Fuel 105 (2013) 739–751

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Fuel
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Methanol synthesis from syngas obtained by supercritical

water reforming of glycerol
F.J. Gutiérrez Ortiz ⇑, A. Serrera, S. Galera, P. Ollero
Departamento de Ingeniería Química y Ambiental, Universidad de Sevilla, Camino de los Descubrimientos, s/n, 41092 Sevilla, Spain

h i g h l i g h t s

" A heat-integrated reforming process of glycerol using supercritical water is established.

" The syngas obtained is conditioned and entered in a methanol synthesis loop.
" Power is produced by a turbine and a fuel cell.
" The aim was to maximize the overall process efficiency in terms of total power and methanol production.
" Optimal conditions were systematically identified.

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

Article history: A process for producing methanol from the synthesis gas obtained by reforming of glycerol using super-
Received 9 August 2012 critical water is studied. The process also produces power from the huge pressure energy of product gas
Received in revised form 25 September just at the outlet of the reformer by a turbine. The expanded product gas is conditioned in a PSA system,
2012
which has three sections so as to produce a H2-rich gas stream, a CO-rich gas stream and CO2 for seques-
Accepted 26 September 2012
Available online 11 October 2012
tration. Thus, it can be achieved the feed required for the methanol synthesis. The surplus hydrogen is
sent to a fuel cell to generate power, and the PSA off-gas, purge from the methanol loop and gases sep-
arated from the crude methanol are burnt in a furnace to achieve an energy self-sufficient process. By
Keywords:
Methanol
changing the reforming temperature, the water-to-glycerol mass ratio and the purge from the methanol
Syngas loop, the conditions for optimizing the overall process relative to methanol and power productions were
Reforming achieved. Thus, by reforming at 1000 °C and 240 atm, and performing the methanol synthesis at 250 °C
Supercritical water and 85 atm, the optimal conditions were a water-to-glycerol mass ratio of 1.68 with a purge ratio of 0.2.
Glycerol Under these conditions 0.270 kg MeOH/kg glycerol and overall energy efficiency of 38.0% were obtained.
The separated CO2 for sequestration is 0.38 kg/kg of glycerol.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction The syngas obtained from glycerol reforming using supercritical

A great deal of research has been carried out following a ther-
mochemical route to valorize the biodiesel-derived crude glycerol
from the transesterification process to obtain synthesis gas (syn-
gas), by different types of reforming [1–6]. As an emerging and
promising media, supercritical water (SCW) may be used to obtain
syngas due to its relevant thermophysical properties such as a high
capability to solubilize gaseous organic molecules and high reac-
tivity, among others [7–9]. Besides, the reactions in SCW are con-
ducted in a single phase [10]. As a result, it may be possible to
perform the process in the absence of a catalyst, although this pre-
mise requires to be experimentally verified [11].
⇑ Corresponding author. Tel.: +34 95 448 72 68/60.
E-mail address: frajagutor@etsi.us.es (F.J. Gutiérrez Ortiz).
water can be used for the synthesis of chemicals such as methanol.
Methanol is an important industrial chemical, which is used as a
feedstock for further chemicals, such as formaldehyde, methyl ter-
tiary butyl ether (MTBE) and acetic acid [12], apart from as reagent
in the biodiesel production. Methanol can also serve as a basic
chemical for polymer production [13,14]. In addition, methanol
has a high octane number and is considered to play a significant
role as a synthetic fuel [15]; furthermore, hydrocarbon fuels may
also be generated from methanol with the help of the methanol
to gasoline (MTG) technology [16]. Thus, methanol represents a
critical link in synthesis gas based product network structures [17].
Methanol is produced by the hydrogenation of carbon oxides
over a suitable (copper oxide, zinc oxide, or chromium oxide
based) catalyst:
CO þ 2H2 $ CH3 OH ð1Þ

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.09.073
740 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751
Nomenclature
B_ exergy flow (kW)
H_ enthalpy flow (kW)
LHV Lower Heating Value (kJ/kg)
LW _ exergy flow loss (kW)
m _ mass flow rate (kg/s)
Q_ heat flow (kW)
S_ entropy flow (kJ/(sK))
T temperature (K)
W_ power (kW)
Greek
g efficiency (%)
CO2 þ 3H2 $ CH3 OH þ H2 O
Methanol synthesis catalysts also have water gas shift activity,
which may account for their ability to synthesize methanol from
either carbon monoxide or carbon dioxide:
CO þ H2 O $ CO2 þ H2
Only two of these three reaction equations are stoichiometrically
independent. The first reaction is considered as the primary meth-
anol synthesis reaction, but a small amount of CO2 in the feed
(2–10%) acts as a promoter of this primary reaction and helps to
maintain catalyst activity. In fact, the lack of carbon dioxide makes
the Boudouard reaction going in its reverse direction, leading to
catalyst deactivation by carbon deposition:
2 COðgÞ $ CO2 ðgÞ þ CðsÞ
For methanol synthesis, the so-called stoichiometric number
(SN) of inlet syngas is frequently used, which is defined as:
½H2   ½CO2 
SN ¼
½CO þ ½CO2 
where [H2], [CO2] and [CO] express the molar concentrations of H2,
CO2 and CO, respectively. The ideal SN is about 2.0–2.1, because the
stoichiometry of reactions 1–3 is satisfied [18]. This SN corresponds
to a H2-to-CO ratio from 2.4 to 3.0 [19], depending on the CO2
content.
Since the syngas coming from supercritical water reforming of
glycerol does not match this SN value, it must be conditioned be-
fore entering the methanol synthesis loop. Particularly, as carbon
dioxide and hydrogen have relatively high concentrations, they
must be removed by physical or chemical processes [20].
The most frequently used technologies for CO2 removal from
syngas obtained from fossil fuels are absorption systems such as
the Rectisol, Selexol and MEA-based processes [21], specially the
Selexol process, which uses dimethyl ether of polyethylene glycol
as solvent and operates at low temperature (5–35 °C) and medium
pressure (15–30 atm), making it possible to achieve a CO2 capture
efficiency higher than 90% [22]. However, the Selexol process is
expensive and requires significant utility consumption during
operation, which only escalates with increasing levels of CO2 cap-
ture [23]. An adsorption process, and especially pressure swing
adsorption (PSA) technology, may be a potentially attractive alter-
native to capture CO2 from stationary sources in the context of Car-
bon Capture and Sequestration (CCS) technologies [24].
Traditionally, PSA technology has proven to be economical in
hydrogen purification from steam methane reforming off-gases
[25], and typically produce a very pure hydrogen stream (up to
Subscripts
Gly glycerol
in referred to some entering the control volume consid-
ered (unit, subsystem or system)
MeOH methanol
net referred to the net power of the turbine
out referred to some leaving the control volume considered
(unit, subsystem or system)
SRSG supercritical reforming reactor for syngas production
PEMFC proton exchange membrane fuel cell
DIST distillation column
HE heat exchanger
ð2Þ 99.999 mol% H2) [26]. However, this is not the requirement for
upgrading the syngas before feeding into the methanol synthesis
loop, because only the carbon dioxide and other impurities should
be retained in the bed, but a mixture of H2 and CO must be ob-
tained, and in the suitable concentrations for reaching the SN re-
ð3Þ quired at the inlet of the methanol synthesis loop. Several
methods for separating hydrogen and carbon monoxide by PSA
processes have been patented during the last years. Kumar and
Kratz [27] developed a PSA process (called Gemini-9 and owned
by Air Products and Chemicals) comprising six parallel beds for
CO2 removal, followed by three parallel beds for H2 purification.
Sircar [28] showed how to get the adjustment of the H2/CO ratio
of a stream obtained from steam methane reforming after CO2 re-
moval, using a rinse step for the recovery of the fraction of the CO
ð4Þ adsorbed on activated carbon. Krishnamurthy [29] disclosed a
method for separating hydrogen and carbon monoxide using two
PSA systems. The first one separates H2 from the feed mixture as
a pure non-adsorbed product and CO2, CH4, and CO as an adsorbed
fraction. The adsorbed fraction is then desorbed and passed to a
ð5Þ second PSA system, which separates CO as an adsorbed fraction
and CO2, CH4, and somewhat of H2, as a non-adsorbed fraction. Re-
cently, Batdorf [30] proposed a method to remove carbon dioxide
from the effluent gas, while allowing the carbon monoxide and
hydrogen to pass through the PSA, producing a gas stream amena-
ble to the production of methanol and other liquid fuels.
This paper proposes an overall process where syngas is obtained
from glycerol reforming using supercritical water, expanded in a
turbine, next upgraded in a PSA system (adjustment of the SN)
and then fed into a methanol synthesis loop, where unreacted syn-
thesis gas from methanol reactor is separated from crude metha-
nol, compressed and recycled. A fraction of recycle gas is purged
to avoid inerts accumulation. Finally, the crude methanol is puri-
fied by distillation. The off-gases from the different sections are
burnt to achieve the thermal energy required in the process, mak-
ing it energy self-sufficient. Fig. 1 depicts the concept in a simple
way using a block flow diagram. The main aim is to achieve the
optimal operating conditions for maximizing the overall process
efficiency in terms of methanol production and power generation
by a turbine and a fuel cell, fed with the surplus of the H2-rich
stream leaving the PSA, as well as obtaining maximum exergy
efficiency.
2. Process design and simulation
Fig. 2 shows the overall process flow-sheet, which includes heat
exchangers suitably located following a strategy based on
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 741

POWER

PEM FUEL CELL

Pure H2
Gas

1 atm.,80 ºC METHANOL METHANOL

REFORMER
SYNTHESIS PURIFICATION
EXPANDER
PSA SYSTEM
Product gas CH3OH

CO, H2, CO2 SN

C3H8O3 + H2O

30 atm., 35 ºC
POWER
85 atm., 250 ºC 1 atm

Flue gas
Supercritical water
240 atm
700 –1000 ºC
HEAT REQUIRED PSA off-gas
FOR REFORMING

FURNACE

Fig. 1. Block flow diagram of the process.

minimizing the lost exergy, so small temperature-driving forces
must be achieved by using countercurrent flow and small temper-
ature approaches at the ends of the exchangers.
2.1. Supercritical water reforming of glycerol section
A glycerol–water mixture is pumped into the supercritical
water reforming reactor after heating it as much as possible by
means of three heat exchangers taking heat from hot streams leav-
ing first the reformer-furnace, and then the reforming reactor. In
the reformer, glycerol is converted at established temperature
and pressure. The pressure used in this work was 240 atm [11].
The reforming reactor was simulated as a Gibbs reactor, where
the products composition and the heat of overall reaction were cal-
culated under conditions that minimize the Gibbs free energy. The
furnace-combustor, where the off-gas PSA as well as the purge gas
of the methanol synthesis loop and even the gas separated from
the crude methanol are burnt, was simulated by a stoichiometric
reactor, which transfers the heat released from the combustion
reaction to the reforming reactor to operate at the specified tem-
perature. The flue-gas temperature is set at 1000 °C. The flow-rate
of the gas to be burnt is computed as that needed to match the heat
flow required in the reforming reactor. Every operating condition
leading to have a deficit or surplus of heat flow in the reformer-
furnace is outside the admissible operation window, as described
below. The air enters the furnace by a fan with such an excess that
there is an O2 content of 3 vol% in the flue-gas. The product gas
leaving the reformer is expanded in a turbine up to 30 atm, con-
verting thus the syngas pressure energy into power.
2.2. Syngas conditioning section
The syngas is cooled down to 35 °C by two serially connected
heat exchangers and the condensed water is separated from the
gas stream by means of a knock-out drum. The gas stream enters
the PSA system, which consists of three units, as shown in Fig. 3.
The PSA produces a H2-rich stream to adjust the stoichiometric ra-
tio of the methanol feed and simultaneously captures CO2 for fu-
ture sequestration. Within the first unit, the H2 is separated with
a high purity as a non-adsorbed stream and exits the PSA bed at
a pressure close to the PSA inlet pressure. The first PSA unit is
depressurized to regenerate the adsorbent, so the tail gas leaves
the bed and then is compressed to 30 atm, passing to the second
PSA unit, where the CO is separated as the adsorbed component,
recovered in the depressurization, and mixed first with a fraction
of the CO2-rich stream coming from the third PSA unit. Then, the
mixture of CO and CO2 is compressed up to 30 atm and mixed with
the H2-rich stream, so as to adjust the stoichiometric ratio required
for the feed of the methanol synthesis loop to approximately 2.1, so
the H2-to-CO ratio ranges from 2.4 to 2.5 and the CO2-to-CO ratio is
about 0.14. As the syngas produced in the reformer has an excess of
H2, a fraction of the hydrogen separated in the PSA system is sent
to a PEM fuel cell to be converted into power or to the furnace if
necessary. For achieving a CO2-rich gas stream to be led for future
sequestration, a third PSA unit is necessary (although it could be
also used a membrane-based technology), where CH4 can be sepa-
rated. After depressurization, the CH4-rich stream is available at
low pressure as a fuel.
The three PSA units have been simulated in a simplified way, by
ideal separators, but working at realistic pressure and temperature
(30 atm and 35 °C, respectively). The depressurization steps are
simulated by a valve located at the PSA off-gas stream of the cor-
responding unit. The PSA system is assumed to give a high purity
H2 (99%) with a hydrogen recovery of 90% (somewhat lower than
the maximum found in the literature [31]), as well as a CO2 stream
of +95% purity, which is the specification required for transport and
sequestration of CO2 [32]. In addition, it is assumed that the PSA
system recovers 98% of the produced CO with a purity of +90%.
 742
F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751
Fig. 2. Heat-integrated flow-sheet for producing methanol and power by supercritical water reforming of glycerol.
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 743

H2 to PEMFC H2 to furnace

CH4-rich stream
1 atm
H2-rich stream To furnace

PSA unit 3
30 atm
35 ºC

35 ºC PSA unit 1 30 atm

SYNGAS 35 ºC PSA unit 2

30 atm For sequestration Compress to: 85 atm
Heat to: 250 ºC
30 atm
CO2-rich stream
1 atm

Methanol
30 atm
converter
1 atm
H2 − CO 2
≈ 2 .1
CO + CO 2

CO-rich stream
% recovery (PSA system)
PSA-1 (top) PSA-2 (bottom) PSA-3 (top) PSA-3 (bottom) Gas specifications:
H2 95 - 4.5 0.5 • H2/CO = 2.4 – 2.5
CO - 98 1.5 0.5 • CO2/CO = 0.13 – 0.14
CO2 - 1 9 90 • CH4 < 3 vol%
CH4 - 1 90 9
H2-rich stream CO-rich stream CH4-rich stream CO2-rich stream

Fig. 3. PSA system flow-sheet for syngas conditioning.

Also, in this PSA system, CH4 is the second relevant component in
the CO2-rich gas stream (Fig. 3).
2.3. Methanol synthesis and purification section
The typical operation conditions of the synthesis are in the
ranges of 220 to 280 °C and 50 to 100 atm. Beyond 280–300 °C,
the catalyst would be subjected to sintering and fusion, which
would result in permanent damage of the catalyst; on the other
hand, the decrease in the reaction temperature favors the right
shift in the equilibrium although significantly reduces the reaction
rate. Therefore, the operating temperature range is a compromise.
In addition, higher pressures favor methanol from the equilibrium
standpoint but the increase above 80 atm is not very significant. In
this work, the upgraded syngas coming from the PSA is first com-
pressed to 85 atm and then heated to 250 °C, which are the oper-
ating conditions to be used in the methanol reactor that operates
in gas phase and is cooled to remove the heat of reaction.
The reactor operates with low conversion per pass of syngas
due to the high temperature sensitivity of the catalyst and the
thermodynamic equilibrium, which implies a large recycle of
unconverted gas. Normally, a gas phase reactor has a CO conver-
sion per pass lower than 16–20%. A high CO to CO2 ratio increases
the reaction rate and the conversion per pass (up to 40% [20]), as
well as it lessens the formation of water, reducing the catalyst
deactivation rate.
Several types of methanol synthesis reactors are used in produc-
tion plants. They may be adiabatic (e.g., ICI) or quasi-isothermal
(e.g., Lurgi). In this paper, the temperature at the reactor outlet
was specified as constant (250 °C) and the reaction heat is released
to a cooler so saturated steam is produced at 230 °C. The methanol
reactor has been simulated as a stoichiometric reactor and it was
specified a CO conversion per pass of 20% as well as a CO2 conversion
per pass of 3%. If an equilibrium reactor was selected for once-
through operation, the CO conversion and CO2 conversion would
be 76.8% and 9.6% (thermodynamic limits), respectively, which are
much higher than real conversions per pass in industrial reactors.
The reactor effluent is cooled down to 30 °C in order to conden-
sate the crude methanol, and to separate it from the gas phase in a
gas–liquid separator. The gas is recompressed and recycled to in-
crease the overall CO conversion into MeOH, and a fraction of the
recycled gas that is purged to prevent the accumulation of inert
gases (mainly, methane) is sent to the furnace for aiding to achieve
the energy self-sufficiency. This has a direct effect on the overall
CO conversion as well as on the performance of the energy-inte-
grated process. Thus, the overall process performance depends on
the purge ratio or purge-to-recycle ratio, which is one of the
parameters to take into account in the global process optimization,
as below described.
The crude methanol typically contains water and also low con-
centrations of dimethyl ether (about 100 ppm), carbonyl com-
pounds (20 ppm) and higher alcohols, C2+, (about 400 ppm). In
fact, high selectivity is a key requirement for methanol catalyst,
and it is around 99.8% if a Cu/ZnO/Al2O3 catalyst is used. Usually,
distillation is normally used to purify the crude methanol product
to meet specifications [33]. In this paper, minor by-product forma-
tion was not considered (a selectivity of 100% is assumed), but a
subsequent purification of the crude methanol is included in order
to separate water and dissolved gases. Thus, the liquid stream leav-
ing the loop, which contains methanol, water and some dissolved
gases, is heated and expanded to the atmospheric pressure by a
valve, to separate the dissolved gases in a flash separator, from
which they are sent to the furnace. Finally, the crude methanol en-
ters a distillation column where methanol is separated from water
744 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

Table 1
Specifications of the individual process units for the simulation of the methanol synthesis process from the reforming of glycerol using supercritical water.

Code Equipment Specifications

P1 Pump Efficiency: 0.8
Outlet pressure: 240 atm
HE01 Heat exchanger Hot stream outlet temperature: 200 °C
HE02 Heat exchanger Touthotfluid–Toutcoolfluid = 3 °C
HE03 Heat exchanger Hot stream outlet temperature: 400 °C
SRSG Supercritical Reforming Reactor Operating temperature: variable (700–1000 °C)
TURB Turbine Type: Isentropic; Isentropic Efficiency: 0.72
Outlet pressure: 30 atm
HE04 Heat exchanger Hot stream outlet temperature: 35 °C
PSA1 Pressure swing adsorption unit It removes most the H2 (95%) from the other gases (Fig. 3)
Outlet pressure if valve: 1.1 atm (30 atm in other case)
PSA2 Pressure swing adsorption unit Specified on details given in Fig. 3
Outlet pressure if valve: 1.1 atm (30 atm in other case)
PSA3 Pressure swing adsorption unit Specified on details given in Fig. 3
Outlet pressure if valve: 1.1 atm (30 atm in other case)
COMP1 Train of compression with two intermediate coolers and one final Type: Isentropic; Isentropic Efficiency: 0.72
Three compression stages; intermediate cooling to 35 °C
Outlet pressure: 30 atm
COMP2 Train of compression with two intermediate coolers Type: Isentropic; Isentropic Efficiency: 0.72
Three compression stages; intermediate (and final) cooling to 35 °C
Outlet pressure: 30 atm
COMP3 Compressor Type: Isentropic; Isentropic Efficiency: 0.72
Outlet pressure: 85 atm
HE05 Heat exchanger Cold stream outlet temperature: 250 °C
RMETOH Methanol reactor 250 °C @ 85 atm
Pressure drop: 0.1 atm
CO + 2H2 ? CH3OH; CO conversion per pass: 0.20
CO2 + 3H2 ? CH3OH + H2O; CO2 conversion per pass: 0.03
Surplus heat flow to COOLER2
HE06 Heat exchanger Hot stream outlet temperature: 30 °C
HE07 Heat exchanger Cold stream outlet temperature: 50 °C
HE08 Heat exchanger Hot stream outlet temperature: 120 °C
FURNACE Furnace–combustor Combustion of everything able to be oxidized
1000 °C @ 1 atm
Surplus heat flow to SRSG
FAN1–FAN3 Fans Type: Isentropic; Isentropic Efficiency: 0.72
Outlet pressure: 1.1 atm
HE08 Heat exchanger Hot stream outlet temperature: 140 °C
P2–P5 Pumps Efficiency: 0.8
Outlet pressure: 1.1 atm
HE09 Heat exchanger Cold stream outlet temperature: 80 °C
HE10 Heat exchanger Hot stream outlet temperature: 120 °C
PEMFC PEM fuel cell (stoichiometric reactor) Heat + work to SPLIT5
H2 + 0.5 O2 ? H2O
Isothermal reactor: 80 °C
COOLER1 Heat exchanger Cooling water outlet temperature: 40 °C
COOLER2 Heat exchanger Saturated steam at 230 °C (27.97 atm) – heat flow from RMETOH –
DEST Operating pressure: atmospheric (1 atm)
Total condenser
Reflux ratio: 1.5Rmin
Methanol recovery (distillate stream): 99%
Water recovery (bottom stream): 97%
HEATER1 Heat exchanger Source of heat flow towards the reboiler of the distillation section
COOLER3 Heat exchanger Sink of heat flow coming from the condenser of the distillation section
P6 Pump Efficiency: 0.8
Outlet pressure: 27.97 atm

with a recovery of 99%. This section is also energy-integrated with
the overall process, so the reboiler duty is provided by the satu-
rated steam produced in the methanol reactor cooling and the con-
denser duty is released to the cooling water circuit of the process.
2.4. Simulation remarks
Specifications of the main units used in the simulation are
shown in Table 1. The computation has been made with the
aid of AspenPlus™ version 2006.5 (Aspen Technology, Inc.,
USA). The predictive Soave–Redlich–Kwong (PSRK) thermody-
namic method was used as the most suitable dealing with
supercritical conditions [11], although for the distillation column
and the saturated steam were used the NRTL and STEAMNBS
methods, respectively.
The simulation did not predict coke formation in the supercrit-
ical reformer for any of the experimental conditions used in this
paper, and any other compound apart from those mentioned has
a mole fraction lower than 1012. Likewise, for all operating condi-
tions, the calculated glycerol conversion was always 100%, at equi-
librium condition.
3. Method of optimization
The aim was to maximize the overall process efficiency in terms
of total net power and methanol production, for a given mass flow-
rate of glycerol fed into the process. As a constraint, the process
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 745

Table 2
Main concepts considered in the energy and exergy analysis.

Concept Equation
Lost power for the overall process
X X X   
_ overall ¼ T0 _ 
LW ðB_ in  B_ out Þ  _ out þ
W _ in  1 
W Q cooling 
system
T PEMFC

Overall energy efficiency (for pure

glycerol)
_ net þ m
W _ MeOH LHVMeOH
genergy ¼ _ Gly LHVGly
m
Heat exchangers
X X X X
_ HE ¼ T 0
LW ðS_ out  S_ in Þhotfluid þ T 0 ðS_ out  S_ in Þcoolfluid ¼ T 0 S_ out  T 0 S_ in
Reforming reactor
X
_ SRSG ¼ B_ lost ¼ B_ out þ
LW B_ in ; Q_ SRSG ¼ 0
Furnace
X   
T0 _ 
_ FURNACE ¼ B_ out þ
LW B_ in  1  Q Furnace ; Q_ Furnace ¼ H_ out  H_ in < 0
T Furnace
SRSG and furnace coupled
X X
_ SRSG—Furnace ¼ 
LWS ðB_ out  B_ in ÞFurnace  ðB_ out  B_ in ÞSRSG
Train of compression with intermediate
cooling
X X  
_ COMP ¼ B_ out þ B_ in þ _ i T0
LW W ðH_ out  H_ in Þj 1 
i;8stage j;8int cool
ðT out þ T in Þ=2 j

Methanol reactor
  
_ RMeOH ¼ B_ lost ¼ B_ out þ B_ in  1  T0 _ 
LW Q RMeOH 
T RMeOH
Heater
  
_ Heater ¼ B_ out þ B_ in þ 1  T0 _ 
LW Q heating 
T source
Exergy loss of the PEM fuel cell
subsystem
X   
_ PEMFC ¼ B_ out þ T0 _ 
LW B_ in  1  _ PEMFC
Q cooling   W
T PEMFC
Electric power generated by the fuel cell
()
_ PEMFC ¼ g m
W _
FC H2 LHVH2

Cooler
  
_ Cooler ¼ B_ out þ B_ in  1  T0 _ 
LW Q cooling 
T heatsource
Distillation column
  !
X T0  T0  
_ DIST ¼  _  _ 
LW B_ out þ B_ in þ 1  Q Reboiler   1  Q Condenser 
T saturatedsteam ðT out þ T in Þcoolingwater =2

Note 1: For the analysis, it is assumed that to obtain a power of 1 kW in the PEMFC unit, the required molar flow rate of hydrogen is 33.3 mol/h [34], corresponding to an
efficiency of the fuel cell stack of about 0.45 [35].
Note 2: Lower Heating Value of glycerol: 16 MJ/kg; Lower Heating Value of methanol (19 MJ/kg).

must be energy self-sufficient, so residual gases with chemical en-
ergy must be sent to the furnace. The total net power is the PEM
fuel cell power plus the power of the turbine minus the consumed
power in all the pumps, blowers and compressors.
Among all the possible optimization variables, some of them
were fixed in this study. First, the reforming pressure did not
significantly affect the process in the range from 200 to
300 atm [11] and a fixed value of 240 atm was chosen. Likewise,
the outlet pressure of the expander was the minimum required
to perform the separation of gases in the PSA system (30 atm),
allowing a high power recovery in the turbine. The pressure
and temperature of the methanol reactor were the usual in these
reactors. Thus, there are still three independent variables for
optimization: the reforming temperature (RT), the water-to-glyc-
erol mass ratio in the feed (W/G), and the purge ratio in the
methanol synthesis loop (PR).
746 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

Fig. 4. Methanol production versus W/G mass ratio, when reforming using SCW at 800 °C, for the range of purge ratio from 0.1 to 0.5.

Fig. 5. Methanol production versus W/G mass ratio, when reforming using SCW for the two range limits of purge ratio and four reforming temperatures.

Fig. 6. Total net power and PEM fuel cell power versus W/G mass ratio when reforming using SCW at 800 °C for three purge ratios (0.1, 0.3 and 0.5).

The reforming temperature is ranged from 700 to 1000 °C, as higher reforming temperature will provide a higher content of
the best ones for the supercritical reformer performance [11]. A CO and H2 in the syngas and then, the methanol production will in-
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 747

Fig. 7. Total net power and PEM fuel cell power versus W/G mass ratio when reforming using SCW for the two range limits of purge ratio and four reforming temperatures.

Fig. 8. Specific production of methanol (kg of produced MeOH per kg of glycerol fed) versus W/G mass ratio.

crease, although a higher hydrogen fraction is needed to reach the
energy self-sufficiency and thus the power obtained in the fuel cell
will be lower.
The range of values for the purge ratio was from 0.1 to 0.5 (re-
cycle-to-purge ratio from 9 to 1), which is somewhat wider than
usual [20]. A minimum purge is necessary to avoid accumulation
of inerts in the methanol loop, but if the purge ratio increases,
the overall CO conversion and methanol production will decrease
although, at the same time, the higher flow-rate of residual gases
will provide more energy for the reformer-furnace and less hydro-
gen fraction would be needed, leading to generate more power in
the fuel cell.
Regarding with the W/G mass ratio range, at low glycerol feed
concentrations, i.e., a high W/G ratio, the energy demand will greatly
increase and external fuel will be needed thus violating the energy
self-sufficiency constraint. Likewise, at high glycerol feed concentra-
tions, there will be a heat surplus in the overall process, even sending
all the hydrogen not used in the methanol production to the fuel cell.
The admissible W/G ratio range depends on the RT and the PR used.
So, for each pair RT–PR the lower and upper limits of W/G correspond
to hydrogen fractions sent to the furnace of 0.0 and 1.0 respectively.
By this way, an operation window is established.
Finally, to complete the study, an exergy analysis was also car-
ried out to assess the process performance from this standpoint
under the optimal conditions. Table 2 shows some details of this
analysis, so as to compute the exergy loss of all the units and to
know where the more significant irreversibilities occur. In this ta-
_ represents the energy flow (power)
ble, the term of Lost Work ðLWÞ
loss due to the process irreversibilities.
4. Results and discussion
In this study, a base feed of 1000 kg/h of glycerol was selected.
The required W/G mass ratio is achieved by adding more or less
water.
As a first result, Fig. 4 illustrates that, for a given RT, the meth-
anol production slightly increases as the W/G mass ratio in-
creases, and still more for low values of PR. The two gray
dashed lines bound the admissible operation window as they rep-
resent points corresponding to fractions of H2 sent to the furnace
of 0.0 and 1.0. Likewise, Fig. 5 shows the joint effect of RT and PR
on the methanol production, which increases when reducing the
PR but also if the RT is increased. It should be noted that when
reforming at 1000 °C and the purge ratio is of 0.1 the process does
748 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751

(a)

(b)

(c)

Fig. 9. Indexes of the process performance versus W/G mass ratio: (a) Specific production of methanol production, (b) total net specific power generated, and (c) overall value
of MeOH plus power.

not become energy self-sufficient. When changing the PR, the dif- minimum purge ratio lead to maximum methanol production
ferences in the methanol production are more notorious at high accordingly to higher glycerol feed concentrations (lower W/G
temperatures. Therefore, maximum reforming temperature and mass ratio).
 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751 749

Fig. 10. Overall energy efficiency versus W/G mass ratio.

Distillation column;
2,30 PEM fuel Mixers; 2,86
PSA system; 1,62 cell; 2,29
Pumps; 0,90
Methanol reactor; 0,93 Heat exchangers;
37,40

Furnace; 28,91

Supercritical reformer; Turbine; 2,53 Compressors; 4,33

15,93
Mixers Pumps Heat exchangers
Compressors Turbine Supercritical reformer
Furnace Methanol reactor PSA system
Distillation column PEM fuel cell

Fig. 11. Exergy losses per units or set of units as percentage of the overall lost exergy flow (case study: RT of 1000 °C, all the hydrogen sent to the fuel cell and PR of 0.2).

Fig. 6 depicts that, at a given RT, both the power of the PEM fuel
cell and the total net power increase as the W/G ratio increases,
reaching a maximum just for the W/G in which all the excess of
hydrogen is sent to the fuel cell. If W/G continues to rise, an
increasing fraction of hydrogen is sent to the furnace, decreasing
thus the power of the PEM fuel cell and the total net power. In
addition, the trends are drawn in an almost parallel way, at a given
PR, since the power of the turbine barely changes because the flow-
rate of the feed is fairly constant due to the narrow allowable W/G
range. As a consequence, the maximum total net power matches
the maximum for the power of the PEM fuel cell. Besides, the max-
imum shifts to higher W/G ratios as the PR increases. Thus, when
changing the PR, the highest power is obtained at the upper limit
of the PR. In Fig. 7 the effect of the reforming temperature (RT)
on the total net power is depicted for the two limits established
for the PR. It can be observed as there is a maximum for each pair
of RT and PR, corresponding to the W/G ratio in which all the sur-
plus hydrogen is sent to the fuel cell. However, and making a com-
parison for a given purge ratio, the highest power is achieved at
800 °C for a PR of 0.5.
Fig. 8 shows that the production of methanol per kg of glycerol
(specific production) scarcely varies as the W/G ratio increases, at a
given RT and PR, although it increases as the RT rises at a given PR
and as the PR decreases at a given RT.
In Fig. 9 the PR is withdrawn from the discussion, so the trends
corresponds to the optimal conditions for the RT and the W/G in
which all the residual gas is sent to the furnace and all the excess
of hydrogen is sent to the PEM fuel cell, within the admissible
operation window, which includes a purge ratio range from 0.1
to 0.5. In this graph, it seems that there are some W/G values for
which no solution. However, this is only apparent, and indeed
these points exist for intermediate temperature between 700 and
800 °C. Fig. 9a illustrates an almost linear relationship between
the specific production of methanol and the W/G ratio, indepen-
dently of the RT, which only would set the allowable W/G ratio.
Fig. 9b depicts a different behavior of the total net power per kg/h
of glycerol (specific power), which always increases as the W/G ratio
increases for every RT. Fig. 9c is drawn to show how the weighted
sum of methanol production and net power varies with W/G and
RT, within the admissible overall operation window. The weights
were calculated according to their current market prices [36,37],
and thus it was obtained the following equation:
_ total =m
_ MeOH =m
Overall specific value ¼ 3:5ðm _ Gly Þ þ 1:0ðW _ Gly Þ ð6Þ
750 F.J. Gutiérrez Ortiz et al. / Fuel 105 (2013) 739–751
since, nowadays, 1 kg/h of MeOH worth 3.5 times more than 1 kW
power.
The linear relationship shown in Fig. 9c may be explained taking
into account the higher weight of the methanol in the computa-
tion. Therefore, the maximum value of methanol plus power is ob-
tained for the lower limit of the W/G mass ratio, and the
corresponding reforming temperature, that is, W/G = 1.68 and
RT = 1000 °C. The corresponding purge ratio is 0.2. Fig. 10 illus-
trates the overall energy efficiency versus the W/G ratio, showing
similar trends to those of the overall specific value of methanol
and power. In addition, an exergy analysis was performed to deter-
mine the direction for potential improvements for the system and
process units. Thus, Fig. 11 illustrates the contribution of some of
the units or set of units to the exergy losses expressed as percent-
age of the overall exergy losses, at 1000 °C reforming temperature,
and a purge ratio of 0.2. This graph has been obtained for each case
study (but not shown for simplicity), and the same qualitative re-
sults arise. It can be seen that 37.4% of the exergy losses are due to
the heat exchangers. Furthermore, the contribution of reactors
SRSG and Furnace, as they are coupled, is 44.8% of the total exergy
losses. For the rest of units or sets of units the exergy losses are
lower than 5.0%.
Finally, a comparison of the results obtained in this study with
other published results was carried out for the main process units
(supercritical reformer and methanol synthesis reactor).
Although the number of publications on the reforming of glyc-
erol using supercritical water is fairly limited, the few experimen-
tal results found in the literature match reasonably well with the
results obtained in this study based on the assumption of reach-
ing chemical equilibrium. Thus, at feed concentration of 30 wt.%
glycerol, Byrd et al. [38] obtained a product gas composition
H2/CO/CO2/CH4 of 47.2/3.2/34/15.6, at a temperature of 800 °C
and a pressure of 241 bars, over Ru/Al2O3 catalysts in a tubular
fixed-bed flow reactor. In the present study, in the case of sending
all the excess of hydrogen to the fuel cell, the product gas compo-
sition H2/CO/CO2/CH4 ranged from 43.9/11.4/25.8/18.9, when
using a glycerol feed concentration of 31.2 wt.% (W/G equal to
2.2) corresponding to a purge ratio of 0.1, to 46.9/11.1/25.5/
16.5, when using a feed concentration of 27.3 wt.% (W/G equal
to 2.6) corresponding to a purge ratio of 0.5, at 800 °C and
240 atm. Experimental yields of CO and CO2 are somewhat differ-
ent from the predicted values at equilibrium, but it should be
noted that the former were obtained in a catalytic reactor with
a small residence time (1 s), in which probably equilibrium was
not attained.
Regarding with the methanol synthesis reactor and loop, previ-
ous experimental or simulated data coincide very well with simu-
lation results illustrated in this study. First, Graaf et al. [39,40]
concluded that the chemical equilibria of the reactions involved
could be described very well with the use of thermochemical data
based on ideal gas behavior in combination with a correction for
non-ideality of the gas mixture as predicted by the Soave–
Redlich–Kwong equation of state (SRK EOS). In addition, the results
obtained with the Peng–Robinson equation of state (PR EOS) gave
similar results to those of SRK EOS. By this way, it has been con-
firmed that the results of simulation PSRK EOS used in this study
match quite well the results using the SRK or PR equations of state.
Later, Graaf and Beenackers [41] considered a complete synthesis
loop that included a five-fixed bed reactor. With a CO2/CO/H2/
CH4 synthesis gas composition equal to 10.8/17.8/69.7/1.7
(SN = 2.06), they obtained a methanol mole fraction of 0.06 at the
reactor outlet, at 242 °C, 85 bar and a recycle ratio of 5, equivalent
to a purge ratio of 0.17 (typical of Haldor Topsøe methanol technol-
ogy [42]). In the present study, the methanol mole fraction at the
reactor outlet varied from 0.053 to 0.059 in the purge ratio range
from 0.1 to 0.2. Afterwards, Kordabadi and Jahanmiri [43] achieved
a methanol mole fraction of 0.056 in a 7 m length reactor.
Klier et al. [44] showed the dependence of carbon conversion to
methanol using a CO2/CO/H2 synthesis gas containing 70% H2 and a
variable ratio of CO2 and CO. Thus, they obtained a percent carbon
conversion to methanol of about 62% for a composition CO2/CO/H2
of 6/24/70, at 250 °C and 75 atm. In this study, in the case of using a
composition of the syngas entering the methanol synthesis reactor
CO2/CO/H2 equal to 5.8/21.6/70.6 (purge ratio of 0.1), it was ob-
tained a 64.9% conversion to methanol. Vanden Bussche and Fro-
ment [45] proposed the kinetic model for the methanol synthesis
and verified that their model describes well the experimental data
obtained by Klier et al. [44].
Likewise, Abrol and Hilton [46] obtained a mole fraction of
methanol at the loop outlet, before entering the purification sec-
tion, of 0.8998 for a syngas composition CO2/CO/H2/CH4 equal to
3.2/28.5/67.5/0.6 and using a purge ratio of 0.18 (recycle-to-purge
ratio of 4.5), operating at 250 °C and 51 atm.. In this study, a mole
fraction of methanol in crude stream of 0.8969 for a syngas compo-
sition CO2/CO/H2/CH4 equal to 3.7/26.9/68.1/0.6, using a purge ra-
tio of 0.20.
5. Conclusions
A comprehensive process for methanol and power production
from syngas obtained by reforming of glycerol using supercritical
water was proposed and studied. The aim was to maximize the
overall process efficiency in terms of total net power and methanol
production, under the criterion of making the overall process en-
ergy self-sufficient. The optimal conditions relative to the reform-
ing temperature and W/G ratio, along with the purge ratio in the
methanol synthesis loop, were identified. The results show that
the objective is achieved with the use of maximum reforming tem-
perature and minimum W/G ratio, corresponding to the admissible
minimum purge ratio. The overall specific value of methanol pro-
duction and power generation was computed using relative
weights for both variables, as well as the overall energy efficiency.
As a result of this research, the maximum value of these two in-
dexes were obtained using a reforming temperature of 1000 °C, a
W/G mass ratio of 1.68 and a purge ratio of 0.2, so a specific meth-
anol production of 0.270 kg MeOH/kg glycerol is obtained. The to-
tal net specific power from the expander and the fuel cell is
0.265 kW/kg glycerol. The overall energy efficiency is 38.0%, under
these conditions. In addition, the separated CO2 for sequestration is
0.38 kg/kg glycerol, which gives added value to the proposed
process.
Acknowledgments
This research is supported by the Science and Technology
Ministry of Spain under the research Project ENE2009-13755, as
a Project of Fundamental Research inside the framework of the
National Plan of Scientific Research, Development and Technologi-
cal Innovation 2008–2011.
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