nevertheless, PteMo/C showed higher turn- of deactivation in nickel-catalysed APR [38].
over rate than Pt/C with comparable APR conversion. On the Among the monometallic Ni-based catalysts, the hexago-
other hand, the addition of Mo lowered the binding energy of nal closed-packed Ni nanoparticles (hcpNi) supported on g-
PteCO. This reduced the activation energies of dehydrogena- Al2O3 was stable in aqueous-phase reforming up to 227 C and
tion and cleavage of CeO bonds. As a result, lower H2 yields 100 bar [108]. Ni/LaAlO3 (perovskite-type catalyst) also
were obtained [101]. exhibited high reforming performance, and stability and
Multiwalled carbon nanotubes (MWCNTs) were modified resistance against coking [109].
by Pt in combination with Ni and other metals, including Co, Utilization of Ni based catalysts was compared with Pt
Cu, Pd and Ru. Carbon conversion to gas was superior over modified materials by Shabaker et al. [16]. Alumina supported
PteNi catalyst. The addition of Ni improved dehydrogenation- catalysts, such as Pt/Al2O3, Ni/Al2O3 and NieSn/Al2O3, and
decarboxylation and dehydrationehydrogenation reactions Raney-nickel (RaeNi) catalysts, including Raney-Ni and Ra-Ni-
which increased the conversion. Furthermore, the catalytic Sn, were tested in hydrogen production by APR of oxygenated
performance was recovered after catalyst regeneration [84]. hydrocarbons. The addition of Sn to Ni improved the selec-
PteCo supported on multiwalled carbon nanotubes and sin- tivity to H2, and decreased the formation of methane and total
glewalled carbon nanotubes (SWNTs) showed higher activity selectivity to alkanes [23]. Superior catalytic performance was
and similar hydrogen selectivity in aqueous-phase reforming also exhibited by Sn-Ra-Ni than by pure Raney-Ni [29]. More-
compared to the monometallic system. Co appears to promote over, Pt/Al2O3, Raney-Ni and Ra-Ni-Sn showed significant
the Pt functionality by increasing the rate of the WGS reaction stability. In contrast, Ni/Al2O3 and NieSn/Al2O3 deactivated by
on the catalyst surface, or by decreasing the energy of CO sintering [16] and leaching of the active metal, or Ni(CO4)
binding on the PteCo surfaces [102,103]. Other bimetallic and formation [59]. Modification of Raney-nickel catalysts with
trimetallic combinations of Pt with Ru, Ni and Sn were sup- other metals such as Ce was also successful. Ce effectively
ported on MWCNTs, and on activated carbon (AC). These poisoned the active sites that promote methanation. There-
catalysts were evaluated in APR of lignocellulosic biomass fore, the hydrogen selectivity was considerably enhanced, and
hydrolysate or glucose. The addition of Ru to Pt/MWCNT the H2 yield achieved comparable values to the yield obtained
significantly increased the catalytic activity. PteRu/MWCNT, with Pt/AC [110].
as well as PteRu/AC and PteNi/AC exhibited superior perfor- The addition of Cu to Ni supported on hydrotalcite-like
mance in aqueous-phase reforming [104]. compounds reduced the methane formation in APR of glyc-
Modification of platinum-based catalysts by rhenium has erol. However, formation of acetol increased due to higher
been the focus of many publications [86,105e107]. The prep- acidity of the catalyst [111]. NieSn and NieZn catalysts sup-
aration methods and performance of PteRe catalysts supported on hydrotalcite-like compounds were also applied in
ported on activated carbon were compared with APR of ethylene glycol [37,76]. Ni/Sn/Al-HT and Ni/Zn/Al-HT
monometallic platinum catalyst [86]. Pt/C showed consider- showed high H2 production rate and selectivity, as well as
able selective to hydrogen production in APR, whereas the constant catalytic stability. Ni/Sn/Al-HT exhibited superior
activity was poor. The addition of Re significantly increased catalytic performance related to the formation of Ni3Sn alloy
the conversion. However, hydrothermal conditions and the via reduction of Ni/Sn/Al-HT [76].
oxidation of Re increased the acidity on the surface of the
catalyst. The acidity favoured the cleavage of CeO bonds, light Other catalysts. Catalytic aqueous-phase reforming over other
hydrocarbons and water-soluble oxygenates were formed and metallic catalysts such as Pd, Co, Ru, Re and Rh has been less
the H2 selectivity decreased [105,106]. The activity of bime- frequently applied (Table 6). The performance of Pd supported
tallic PteRe and RheRe catalysts supported on activated car- on oxides, including Fe3O4, Fe2O3, NiO, Cr2O3, Al2O3 and ZrO2,
bon were compared in APR of glycerol. The addition of Re has been evaluated. Palladium on magnetite (Pd/Fe3O4) ach-
increased the conversion of glycerol. Nonetheless, the highest ieved superior results in terms of activity and stability. The
activity in APR and WGS reactions was achieved using RheRe/ high catalytic performance was attributed to the synergistic
C. Re and Rh, and Re and Pt showed strong synergies in WGS effect between Pd nanoparticles and the magnetite which
that resulted in superior WGS activity due to a stronger promoted the WGS reaction [39]. Bimetallic PdeZn catalysts
binding of hydroxyl groups to Re. This metal also facilitated supported on carbon were tested in APR of ethanol with high
water dissociation which increased the WGS activity, and hydrothermal stability. This catalyst favoured the production
consequently decreased the CO coverage. Furthermore, glyc- of CO-free hydrogen. Additionally, the formation of interme-
erol conversion and H2 yield were improved by promoting the tallic PdZnb resulted in higher hydrogen yield and decreased
cleavage of CeC bonds [107]. the yield of methane [112]. Co and CoeZnO supported on
carbon were also applied in APR. Addition of ZnO inhibited the
Nickel based catalyst. Nickel-based catalysts are a highlighted reduction of cobalt oxides by H2 and created surface sites for
group of catalysts applied in aqueous-phase reforming for H2O activation. However, Co/C and CoeZnO/C rapidly
Table 5 e Supported nickel catalysts for hydrogen production.

Metal Support Metal loading Preparation Feedstock Feedstock T ( C) P (bar) Reactor type Ref.
(wt.%) method concentration (wt.%)
Pt Al2O3 Pt/Al2O3 (3 wt.% Pt) Incipient wetness Sorbitol 5 225 25.8 Fixed-bed flow [16]
Ni Raney-Ni Ni/Al2O3 (14.8 wt.% impregnation Glycerol 265 51.3 system
NieSn Ni) Ethylene glycol
NiSn/Al2O3
(14.8 wt.% Ni, 3 wt.%
Sn)
Ra-NiSn (0.7
e31 wt.% Sn)
Hexagonally g-Al2O3 e hcpNi- in triethylene Glycerol 1 225 27.6 Fixed-bed flow [108]
packed Ni glycol with high system
(hcpNi) ionic Ni
concentration under
the presence of
protective agent
Ni LaAlO3 15 Deposition- Glycerol 15 250 20 Fixed-bed flow [109]
CeO2 precipitation system
MgO
MgAl
Pt Raney Ni (ReNi, Sn (0e31) Incipient wetness Ethylene glycol 1e10 225 25.8 Fixed-bed flow [23]
NieSn Grace Davison) impregnation 265 51.3 system
Al2O3 (Catapal B-
g-Al2O3, Grace)
NieSn Raney Ni (ReNi, Sn (9.4 wt.%) Reduction of Raney Ethylene glycol 5e63 225 Autogenous Fixed-bed flow [59]
Grace Davison) Ni (15, 14 and 4 wt.%) Ni and addition of Sn system
solution
Ni Raney-Ni Pd (5 wt.%) Incipient wetness Model compounds (phenol, e 225e270 25e56 Fixed-bed flow [29]
SneNi Activated carbon impregnation THF, aniline, toluene, system and batch
Pd nitrobenzene,
cyclohexanol, DMF)
NieCe Ce-modified Ce:Ni molar Incipient wetness Cellulose (filter paper) e 260 Autogenous Autoclave [110]
Raney-nickel ratio ¼ 0.005, 0.024, impregnation
0.048, 0.054 and 0.099
NieCu Hydrotalcite-like 20 wt.% of NiO Hydrotalcite-like Glycerol 10 vol% 250 35 Fixed-bed flow [52]
compounds 0, 5 or 10% of CuO compounds 270 50 system
prepared by co-
precipitation
method
NieSn Hydrotalcite-like (Ni þ Sn):Al ¼ 3 Hydrotalcite-like Ethylene glycol 5 210e240 26e30 Fixed-bed flow [76]
compounds Ni:Sn ¼ 2, 4, 8, 12, 16, compounds system
20, 24 and 48 prepared by co-
precipitation
method
15
16
Table 6 e Other catalysts for hydrogen production.
Metal Support Metal loading (wt.%) Preparation method Feedstock Feedstock T ( C) Pressure (bar) Reactor Ref.
concentration (wt.%) type
Pd Fe3O4 4.7 Co-precipitation Ethylene glycol 5 225 25.8 Fixed-bed [39]
Fe2O3 Incipient wetness flow system
NiO impregnation
Cr2O3
Al2O3
ZrO2
PdeZn Carbon black (CB) Monometallic: Incipient wetness Ethanol 10 200e260 55e65 Fixed-bed [112]
Carbon nanotubes (CNTs) Pd (5 wt.%) impregnation flow system
Bimetallic:
Pd (5 wt.%)
Zn (3.1 and 5 wt.%)
Co Carbon (carbon black, XC- 10 wt.% of Co Incipient wetness Methanol 10 250 55 Autoclave [113]
CoeZn 72R) 5 wt.% of ZnO impregnation Ethanol
Ru TiO2 0.5 Incipient wetness Ethanol 10 vol% 200 25e30 Autoclave [42]
1 impregnation Acetic acid
2
5
Ru Carbon nanotubes (CNT) 11.1 Adsorption Acetic acid 1 Subcritical water Fixed-bed [114]
5 340 225 flow system
15 400 250
25
Rh TiO2 Monometallic: Incipient wetness Ethanol 10 200 20 Autoclave [65]
Ir Rh (5 wt.%) impregnation
ReeRh Ir (5 wt.%)
ReeIr Re/Rh or Re/Ir ¼ 0.1e2
oxidized under APR conditions [113]. Utilization of Ru sup-
[116]
[119]
[118]
[117]
Ref.
[30]
ported on TiO2 promoted the undesired methanation of CO2
over larger catalyst particles. Nevertheless, methanation was
completely suppressed over catalysts with 0.5 wt-% Ru and
Reactor type
particle size of 1 nm [42]. Furthermore, Ru supported on car-
Autoclave
Autoclave
Autoclave
Autoclave
bon nanotubes (CNTs) showed high resistance to deactivation
commonly caused by acetic acid reforming in supercritical
water [114]. Re has been tested in combination with metals,
such as Rh and Ir. The addition of Re to Rh/TiO2 and Ir/TiO2
catalysts increased the initial formation rates of H2, CH4 and
Pressure (bar)
Autogenous
CO2, and improved the ethanol conversion. However, Re also
accelerates the hydration of acetaldehyde which resulted in
40e65
20e40
acetic acid formation and suppresses the decomposition of
45
40
acetaldehyde to form CH4 and CO. In the same study, Rh and
Ru promoted the decomposition of acetaldehyde and subse-
225e250
240e265
180e250
T ( C)
quent WGS reaction [65]. RheRe combination exhibited high
270
240
activity in APR and WGS reactions also on carbon supports.
This catalyst demonstrated a strong synergy between Re and
concentration (wt.%)
Rh in the WGS reaction [107].
Feedstock
3.1 mol%
Alkanes and carbohydrates formation
8e12
Alkane formation occurs in aqueous-phase reforming by
10
6
methanation and FT reactions in the gas phase, and by
dehydration and hydrogenation in the liquid phase. The
extent of these reactions can be adjusted by appropriate
1,2-propanediol
1,2-propanediol
catalyst selection. As previously mentioned, the acidity of the
Product
catalytic system is crucial for the formation of alkanes. For

instance, higher acidity of the catalysts promoted the selec-
Propane
Pentane
Pentane
tivity of alkanes by dehydration reactions [115].
Various zeolites such as H-ZSM5, H-Mordenite, USY and
Beta, were tested as suitable supports for Pt to produce al-
Feedstock
Glycerol
Glycerol
Glycerol
kanes in APR [116] (Table 7). Zeolites favour dehydration re-
Xylitol
Xylitol
actions on the surface acid sites. Therefore, higher selectivity
to alkanes can be obtained at the expense of H2 formation. Pt/
H-ZSM5 is an active catalyst to produce propane by APR of
Incipient wetness
Incipient wetness
Incipient wetness
Incipient wetness
Incipient wetness
glycerol [116], and pentane by APR of xylitol [117]. Zeolites
Preparation
method
HZSM-5 and MCM-22 were also modified by Ni and applied in

impregnation
impregnation
impregnation
impregnation
impregnation
APR of xylitol to produce pentane. MCM-22 was characterized
Table 7 e Catalysts for alkane and carbohydrates production.
by larger surface area, higher pore diameters and less strong

acid sites. The catalytic activities of both catalysts increased
with higher Ni loading within the range of 0e2 wt.%. Ni/HZSM-
Metal loading (wt.%)
5 significantly deactivated because of partial dealumination

and coke formation. In contrast, Ni/MCM-22 remained stable
under APR conditions [30].
1e5
1e4
0e4
Hydrotalcites (HT) were tested to support platinum in the

5
aqueous-phase hydrogenolysis of glycerol (Table 7). This basic

catalyst showed high activity to produce 1,2-propanediol. In
addition, no catalyst deactivation caused by leaching of plat-
inum was observed after several runs [118,119].
(Al2O3:MgO ¼ 80:20e60:40)
Reactor types
(Al2O3:MgO ¼ 80:20)
Support
Hydrotalcite (HT)
Pt/Al2O3 þ MgO
Three-phase systems such as aqueous-phase reforming may

H-Mordenite
Hydrotalcite
present mass transfer limitations that should be considered in

the reactor design. For instance, the hydrogen production in
MCM-22
H-ZSM5
H-ZSM5
HZSM-5
g-Al2O3
Al2O3
APR is limited by diffusion of the gas molecules from the

CeO2
ZrO2
MgO
Beta
SiO2
SiO2
USY
catalyst surface, and through the liquid phase. Reactor design

and catalyst selection are the main tools to enhance the
Metal
availability of active sites and promote the selectivity towards

Ni
Ni
Pt
Pt
Pt
Pt
target products. Slurry reactors (bubble columns and stirred
tanks), packed bed, and fluidized bed are different reactor applied in laboratory scale for APR. In this study, a packed-bed
types commonly applied in three-phase systems [120]. tubular reactor was also tested for comparison. APR reached
Laboratory scale tubular packed-bed and autoclave re- similar conversions in both reaction systems. Nevertheless,
actors represent the main reactor types applied in aqueous- the selectivity towards hydrogen was higher in the micro-
phase reforming. In laboratory scale, stirred tanks constitute channel reactor. This type of reactor facilitated efficient
a suitable reactor type that reaches high mass transfer rates transport of hydrogen from the catalyst surface to the gas bulk
with vigorous stirring and small catalyst particles. However, through a thin catalyst layer. Consequently, the participation
the stability and deactivation behaviour of the catalyst are of hydrogen in side reactions was minimized, and the pro-
difficult to evaluate in experiments conducted in batch mode. duction of alkanes and other side products decreased. How-
Moreover, these reactors are unsuitable for larger scales with ever, this developing technology presents barriers regarding
operation in diluted conditions as in APR. On the other hand, catalyst loading and scaling up [70]. A single channel micro-
packed-bed reactors present significant mass transfer de- reactor was also tested in APR. This reactor configuration
ficiencies that decrease the product efficiency of the process. achieved high heat transfer rates which allowed close to
Nevertheless, the external mass transfer improves in indus- isothermal conditions in APR of glycerol [86]. Membrane re-
trial scale where linear flow velocities are higher. Packed-bed actors can be additionally applied to intensify the selectivity of
has been therefore selected as a suitable APR reactor by most APR. The membrane introduces selective permeability and
of the research groups. Fig. 14 shows an example of the pro- equilibrium adjustability features that enhance the product
cess flow diagram typically applied for aqueous-phase efficiency. An application example of this reactor type con-
reforming in an up-flow, packed-bed reactor. sisted on a coated tubular membrane that facilitated
The difference in residence time of batch and continuously hydrogen permeability. As a result, the supportewater in-
fed reactors affects the process performance. Applying teractions were reduced due to the hydrophobic properties of
different reaction systems frequently hinders result compar- the membrane, increasing the stability of the catalyst, and the
ison. Therefore, the comparison of results obtained with batch hydrogen selectivity was improved [121,122].
and continuously fed reactors, or continuously fed reactors
operated with significantly different flow velocities is
discouraged. Conclusions
Intensified reactors can be applied to overcome operational
challenges typically found in conventional reactors. Reactor The performance of APR is affected by the nature of the
intensification introduce characteristics such as improved feedstock, operation conditions, and catalyst. Considering the
heat and mass transfer, and reduced size. Mass transfer model compounds commonly used as feedstock in laboratory
commonly constitutes a significant barrier in conventional scale studies, H2 selectivity increased in the APR of more
three-phase reactors. This barrier can be overcome applying diluted solutions and more reduced compounds. Regarding
intensified technologies such as microchannel, structured the operation conditions, the conversion of oxygenated hy-
and membrane reactors. Neira et al. [15] introduced a wash- drocarbons was higher at higher temperatures and pressures.
coated microchannel reactor as a novel configuration Conversely, hydrogen yields and conversion of carbon
Equipment List
ID Description
HE-1
DC-1 Reactor
GA-1 FA-1 Feed vessel

DC-1 Cooling Cooling
FA-2 Feed vessel
water water
GA-1 Pump
FA-1 FA-2
HD-1 G-L Separator
Organic
H2O HE-1 Cooler
solution
PC
V-21 Pressure control valve
Scale
HD-1 V-21
Vent
H2 N2
Liquid analyzer Gas analyzer
Fig. 14 e Process flow diagram of aqueous-phase reforming.
monoxide to carbon dioxide were favoured at milder condi-
(continued on next page)

[123]
[124]
[124]
[125]
Ref.
[56]
[89]
[31]
[55]
[33]
[35]
[31]
[78]
[53]
[53]
[31]
[31]
[89]
[89]
tions. Longer residence times improved the feedstock con-
[5]
version and carbon conversion to liquid products, while
Si (%)
5.0
shorter times enhanced hydrogen selectivity. The addition of
15
13
CH4
acidic substances promoted the formation of side products.
Conversely, alkaline medium increased the production of
h1
hydrogen. Furthermore, nitrogen co-feeding improved the
gas mass transfer in the system, which resulted in higher
Si (%)
42.0
87.0
87.0
82.0
62.5
75
66
90
50
60
56
hydrogen selectivity. Alternative initiatives to overcome the
mass transfer limitations of APR aim at intensified technol-
h1
ogies as potential reactor configurations.
A wide range of catalysts has been tested in aqueous-
mmol min1 gCat1

phase reforming of different feedstock. The highest activity
H2
Results
in reforming reactions and highest hydrogen selectivity are
frequently achieved over Pt-based catalysts. However,
572.2
430
94
similar activities can be reached over less expensive, nickel
catalysts. In order to improve the catalytic properties of
platinum and nickel catalysts, the addition of other metals is
commonly applied. The addition of Ni, Co, Fe, Ru, Mn or Re to
CtoG (%)
Pt catalyst promotes the activity, selectivity and hydrother-
6.5
18.9
69.0
i
38
79
46
48
27
mal stability. On the other hand, modification by Ce, Sn and
Cu improves the performance of Ni-based catalyst. More-
over, supports play a key role in APR activity, hydrogen
X (%)
6.4
21.2
71.0
87.0
96.0
14.4
selectivity and stability of the catalysts. The oxides applied in
19
13
26
27
APR frequently undergo deactivation. In contrast, stable ac- i
tivity can be achieved by using carbonaceous supports such
Al2O3eLa2O3
Al2O3eLa2O3
Al2O3eCeO2
Al2O3eCeO2
Al2O3eCeO2
as ordered mesoporous carbon materials (CMK-3, CMK-5 and
Mg(Al)O
i
Su
CMK-9) and carbon nanotubes. However, to obtain a satis-

Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
Al2O3
MgO
TiO2
factory combination of activity, selectivity and stability
Catalyst
under APR conditions remains as a challenging task. The
Cu
i
Ni
Ni
Ni
Ni
P
selection of a stable support material is crucial to prepare

Table A1 e Glycerol aqueous-phase reforming. Operation conditions and results.
catalysts with high hydrothermal stability, and possibility for

reutilization or regeneration.
i
AM
Catalytic aqueous-phase reforming is a highly potential

route to obtain hydrogen and alkanes from the water frac-
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
tions of biorefineries due to the energy efficiency of the
Reactor type
Semi-batch
process. However, significant research effort is still required
Autoclave
to increase the conversion of reactants and promote the

selectivity of desired products. In spite of the increasing
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
FBR
number of publications over the last 10 years, mass transfer
limitations and catalyst deactivation still represent signifi-
P (bar)
27.6
29.3
27.6
27.6
cant barriers to further development of aqueous-phase
29
40
30
32
29
45
40
30
30
40
40
40
40
29
reforming of oxygenated hydrocarbons. To enhance the

production efficiency of APR, reactor and catalyst engineer-
T ( C)
220
225
225
225
225
230
230
225
240
225
230
230
240
240
225
225
225
225
225
ing research activities should be directed towards systems

that maximize mass transfer, and more durable and active
WHSVi (h1)
catalysts.
2.6
4.2
2.6
5
2
2
2
5
5
Acknowledgements
wt-%
The authors would like to thank Prof. Dr. Klaus Hellgardt,

10
10
10
10
20
80
10
10
10
10
10
1
1
5
1
1
1
5
5
member of the scientific advisory board of the AQUACAT

project, for his guidance and support. This work was funded
by Academy of Finland (Grant no. 285398).
Feedstock
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Glycerol
Appendix. APR performance
Table A1 e (continued )
Feedstock wt-% WHSVi (h1) T ( C) P (bar) Reactor type Catalyst Results Ref.
20
AMi Pi Sui Xi (%) CtoGi (%) H2 CH4

mmol min1 gCat1 h1 Si (%) h1 Si (%)
Glycerol 5 5 225 27.6 FBR Pt SiO2 20 70 7 [89]
Glycerol 20 4.2 225 29 Pt SiO2 1 6 1.5 [33]
Glycerol 20 4.2 225 29 Pt ASAa 3.2 29 60 [33]
Glycerol 5 5 225 27.6 FBR Pt CeO2 35 61 13 [89]
Glycerol 10 225 25 Autoclave Pt Re CeO2 167b 1.4 [50]
Glycerol 10 225 25 Autoclave Pt Re CeZrO2 345b 3.9 [50]
Glycerol 10 225 25 Autoclave Pt C 117b 9.3 [50]
Glycerol 10 5 225 29 mchannel Pt C 41.5 299g 210 14.4 [86]
Glycerol 10 1.5 225 29 mchannel Pt C 30 [105]
Glycerol 10 6 225 29.3 FBR Pt C 18.5 5.4 15.2 [126]
Glycerol 10 225 25 Autoclave Pt Re C 546b 5 [50]
Glycerol 10 5 225 29 mchannel Pt Re C 89.4 1246g 1506 26.1 [86]
Glycerol 10 15 225 29 mchannel Pt Re C 30 20 [105]
Glycerol 30 230 30 FBR Pt Mo C 26 [101]
Glycerol 10 2 250 45 FBR Pt AC 35.9 24.2d 98.1 [62]
Glycerol 10 2 250 45 FBR Pt 3D-UMCe 59.8 41d 90.3 [62]
Glycerol 10 2 250 45 FBR Pt 3D-BMCf 73.9 54.3d 100.3 [62]
Glycerol 5 230 30 Autoclave Pt Ni MWCNTc 295 [84]
Glycerol 10 2 250 45 FBR Pt CMK-3 55.4 35.6d [61]
Glycerol 10 2 250 45 FBR Pt CMK-5 73.8 44.7d [61]
Glycerol 1 225 27.6 FBR Ni Al2O3 52 64 5 [108]
Glycerol 1 1.25 225 30 FBR Ni Al2O3 25 [32]
Glycerol 10 2.6 230 30 FBR Ni Al2O3 34 [124]
Glycerol 10 230 32 FBR Ni Al2O3 15.8 167.7 [55]
Glycerol 1 1.25 225 30 FBR Ni Al2O3eLa2O3 37 [32]
Glycerol 1 1.25 225 30 FBR Ni Al2O3eMgO 15 [32]
Glycerol 1 1.25 225 30 FBR Ni Al2O3eZrO2 30 [32]
Glycerol 1 1.25 225 30 FBR Ni Al2O3eCeO2 36 [32]
Glycerol 1 240 40 FBR Ni Al2O3eCeO2 26 57.0 [53]
Glycerol 10 250 38 Autoclave Ni HT 34 82 5 [111]
Glycerol 10 5 270 50 FBR Ni HT 67 95 311 37.1 12 [52]
Glycerol 10 250 38 Autoclave Ni Cu HT 29 85 0 [111]
Glycerol 10 5 270 50 FBR Ni Cu HT 80 100 411 42.8 2.1 [52]
Glycerol 10 225 27.6 FBR Ni (AP)h 8.4 158 82 8 [44]
Glycerol 1 225 25.8 Autoclave NiSn-Raney 81 [23]
Glycerol 10 225 27.6 FBR NiSn-Raney 104.1 45 23 [44]
Glycerol 10 230 32 FBR Co Al2O3 21 110.2 [55]
Glycerol 10 230 32 FBR Cu Al2O3 2 409.8 [55]
Glycerol þ ethanol 10 þ 10 225 29.3 Pt Al2O3 59 300 [123]
a
ASA ¼ Amorphous silica-alumina.
b
mol h1mol(Pt)1.
c
MWCNT ¼ Multi-Walled Carbon Nanotubes.
d
cm3 gCat1 min1.
e
3D-UMC ¼ three dimensions unimodal mesoporous carbon.
f
3D-BMC ¼ three dimensions bimodal mesoporous carbon.
g
l lCat1h1.
h
AP ¼ Amorphous alloy.
i
WHSV ¼ weight hourly space velocity, AM ¼ active metal, P ¼ promoter, Su ¼ support, X ¼ conversion, CtoG ¼ conversion of carbon to gas, S ¼ selectivity, FBR ¼ fixed-bed reactor.
Table A2 e Ethylene glycol aqueous-phase reforming. Operation conditions and results.
Feedstock wt-% WHSVk (h1) T ( C) P (bar) Reactor type Catalyst Results Ref.
AMk Pk Suk Xk (%) CtoGk (%) H2 CH4
mmol min1 gCat1 h1 Sk (%) h1 Sk (%)
Ethylene glycol 225 25.8 Autoclave Pt Al2O3 5.2 178.2 0 [23]
Ethylene glycol 1 1.2 275 200 Pt Al2O3 78 [66]
Ethylene glycol 1 225 29 FBR Pt Al2O3 96 [5]
Ethylene glycol 5 225 25.8 Autoclave Pt Al2O3 5.4 449e 318 97.9 0 [23]
Ethylene glycol 5 6 227 33 FBR Pt Al2O3 11.4 97.1 [115]
Ethylene glycol 10 225 29.3 FBR Pt Al2O3 516 [57]
Ethylene glycol 10 225 29.3 FBR Pt Al2O3 1.4 112.2 92.3 0 [97]
Ethylene glycol 10 230 Aa Autoclave Pt Al2O3 13.6 35 19.2f 61.4 [38]
Ethylene glycol 10 2 250 45 FBR Pt Al2O3 38.6 14.3c 55.7 [58]
Ethylene glycol 10 225 29.3 FBR Pt Ni Al2O3 3.9 310.8 88.3 0 [97]
Ethylene glycol 10 225 29.3 FBR Pt Co Al2O3 3.6 288 96.2 0 [97]
Ethylene glycol 5 225 25.8 FBR Pt Fe Al2O3 48.1 379.2 100 1.2 [97]
Ethylene glycol 10 2 250 45 FBR Pt Re Al2O3 43.8 22.4c 77 [73]
Ethylene glycol 10 2 250 45 FBR Pt Mn Al2O3 22.7 19.6c 9756 [98]
Ethylene glycol 220 25 mchannel Pt AlO(OH) 12 93.7 [70]
Ethylene glycol 10 2 250 45 FBR Pt Re SiO2 63.1 25.9c 61.7 [73]
Ethylene glycol 10 2 250 45 FBR Pt CeO2 15.8 11.6c 75.3 [127]
Ethylene glycol 10 2 250 45 FBR Pt CeO2eZrO2 43.3 30c 74.3 [127]
Ethylene glycol 5 210 19.6 FBR Pt Fe2O3 3.9 158.7 0 [97]
Ethylene glycol 10 10.7 225 29.5 FBR Pt Fe2O3 15 0.02 [94]
Ethylene glycol 10 10.7 225 29.5 FBR Pt FeeCr 63 0.06 [94]
Ethylene glycol 10 2 250 45 FBR Pt AC 38.1 18c 70.8 [58]
Ethylene glycol 10 225 22.7 FBR Pt AC 14.3 790 100 [128]
Ethylene glycol 10 2 250 45 FBR Pt Re AC 80 30.4c 57.1 [73]
Ethylene glycol 10 2 250 45 FBR Pt Mn AC 34.2 22.7c 10 404 [98]
Ethylene glycol 10 225 22.7 FBR Pt SWNTg 13.3 1450 93 [128]
Ethylene glycol 10 225 22.7 FBR Pt Co SWNTg 42.3 4560 100 [128]
Ethylene glycol 10 230 Aa Autoclave Pt CNFb 17 26.7 15.5f 52.5 [38]
Ethylene glycol 10 2 250 45 FBR Pt CMK-3 84.7 51.3c [61]
Ethylene glycol 10 2 250 45 FBR Pt CMK-3 46 30.8c [73]
Ethylene glycol 10 2 250 45 FBR Pt CMK-3 75.8 37.8c 74.8 [58]
Ethylene glycol 10 2 250 45 FBR Pt CMK-3 25.4 17.7c 6180 [98]
Ethylene glycol 10 2 250 45 FBR Pt Re CMK-3 89.3 36.6c [73]
Ethylene glycol 10 2 250 45 FBR Pt Re CMK-3 44.2 19.9c [98]
Ethylene glycol 10 2 250 45 FBR Pt Mn CMK-3 39.7 26.8c [98]
Ethylene glycol 10 2 250 45 FBR Pt Fe CMK-3 30.4 22.1c [98]
Ethylene glycol 10 2 250 45 FBR Pt Cs CMK-3 20.1 12.5c [98]
Ethylene glycol 10 2 250 45 FBR Pt Ba CMK-3 15.3 10.6c [98]
Ethylene glycol 10 2 250 45 FBR Pt Ga CMK-3 5.7 5.5c [98]
Ethylene glycol 10 2 250 45 FBR Pt Ag CMK-3 0.2 0.3c [98]
Ethylene glycol 10 2 250 45 FBR Pt Mo CMK-3 5.8 3.1c [98]
Ethylene glycol 10 2 250 45 FBR Pt CMK-5 88 57.5c [61]
(continued on next page)
21
22
Table A2 e (continued )
Feedstock wt-% WHSVk (h1) T ( C) P (bar) Reactor type Catalyst Results Ref.
AMk Pk Suk Xk (%) CtoGk (%) H2 CH4
mmol min1 gCat1 h1 Sk (%) h1 Sk (%)
c
Ethylene glycol 10 2 250 45 FBR Pt CMK-9 89.2 62.7 6423 [129]
Ethylene glycol 10 225 29.3 FBR Ni Al2O3 0.9 17.4 38.5 4.8 [97]
Ethylene glycol 5 225 25.8 FBR Ni Al HTj 60d 71.5 [76]
Ethylene glycol 5 225 25.8 FBR Ni Sn/Al HTj 292d 100 [76]
Ethylene glycol 20 225 26 Autoclave Ni Zn/Al HTj 99.7 100 [37]
Ethylene glycol 10 230 Aa Autoclave Ni CNFb 14.5 33.3 5.2f 14.6 [38]
Ethylene glycol 10 3 230 29 FBR Ni CNFb 27 306 99 1.08 [85]
Ethylene glycol 1 225 25.8 Autoclave NiSn-Raney 95 [23]
Ethylene glycol 5 225 25.8 Autoclave NiSn-Raney 32.6 431e 84 57.1 13.9 [23]
Ethylene glycol 225 25.8 Autoclave NiSn-Raney 9.5 66 1.2 [23]
Ethylene glycol 5 225 25.8 NiSn-Raney 11.8 21e 13.2 9.54 [130]
Ethylene glycol 5 3.6 225 25.8 FBR NiSn-Raney 5.4 151.8h 22.2 58 4.5 [131]
Ethylene glycol 5 3.6 225 25.8 FBR Ni-NPi 8.2 249.5h 13.2 63 2.3 [131]
Ethylene glycol 5 3.6 225 25.8 FBR Pd Fe3O4 101.1 99.6 94.2 [39]
Ethylene glycol 5 3.6 225 25.8 FBR Pd Fe2O4 51.6 41.8 96 [39]
Ethylene glycol 5 3.6 225 25.8 FBR Pd Cr2O3 52.3 97.5 97.5 [39]
Ethylene glycol 5 3.6 225 25.8 FBR Pd NiO 61.8 50 15.6 [39]
Ethylene glycol 5 225 25.8 FBR Pd Fe Al2O3 6.2 203.4 99.2 79.8 [97]
Ethylene glycol 10 230 Aa Autoclave Cu CNFb 1 3.3 1.4f 37.1 [38]
Ethylene glycol 10 225 29.3 FBR Co Al2O3 0.1 16.2 128.9 1.2 [97]
Ethylene glycol 5 0.59 225 25.8 FBR Co e ZnO 5.2e8.6 101.4e27.9 89e52 8.1e6.7 [132]
0.09 35.5
Ethylene glycol 10 230 Aa Autoclave Co CNFb 8.5f 61.7 13 21.4 [38]
Ethylene glycol 10 2 250 45 FBR Re CMK-3 2.1 0.7c [73]
Ethylene glycol 10 2 250 45 FBR Mn CMK-3 1.9 2c [98]
a
A ¼ Autogenous pressure.
b
CNF ¼ Carbon Nanofiber.
c
cm3 gCat1 min1.
d
mmol min1.
e
mmol cm3 reactor min1.
f
Turn over frequency for conversion of ethylene glycol.
g
SWNT ¼ single walled carbon nanotube.
h
mmol min1 gNi1.
i
NP ¼ non-pyrophoric.
j
HT ¼ hydrotalcite.
k
WHSV ¼ weight hourly space velocity, AM ¼ active metal, P ¼ promoter, Su ¼ support, X ¼ conversion, CtoG ¼ conversion of carbon to gas, S ¼ selectivity, FBR ¼ fixed-bed reactor.
Table A3 e Sorbitol and xylitol aqueous-phase reforming. Operation conditions and results.
Feedstock wt-% WHSVe (h1) T ( C) P (bar) Reactor type Catalyst Results Ref.
e e e e e
AM P Su X (%) CtoG (%) H2 CH4
mmol min1 gCat1 h1 Se (%) h1 Se (%)
Sorbitol 1 225 29 FBR Pt Al2O3 66 [5]
Sorbitol 10 225 29.3 Pt Al2O3 78 150 [123]
Sorbitol Pt Ni Al2O3 3 60 [133]
Sorbitol Pt Ni ZrO2 6 68 [133]
Sorbitol 1 220 35 mchannel Pt AlO(OH) 25 46.5 [15]
Sorbitol 1 220 35 mchannel Pt Ru AlO(OH) 12 10.8 17 [82]
Sorbitol 1 220 25 Membrane Pt C 10 22 [122]
Sorbitol 2.4 260 Aa Autoclave Pt C 94.8 76.4 35.4 [19]
Sorbitol Ni Al2O3 1.8 42 [133]
Sorbitol Ni Pt Al2O3 7 62 [133]
Sorbitol Ni ZrO2 5.7 51 [133]
Sorbitol Ni Pt ZrO2 5.9 73 [133]
Sorbitol Ni Pt CeO3eZrO2eAl2O3 5.1 73 [133]
Sorbitol 1 225 25.8 Autoclave NiSn-Raney 65 [23]
Sorbitol 1 220 35 mchannel Ru AlO(OH) 14 0 0 [82]
Sorbitol þ ethanol 10 þ 10 225 29.3 Pt Al2O3 62 710 [123]
Xylitol 10 1.8 225 29.3 Pt Al2O3 66 558 83.4 [83]
Xylitol 10 1.8 225 29.3 FBR Pt Re TiO2 94 618 28 [106]
Xylitol 10 1.2 225 29.3 FBR Pt C 76 49 60 [134]
Xylitol 10 2 250 45 FBR Pt 3D-UMCc 29.1 16b 57.2 [62]
Xylitol 10 2 250 45 FBR Pt 3D-BMCd 56.2 29.1b 63 [62]
a
b
cm3 gCat1 min1.
c
3D-UMC ¼ three dimensions unimodal mesoporous carbon.
d
3D-BMC ¼ three dimensions bimodal mesoporous carbon.
e
WHSV ¼ weight hourly space velocity, AM ¼ active metal, P ¼ promoter, Su ¼ support, X ¼ conversion, CtoG ¼ conversion of carbon to gas, TOF ¼ turn over frequency, S ¼ selectivity.
23
Table A4 e Methanol, ethanol and butanol aqueous-phase reforming. Operation conditions and results.
Feedstock wt-% WHSVd (h1) T ( C) P (bar) Reactor type Catalyst Results Ref.
24
d d d d d
AM P Su X (%) CtoG (%) H2 CH4
mmol min1 gCat1 h1 Sd (%) h1 Sd (%)
Methanol 225 25.8 Autoclave Pt Al2O3 4.9 98.4 0 [23]
Methanol 0.008 225 28.6 FBR Pt Al2O3 78.9 9.5 9.6 97.9 [74]
Methanol 1 225 29 FBR Pt Al2O3 99 [5]
Methanol 10 225 29.3 FBR Pt Al2O3 510 [57]
Methanol 80 Pt TiO2 1.0 1.7 [135]
Methanol 80 Pt Sn TiO2 0.06 [135]
Methanol 80 Pt Fe TiO2 5.7 3.3 [135]
Methanol 80 Pt Co TiO2 2.4 3.3 [135]
Methanol 80 Pt Ni TiO2 1.3 3.0 [135]
Methanol 80 Pt Mo TiO2 15.5 12.1 [135]
Methanol 80 Pt Ru TiO2 3.4 2.3 [135]
Methanol 0.008 225 28.6 FBR Pt NaY 81.0 9.7 49.2 97.9 [74]
Methanol 225 25.8 Autoclave NiSn-Raney 18.6 87.6 0.6 [23]
Methanol 5 0.09 225 25.8 FBR Co ZnO 41.7 [132]
Methanol 10 105 Autoclave Ir TiO2 1.0 0.6 [136]
Methanol 10 105 Autoclave Ir Mo TiO2 3.6 3.9 [136]
Methanol 10 105 Autoclave Ir SiO2 0.6 0.4 [136]
Methanol 10 105 Autoclave Ir Re SiO2 2.1 10 [136]
Methanol 10 105 Autoclave Ir ZrO2 0.6 0.2 [136]
Methanol 10 105 Autoclave Ir Re ZrO2 3.2 6.1 [136]
Ethanol 225 25.8 Autoclave Pt Al2O3 8.9 120 57 [23]
Ethanol 1 0.008 225 28.1 FBR Pt Al2O3 97.2 59.2 [74]
Ethanol 10 225 29.3 Pt Al2O3 91 440 [123]
Ethanol 10 200 Autoclave Pt TiO2 4.3 29.2a 1.6a [65]
Ethanol 10 200 Autoclave Pt Re TiO2 5.5 52.5a 0.6a [65]
Ethanol 1 0.008 225 28.1 FBR Pt NaY 89.8 69.2 [74]
Ethanol 10 155 8.3 FBR Ni Al2O3 7.4 95 [81]
Ethanol 10 175 12.4 FBR Ni Al2O3 76.5 64 [137]
Ethanol 10 155 13.8 FBR Ni CeO2 5.5 35 87 [138]
Ethanol 225 25.8 Autoclave NiSn-Raney 15.4 60.6 24 [23]
Ethanol 10 200 Autoclave Re TiO2 3.3 28.9a 0.3a [65]
Ethanol 10 200 Ru TiO2 28.4 2.8 3 [42]
Ethanol 10 200 Autoclave Ru TiO2 30.1 34.5a 124a [65]
Ethanol 10 200 Autoclave Ru Re TiO2 36.4 85.2a 109.3a [65]
Ethanol 10 200 Autoclave Rh TiO2 14.2 61.2a 45.3a [65]
Ethanol 10 200 Autoclave Rh Re TiO2 36.1 131.3a 89.0a [65]
Ethanol 10 200 Autoclave Ir TiO2 5.9 40.9a 6.2a [65]
Ethanol 10 200 Autoclave Ir Re TiO2 14.7 86.6a 5.6a [65]
Ethanol 5 0.09 225 25.8 FBR Co ZnO 0.1 [132]
Ethanol 10 250 65 FBR Pd CBb 16.9 74.4 [112]
Ethanol 10 250 65 FBR Pd Zn CBb 10.8 43.2 [112]
Ethanol 10 250 65 FBR Pd Zn CNTc 29.5 1398 [112]
Butanol 5 215 27.6 FBR Ni Al2O3 5 42 5 [25]
Butanol 5 215 27.6 FBR Ni CeO2 17.5 68.0 35 [25]
a
mmol gCat1.
b
CB ¼ carbon black.
c
CNT ¼ carbon nanotube.
d
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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 6 ) 1 e3 0

Available online at www.sciencedirect.com

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

A review of catalytic aqueous-phase reforming of

I. Coronado a,*, M. Stekrova b, M. Reinikainen a, P. Simell a, L. Lefferts c,

article info abstract

* Corresponding author. Tel.: þ358 40 668 2831.

addition, hydrogen is utilized in the hydrotreatment of sus-

Cn H2nþ2 On þ nH2 O4nCO þ ð2n þ 1ÞH2 DH > 0 (1)

Fig. 2 e Reaction pathways of aqueous-phase reforming of ethylene glycol [13].

Table 1 e Parameters and formulas conventionally applied to evaluate APR performance.

2 Hydrogen yield Yð%Þ ¼ 100 molmol out H2

3 Hydrogen selectivity (I) molout H2

4 Hydrogen selectivity (II) SII H2 ð%Þ ¼ 100 C atHin2 produced

5 Hydrogen selectivity (III) SIII H2 ð%Þ ¼ 100 P molmolout H2

6 Hydrogen formation rate mmolðH2 Þ=min

CtoLd ð%Þ ¼ 100 C at liquid product

Table 2 e Liquid products from aqueous-phase reforming of different model compounds.

Fig. 5 e Effect of feedstock concentration on glycerol APR

carbon concentration in the liquid products decreased at

Effect of nitrogen co-feeding

Fig. 11 e Effect of modifiers on the APR of 5 wt-% ethylene

reducing the participation of hydrogen in secondary reactions.

observed over Pt supported on CeO2eAl2O3. Pt supported on a-

Table 3 e Supported platinum catalysts for hydrogen production.

Table 4 e Supported bimetallic platinum catalysts for hydrogen production.

Table 5 e Supported nickel catalysts for hydrogen production.

Table 6 e Other catalysts for hydrogen production.

oxidized under APR conditions [113]. Utilization of Ru sup-

catalytic system is crucial for the formation of alkanes. For

HZSM-5 and MCM-22 were also modified by Ni and applied in

by larger surface area, higher pore diameters and less strong

5 significantly deactivated because of partial dealumination

Hydrotalcites (HT) were tested to support platinum in the

aqueous-phase hydrogenolysis of glycerol (Table 7). This basic

Three-phase systems such as aqueous-phase reforming may

present mass transfer limitations that should be considered in

APR is limited by diffusion of the gas molecules from the

catalyst surface, and through the liquid phase. Reactor design

availability of active sites and promote the selectivity towards

target products. Slurry reactors (bubble columns and stirred

GA-1 FA-1 Feed vessel

Liquid analyzer Gas analyzer

Fig. 14 e Process flow diagram of aqueous-phase reforming.

monoxide to carbon dioxide were favoured at milder condi-

(continued on next page)

mmol min1 gCat1

tivity can be achieved by using carbonaceous supports such

CMK-9) and carbon nanotubes. However, to obtain a satis-

under APR conditions remains as a challenging task. The

selection of a stable support material is crucial to prepare

catalysts with high hydrothermal stability, and possibility for

Catalytic aqueous-phase reforming is a highly potential

to increase the conversion of reactants and promote the

reforming of oxygenated hydrocarbons. To enhance the

ing research activities should be directed towards systems

The authors would like to thank Prof. Dr. Klaus Hellgardt,

member of the scientific advisory board of the AQUACAT

Appendix. APR performance

AMi Pi Sui Xi (%) CtoGi (%) H2 CH4

Tester JW. Thermochemical biofuel production in

[3] Wikberg H, Gro € nberg V, Jermakka J, Kemppainen K,

an overview and future perspectives. Tappi J