Chapter 18

Theoretical insight into methanol

sono-conversion for hydrogen
production
Aissa Dehane, Leila Nemdili, Slimane Merouani and Atef Chibani
Laboratory of Environmental Process Engineering, Department of Chemical Engineering, Faculty of Process Engineering, University Salah
Boubnider Constantine 3, El Khroub, Algeria

1. Introduction
Over the past several decades, the consumption of fossil fuels has continuously expanded due to the rapid rise in global
population and the industrial revolution of today’s society [1]. Nowadays, governments recognize the need of using
sustainable energy sources to increase their energy reserves and reduce carbon emissions [2]. In order to satisfy present and
future energy needs without increasing carbon emissions, hydrogen can be used as an energy vector. Hydrogen is abundant
in the environment and has the largest energy capacity (i.e., 120.7 kJ g
1) of any known fuel [3]. Indeed, gasification,
partial oxidation, and steam reforming were the main ways that hydrogen (H2) was made from fossil fuels [4e6]. Even
while these techniques are incredibly effective, they are not environmentally friendly because they release CO2 [7].
Alternative methods for producing hydrogen, such as water electrolysis, biological photosynthesis, and photocatalysis,
have been developed as clean technologies [1,8,9].
Scientists have been attracted to employ ultrasound as a clean technique for hydrogen production because of the high-
energy phenomena generated by power ultrasound propagation in water (water sonolysis) [10e20]. Furthermore, pure
water sonolysis has been determined to provide lower hydrogen yields (<40 mM min
1) [10]. To overcome this issue, a
variety of chemicals can be added to enhance the sonolytic hydrogen producing process, either in the saturating gas or the
sonicated water. For example, the inclusion of hydrocarbons including methane and ethane massively improves the
generation of hydrogen [21]. Methane and ethane can pass through the bubble’s hot gas phase, and their pyrolysis produces
an excessive quantity of hydrogen [21]. Alcohols, on the other hand, perform the same role as CH4 within the bubble and
follow a similar pyrolytic process [22,23]. On the other hand, the concentration of these additives needs to be carefully
monitored since excessive amounts of it can lower (or suppress) the generation of of hydrogen.
Recently, many investigations have been carried out on the sono- production of hydrogen in the presence of methanol
[10,24e27]. Generally, the oxidation process was decreased when methanol is included in the sonicated solution, although
hydrogen generation is considerably increased [22,28,29]. In order to (i) increase the yield of hydrogen and (ii) improve the
conversion capacity of methanol inside the acoustic bubble, several researchers have been interested in those findings.
In this chapter, the sono-production of hydrogen by methanol sonolysis are discussed. The impact of the crucial
medium and operational conditions (such as methanol concentration, argon saturation degree, ultrasound frequency, and
acoustic power) on the hydrogen generation yield by methanol sono-pyrolysis within an acoustic bubble was highlighted.
Before starting, an overview of the instruments and concepts of sonochemistry is presented.

2. The sonochemical process

Fig. 18.1 depicts the most physical and chemical effects of ultrasound in aqueous solution. Cavitation bubbles created by
water sonolysis grow and collapse violently in a matter of microseconds, creating intense pressures and temperatures

Green Approach to Alternative Fuel for a Sustainable Future. https://doi.org/10.1016/B978-0-12-824318-3.00002-3

Copyright © 2023 Elsevier Inc. All rights reserved. 243
244 Green Approach to Alternative Fuel for a Sustainable Future

(a)

Amplitude
Compression Cycle

Time

Rarefaction
Cavitation
threshold

Formation growth Collapse (b)

Radicals Gas/liquid interface
(c) attack
1900 K, 1 atm Bubble interior
Solution 5000 K, 500 atm
(ambient HO diffusion HO + H H2O
conditions)
(a)
Hydrophilic
pollutants Hydrophobic (b)
Acoustic microstreaming pollutants
(c)

(c)
(d) (d)
(e)
Supersonic
microjet

Surface damage
Shockwaves
(erosion)

FIGURE 18.1 Acoustic cavitation (A) and its chemical (B) and physical consequences (C, D, and E). From A. Dehane, S. Merouani, O. Hamdaoui, M.
Ashokkumar, Sonochemical and sono-assisted reduction of carbon dioxide: a critical review, Chem. Eng. ProcessdProcess Intensif. (2022) 109075.
https://doi.org/10.1016/j.cep.2022.109075.

(about w5200 K and w500 atm) inside the bubbles [30,31]. Due to the this phenomena, known as acoustic cavitation,
ultrasound has several applications, ranging from cleaning [32], polymers synthesizing [33], pollutants destruction [34,35],
and nanomaterials manufacturing [36,37] to biomedical uses [38e40] and food sciences [41,42]. The bubbles may be
inertial (i.e., transient) and develop for one acoustic cycle (or less) before exploding during the compression phase of the
wave, or they may be stable and bounce around their equilibrium (ambient) radius for multiple cycles [43].
In fact, inertial cavitation provides the most promising sonication performance [43]. The fast collapse of these bubbles
is quite adiabatic, which leads to high energy chemistry in the interior of the bubble and its surrounding (Fig. 18.1A and B).
l
Dissolved gases and evaporating H2O molecules decompose (react) to form many reactive species including OH,
l
H , HO2 and O3 [44,45]. Radicals can recombine, react with gaseous species (inside the bubble), or diffuse beyond the
l

bubble [46]. Organic or inorganic volatile substances which have evaporated can also be pyrolyzed or incinerated inside
the hot cavity. As a result, the sonochemical reaction zones are (i) the bubble gas phase (Fig. 18.1B), (ii) the bubble/
solution interface, and (iii) the solution bulk, while the oxidation mechanisms are (i) the gas-phase pyrolytic oxidation for
l
volatile compounds and (ii) reaction with radicals, i.e., HO , at the bubbleesolution interface and in the liquid bulk for
l
nonvolatile compounds [47,48]. Only around 10% of radicals may reach the solution bulk, although the OH concentration
is greater at the liquid shell of the acoustic bubble [49e51].
The major sonication-related physical consequences are the acoustic microjet (Fig. 18.1D), the microstreaming field
(Fig. 18.1C) and the shock wave damage (Fig. 18.1E) [47]. A microjet, which is a stream of quickly moving liquid oriented
to the surface of the solid, is generated during implosion as a result of a self-reinforcing bubble deformation [52]. Localized
erosion/pitting of the surface is caused by the high microjet velocity (i.e., w100 m s
1 [53]). Photographic confirmation of
the ultrasonic pitting was obtained [52], and the solid surface area has improved due to the development of new fine surface
material [52]. Shock waves are also created by the cavity collapse [54]. Shock waves remove particles that are only weakly
 Theoretical insight into methanol sono-conversion for hydrogen production Chapter | 18 245

attached to a solid surface and separate slightly agglutinated grains through existing fissures (increasing surface area) [54].
Sonoluminescence was also produced by the extreme bubble implosion.
For conducting sonochemical reactions, two types of ultrasonic reactors are most frequently used [55e58]: (i) probe
type (also known as horn), in which the solution is directly irradiated by a submerged horn (Fig. 18.2A), and (ii) a standing
waveebased type, in which the transducer is attached to the reactor’s bottom surface. For the standing wave type, there are
two configurations: the indirect sonication bath system (Fig. 18.2B), in which the beaker solution is immersed, and the
direct sonication bath (Fig. 18.2C), within which the ultrasonic waves move directly through the solution. All kinds of
ultrasonic reactors are constructed with unique cooling/heating systems in order to keep the sonicated liquid’s temperature
constant.

3. Some literature data

Experimental research demonstrates hydrogen’s production (from water sonolysis) using diluted aqueous alcohol solu-
tions. Wateremethanol mixtures were sonolyzed at 1 MHz in an argon environment by Buettner et al. [59]. H2 was
produced in deionized water at a rate of 22 mM min
1. When methanol is added to the solution, the H2 rate rises to
100 mM min
1 at 5% (v/v) of methanol and 150 mM min
1 at 10% (v/v), but as methanol concentrations increase, the
molar yield of H2 gradually decreases until no H2 was identified at around 80% (v/v) of methanol. Penconi et al. [60] found
a 1.4-fold increase in the rate of H2 production while utilizing 38 kHz ultrasound in water and water/ethanol (20% v/v)
under argon saturation. Rassokhin et al. [22] reported that when methanol concentration increased from 0.001 to 0.50 M in
the sonicated solutions, the generation rates of the sonolysis products (H2, CH4, and CO) increased (H2: from 33.3 to
167.0 M min
1), where the molar yield of these species is as follows: H2 > CO > CH4. Rassokhin et al. [22] have

(A) (B)
Solution to
Ultrasound control treat

Cooler/heater
Tank device
Transducer

Probe tip

Coolant out Water

Solution to treat
Coolant in
Transducers

Ultrasound
(C) control

Coolant out

Solution to treat
Coolant in
Transducer/vibrating
plate

Ultrasound control

FIGURE 18.2 Schemes of the main types of lab-scale sonoreactors. (A) Probe system, (B) bath system (indirect sonication), and (C) standing wave
reactor with direct sonication. From S. Merouani, O. Hamdaoui, Sonochemical treatment of textile wastewater, in: M.P. Inamuddin, A. Asiri (Eds.), Water
Pollution and Remediation: Photocatalysis, Springer-Nature Switzerland, 2021. https://doi.org/10.1007/978-3-030-54723-3_5.
246 Green Approach to Alternative Fuel for a Sustainable Future

demonstrated that the optimal medium temperature for the maximum hydrogen production is retrieved depending on the
mole fraction of methanol in the bulk solution ([H2]max ¼ 200 mM min
1 at w30 C and xMeOH ¼ 0.018), where the rise of
methanol concentration reduces the temperature at which the maximal H2 formation rate is reached.
Various numerical investigations have focused on sonochemical hydrogen production [10,12,24,26,27]. These re-
searches have demonstrated promising results of clean and efficient hydrogen production. Recent reviews on sonochemical
hydrogen production by Merouani et al. [10,61] are noteworthy. In a numerical investigation of the influence of the
saturating gas (O2 and Ar) on the sono-pyrolysis of CH3OH, Kerboua et al. [17] found that solution containing 40%
CH3OH produced the highest molar yield, despite of the amount of argon used. Kerboua et al. [17] revealed that the highest
molar output is achieved at a methanol concentration of 40% and an argon molar fraction of 40%. According to Kerboua
et al. [26], a solution with 20% methanol (v/v) saturated with 70% concentration of argon provides the best results for H2
production and CH3OH conversion. As a result, 99.9% of the methanol is eliminated and roughly 60% of the methanol is
converted to hydrogen. Dehane et al. [62] investigated the impact of methanol dosage (in the bulk phase) on the maximum
sonochemical performance for hydrogen production, CH3OH consumption, and the range of active bubbles using a
comprehensive mathematical model for single bubble sono-pyrolysis of methanol. They revealed that the range of active
bubble sizes for CH3OH consumption is mostly unaffected by the dose of aqueous phase methanol (0%e100% (v/v)).
Nevertheless, in the case of hydrogen production, the active bubble range progressively decrease for methanol concen-
trations greater than 20%. The greatest performance for CH3OH conversion, hydrogen production and the width of active
bubble sizes (for H2 production and CH3OH disintegration) is achieved at 80% argon (in the initial gas matrix) with a
methanol concentration of 7%e20%. However, Dehane et al.’s research [62] is not sufficient because all findings were
obtained for a single matrix of operational parameters (frequency: 355 kHz, In ¼ 1 W cm
2, and Tliq ¼ 20 C). Theoretical
researches [17,26,62] on methanol sono-decomposition indicate that the impacts of operational conditions, such as ul-
trasound frequency, acoustic intensity and bulk temperature have not yet been studied.

4. Methanol pyrolysis model

The model was developed by our research group and it is available with results in [62,63]. Only the model’s principle
outcomes will be discussed herein. Briefly, the principal mechanism of methanol degradation is pyrolysis within acoustic
bubbles due to its high volatility [62]. The model is based on a set of ordinary differential equations that take into account
chemical processes, thermal conduction both within and outside of a bubble, and nonequilibrium evaporation and
condensation of water vapor and methanol at the bubble wall. Bubble interactions are not considered. The chemical
pathways used to examine the interior bubble chemistry for the AreO2eCH3OH bubble are shown in Table 18.1.
Applying relevant experimental data from the literature [62,63], the model has been validated. For instance, the model’s
predicted bubble temperatures for an argonemethanol aqueous solution at various methanol dosages were compared to
those empirically reported by Rae et al. [64]. Especially for lower alcohol dosages, the model effectively reflects the data
on methanol’s effect on bubble temperature [63]. The model predicted 4570 K for 0 mM methanol compared to Rae et al.
[64] data of 4600 K, indicating a divergence of less than 1% [63]. For 60 and 150 mM of methanol, unappreciable
deviations of w1.8 and 2.5% were also obtained. Nevertheless, with higher CH3OH concentrations (> 200 mM), a
comparatively higher deviation is observed. Furthermore, the model performed an excellent fit of reflecting the overall
tendency of the bubble temperature variation with alcohol dosage. Comparing the results of H2 production obtained
theoretically using the model to those retrieved experimentally by Buettner et al. [59] at 1000 kHz [62,63] has provided
additional evidence of the model’s accuracy.

5. Optimal gas conditions

In order to clearly understand how methanol affects hydrogen sono-production, the optimum bubble composition (argon
content) should be established. At 355 kHz and 1 w/cm2, Dehane et al. [62,63] estimated the evolution of hydrogen
production by a single bubble as well as the corresponding methanol conversion as a function of the molar quantity of
argon (within the bubble) and methanol concentration in the bulk liquid [% (v/v)] (Fig. 18.3). For the majority of methanol
concentrations, the optimum values are found at 80% and 60%e80% of argon mole fraction (within the bubble) for the
generation of hydrogen (Fig. 18.3A) and the conversion of methanol (Fig. 18.3B), respectively. At 3% (v/v) of CH3OH and
70% of argon mole fraction (Fig. 18.3B), which corresponds to 9.46  10
19 mol for the highest generation of hydrogen
(Fig. 18.3A), the maximum conversion of methanol (1.38  10
17 mol) is recovered.
On the other hand, at 7% (v/v) of methanol and 80% argon (mole fraction), the maximum yield of hydrogen is achieved,
providing a value of 1.13  10
18 mol (19.45% of increase compared to the previous case (Fig. 18.3A). In comparison to the
 Theoretical insight into methanol sono-conversion for hydrogen production Chapter | 18 247

TABLE 18.1 Adopted reaction scheme inside a collapsing AreO2eCH3OH bubble.

N8 Reaction A N Ea DH
1 H2O þ M / H þ OH þ M l l
1.912  107
1.83 28.35 508.82
2 CH3OH þ O2 / CH2OH þ H2O2 2.0  10 7
0.0 1.88  10 5
196.492
3 CH3OH þ HO2/ CH2OH þ H2O2 l
8.0  10 7
0.0 8.11  10 4

35.508

3
4 CH3OH þ H / CH2OH þ H2 l l
1.35  10 3.2 1.46  10 4

34.057
5 l
OH þ OH / HO2 þ H l
l
l
1.08  1005 0.61 1.51  1005 154.957
6 HO2 þ OH / H2Oþ O2
l
l
2.89  10 07
0.00
2.08  10 03

291.451
7 HO2 þ O / OH þ O2
l
l
2.00  10 07
0.00 0.00
224.131
8 HO2 þ H / H2Oþ O
l
l
3.10  10 07
0.00 7.20  10 03

22.957
9 HO2 þ H / H2 þ O2
l
l
1.66  1007 0.00 3.44  1003
230.293
10 HO2 þ H / 2 OH
l
l l
7.08  1007 0.00 1.23  1003
155.613
11 CH2OH þ O2 / CH2Oþ HO2
l
l 5.00  10 06
0.00 0.00
79.404
12 CH3OH þ OH / CH3O þ H2O l l
4.4  1000 2.0 6.3  103
54.215
13 CH3OH þ OH / CH2OH þ H2O l l
1.44  1000 2.0
3.51  103
95.215
14 CH3O þ M / CH2OH þ M
l l
1.00  10 08
0.00 8.00  10 04

38.000
15 CH3O þ M / CH2Oþ H þ M
l l
7.78  10 07
0.00 5.65  10 04
126.297
16 CH3O þ O2 / CH2Oþ HO2
l
l 4.28  10
19 7.60
1.48  1004
117.404
17 CH2Oþ HO2 / HCO þ H2O2 l
l
4.11  10
02 2.50 4.27  1004
48.976
18 CH2Oþ OH / HCO þ H2O l l
3.90  10 04
0.89 1.70  10 03

128.159
19 CH2Oþ O / HCO þ OH l l
3.50  10 07
0.00 1.47  10 04

60.839
20 CH2Oþ H / HCO þ H2 l l
5.74  1001 1.90 1.15  1004
67.001
21 HCO þ O2 / CO þ HO2
l
l 7.58  10 06
0.00 1.72  10 03

140.530
22 HCO þ M / CO þ H þ M
l l
1.86  10 11

1.00 7.11  10 04

65.171
23 CO þ OH / CO þ H þ CO2
l l
4.40  10 00
1.50
3.10  10 03

212.853
24 2 HO2 / H2O2 þ O2
l 3.02  1006 0.00 5.80  1003
212.268
25 H2O2 þ M / 2 OH þ M k0 kN l
8.15  10 17

1.92 2.08  10 05
262.356
2.62  1013
1.39 2.15  1005
26 H þ O2 þ M / HO2 þ M k0 kN
l
l 5.75  10 7
1.40 0.00
205.701
4.65  1000 0.44 0.00
27 H2 þ O / OH þ H l l
5.06  10
02 2.67 2.63  1004 6.162
28 H þ O2 / OH þ O
l l
3.52  10 10

0.70 7.14  1004 68.518
29 CH2OH þ H / CH2Oþ H2l l
3  107 0.0 0.0
309.578
30 2 OH / H2O2
l
1.08  10 5
0.61 1.51  10 5
154.957
31 CH2OH þ OH / CH2Oþ H2O
l l
2.4  107 0.0 0.0
370.7

32 l
CH3þ HO2 / CH4þO2 l 3.61  106 0.0 0.0
233.852

From A. Dehane, S. Merouani, O. Hamdaoui, Methanol sono-pyrolysis for hydrogen recovery: effect of methanol concentration under an argon atmo-
sphere, Chem. Eng. J. 426 (2021) 130251. https://doi.org/10.1016/j.cej.2021.130251.

previous case (1.38  10
17 mol), this production (1.13  10
18 mol) results in a 1.3  10
17 mol methanol conversion, a
reduction of 5.79% (Fig. 18.3B). Over the full range of methanol concentration (0%e100% (v/v)), it is indicated that the
majority of maximal productions for the total yield of acoustic cavitation are produced at 80% (mole fraction) of argon inside
the bubble [62]. Furthermore, the overall production of the bubble was slightly less than the maximum conversion of
methanol. Figs. 18.3A and B show that the bubble performs at its maximum efficiency at 80% argon and 20% oxygen, with 7%
248 Green Approach to Alternative Fuel for a Sustainable Future

0% 1% 2% 3% 4% 5% 6% 7% 8% 9%
10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

1E-17

1E-18

1E-19
M olar production of H

1E-20

1E-21

1,2E-18
1E-22
1,0E-18

8,0E-19
1E-23
6,0E-19
70 80 90
1E-24
0 10 20 30 40 50 60 70 80 90 100

Molar amount of argon (%)

1% 2% 3% 4% 5% 6% 7% 8% 9% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
1,6E-17

1,4E-17
M ethanol conversion (mol)

1,2E-17

1E-17

8E-18

6E-18

4E-18

2E-18

0
0 5 10 20 30 40 50 60 70 80 90 100
Molar quantity of argon (%)
FIGURE 18.3 Hydrogen production (A) and methanol conversion (B), at 355 kHz and 1 w/cm2 (R0 ¼ 3.2 mm), as functions of the molar quantity of
argon (inside the bubble) and methanol concentration in the bulk liquid [% (v/v)]. From A. Dehane, S. Merouani, O. Hamdaoui, Methanol sono-pyrolysis
for hydrogen recovery: effect of methanol concentration under an argon atmosphere, Chem. Eng. J. 426 (2021) 130251. https://doi.org/10.1016/j.cej.
2021.130251.

(v/v) methanol and 80% argon being the optimal ratios for maximum hydrogen generation (1.13  10
18 mol) and methanol
conversion (1.3  10
17 mol). The greatest amount of hydrogen produced at this level, which is 1.13  10
18 mol, is raised
by 32.7 times compared to the maximum value obtained in the absence of methanol (and 100% Ar), i.e., 3.46  10
20 mol.
Figs. 18.3A and B indicate that the concentration of methanol (in solution) may be increased until 20%, so at that point
the yield of hydrogen rises by 22.4 (7.74  10
19 mol) in comparison to the situation in which there is no methanol (and
100% Ar). Methanol’s conversion within the bubble is 22.3% (1.12  10
17 mol) and 13.84% (1.01  10
17 mol),
respectively, at 10% and 20% (v/v) of methanol in the bulk solution, compared to the conversion rate that occurred with its
maximum at 7% (1.3  10
17 mol).
 Theoretical insight into methanol sono-conversion for hydrogen production Chapter | 18 249

6. Ultrasound frequency effect

Dehane et al. [63] have evaluated the yield of H2 generation and CH3OH conversion at 1 W cm
2 in the presence
(20%, v/v) and absence of methanol in the liquid phase as functions of ultrasonic frequency (from 213 to 1000 kHz)
(Fig. 18.4A and B). Initially, as expected, an increase in wave frequency has a negative impact on the molar generation
of hydrogen, the peak temperature of the bubble and the conversion of methanol, either in the presence or absence of
methanol (Fig. 18.4A and B). These phenomena have been widely discussed in several experimental and theoretical

7000 10-14
Temp (0%) 10-16

Number of moles of H2
Bubble temperature (K)

6000 Temp (20%)

H2 (0%) 10-18
5000 H2 (20%) 10-20

10-22
4000
10-24
3000
10-26

2000 10-28

(a) 10-30
1000
10-32

0 10-34
100 200 300 400 500 600 700 800 900 1000 1100

Frequency (kHz)

4500 18
Temperature
Bubble temperature (K)

4000 16
Methanol conversion (%)
MeOH Conversion
3500 14

3000 12
(b)
2500 10

2000 8

1500 6

1000 4

500 2

0 0
100 200 300 400 500 600 700 800 900 1000 1100

Frequency (kHz)
FIGURE 18.4 Frequency effect (from 213 to 1000 kHz) on (A) the bubble temperature and hydrogen production per collapse, and (B) methanol
conversion (In ¼ 1 W cm
2, Tliq ¼ 20 C). From A. Dehane, S. Merouani, A. Chibani, O. Hamdaoui, Influence of processing conditions on hydrogen
sonoproduction from methanol sono-conversion: a numerical investigation with a validated model, Chem. Eng. ProcessdProcess Intensif. 179 (2022)
109080. https://doi.org/10.1016/j.cep.2022.109080.
250 Green Approach to Alternative Fuel for a Sustainable Future

investigations [65e68]. This tendency was mainly attributed to the decrease of bubble collapse’s intensity (and
activity) proportionally with the increase in wave frequency [65,67,69]. In other words, a milder collapse occurs as the
wave frequency rises because less water vapor and, if any methanol molecules remain present in solution, few of them
enter the acoustic cavitation during the expansion phase. As a result, the bubble temperature at the end of its
compression period will be lower, which implies that fewer molecules of hydrogen (and methanol conversion) will be
produced by water vapor dissociation (and methanol combustion). Moreover, due to an increase in the bubble’s heat
capacity and the endothermic dissociation of methanol, the addition of methanol (20% in solution) drops the bubble’s
maximum temperature more (particularly at 213 and 355 kHz) [63,70]. The peak temperature of the bubble is slightly
affected by the presence of methanol, as can be seen in Fig. 18.4A and B, for wave frequencies greater than or equal to
515 kHz. For example, at 515 and 1000 kHz, the maximal temperatures are 2593 K (2741 K in the absence of
methanol) and 1481 K (1489 K in the absence of methanol), respectively. This may be attributed to a rise in ultrasonic
frequency, where a reduced bubble lifetime results in less methanol being entrapped within the bubble at the moment of
collapse. Because methanol increases the bubble’s heat capacity and the number of endothermal reactions its existence
will only have a minor impact on the intensity of bubble collapse (its maximum temperature) [65]. On the other hand,
regardless of the applied frequency, the yield of H2 in the presence of methanol is higher than that recovered in the
absence of methanol. Experimentally, Rassokhin et al. [22] (724 kHz) and Buttner et al. [59] (1000 kHz) both revealed
a similar trend. This behavior (increase in H2 yielding) is mostly attributed to methyl alcohol’s ability to scavenge
l
hydroxyl radicals and its association with hydrogen atoms. As a result, the amount of OH radicals that react with
hydrogen atoms is lowered proportionally as hydrogen generation is increased. When CH3OH is present or absent, a
close generation of H2 is produced at 213 kHz. This is attributed to the significant drop in the bubble temperature
(4000 K) in the methanol-containing system. Consequently, less H2 is generated at 213 kHz. However, a sharp decline
in hydrogen generation is shown for ultrasound frequencies higher than 355 kHz and in the presence of methanol:
1.16  10
18 mol at 355 kHz, 1.7  10
21 mol at 515 kHz, and 1.8  10
31 mol at 1000 kHz (Fig. 18 4A).
The maximal conversion of methanol (per collapse) is depicted in Fig. 18.4B as a function of its maximum quantity at
the end of bubble growth. At first look, these conversions (<16.7%) appear to be quite low in comparison to the recorded
spectrum of bubble temperatures (4000e1481 K) throughout the whole frequency range (213e1000 kHz). Furthermore, it
is evident from Fig. 18.4B that significant amounts of methanol are converted, particularly in the region of ultrasonic
frequency from 213 (1.73  10
16 mol, 85.22%) to 355 kHz (7.22  10
18 mol, 71.2%), compared to the entire pro-
duction of the bubble [from 2.03  10
16 to 1.52  10
22 mol]). The comparison of Fig. 18.4A and B indicates that the
range of ultrasonic frequency between 213 and 355 kHz may provide the highest amount of methanol breakdown and
hydrogen generation. This conclusion is supported, in particular, by the fact that the number of bubbles increases according
to ultrasonic frequency increase [61,71,72], which may enhance the molar yield of H2 and the conversion rate of methanol.

7. Acoustic intensity effect

Fig. 18.5B displays the molar yield of hydrogen generation and the bubble temperature as functions of acoustic intensity
(0.7, 1, and 1.5 W cm
2) at 355 kHz. At 0.7 W cm
2, it is found that the bubble temperatures are almost the same in both
cases, i.e., the presence and absence of CH3OH, while the generation of hydrogen is higher when methanol is present in the
bulk liquid. This obviously demonstrates that the molar generation of the acoustic bubble depends on both the maximum
amount of water vapor and volatile species (methanol) present at the end of the rarefaction phase as well as the peak
temperature of the bubble. In other words, even if the temperatures in the presence and absence of methanol were nearly the
l l
same, the favorable effects of methanol on the bubble (limiting H and OH recombination and promoting the production
of H2 molecules) exceed the temperature drop (resulting from the increase in its heat capacity and the combustion of
methanol). A similar behavior was observed when volatile CCl4 is present during the bubble implosion [73]. In the absence
of methanol, an increase in acoustic intensity from 1 to 1.5 W/cm2 results in an increase in the production of H2 (and
bubble temperature) from 6.92  10
21 mol (4205 K) to 7.36  10
18 mol (6646 K). Despite the rise in acoustic intensity
from 1 (H2: 1.16  10
18 mol, Tmax: 3456 K) to 1.5 W cm
2 (H2: 8.97  10
18 mol, Tmax: 3801 K), it is clear that the
presence of methanol amortizes the rise in the molar production of hydrogen (and the bubble’s peak temperature). This is
evidently due to the detrimental effects of evaporating methanol within the bubble at 1.5 W cm
2 on both the bubble
temperature and the molar yield of H2 (by raising the bubble heat capacity and the combustion of CH3OH). This is due to
the fact that increased acoustic intensity leads to higher maximum radius (Rmax), which permits massive volumes of water
vapor and methanol (more volatile than water) to penetrate into the bubble. As a result, thanks to the presence (within the
bubble) of significant amounts of methanol and water vapor, a milder collapse is obtained. Similar results were obtained by
l
Yasui et al. [74] for the maximum bubble temperature at 1 MHz and by Ferkous et al. [75] for the yield of OH radicals at
 Theoretical insight into methanol sono-conversion for hydrogen production Chapter | 18 251

7000 10-16
Temp (0%)
Temp (20%) 10-17

Bubble temperature (K)

Number of moles of H2
H2 (0%)
6000 H2 (20%) 10-18
10-19
5000 10-20
10-21
4000 10-22
10-23
3000 10-24
(a) 10-25
2000 10-26
0.6 0.8 1.0 1.2 1.4 1.6

Acoustic intensity (W/cm2)

80 10-16
Conversion of methanol (%)

70
10-17
60

Number of moles
50
10-18
40 (b)
30 10-19

20
MeOH conversion (%) 10-20
10 MeOH conversion (mol)
Total production
0 10-21
0.6 0.8 1.0 1.2 1.4 1.6

Acoustic intensity (W/cm2)

FIGURE 18.5 Acoustic intensity effect on (A) the bubble temperature and hydrogen production and (B) the quantity of converted methanol
(f ¼ 355 kHz, Tliq ¼ 293.15 K). From A. Dehane, S. Merouani, A. Chibani, O. Hamdaoui, Influence of processing conditions on hydrogen sonopro-
duction from methanol sono-conversion: a numerical investigation with a validated model, Chem. Eng. ProcessdProcess Intensif. 179 (2022) 109080.
https://doi.org/10.1016/j.cep.2022.109080.

585, 860 and 1140 kHz. This finding shows that an optimum acoustic intensity of 1 W cm
2 is recommended for an
efficient sono-generation of hydrogen.
According to Fig. 18.5B, the conversion of methanol is shown to be promoted between 0.7 W cm
2 (1.1  10
21 mol,
0.33% of the total bubble production) and 1 W cm
2 (7.22  10
18 mol, 71.24% of the total bubble yield). Nonetheless,
increasing In to 1.5 W cm
2 seems inefficient for methanol decomposition (3.72  10
17 mol, or 75.09% of the total
bubble production), owing to a decrease in the maximum bubble temperature at this ultrasonic intensity (1.5 W cm
2)
(3801 K, Fig. 18.5A). These outcomes are in line with the results of Alippi et al. [76] and Weissler et al. [77] for the yield
252 Green Approach to Alternative Fuel for a Sustainable Future

of iodine in a sonicated solution of CCl4 for electrical powers in the range of 200e450 W and from 0 to 600 W,
respectively. It is clear from Figs. 18.4A and 18.5B that the acoustic intensity needs to be adequately adjusted for maximal
H2 production and CH3OH conversion with respect to the supplied energy into the sonoreactor.

Acknowledgements
This study was supported by the Ministry of Higher Education and Scientific Research of Algeria (project No.
A16N01UN250320220002) and the General Directorate of Scientific Research and Technological Development
(GD-SRTD).

8. Conclusion
The acoustic production of hydrogen and methanol conversion can be controlled by the dissociation of methanol within
bubbles. The optimal combination for the maximum H2 generation and CH3OH conversion is reached at 7% (v/v) of
methanol and 80% of argon, which was used to achieve the highest sonochemical efficiency of bubbles.
On the other hand, the peak temperature of the bubble, the generation of hydrogen and the conversion of methanol all
decrease proportionally with an increase in the frequency, whether methanol is present or not. The addition of methanol has
a slight effect on the maximum temperature of the bubble for ultrasound frequencies equal to or higher than 515 kHz.
Moreover, regardless of the employed frequency, the yield of H2 in the presence of methanol is higher than that obtained
when it is absent in the bulk liquid. In the range from 213 to 355 kHz, a maximal efficiency is observed for hydrogen
production and methanol conversion. In addition, an accurate control of acoustic intensity is required for maximum H2
generation and CH3OH conversion in the sonicated solution.

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