Chemical Engineering & Processing: Process Intensification 179 (2022) 109080

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Chemical Engineering and Processing - Process

Intensification
journal homepage: www.elsevier.com/locate/cep

Influence of processing conditions on hydrogen Sonoproduction from

methanol sono-conversion: A numerical investigation with a
validated model
Aissa Dehane a, Slimane Merouani a, *, Atef Chibani a, Oualid Hamdaoui b,
Muthupandian Ashokkumar c
a
Laboratory of Environmental Process Engineering, Department of Chemical Engineering, Faculty of Process Engineering, University Salah Boubnider-Constantine 3, P.O.
Box 72, 25000, Constantine, Algeria
b
Chemical Engineering Department, College of Engineering, King Saud University, P.O. Box 800, 11421, Riyadh, Saudi Arabia
c
The University of Melbourne, Department of Chemistry, Parkville, Victoria, 3010, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: A comprehensive numerical investigation was conducted to analyze the effect of ultrasound frequency (213-1000
Methanol sonolysis kHz), ultrasonic intensity (0.7-1.5 W/cm2) and medium temperature (293.15-333.15 K) on the production of
Hydrogen production hydrogen from methanol decomposition inside acoustic bubbles (methanol sono-conversion). The adopted model
Ultrasound frequency
was firstly compared with some reference data. It was found that in the absence of methanol (in the presence of
Acoustic intensity
Liquid temperature
methanol), the bubble temperature, hydrogen production (and methanol conversion) are decreased monoto­
nously with an increase in frequency. The maximal bubble temperature is slightly impacted by the presence of
methanol under ultrasonic frequencies that are equal to or greater than 515 kHz. In addition, the yield of H2 is
larger in the presence of methanol, regardless of the utilized frequency. Between 213 to 355 kHz, methanol
conversion and hydrogen production are most efficient. Both H2 production and CH3OH degradation are
accelerated under an ideal acoustic intensity of 1 W/cm2. At a liquid temperature of 303.15 K, a turning point in
bubble temperature may be noticed in the absence of methanol, and at a liquid temperature of 323.15 K, the
highest hydrogen production can be achieved. Hydrogen production and methanol conversion are most efficient
at liquid temperatures between 293.15 and 303.15 K.

mixtures have to be used to avoid the formation of nitrogen oxides [10].

1. Introduction
In comparison to other traditional energy sources (methane, diesel
and gasoline), hydrogen has numerous advantages, including higher
heating value (141.9 kJ g− 1) [1], ability of storage in different forms
(liquid, gas, or in combination with metal hybrid), availability, and the
fact that it is a clean fuel with really no CO2 emissions, as well as being
able to be utilized in fuel cells to generate electricity [2–4]. Fossil fuels
are now the primary source of hydrogen production, which can be
accomplished by a variety of techniques like gasification, vapor
reforming and partial oxidation [1,5,6]. Alternative methods for
hydrogen production, such as water electrolysis, biological photosyn­
thesis and photocatalytic processes have been developed [7–9]. Once
produced, hydrogen is a clean synthetic fuel: when burnt with oxygen,
the only exhaust gas is water vapor, but when burnt with air, lean
The hydrogen as a fuel is a great source of energy that could be used in
different applications including space industry, transportation, fuel
cells, rockets, pumping and heating and more [10,11].
The sonochemical production of hydrogen has gained the interest of
many researchers as a clean, non-toxic and low-cost technique [12–22].
However, lower hydrogen yields has been reported from pure water
sonolysis (<40 µM/min) [12]. To overcome this inconvenient, many
different additives, either in the saturating gas or in the sonolyzed water,
can be used to increase the efficiency of the sonolytic yielding of
hydrogen. For example, the inclusion of hydrocarbons such as methane
and ethane results in a weighty increase in the production of hydrogen
[23]. In the hot gas phase of the bubble, methane and ethane can
penetrate, and their pyrolysis results in excessive amounts of hydrogen
[23]. Alcohols such as conventional and bio-methanol, on the other
hand, serve the same role as CH4 within the bubble, following the same

* Corresponding author.
E-mail address: s.merouani03@gmail.com (S. Merouani).

https://doi.org/10.1016/j.cep.2022.109080
Received 3 April 2022; Received in revised form 18 July 2022; Accepted 28 July 2022
Available online 30 July 2022
0255-2701/© 2022 Elsevier B.V. All rights reserved.
A. Dehane et al.
Nomenclature
Af (Ar) Pre-exponential factor of the forward (reverse) reaction,
[(cm3 mol− 1 s− 1) for two body reaction and (cm6 mol− 2
s− 1) for three body reaction].
bf (br) Temperature exponent of the forward (reverse) reaction.
c Speed of sound in the liquid medium, (m s− 1).
Eaf (Ear) Activation energy of the forward (reverse) reaction, (cal
mol− 1).
f Frequency of ultrasonic wave, (Hz).
Ia Acoustic intensity of ultrasonic irradiation, (W m− 2).
kf (kr) Forward (reverse) reaction constant, [(cm3 mol− 1 s− 1) for
two body reaction and (cm6 mol− 2 s− 1) for three body
reaction].
p Pressure inside a bubble, (Pa).
pmax Maximum pressure inside a bubble (Pa).
p∞ Ambient static pressure, (Pa).
PA Amplitude of the acoustic pressure, (Pa).
Pv Vapor pressure of water, (Pa).
R Radius of the bubble, (m).
Rmax Maximum radius of the bubble, (m).
R0 Ambient bubble radius, (m).
Rg Ideal gas constant (J mol− 1 K− 1).
t Time, (s).
T Temperature inside a bubble, (K).
pyrolytic pathway [24,25]. The concentration of these additives, on the
other hand, should be carefully controlled because an excessive con­
centration could reduce (or suppress) the yield of hydrogen production.
On the other hand, hybrid technologies, such as sonocatalysis, photo­
sonolysis and sonophotocatalysis are being developed to improve the
efficiency of the sono-generated hydrogen. An interesting review tracing
the different studies on hydrogen production by ultrasound has been
provided by Merouani and Hamdaoui [12].
The intensification of hydrogen sono-production (from water
sonolysis) using alcohols dilute aqueous solution has been proven
experimentally. Buettner et al. [26] have studied the sonolysis of
water-methanol mixtures at 1 MHz under argon atmosphere. In deion­
ized water, H2 was generated at 22 µM/min. When methanol is added to
the solution, the H2 rate increased to 100 µM/min at 5% (v/v) of
methanol and 150 µM/min at 10% (v/v) of methanol, but as methanol
higher concentrations rise, the molar yield of H2 progressively goes
down until no H2 was detected at roughly 80% (v/v) of methanol. When
using 38 kHz ultrasound in water and water/ethanol (20% v/v) under
argon saturation, Penconi et al. [27] observed a 1.4-fold increase in the
rate of H2 generation. Rassokhin et al. [24] have noted that the gener­
ation rates of the sonolysis products (e.g. H2, CH4 and CO) of methanol
increase (H2: from 33.3 to 167.0 µM/min) with the increase of its con­
centration from 0.001 to 0.50 M in the sonicated solutions, where the
molar yield of these species is as: H2>CO>CH4. Rassokhin et al. [24]
have shown that depending on the mole fraction of methanol in the bulk
solution, an optimum medium temperature is retrieved for the maximal
hydrogen production ([H2]max = 200 µM/min at ~30◦ C and xMeOH=
0.018), where the increase of methanol concentration decreases the
temperature at which the maximal H2 formation rate is reached.
Several numerical studies have focused on hydrogen synthesis using
sonochemistry [12,14,28–30]. These studies have shown promising
outcomes of clean and efficient hydrogen generation. Merouani et al.
[12] and Kerboua et al. [17] have recently published fascinating reviews
on hydrogen generation using sonochemistry. Kerboua et al. [19] stud­
ied numerically the influence of the saturating atmosphere (O2 and Ar)
on the sono-pyrolysis of CH3OH, finding that regardless of the quantity
of argon, a maximum molar yield was obtained for a solution comprising
2
Chemical Engineering and Processing - Process Intensification 179 (2022) 109080
Tmax Maximum temperature inside a bubble, (K).
T∞ Bulk liquid temperature, (K).
x Thermal diffusivity inside the bubble, (m2 s− 1)
Cp Heat capacity concentration inside the bubble, (J m− 3 K− 1)
MH2O Molar mass of water (kg mol− 1).
ṁ Evaporation-condensation rate of water, (kg m− 2 s− 1).
Q Energy transferred by heat exchange, (J s− 1)
n Molar amount, (mol).
PB Liquid pressure on the external side of the bubble wall,
(Pa).
V Volume of the bubble, (m3).
Greek letters
σ Surface tension of liquid water, (N m− 1).
ρl Density of liquid water, (kg m− 3).
ρg Density inside the bubble (kg m− 3).
λmix Thermal conductivity of the mixture (W m− 1 K− 1).
λi Thermal conductivity of species i (W m− 1 K− 1).
µ Dynamic viscosity (Pa s).
α Accommodation coefficient.
ρH2O Density of water vapor inside the bubble (kg m− 3).
ρsat,H2O Saturated vapor density (kg m− 3).
υki Stoichiometric coefficient of the kth chemical species in the
ith reaction.
U̇k Production rate of the kth species (mol s− 1 m− 3).
40% of CH3OH. Kerboua et al. [19] also reported that a 40% methanol
concentration and a 40% molar fraction for argon provide the maximum
molar output. Kerboua et al. [29] determined that the optimal combi­
nation for H2 generation and CH3OH conversion is achieved for a so­
lution with 20% methanol (v/v) saturated with 70% molar of argon,
thereby 99.9% of the methanol is removed and about 60% of the
methanol is converted to hydrogen. Dehane et al. [31] used a compre­
hensive mathematical model for single bubble sono-pyrolysis of meth­
anol to investigate the effect of methanol dosage (in the bulk phase) on
the maximum sonochemical performance for hydrogen production,
CH3OH consumption and the range of active bubbles. They discovered
that the aqueous phase methanol dosage (0-100 % (v/v)) has little
impact on the spectrum of active bubble sizes for CH3OH consumption.
In the case of hydrogen generation, however, for methanol concentra­
tions more than 20%, the active bubble ranges gradually diminish. At
80% argon (in the initial gas composition) and a methanol content of 7
to 20%, the maximum efficacy for CH3OH conversion, hydrogen pro­
duction and the width of active bubble sizes (for H2 generation and
CH3OH decomposition) is reached. Nevertheless, the Dehan’s investi­
gation [31] is not complete as all results were done for single matrix of
operational conditions (frequency: 355 kHz, In = 1 W/cm2 and Tliq =
20◦ C). According to the available theoretical studies [19,29,31] focusing
on methanol sono-decomposition, the effect of operational conditions
(ultrasound frequency, acoustic intensity and the bulk temperature)
have not covered yet.
In the present paper, the sono-production of hydrogen from meth­
anol sono-conversion in a single bubble is analyzed at varying ultra­
sound frequencies (213-1000 kHz), acoustic intensities (1 and 2 W/cm2)
and liquid temperatures (293.15-333.15 K). The model developed early
[31] by our research group is adopted for this task. To the best of our
knowledge, the effects of these operational conditions have not been
treated previously. For this purpose, a reaction mechanism for methanol
combustion within the cavity has been adopted. The model was firstly
validated by some available experimental data before assessing the pa­
rameters’ influence. It should be stressed here that a deep analysis of the
effects of these operating conditions (wave frequency, acoustic power,
and liquid temperature) enables us to better understand their impacts on
A. Dehane et al. Chemical Engineering and Processing - Process Intensification 179 (2022) 109080

the formation of H2 from CH3OH sono-conversion as well as to deter­
mine the appropriate conditions (of ultrasound frequency, acoustic in­
tensity and liquid temperature) for the maximal production
(intensification) of H2 (from methanol sono-combustion).
2. Model
In the presence of CH3OH, the single-bubble model we developed
early [31] is adopted herein. The essential points of this model are given
in this section. Based on ordinary differential equations, our model takes
into consideration chemical processes (of both water and methanol
pyrolysis), methanol and water molecules’ non-equilibrium condensa­
tion and vaporization at the bubble wall, as well as heat transfer
between the bubble and the neighboring liquid. Table 1 outlines the
equations that govern the model. All numerical calculations were done
for a bubble in Ar-O2-saturated water with 20 (vol.)% methanol. The
interactions between bubbles are disregarded. Tables 2 and 3 indicate
the reaction pathways utilized to analyze the interior bubble chemistry
for the cases of Ar-O2-bubble (0% of methanol, Table 2, 38 reactions)
and Ar-O2-CH3OH bubble (Table 3, 32 reactions). The physical proper­
ties of the surrounding liquid in presence of methanol (20%, v/v) are
calculated according to the molar fraction contribution of water and
methanol (see Table 4). Table 1 provides the following main equations:
1 Eq. 1 (the Keller-Miksis modified model [32]) describes the
bubble-radius dynamics, R(t), in an aqueous methanol solution.

Table 1
Principal equations of the model (see detail in Refs. [31,35])*.
Bubble dynamics:
( ) ( ) ( →)[ ( ( )) ]
R̂ ṁ 3 2 R 2ṁ 1 R R
1− + RR̈ + Ṙ 1 − + = 1+ PB (t) − PA sin 2πf t + − P∞
c CpL 2 3C 3cL ρL C C
(Eq. 1)
( ) ( )
m̈R Ṙ ṁ ṁ ṁ Ṙṁ R dPB
+ 1− + + Ṙ + + +
ρL C CρL ρL 2ρL 2CρL CρL dt
- Pressure at the external bubble wall:
2σ 4μṘ
PB (t) = P(t) − − (Eq. 2)
R R
- Bubble pressure and Temperature:
nRg T an2
P(t) = + (Eq. 3)
V − nb) V2
2
( an
E+
V
T= (Eq. 4)
Cv nt
Mass transfer (water vapor and methanol condensation and evaporation):
{Psat,i [R] − Pi
ṁ = α √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ i = H2 O or CH3 OH (Eq. 5)
2πT[R] Rg
Mi
Heat transfer (thermal conduction):
(Tliq− T)
Q̇ = 4πR2 λmix (Eq. 6)
Lth
}
{ R √̅̅̅̅̅̅
RX
Lth = min ′ (Eq. 7)
π R
(n ) ( ) ( ) ( )
nAr nCH3OH nO2
(Eq. 8)
H2 O
λmix = λH2 O (T) + λAr (T) + λCH3OH (T) + λO2 (T)
nt nt nt nt
Internal bubble energy:
ṁ,H2O (TIiq − T) 4 3 ∑n ṁ,CH3OH
ΔE = − P(t)ΔV(t) + 4πR2 Δt eH2O + 4πR2 Δtλ − πR Δt i=1 ΔHi ri + 4πR2 Δt eCH3OH (Eq. 9)
MH2O Lth 3 MCH3OH
Change in species quantities (mol)
- For H2O and CH3OH:
ṁ,i
ni (t +Δt) = ni (t) + 4πR2 Δt + VΔtU̇i i = H2 O or CH3 OH (Eq. 10)
Mi
- For other species k (except Ar):
nk (T + Δt) = nk (T) + VΔtUk (Eq. 11)
Where:
1 dnk ∑I
U̇k = (υ′′ − υ )ri (k = 1, …, K) (Eq. 12)
′

v dt i=1
∏K ∏ x
ri = kfi k=1 [Xk ]υ ki − kri Kk=1 [Xk ]υki (Eq. 13)
′

( Ea )
kfi = Afi Tbfi exp − fi
(Eq. 14)
Rg T
( E )
a
kri = Ari Tbri exp − ri
(Eq. 15)
Rg T

*Variables description: dots denoted here time derivative (d/dt), R is the bubble radius, C is the sound speed in the medium (water), ρL is the liquid density, ṁ is the net
rate of evaporation per unit area and unit time and P∞ is the ambient static pressure. PA is the acoustic amplitude (linked to the acoustic intensity Ia by: PA=(2IaρLC)1/2),
PB(t) is the liquid pressure at the liquid side of the bubble, P(t) is the pressure inside the bubble. σ is the surface tension, μ is the liquid viscosity), f is the sound
frequency, Pv is the vapor pressure within the bubble, a and b (in Eqs. 3and 4) are the Van de Waals constants (given in [36]), Rg is the universal gas constant. V is the
volume of the bubble [V=4/3(πR3)], T is the temperature inside the bubble, E is the internal bubble energy, Psat[R] is the saturated vapor pressure (calculated by using
Antoine’s equation) at the interface temperature T[R] = Tliq, MH2O or CH3OH is the molecular weight of water vapor or methanol. ‘α’ is the accommodation coefficient
(given in [29]). λmix, χ and Lth are the heat conductivity, thermal diffusivity of the gas mixture and the thickness of the thermal boundary layer, respectively. [In­
dividual λi of gases [36–38]: λH2O(T) = 9.967213 × 10− 5T - 1.1705 × 10− 2, λAr(T) = 3.5887 × 10− 5T + 6.81277 × 10− 3, λCH3OH(T) = -0.0161+1.02 × 10− 4T, λO2(T)=
7.2211 × 10− 3+6.4478 × 10− 5T, χ =[λmix/Cp]. Cp is the heat capacity concentration (J m− 3 K− 1) for H2O, Ar and CH3OH mixture, Cv is the molar heat of gases and
vapor in the bubble [Cv = (3/2)Rg for monoatomic gases (Ar, H…), (5/2)Rg for diatomic gases (O2, N2, …) and (6/2)Rg for triatomic gases]. ΔHi and ri are the enthalpy
change and the rate of the ith reaction, respectively, and eH2O (eCH3OH) is the energy transported by 1 mole of an evaporating or condensing water vapor (methanol) [e,i
= Cv,iT, i=H2O or CH3OH], U̇i (U̇k ) is the production rate of H2O or CH3OH (kth species) within the bubble. It should be noted that the physical properties of liquid in
presence of methanol are calculated according to the molar fraction contribution of water and methanol (20%, v/v) (see Table 4).

3
A. Dehane et al. Chemical Engineering and Processing - Process Intensification 179 (2022) 109080

Table 2 Table 3
Scheme of the possible chemical reactions inside a collapsing Ar-O2-bubble [39, Scheme of the possible chemical reactions inside a collapsing Ar-O2-CH3OH
40]. M is the third Body. A is in (m3 mol− 1 s− 1) for two body reaction [(m6 mol− 2 bubble [19,29,41,42]. M is the third Body. A is in (m3 mol− 1 s− 1) for two body
s− 1) for a three body reaction], and Ea is in (kJ mol− 1) and ΔH in (kJ mol− 1). reaction [(m6 mol− 2 s− 1) for a three body reaction], and Ea is in (kJ mol− 1) and
N◦ Reaction A n Ea ΔH
ΔH in (kJ mol− 1).
7 N◦ Reaction A n Ea ΔH
1 H2O+M → H + OH+M
• •
1.912 × 10 -1.83 28.35 508.82
2 O2+M → O+O+M 4.515 × -0.64 28.44 505.4 1 H2O+M → H•+•OH+M 1.912 × -1.83 28.35 508.82
1011 107
3 •
OH+M →O+H•+M 9.88 × 1011 -0.74 24.43 436.23 2 CH3OH + O2 → CH2OH 2.0 × 107 0.0 1.88 × 105 196.492
4 H•+O2 →O+•OH 1.915 × 108 0.0 3.93 69.17 + H2O2
5 H•+O2 +M →HO•2 +M 1.475 0.6 0.0 -204.80 3 CH3OH + HO2→ 8.0 × 107 0.0 8.11 × 104 -35.508
6 O+H2O → •OH+•OH 2.97 2.02 3.21 72.59 CH2OH• + H2O2
7 HO•2+H• → H2+O2 1.66 × 107 0.0 1.97 × 10− 1
-239.67 4 CH3OH + H• → CH2OH• 1.35 × 3.2 1.46 × 104 -34.057
8 HO•2+H• →•OH+•OH 7.079 × 107 0.0 7.06 × 10− 2
-162.26 + H2 10− 3
9 HO•2+O → •OH+O2 3.25 × 107 0.0 0.0 -231.85 5 •
OH + •OH → HO•2 + H• 1.08 × 0.61 1.51 × 154.957
10 HO•2+•OH → H2O+O2 2.89 × 107 0.0 - 1.19 × -304.44 1005 1005
10− 1 6 HO•2 + •OH → H2O+ O2 2.89 × 0.00 − 2.08 × − 291.451
11 H2+M → H•+H•+M 4.577 × -1.4 24.98 444.47 1007 1003
1013 7 HO•2 + O → •OH + O2 2.00 × 0.00 0.00 − 224.131
12 O+H2 → H•+•OH 3.82 × 106 0.0 1.9 8.23 1007
13 •
OH+H2 → H•+H2O 2.16 × 102 1.52 8.25 × 10− 1
-64.35 8 HO•2 + H → H2 O+ O
•
3.10 × 0.00 7.20 × –22.957
14 H2O2+O2 → HO•2+HO•2 4.634 × -0.35 12.12 175.35 1007 1003
1010 9 HO•2 + H → H2 + O2
•
1.66 × 0.00 3.44 × − 230.293
15 H2O2+M → 2.951 × 108 0.0 11.59 217.89 1007 1003
•
OH+•OH+M 10 HO•2 + H• → 2 •OH 7.08 × 0.00 1.23 × − 155.613
16 H2O2+H• → H2O+•OH 2.410 × 107 0.0 9.5 × 10− 1
-290.93 1007 1003
17 H2O2+H• → H2+HO•2 6.025 × 107 0.0 1.9 -64.32 11 CH2OH• + O2 → CH2O+ 5.00 × 0.00 0.00 − 79.404
1
18 H2O2+O → •OH+HO•2 9.550 2.0 9.5 × 10− -56.08 HO•2 1006
19 H2O2+•OH → 1.0 × 106 0.0 0.0 -128.67 12 CH3OH + •OH → 4.4 × 1000 2.0 6.3 × 10 3
-54.215
H2O+HO•2 CH3O•+ H2O
10
20 H•+•OH+M → H2O+M 2.2 × 10 -2.0 0.0 - 508.82 13 CH3OH + •OH → 1.44 × 2.0 -3.51 × -95.215
21 O+O+M → O2+M 6.165 × 103 -0.5 0.0 -505.4 CH2OH• + H2O 1000 103
22 O+H•+M → •OH+M 4.714 × 106 -1.0 0.0 -436.23 14 CH3O•+ M → CH2OH• + 1.00 × 0.00 8.00 × − 38.000
23 O+•OH → H•+O2 5.481 × 105 0.39 -7.01 × -69.17 M 1008 1004
10− 2 15 CH3O•+ M → CH2O+ 7.78 × 0.00 5.65 × 126.297
24 HO•2 +M → H•+O2 +M 3.09 × 106 0.53 11.7 204.80 H•+ M 1007 1004
25 •
OH+•OH → O+H2O 1.465 × 2.11 -6.94 × -72.59 16 CH3O•+ O2 → CH2O+ 4.28 × 7.60 − 1.48 × − 117.404
10− 1 10− 1 HO•2 10− 19 1004
26 H2+O2 → HO2• +H •
3.164 × 106 0.35 13.3 239.67 17 CH2O+ HO•2 → HCO• + 4.11 × 2.50 4.27 × − 48.976
27 •
OH+•OH → HO•2+H• 2.027 × 104 0.72 8.8 162.26 H2O2 10− 02 1004
28 •
OH+O2 → HO•2+O 3.252 × 106 0.33 12.75 231.85 18 CH2O+ •OH → HCO• + 3.90 × 0.89 1.70 × − 128.159
29 H2O+O2 → HO•2+•OH 5.861 × 107 0.24 16.53 304.44 H2O 1004 1003
30 H•+H•+M → H2+M 1.146 × 108 -1.68 1.96 × 10− 1
- 444.47 19 CH2O+ O → HCO• + 3.50 × 0.00 1.47 × − 60.839
31 H•+•OH → O+H2 2.667 × 2.65 1.17 - 8.23 •
OH 1007 1004
10− 2 20 CH2O+ H• → HCO •+ H2 5.74 × 1.90 1.15 × − 67.001
32 H•+H2O → •OH+H2 2.298 × 103 1.40 4.38 64.35 1001 1004
33 HO•2+HO•2 → H2O2+O2 4.2 × 108 0.0 2.87 - 175.35 21 HCO• + O2 → CO + HO•2 7.58 × 0.00 1.72 × − 140.530
34 •
OH+•OH+M → 1.0 × 102 -0.37 0.0 - 217.89 1006 1003
H2O2+M 22 HCO + M → CO + H +
• •
1.86 × − 1.00 7.11 × − 65.171
35 H2O+•OH → H2O2+H• 1.269 × 102 1.31 17.08 290.93 M 1011 1004
36 H2+HO•2 → H2O2+H• 1.041 × 105 0.70 5.74 64.32 23 CO + •OH → CO + H•+ 4.40 × 1.50 − 3.10 × − 212.853
37 •
OH+HO•2 → H2O2+O 8.66 × 10− 3 2.68 4.45 56.08 CO2 1000 1003
38 H2O+HO•2 → 1.838 × 104 0.59 7.4 128.67 24 2 HO•2 → H2O2 + O2 3.02 × 0.00 5.80 × − 212.268
H2O2+•OH 1006 1003
25 H2O2 + M → 2 •OH + M 8.15 × − 1.92 2.08 × 262.356
Third body efficiency factors: R1: αH2 = 0.73, αH2O = 12, αAr = 0.38; R2: αH2 =
k0 1017 − 1.39 1005
2.5, αH2O = 12, αAr = 0.75; R3: αH2 = 2.5, αH2O = 12, αAr = 0.83; R5: αH2 = 1.3, k∞ 2.62 × 2.15 ×
αH2O = 14, αAr = 0.67; R11: αH2 =2.5, αH2O=12. R15: αH2 = 2.5, αH2O = 12, αAr = 1013 1005
0.64; R20: αH2 = 0.73, αH2O = 12, αAr = 0.38; R21: αH2 = 2.5, αH2O = 12, αAr = 26 H•+ O2 + M → HO•2 + M 5.75 × − 1.40 0.00 − 205.701
0.75; R22: αH2 = 2.5, αH2O = 12, αAr = 0.83; R24: αH2 = 1.3, αH2O = 14, αAr = 0.67; k0 1007 0.44 0.00
R30: αH2 =2.5, αH2O=12; R34: αH2 = 2.5, αH2O = 12, αAr = 0.64. k∞ 4.65 ×
1000
27 H2 + O → •OH + H• 5.06 × 2.67 2.63 × 6.162
2 Eqs. 3 and 4 provide the internal bubble pressure and temperature 10− 02 1004
during oscillation. 28 H + O2 → OH + O
• •
3.52 × − 0.70 7.14 × 68.518
3 Eq. 5 describes the Hertz-Knudsen model [33] for water vapor and 1010 1004
29 CH2OH•+ H• → CH2O+ 3 × 107 0.0 0.0 -309.578
methanol mass transport.
H2
4 Eqs. 6-8 (heat dissipation by conduction [34]) describe the heat ex­ 30 2 •OH → HO•2 1.08 × 0.61 1.51 × 105 154.957
change dQ/dt inside and outside the bubble during oscillation. 105
5 Eq. 9 describes the change vs. time of the internal bubble energy. 31 CH2OH + OH →
• •
2.4 × 107 0.0 0.0 -370.7
6 Eqs. 10-15 describe the change, with time, in quantities of H2O and CH2O+ H2O
32 •
CH3+ HO•2 → CH4+O2 3.61 × 0.0 0.0 -233.852
all other species ‘k’ within the bubble during oscillation. Through
106
applying Eqs. (12)-(15), the temporal production rates (Uk) of all
species (10 species) within the bubble can be established as function Third body efficiency factors: R1:αH2=2.5, αH2O =16, αAr =1, αCO =1.9, αCO2
of concentrations and kinetic parameters (rate constants, k) as (ac­ =3.8, αCH4 =16, αCH3OH =5; R7: αH2= 2, αH2O =6, αAr =0.7, αCO =1.5, αCO2 =2,
αCH4 =, others 1; R15:αH2=2, αH2O =6, αAr =0.7, αCO =1.5, αCO2 =2, αCH4 =2,
cording to Table 2):

4
A. Dehane et al. Chemical Engineering and Processing - Process Intensification 179 (2022) 109080

others 1. R22:αH2=1.9, αH2O =12, αAr =, αCO =2.5, αCO2 =2.5, αCH4 =, others 1; kHz [44], 3 µm for 515 kHz [45] and 2 µm for 1000 kHz [44] were used
R25:αH2=2, αH2O =6, αAr =0.4, αCO =1.5, αCO2 =2, αCH4 =, others 1; R26:αH2=2.5, in the numerical simulation of this study (see also Refs. [21,46,47]).
αH2O =16, αAr =0.7, αCO =1.2, αCO2 =2.4, αCH4 =, others 1. These values are the mean ambient bubble radii of active bubbles at the
given frequencies (determined experimentally). Several numerical in­
vestigations [22,48–50] based on single bubble sonochemistry models
Table 4
supported the R0 values adopted in this study. The variation of the
Physical properties of methanol and water at 293.15 K and 1 atm [43].
bubble temperature (Eq. 4), pressure (Eq. 3), radius and the wall ve­
Compound Surface tension Viscosity Sound velocity Density (kg/
locity (Eq. 1), as well as the mole numbers of all species (except argon,
(N/m) (Pa.s) (m/s) m3)
which is chemically inert) in the bubble (Eqs. 10, 11) are all outputs of
2
Methanol 2.256 × 10− 5.7548 × 1116.2 791.02 Table 1 equations, which are applied throughout the bubble lifetime.
10− 4
− 2 3 The initial pressures of Ar, O2, H2O and CH3OH inside the bubble fulfill
Water 7.245 × 10 1.0 × 10− 1482.0 998.12
the equilibrium relation: P0 = P∞ +2σ /R0, where P0 is the internal
bubble pressure (Pv,0+PCH3OH,0+PAr,0+ PO2,0) at equilibrium, R=R0 (PAr,
• U̇H2O = dn
V dt = -{kf1[H2O][M]- kf20[H][OH][M]} –{kf6[H2O][O]-
H2O
0+ PO2,0: initial gas pressure “Pg,0”). The initial pressure of CH3OH
kf25[OH][OH]}+ {kf10[HO2][OH]- kf29[H2O][O2]}+ {kf13[OH] within the bubble is governed by Raoult’s law: PCH3OH,0=XCH3OH,0 × Psat,
[H2]- kf32[H][H2O]} +{kf16[H2O2][H]-kf35[H2O][OH]} + CH3OH,0 (Psat,CH3OH,0=0.13 bar at 293.15 K), where X CH3OH,0 is the
{kf19[H2O2][OH]-kf38[H2O][HO2]}. CH3OH mole fraction in the aqueous phase (from 0 to 1). The physical
• U̇O2 = dn properties of methanol and water are given in Table 4. The water vapor
V dt = -{kf2[O2][M]- kf21[O][O][M]} – {kf4[H][O2]-kf23[O]
O2

pressure (Pv,0) is calculated through Antoine’s equation (2.33 kPa at

[OH]}- {kf5[H][O2][M]-kf24[HO2][M]}+ {kf7[HO2][H]-kf26[H2]
293.15 K [51]). The initial gas pressure Pg,0 is calculated as Pg,0 = P0-(Pv,
[O2]}+ {kf9[HO2][O]-kf28[OH][O2]}+ {kf10[HO2][OH]-kf29[H2O]
0+P CH3OH,0). Initial mole fractions of CH3OH, H2O, Ar and O2 were
[O2]}- {kf14[H2O2][O2]-kf33[HO2][HO2]}
calculated as Pi,0/P0, where i = CH3OH, H2O, Ar and O2. More details are
• U̇OH = dn OH
V dt = {kf1[H2O][M]-kf20[H][OH][M]}- {kf3[OH][M]-
given in Ref. [31].
kf22[O][H][M]}+ {kf4[H][O2]-kf23[O][OH]}+2 × {kf6[O][H2O]-
kf25[OH][OH]}+ 2 × {kf8[HO2][H]-kf26[OH][OH]}+ {kf9[HO2] 3. Results and discussions
[O]-kf28[OH][O2]}- {kf10[HO2][OH]-kf29[H2O][O2]}+{kf12[O]
[H2]-kf31[H][OH]}- {kf13[OH][H2]-kf32[H][H2O]}+ 2 × According to our previous work [31], the maximal H2 yield and
{kf15[H2O2][M]-kf34[OH][OH][M]}+ {kf16[H2O2][H]-kf35[H2O] CH3OH conversion could be achieved at a specific methanol aqueous
[OH]} + {kf18[H2O2][O]-kf37[OH][HO2]}- {kf19[H2O2][OH]- dosage of 20 (vol)% with 80% (molar %) of argon inside the bubble.
kf38[H2O][HO2]} Consequently, to facilitate our task (analyzing of frequency, temperature
• U̇H = Vdndt
H
= {kf1[H2O][M]-kf20[H][OH][M]}+{kf3[OH][M]- and sound intensity impacts), throughout the present study, the aqueous
kf22[O][H][M]} – {kf4[H][O2]-kf23[O][OH]} – {kf5[H][O2][M]- concentration of methanol is fixed at 20% with a bubble initial gas
kf24[HO2][M]}- {kf7[HO2][H]-kf26[H2][O2]} –{kf8[HO2][H]- content of 80% argon and 20% oxygen (the rest is for methanol and
kf27[OH][OH]}+2 × {kf11[H2][M]-kf30[H][H][M]}+{kf12[O] water vapor). The effects of the operating conditions were investigated
[H2]-kf31[H][OH]}+ {kf13[OH][H2]-kf32[H][H2O]} – {kf16[H2O2] by the variation of the ultrasound frequency (213, 355, 515 and 100
[H]-kf35[H2O][OH]}-{kf17[H2O2][H]-kf36[H2][HO2]}. kHz), acoustic intensity (0.7, 1 and 1.5 W/cm2) and liquid temperature
• U̇O = Vdndt
O
= 2 × {kf2[O2][M] –kf21[O][O][M]}+ {kf3[OH][M]- (293.15 to 333.15 K). Accordingly, their values are injected in the
kf22[O][H][M]}+ {kf4[H][O2]-kf23[O][OH]} - {kf6[O][H2O]- mathematical model resumed in Table 1.
kf25[OH][OH]]}- {kf9[HO2][O]-kf28[OH][O2]} – {kf12[O][H2]-
kf31[H][OH]} – {kf18[H2O2][O]-kf37[OH][HO2]}. 3.1. Model validation
• U̇HO2 = dn
V dt = {kf5[H][O2][M]-kf24[HO2][M]} - {kf7[HO2][H]-
HO2

kf26[H2][O2]} - {kf8[HO2][H]- kf27[OH][OH]} –{kf9[HO2][O]- Before going into the various findings in this paper, we would want
kf28[OH][O2]}- {kf10[HO2][OH]-kf29[H2O][O2]} + 2 × to compare the predicted bubble temperatures achieved by our model to
{kf14[H2O2][O2]-kf33[HO2][HO2]}+ {kf17[H2O2][H]-kf36[H2] those estimated empirically by Rae et al. [52] (by the methyl radical
[HO2]}+ {kf18[H2O2][O]-kf37[OH][HO2]}+ {kf19[H2O2][OH]- recombination technique) for an argon-methanol aqueous solution at
kf38[H2O][HO2]}. varying dosages of the alcohol (0-500 mM), where the frequency, the
• U̇H2 = dn intensity and the bulk solution temperature were 355 kHz, 2W/cm2 and
V dt = {kf7[HO2][H]-kf26[H2][O2]} – {kf11[H2][M]-kf30[H]
H2

[H][M]}- {kf12[O][H2]-kf31[H][OH]} – {kf13[OH][H2]-kf32[H]
[H2O]}+ {kf17[H2O2][H]-kf36[H2][HO2]}.
dnH2O2
• U̇H2O2 = V dt = - {kf14[H2O2][O2]-kf33[HO2][HO2]}-
{kf15[H2O2][M]-kf34[OH][OH][M]}- {kf16[H2O2][H]-kf35[H2O]
[OH]}- {kf17[H2O2][H]-kf36[H2][HO2]}- {kf18[H2O2][O]-kf37[OH]
[HO2]}- {kf19[H2O2][OH]-kf38[H2O][HO2]}.
• U̇Ar = VdnArdt = 0.
The above kinetical equations system (derived from Eq. 12) is
coupled with the two differential equation derived from Eq. 1 (i.e.,
providing dR/dt and d2R/dt2) and Eqs. (4)-(6), (10) and (11), and the
system of all these differential equations are solved using finite differ­
ence method (using FORTRAN 95 software). The initial conditions are:
at t = 0, R = R0, dR/dt = d2R/dt2 = 0, T=T∞, dPdtB = 0, dm
2
d m
dt = 0, dt2 = 0. A
time step of 10− 4 µs is used for the resolution of the system of the dif­
ferential equation. On the other hand, fixed experimental values of
ambient bubble radii of R0 =3.9 µm for 213 kHz [44], 3.2 µm for 355
~293.15 K. According to Fig. 1(a), our model goodly captures the data
of methanol effect on the bubble temperature, particularly for lower
alcohol dosages. For 0 mM methanol, the model provided 4570.2 K
against 4600 K for Rae et al. data, showing a deviation of <1%. Simi­
larly, lower deviations of ~1.8% and 2.5% are also marked for 60 and
150 mM of methanol, respectively. However, a relatively higher devi­
ation is recorded for greater CH3OH concentration (> 200 mM).
Nevertheless, the global tendency of the bubble temperature variation
with the alcohol dosage was excellent followed by the model.
It should be noted that there is no peak temperature at 100 mM of
MeOH, because above 50 mM of MeOH in solution, the experimental
bubble temperature fluctuated around a near plateau value (3500 K).
This phenomenon (trend) is confirmed experimentally by several re­
searchers where the bubble temperature was estimated using different
alcohols (methanol, ethanol, n-propanol, n-butanol and tert-butanol) at
different frequencies [52–54]. On the other hand, the predicted bubble
temperature (using our model) is that achieved at the end of the bubble
collapse (the maximum bubble temperature), without considering the
interactions between bubbles in the sonicated medium (isolated bubble,

5
A. Dehane et al.
Fig. 1. Comparison between (a) our simulated bubble temperature and those
retrieved experimentally by Rea et al. [52] at 355 kHz, In = 2 W/cm2, Tliq =
293.15 K, P∞= 1 atm (the R0, ambient radius, used for this simulation is 3.2 µm
[44]), and (b) our normalized simulated production rate of H2 and those ob­
tained experiemebntally by Butner et al. [26] at 1000 kHz and 2 W/cm2 under
argon atmosphere (the R0, ambient radius, used for this simulation is 2
µm [44]).
as indicate in the model section). Adding alcohol into the sonicated
solution could increase the methanol portion in the bubble, which could
decrease the maximum bubble temperature at certain level of MeOH (i.
e., 50 mM), above which no further bubble reduction is obtained.
Therefore, the numerical intergradation could not yield any peak tem­
perature at 100 mM, because, simply, there is no effective peak tem­
perature (even experimentally) in the presence of methanol. Therefore,
the best trend of temperature variation with methanol additions was
that obtained numerically through our model.
Finally, taking into account the maximum difference (280 K at 500
mM) observed between our findings and those of Rae et al. [52], in
addition to the experimental errors observed in the experimental
method of Rae et al. (±250 K), it can be concluded that our results are
very acceptable. Therefore, our model is reliable in forecasting the
bubble temperature, and as a result, it may be trusted to be used to
investigate the impact of the diverse acoustical and medium parameters
(i.e., for instance: frequency, intensity and liquid temperature) on the
acoustical generation of hydrogen from methanol sono-conversion
within the cavitation bubble. Note that with 100 mM CH3OH, the
temperature of the cavity drops from 4610 to 3940 K due to the
CH3OH-induced augmentation in the heat capacity of the gas mixture in
the bubble, as well as its endothermal dissociation. However, the in­
crease in alcohol dosage above 100 mM has relatively little influence on
the maximum bubble temperature (Tmax ~3910 K).
Further evidence of the precision of our model was done through
6
Chemical Engineering and Processing - Process Intensification 179 (2022) 109080
confronting the results of H2 production obtained theoretically using our
model to those retrieved experimentally by Buttner et al. [26] at 1000
kHz and an acoustic intensity of 2 W/cm2. In Fig. 2(b), the normalized
yields of H2 are given over a range of 0 % to 80 % (v/v) for an aqueous
solution of methanol. As it can be seen, the outputs of our chemical
mechanism (Ar-CH3OH-bubble, Table 2) are in good concordance with
those obtained empirically by Buttner et al. [26] for the whole range of
methanol volume concentration (0-80%).
3.2. Effect of ultrasound frequency on hydrogen production and methanol
conversion
In Figs. 2(a)-(d), the yield of H2 production and CH3OH conversion
are shown as a function of ultrasound frequency (from 213 to 1000 kHz)
at 1 W cm− 2 in the presence (20%, v/v) and absence of methanol in the
liquid. First, as it was expected, the increase of the wave frequency af­
fects negatively (decreases) the molar production of hydrogen and the
peak temperature of the bubble (and methanol conversion when it is
present in solution, Figs. 2(b,c)) either in the presence or absence of
methanol, Fig. 2(a). This trend was largely reported in different exper­
imental and theoretical inquiries [44,47,55,56]. This behavior is logi­
cally ascribed to the reduction of the collapse intensity as well as the
molar production of the acoustic cavitation with the rise of frequency
[47,55,57]. In other words, as the wave frequency increases (the
acoustic period shortens), less water vapor (and methanol molecules, if
present in solution) enters the acoustic cavitation during the expansion
phase, resulting in a milder collapse. Consequently, a lower bubble
temperature will be obtained at the end of bubble compression, which
means that a lesser amount of hydrogen (and methanol conversion)
molecules will be obtained via water vapor dissociation (and methanol
combustion). Additionally, the presence of methanol (20% in solution)
decreases more the maximal temperature of the bubble (especially at
213 and 355 kHz) through the increase of its heat capacity and the
endothermic dissociation of methanol [31,58]. However, as it can be
seen in Fig 2(a), for wave frequencies that are equal to or greater than
515 kHz, the peak temperature of the bubble is slightly affected by the
presence of methanol, where at 515 and 1000 kHz, the maximal tem­
peratures are 2593 K (2741 K in absence of methanol) and 1481 K (1489
K in absence of methanol), respectively. This may be explained by the
rise of ultrasound frequency, where less amount of methanol is encap­
sulated within the bubble at the end of the collapse due to the short
bubble lifetime. Therefore, the intensity of bubble collapse (its maximal
temperature) will be marginally affected by the presence of small
amounts of methanol, which is responsible for the increase in bubble
heat capacity and the number of endothermal reactions within it
(Table 3). On the other hand, in the presence of methanol, the yield of H2
is greater than that retrieved in the absence of methanol independently
of the applied frequency. A similar tendency was obtained experimen­
tally by Rassokhin et al. [24] at 724 kHz and by Buttner et al. [26] at
1000 kHz. This tendency (increase of H2 yielding) is mainly ascribed to
the scavenging effect of methyl alcohol toward hydroxyl radicals (re­
actions 12 and 13, Table 3) and its reaction with hydrogen atoms (re­
action 4, Table 3). As a result, the recombination reaction of •OH
radicals with hydrogen atoms is reduced proportionally with the
enhancement of hydrogen production. At 213 kHz, a close production of
H2 is obtained for both cases [absence (1.22 × 10− 17 mol) and presence
of CH3OH (4.6 × 10− 17 mol)]. This is due to the large decrease in bubble
temperature (4000 K) in the presence of methanol (which causes the
increase in bubble heat capacity and the number of endothermal re­
actions, Table 3). Therefore, lower amount of H2 is produced (at 213
kHz). However, in the presence of methanol and for ultrasound fre­
quencies greater than 355 kHz, a rapid decrease in hydrogen production
is observed: 1.16 × 10− 18 at 355 kHz, 1.7 × 10− 21 at 515 kHz and 1.8 ×
10− 31 mol at 1000 kHz.
In Fig 2(b), the maximal conversion of methanol (per collapse) is
calculated as a function of the maximal amount of methanol found at the
A. Dehane et al.
Fig. 2. Effect of ultrasound frequency (from 213 to 1000 kHz) on (a) the bubble temperature and hydrogen production per collapse, (b) methanol conversion
(calculated according to its maximal amount found at Rmax) and bubble temperature and (c) the quantity of converted methanol, the total yield of the bubble and
methanol conversion percentage (Calculated with respect to the total production of the bubble). Conditions: In= 1 W/cm2, Tliq= 293.15 K and P∞= 1 atm.
end of bubble expansion (Rmax). At first sight, it seems that these con­
versions (<16.7%) are very low compared to the registered spectrum of
bubble temperatures (4000-1481 K) over the whole range of frequency
(213-1000 kHz). However, according to Fig 2(c), it is clearly concluded
that important quantities of methanol (compared to the total yield of
bubble [from 2.03 × 10− 16 to 1.52 × 10− 22 mol]) are converted espe­
cially in the range of ultrasound frequency from 213 (1.73 × 10− 16 mol,
85.22%) to 355 kHz (7.22 × 10− 18 mol, 71.2%). The comparison of Fig 2
(a) and 2(b) shows that the higher decomposition of methanol and
hydrogen production may be obtained in the range of ultrasound fre­
quency from 213 to 355 kHz. This conclusion is sustained especially by
the increase of the number density proportionally with the increase of
ultrasound frequency [59–61], which may increase the molar yield of H2
and the conversion of methanol.
3.3. Effect of acoustic intensity on hydrogen production and methanol
conversion
In Fig 3(a), the molar yield of hydrogen production and bubble
temperature are shown as functions of acoustic intensity (0.7, 1 and 1.5
W/cm2) at 355 kHz. At 0.7 W/cm2, it is observed that approximately the
same bubble temperatures are retrieved for both cases, in the presence
and absence of CH3OH, whereas the production of hydrogen in the
presence of methanol is greater than that obtained without methanol.
This indicates clearly that the molar production of the acoustic bubble is
not only dependent on its peak temperature but also on the maximal
7
Chemical Engineering and Processing - Process Intensification 179 (2022) 109080
amount of water vapor and volatile species (methanol) found at the end
of the rarefaction phase. In other words, in spite of the same observed
temperatures for both cases (in the presence and absence of methanol),
the positive impact of methanol (limitation of H• and •OH recombina­
tion and enhancing the yield of H2 molecules, Table 3) inside the bubble
outweighs the decrease in its temperature (resulting from the increase in
its heat capacity and the combustion of methanol). The same trend was
shown previously in our study [62] in the presence of volatile CCl4. The
rise of acoustic intensity from 1 to 1.5 W/cm2, increases the yield of H2
(and bubble temperature) from 6.92 × 10− 21 mol (4205 K) to 7.36 ×
10− 18 mol (6646 K), respectively, in the absence of methanol. However,
in the presence of methanol, it is clearly observed that the increase in the
molar production of hydrogen (and the peak temperature of the bubble)
is amortized despite the rise of acoustic intensity from 1 (H2: 1.16 ×
10− 18 mol, Tmax: 3456 K) to 1.5 W/cm2 (H2: 8.97 × 10− 18 mol, Tmax:
3801 K). This is obviously owing to the negative effect of evaporating
methanol (via increasing the bubble heat capacity and the combustion of
CH3OH) within the bubble at 1.5W/cm2 on both the bubble temperature
and the molar yield of H2. This is because at high acoustic intensity,
higher maximal radii (Rmax) will be attained, which allows the pene­
tration of huge amounts of water vapor and methanol (more volatile
than water) inside the bubble. As a result, a milder implosion will result
thanks to the existence of these large quantities of water vapor and
methanol. A similar tendency was obtained by Ferkous et al. [63] for the
yield of ●OH radicals at 585, 860 and 1140 kHz and by Yasui et al. [64]
for the maximal bubble temperature at 1 MHz. This result demonstrates
A. Dehane et al.
Fig. 3. Effect of acoustic intensity on (a) the bubble temperature and hydrogen
production and (b) the quantity of converted methanol, the total yield of bubble
and the methanol conversion parentage (calculated with respect to the total
production of bubble). Conditions: f = 355 kHz, Tliq= 293.15 K and P∞= 1 atm.
the existence of an ideal acoustic intensity (1 W/cm2) for the efficient
production of hydrogen by ultrasound.
In Fig 3(b), it is shown that the conversion of methanol is promoted
in the range from 0.7 W/cm2 (1.1 × 10− 21 mol, 0.33% of the total bubble
yield) to 1 W/cm2 (7.22 × 10− 18 mol, 71.24% of the total yield of
bubble). However, a further increase of In to 1.5 W/cm2 seems to be
inefficient for methanol decomposition (3.72 × 10− 17 mol, 75.09% of
the total production of the bubble), mainly due to the lower increase of
the maximum bubble temperature (3801 K, Fig 2(a)) at this acoustic
intensity (1.5 W/cm2). This agrees with the Alippi et al. [65] and
Weissler et al. [66] findings for the yield of iodine in a sonicated solution
of CCl4 for electrical power in the range from 200 to 450 W and from 0 to
600 W, respectively. According to Figs. 2(a) and 3(b), it can be observed
that the acoustic intensity should be accurately controlled for maximal
and efficient production of H2 and CH3OH conversion with respect to the
delivered energy into the sonoreactor.
3.4. Effect of liquid temperature on hydrogen production and methanol
conversion
In this section, the molar production of hydrogen and methanol
decomposition are visualized on a range of liquid temperatures (293.15
to 333.15 K) at 1 W/cm2 and 355 kHz, Figs. 4(a) and 4(b). It should be
noted that according to the different experimental studies, the highest
sono-activity of the micro-bubble is observed around this frequency
(355 kHz) [67–70]. In Fig 4(a), a turning point of the bubble
8
Chemical Engineering and Processing - Process Intensification 179 (2022) 109080
Fig. 4. Variation of (a) the bubble temperature and hydrogen production and
(b) the quantity of converted methanol, total yield of bubble and the percentage
of converted methanol (calculated according to the total production of bubble).
Conditions: In= 1 W/cm2, f = 355 kHz, and Psta= 1 atm.
temperature (4136 K) is observed in the absence of methanol at the
liquid temperature of 303.15 K, then this maximal bubble temperature
gradually decreased with the rise of the bulk temperature [16.8% of
decrease from 303 K (Tmax=4136 K) to 333.15 K (Tmax=3441 K)]. On the
other hand, optimal production of hydrogen (4.26 × 10− 17 mol) has
been obtained at a liquid temperature of 323.15 K in the absence of
methanol in the solution. This optimum of H2 production results from
the competition between the maximal bubble temperature and the
maximal amount of water vapor found at the end of the expansion phase
[22,62]. This means that, over a bulk temperature of 323.15 K, the
decrease in bubble temperature (due to the evaporation of large
amounts of water vapor) is unable to maintain the molar increase of H2
production. As a result, an optimum balance between the decrease of
bubble temperature and the increase of H2 formation is retrieved at the
liquid temperature of 323.15 K. In contrast, a rapid decrease of the
bubble temperature {from 3456 K (at 293.15 K) to 2613.42 K (at 313.15
K)} is observed in the presence of methanol (20% v/v). Nevertheless, the
sono-activity of the bubble is totally suppressed at the liquid tempera­
ture of 323.15 and 333.15 K. Accordingly, a maximal hydrogen pro­
duction of 1.48 × 10− 18 mol is obtained at the liquid temperature of
303.15 K. Our results are consistent with those obtained elsewhere by
Rassokhin et al. [24] at 724 kHz, where an optimum of H2 production
rate (165 µM/min) is observed at the liquid temperature of ~300 K in
the presence of 22.26% of methanol in the bulk liquid. The suppression
of the bubble activity at the liquid temperatures of 323.15 and 333.15 K
(Fig 4(a) and 3(b)), is owing to the huge amounts of water vapor and
A. Dehane et al.
CH3OH evaporated inside the bubble during the rarefaction phase (data
not shown). Therefore, the bubble lifetime at the liquid temperatures of
323.15 and 333.15 K exceeds the acoustic period (2.81 µs at 355 kHz).
This negative effect of methanol is observed through the sonolysis of an
appropriate amount of other volatile substrates such as CO2, N2O and
CH4 [58,71–73]. In Fig 4(b), it is seen that the maximal conversion of
methanol is obtained at the liquid temperatures of 293.15 K (7.22 ×
10− 18 mol, 71.2% of the total yield) and 303.15 K (4.89 × 10− 18 mol,
41.27% of the total yield); however, a critical decrease of methanol
decomposition is observed at the liquid temperature of 313.15 K (6.9 ×
10− 23 mol). The analysis of Fig 4(a) and 4(b) indicates that the maximal
conversion of methyl alcohol and hydrogen production are obtained in a
narrow range of liquid temperature from 293.15 to 303.15 K, which
means that the sonoactivity of the bubble is very sensitive to the increase
of liquid temperature in the presence of CH3OH in the liquid phase.
4. Conclusion
Methanol sono-conversion and H2 production were investigated on a
range of ultrasound frequency (213-1000 kHz), acoustic intensity (1 and
2 W/cm2) and liquid temperature (293.15-333.15 K). Either in the
presence or absence of methanol, the peak temperature of the bubble,
the hydrogen production and the methanol conversion are decreased
proportionally with the rise of the wave frequency. For ultrasound fre­
quencies that are equal or greater than 515 kHz, the maximal temper­
ature of the bubble is slightly affected by the presence of methanol.
Additionally, in the presence of methanol, the yield of H2 is greater than
that obtained in the absence of methanol, independently of the used
frequency. The highest efficacy of methanol combustion and hydrogen
production is obtained for frequencies ranging from 213 to 355 kHz. On
the other hand, accurate control of acoustic intensity is needed for
maximal production of H2 and conversion of CH3OH with respect to the
delivered energy in the sonicated solution. Accordingly, an ideal
acoustic intensity of 1 W/cm2 was observed for H2 yielding and CH3OH
conversion.
In the absence of methanol in the solution, a turning point of bubble
temperature (4136 K) is observed at the liquid temperature of 303.15 K.
Moreover, optimal production of hydrogen is obtained at the liquid
temperature of 323.15 K. Conversely, in the presence of methanol, the
peak temperature of the bubble is decreased proportionally with the rise
of liquid temperature from 293.15 to 313.15 K. However, the bubble
sono-activity is completely suppressed at the liquid temperature of
323.15 and 333.15 K. Consequently, the maximal production of
hydrogen and methanol conversion are obtained in a narrow range of
liquid temperature from 293.15 to 303.15 K, which indicates the
sensitivity of acoustic cavitation to the change of the bulk liquid tem­
perature in the presence of methanol.
CRediT authorship contribution statement
Aissa Dehane: Conceptualization, Methodology, Software, Acqui­
sition of data, Formal analysis, Writing - original draft, Writing - review
& editing. Slimane Merouani: Project administration, Conceptualiza­
tion, Supervision, Visualization, Writing - review & editing Methodol­
ogy, Formal analysis, Writing-review & editing. Atef Chibani:
Acquisition of data, Revision. Oualid Hamdaoui: Visualization, Vali­
dation, Writing - review & editing. Muthupandian Ashokkumar:
Visualization, Formal analysis, Writing - review & editing.
Funding
This work received financial support from The Ministry of Higher
Education and Scientific Research of Algeria (project code:
A16N01UN250320220002) and the General Directorate of Scientific
Research and Technological Development (GD-SRTD).
9
Chemical Engineering and Processing - Process Intensification 179 (2022) 109080
Data Availability Statements
All data generated or analyzed during this study are included in this
manuscript itself.
Declaration of Competing Interest
The authors declare no competing interests.
Data Availability
No data was used for the research described in the article.
Acknowledgements
We acknowledge The Ministry of Higher Education and Scientific
Research of Algeria and the General Directorate of Scientific Research
and Technological Development (GD-SRTD) for their support in con­
ducting the RFU project A16N01UN250320220002, named
“Développement, scale-up et intensification de procédés innovants
d’oxydation et de réduction (POA/PRA) pour la destruction rapide des
micropolluants émergents des effluents aqueux industriels.”
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