Separation and Purification Technology 288 (2022) 120701

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Separation and Purification Technology

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

Experimental and computer simulation of a molecular distillation process

for the dehydration of tetramethylammonium hydroxide solution
Wenhao Deng a, Yuehua Deng a, Wang Zhao a, Rui Zhang a, b, *, Yanbin Jiang a, *
a
Guangdong Provincial Key Lab of Green Chemical Product Technology, School of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou 510640, China
b
Zhuhai Institute of Modern Industrial Innovation, South China University of Technology, Zhuhai 519175, China

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

Keywords: Tetramethylammonium hydroxide pentahydrate (TMAH⋅5H2O) is easily decomposed when heated, which results
Aspen Plus in the difficulty of dehydration. In this study, a new process for dehydration of a TMAH propylene glycol solution
Dehydration using wiped-film molecular distillation was developed. The experiments were carried out to evaluate the effect of
Molecular distillation
operating conditions on the performance of the dehydration with the operating temperature ranging from 65 ◦ C
Optimization
Response surface methodology
to 90 ◦ C, the operating pressure from 100 Pa to 2000 Pa and the mass flow rate from 36 to 162 g/min. The
Tetramethylammonium hydroxide experimental results indicated that molecular distillation was capable of dehydrating TMAH solution to a water
content of 0.65% from 5.82%. Then a modified Flash module in Aspen plus, which used the fitting factor and
linear correlation between the simulated and experimental temperatures, was developed to simulate the dehy­
dration process. The relative error between the modified simulated and experimental data is less than 5%, and
the response surface methodology analysis was conducted to optimize the operating conditions. The optimal
dehydration conditions were 85 ◦ C, 100 Pa and 54 g/min feed flow rate, where the minimum water content in
distilled solution is 0.43%. The results show that the process developed realizes a high efficiency of dehydration
and prevents TMAH from thermal decomposition.

1. Introduction As the main component of the photoresist film stripping solution in

Tetramethylammonium hydroxide (TMAH, [(CH3)4NOH]) has a
strong organic base with strong corrosive properties which are easily
decomposed when heated over 130 ◦ C. It is usually prepared as 10% or
25% aqueous solution, and TMAH⋅5H2O is obtained after the crystalli­
zation of the TMAH aqueous solution. TMAH has been widely used in the
manufacture of microelectronic and micro-electro-mechanical system
(MEMS) devices due to its combination of high etching rate and good
anisotropic etching [1,2]. In the process of photoresist film removal,
alkali metal hydroxides such as KOH will remain on the surface of mi­
croelectronic devices and damage exposed aluminium or copper lines
[3], thus TMAH is the preferred stripping base with an enhancement in
photoresist removal efficiency [4,5]. Moreover, the thermal decompo­
sition of TMAH has been found to yield trimethylamine and dimethyl
ether as the major decomposition products when the temperature is at
135–140 ◦ C [6], which means it can be easily removed completely and
will not remain on the surface of a microelectronic device after the
stripping process [7].
the manufacture of the MEMS [8], high purity of TMAH can be obtained
by electrolysis of a tetramethylammonium salt in a cell with an ion ex­
change membrane [9–11]. However, TMAH obtained by ion-membrane
electrolysis is an aqueous solution, TMAH is alkaline in water, which
will cause copper corrosion leading to the failure of metal wiring on the
chip and result in the decline of the qualification rate of semi-conductor
devices [12]. It is well known that reducing the moisture content of the
photoresist stripping solution could effectively reduce the corrosion rate
of copper when the moisture content drops to less than 0.2%, the
corrosion rate of copper decreases from more than 10 Å/min to less than
2 Å/min. The photoresist stripping solution is a mixture of polyhydric
alcohols, organic bases and other chelating agents (corrosion inhibitors)
[13], water in stripping solution is derived from the crystal water in
TMAH⋅5H2O or water in the aqueous solution. Therefore, TMAH⋅5H2O
crystal or TMAH solution must be dehydrated.
Methods to remove water of crystallization from crystalline hydrate
consist of heating and vacuum desiccation. Harmon et al. [14] dried
TMAH⋅5H2O in a vacuum at 25 ◦ C for 3 days and a trihydrate

* Corresponding authors.
E-mail addresses: 0302zhangrui@163.com (R. Zhang), cebjiang@scut.edu.cn (Y. Jiang).

https://doi.org/10.1016/j.seppur.2022.120701
Received 17 January 2022; Received in revised form 15 February 2022; Accepted 16 February 2022
Available online 18 February 2022
1383-5866/© 2022 Elsevier B.V. All rights reserved.
W. Deng et al.
Fig. 1. Wiped-film molecular distillation apparatus.
(TMAH⋅3H2O) was obtained, which means 40% water was removed;
after four more days in the vacuum at 25 ◦ C, a dihydrate (TMAH⋅2H2O)
was obtained, which means 60% water was removed; and a mono­
hydrate (TMAH⋅1H2O) was also generated after drying in a vacuum at
65 ◦ C for 48 h, which means 80% water in TMAH⋅5H2O was removed.
The preparation of the anhydrous TMAH crystal was also investigated
but all attempts failed [15]. Removing water from TMAH solution is
another method of preparing anhydrous stripping solution. As a non-
volatile solute, TMAH aqueous solution can only yield pentahydrate
after drying, hence distillation must be carried out in an organic solu­
tion. Traditional distillation methods need to be operated at a high
temperature [16–18], which will lead to thermal decomposition of
TMAH. Molecular distillation is a separation technique suitable for the
purification of heat-sensitive substances [19–21]. While molecular
distillation, a method to separate substances under high vacuum and low
temperature [22], would be suitable for dehydrating of TMAH solution,
it will reduce the temperature of distillation to prevent thermal
decomposition of TMAH and realize dehydration simultaneously. For
the molecular distillation process, the evaporator temperature, the feed
flow rate, the feed temperature and the condenser temperature are main
factors for the composition control of the products [23–25]. In the
molecular distillation unit, the distance between the heating surface and
the condensing surface is very short and the material is distributed in the
form of a thin film on the heating surface under high vacuum, which
ensures that the residence time of the material on the heating surface is
short, only seconds [26], and makes the molecular distillation suitable
for separating homogeneous liquid mixtures with low volatility, thermal
sensitivity and high molecular mass [27–29].
Aspen Plus is a powerful tool for developing new processes,
analyzing or improving current processes with a reasonable reliability
[30]. Modelling and simulation of molecular distillation has been used
to establish stable operating conditions, improve the yield and purity of
the final product, or to realize the best performance for this multi-
purpose unit operation [31–34]. Ketenoglu et al. [34] simulated the
molecular distillation process of olive pomace oil deodorizer distillate
using two different methods in Aspen Plus, and experiments were also
carried out to modify the model. Batistella et al. [35] used the equations
that demonstrate the mass, energy and momentum balances to model
the process of centrifugal and falling film molecular distillation.
The aim of this study is to develop a modified model that describes
the dehydration process using molecular distillation and optimize the
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Separation and Purification Technology 288 (2022) 120701
operating conditions for dehydration of TMAH under the temperature
restriction, which is suitable for dehydration and preventing TMAH
from thermal decomposition according to our preliminary study [36].
Experiments were conducted to verify the feasibility. The Flash module
in Aspen Plus was used to simulate the dehydration process, a modified
Aspen Plus model was developed using a fitting factor and a linear
correlation between the simulated and experimental temperature, and
the results of the modified model were verified by the experimental
results. Finally, response surface methodology (RSM) analysis was used
to optimize the dehydration conditions, and the verification experiment
was carried out under optimal conditions.
2. Experimental
2.1. Materials
TMAH was purchased from Aladdin Ltd., China. Propylene glycol
(PG) and methanol were purchased from Guangdong Guanghua Sci.
Tech. Co. Ltd., China. One-component reagent for volumetric Karl
Fischer titration (1 ml ≙ ca. 5 mg H₂O) was purchased from Merck KGaA,
Germany. All reagents were analytical grade and used without further
purification.
2.2. Molecular distillation apparatus and procedure
The TMAH PG solution is distilled using the wiped-film molecular
distillation system (MD-80, self-built) shown in Fig. 1. The molecular
distillation system consists of a distiller with a wiper, a heating system, a
cooling system and a vacuum system. The vacuum system consists of a
mechanical pump (roots pump) and a diffusion pump, which is capable
of keeping the static pressure as low as 0.1 Pa. The temperature of the
evaporation system, pre-heating system and cooling system is precisely
controlled by a hot oil bath and water bath respectively. The wiper is
driven by the top motor to control the rolling speed.
The experimental conditions in this study are as follows: the heating
surface area is 0.126 m2, the cooling surface area is 0.062 m2, the feed
mass flow rate ranged from 36 to 162 g/min (volumetric flow rate:
24–108 ml/min), the feed temperature was 25 ◦ C, the heating temper­
ature ranged from 65 ◦ C to 90 ◦ C, the operating pressure ranged from
100 Pa to 2000 Pa, the wiper rolling speed was kept at 220 rpm, the
condenser temperature was kept at 8 ◦ C.
W. Deng et al.
To prepare the feed solution, 50 g of TMAH is weighed and added to
a 500 ml beaker, and then 450 g of PG was introduced into the beaker,
the TMAH⋅5H2O-PG ratio is 1:9 (w/w), then stirred until TMAH⋅5H2O is
completely dissolved. Based on the preliminary experiments, the heating
temperature, operating pressure and feed flow rate were selected as the
main factors and studied in detail using a single factor method while
other conditions were fixed.
The moisture content of the solution in this study was measured
using a volumetric method using a Karl Fischer moisture titrator (V30S,
METTLER TOLEDO, Switzerland). The moisture titrator used a volu­
metric method which can be used for automatic potentiometric titration.
The selected titrant is a one-component reagent and the dispersing agent
is methanol.
The content of TMAH in the distilled solution was determined by
acid-based titration using a pH meter (ST2100, OHAUS, Shanghai). The
TMAH was neutralized with a standard HCl solution (0.5 N). The
amount of TMAH was calculated using the sample mass and the volume
of acid used for each titration. The percentage of TMAH in the product is
calculated using the formula: TMAH(%)=(V × N × M)/m, where V is the
volume of the HCl solution, N is the normality of the hydrochloric acid
solution, M is the molar mass of TMAH and m is the mass of the sample.
3. Modelling of the molecular distillation using Aspen plus
Molecular distillation is a complex process of mass and heat transfer,
many parameters are involved in the process of molecular distillation,
which requires a considerable amount of experimental work to optimize
the operating conditions of molecular distillation, which also means a
massive amount of time and costs are required [37]. Many researchers
successfully modelled and simulated the molecular distillation process
with different methods31-36, which is useful for optimizing the operating
conditions. In this study, the Flash module in Aspen Plus v8.8 (Aspen­
Tech, Bedford, MA, USA) is employed to simulate and optimize the
molecular distillation process, where Peng-Robinson (PR) and Non-
Random Two-Liquid (NRTL) models are used, respectively. The ther­
modynamic model of PR is activity coefficient approach and the ther­
modynamic model of NRTL is equation of state. The physical properties
of PG, H2O and TMAH are obtained from the databank in Aspen Plus.
TMAH has no binary interaction with water and PG since TMAH does
not evaporate in the mixture. NRTL and PR equation are used to
correlate the VLE data and the binary interaction parameters of PG and
H2O in Aspen Plus. To simplify the model, the following assumptions are
made: simulation takes place at a constant feed flow rate and operating
pressure, the speed of scraping film is constant. The procedure of the
Flash module in Aspen Plus is as follows.
The Phase Equilibrium equation is:
y i = Ki x i (1)
where yi and xi are the mole fraction of the i-th component in the vapour
and liquid phases, Ki is the equilibrium ratio.
The material balance equation is:
Fzi = Vyi + Lxi (2)
where F is the molar feed rate, zi is the mole fraction of the i-th
component, V is the molar vapour rate, L is the molar liquid rate.
Since L = F − V, then by material balance:
zi = ψyi + (1 − ψ)xi (3)
where ψ is the mole fraction of the components in the vapour phase.
V
ψ= (4)
F
By the Mole Fraction Summations
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Separation and Purification Technology 288 (2022) 120701
∑ ∑ ∑
zi = xi = yi = 1 (5)
i i i
or
⎧ zi
⎪
⎨ xi = (Ki − 1)ψ + 1
⎪
(6)
⎪ Ki zi
⎪
⎩ yi =
(Ki − 1)ψ + 1
the Rachford-Rice equation [38] is obtained:
∑n (Ki − 1)zi
F(ψ, Ki , zi ) = =0 (7)
i − 1)ψ + 1
i=1 (K
For any set of Ki and zi must be solved for root ψ . In the operating
unit, zi is given, Ki is a function of T and P:
Ki = f (T, P) (8)
where T is the temperature and P is the pressure of the Flash vessel, then
yi = G(ψ, Ki , zi ) = G(ψ, f (T, P), zi ) (9)
The simulated results at different heating temperatures and oper­
ating pressures are obtained by Aspen Plus simulation. However, mo­
lecular distillation is a non-equilibrium mass transfer process, since the
Flash vessel of the simulator operates at equilibrium with 100% effi­
ciency, and molecular distillation is a non-ideal system which operates
at non-equilibrium mechanisms, thus significant differences between
the experimental and simulated temperatures are inevitable. Ketenoglu
et al. [34] found that simulated evaporation temperatures were different
than actual experimental temperatures, which was likely due to
different efficiencies at equilibrium, they adjusted temperatures with a
fitting factor calculated as equation (10), Mallmann et al. [39] also used
an adjusting equation to correlate the molecular distillation unit oper­
ation temperature to the Flash operation temperature, which was used
to correct the fact that a rate-based process was represented by an
equilibrium operation unit. Therefore, in this study, a fitting factor f,
which is calculated by equation (10), is introduced to make the simu­
lated model closer to the experimental conditions.
Ts
f = (10)
Te
where Ts is the simulated heating temperature (K), Te is the experi­
mental heating temperature (K).
To verify the simulated results and optimize the operating conditions
of molecular distillation, the RSM analysis based on the results of a
single-factor experiment and simulation was conducted.
4. Results and discussion
4.1. Experimental results
The influence of different parameters on the dehydrating effect of the
solution was determined by single-factor experiments. In this study, feed
temperature, heating temperature, operating pressure and feed flow rate
were selected as the main factors to investigate their effects on moisture
content. Theoretically, the higher temperature and the lower pressure
are conducive to the dehydration process. The feed flow rate affects the
residence time of the solution on the evaporating surface, if the flow rate
is too fast, the residence time of the solution will be too short, this will
lead to insufficient heating of the solution and be unable to realize the
separation effect [21]. However, if the residence time is too long, TMAH
will be heated continuously, which may lead to the thermal decompo­
sition of TMAH.
4.1.1. Effect of feed temperature
The effect of feed temperature on dehydration was investigated, the
W. Deng et al.
Fig. 2. Effects of feed temperature on water and TMAH content at 80 ◦ C, 500
Pa, 36 g/min.
Fig. 3. Effects of heating temperature on water and TMAH content at 500 Pa,
36 g/min.
selected temperatures were 25, 35, 45 and 55 ◦ C, where the initial water
content of the solution was 5.01%, the heating temperature was constant
at 80 ◦ C, the pressure was constant at 500 Pa, and the feed mass flow rate
was constant at 36 g/min. Fig. 2 shows the effect of feed temperature on
the dehydration. The results show that the change of feed temperature
has no obvious effect on the water content of the product. In some cases
of material separation in bio-oil, the heating temperature are generally
more than 200 ◦ C, so the material usually needs to be preheated to
improved separation efficiency, while the feed temperature of the ma­
terial after preheating is generally 150–200 ◦ C, and the difference be­
tween the feed and heating temperature is 30–80 ◦ C. In this study, the
difference between feed temperature and heating temperature is lower
(25–55 ◦ C), thus preheating has no obvious influence on the separation
effect.
4.1.2. Effect of heating temperature
The effect of heating temperature on dehydration was investigated,
the selected temperatures were 65, 70, 75, 80, 85 and 90 ◦ C, where the
initial water content of the solution was 5.01%, the pressure was con­
stant at 500 Pa, and the feed mass flow rate was constant at 36 g/min.
Fig. 3 shows the effect of the heating temperature on the dehydration.
The results indicate that the water content in the product decreases with
the increase of temperature. Clearly, more water evaporates to the
condensing surface and is distilled out at higher temperature. Hence, the
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Separation and Purification Technology 288 (2022) 120701
Fig. 4. Effects of pressure on water and TMAH content at 80 ◦ C, 36 g/min.
Fig. 5. Effects of feeding flow rate on water and TMAH content at 80 ◦ C,
500 Pa.
higher the temperature, then better dehydration would be realized.
However, while the temperature is too high, TMAH will decompose. The
TMAH content in the product increases with the increase in temperature
from 65 ◦ C to 85 ◦ C, but once the temperature is greater than 85 ◦ C, the
TMAH content does not increase significantly, which is due to the
decomposition of TMAH at high temperature. Thus, the operating
temperature is apparently a significant factor for the water and TMAH
content of the product, an appropriate temperature (<85 ◦ C) must be
considered to prevent the decomposition of TMAH.
4.1.3. Effect of the pressure
The effect of pressure on dehydration was investigated, the selected
pressures were 100, 500, 1000, 1500 and 2000 Pa. The experiments
were carried out at a heating temperature of 80 ◦ C and a feed mass flow
rate of 36 g/min, the initial water content of the solution was 5.34%.
Fig. 4 shows the effect of pressure on the water and TMAH content, it
indicates that the water content decreases with the decrease in the
operating pressure, which is due to the increase of the evaporation rate
at low pressure. Lower pressure will lead to a greater mean free path for
liquid molecules, and the volatile component will reach the condensing
surface easily, hence the removal rate is higher at low pressure.
TMAH content gradually increases with the decrease in the operating
pressure. The lower the pressure decreases, the faster TMAH content
increases, because water and PG evaporate at a faster rate under a higher
W. Deng et al. Separation and Purification Technology 288 (2022) 120701

Table 1 rate facilitates the dehydration process, at the same time, TMAH does
Comparison between the experimental and simulated temperatures at 500 Pa not exhibit significant thermal decomposition at low feed flow rate. The
and 100 Pa. highest TMAH content (11.96%) and the lowest water content (0.79%)
Pressure Water (%) T (K) is obtained at a flow rate of 36 g/min. But lower flow rate leads to lower
Experimental Simulated processing capacity.
PR NRTL

500 Pa 0.99% 338.15 276.85 291.15

0.83% 343.15 279.15 293.15
4.2. Modification of Aspen plus simulation
0.73% 348.15 281.15 294.8
0.56% 353.15 285.15 298.15 The simulation using the Flash module in Aspen Plus was carried out
0.47% 358.15 287.15 300.15 under the same operating pressure and water content in the product of
100 Pa 1.06% 338.15 302.15 316.15
the experiment. Table 1 shows the comparison between the experi­
0.90% 343.15 305.15 318.15
0.83% 348.15 306.15 319.15 mental and simulated temperatures, it shows that the simulated tem­
0.78% 353.15 308.15 320.15 perature is far lower than the experimental temperature at the same
0.65% 358.15 311.15 322.15 operating pressure and water content in the product, which is due to the
equilibrium process used in the simulation, while molecular distillation
is a non-equilibrium process. Therefore, T would be the variable that
vacuum. The lowest water content (0.82%) and the highest TMAH
results in the difference between the experiment and the simulation,
content (14.56%) were realized at 100 Pa. However, not only water but
while T is a variable in equation (9), a modification is advised, according
also more PG will be distilled out at extremely low pressure, which re­
to equation (10). The average value of the fitting factor f at different
sults in a lower recovery rate of PG in the product and increases the cost
pressure was calculated to adjust Ts which is used to predict the simu­
of PG recovery.
lated water content.
The comparison between the simulated and the experimental results
4.1.4. Effect of the feeding flow rate
is shown in Fig. 6, which indicates that the error between the simulated
The effect of the feed flow rate on dehydration was investigated, the
and experimental water content is considerable, especially for the NRTL
selected feed mass flow rates were 36, 54, 72, 90, 108, 126, 144 and 162
method, which is due to TMAH in solution does not evaporate, and it
g/min. The experiments were carried out at a heating temperature of
affects the evaporation of water and PG. It is found that the simulated
80 ◦ C and an operating pressure of 500 Pa, the initial water content of
results of water content are over-predicted at high temperature (75 ◦ C,
the solution was 4.77%. Fig. 5 shows the effects of different flow rates on
80 ◦ C, 85 ◦ C), and under-predicted at low temperature (65 ◦ C, 70 ◦ C) for
the water and TMAH content. The mass flow rate also affects the film
both 500 Pa and 100 Pa. The reason for the considerable error is that Ts
thickness in molecular distillation, as film thickness is an important
is not directly proportional to Te, but linearly dependent, to modify the
phenomenological characteristic that influence the separation perfor­
model, a linear correlation between Ts and Te was defined as follows:
mance. An appropriate feed flow rate is beneficial to the uniformity of
liquid film and the improvement of treatment capacity, however, if the Ts = Φ(Te ) = ATe + B (11)
feed flow is too fast, the film thickness will be too thick and lead to the
where A is the coefficient, and B is a constant. Thus equation (9)
turbulence phenomenon, which will cause uneven heating and ineffi­
transfers as follows:
cient separation. It was found that the water content increased with the
increase in the feed flow rate, because when the feed flow rate is too fast, yi = G(ψ, f (Φ(Te ), P), zi ) (12)
the film becomes too thick and the turbulence phenomenon occurs, most
The linear correlation between Ts and Te were correlated by the
of the solution passes into heavy phase before it can be heated and
linear fitting, and the fitting results are shown in Fig. 7. The R value of
separated.
Pearson is ≥ 0.98 at 500 Pa and ≥ 0.99 at 100 Pa respectively, which
When the flow rate decreases from 54 to 36 g/min, the content of
indicates the strong linear correlation between Ts and Te. Then equation
TMAH in the product increases significantly, which is due to PG staying
(12) is used to modify the simulated water content in the product.
on the evaporation surface long enough to be fully heated when the feed
Fig. 8 shows the comparison between the modified simulated and
flow rate is as low as 36 g/min. A large amount of evaporation of PG
experimental water content, it shows that the relative error between the
results in a large reduction for the solvent content in the product, thus
modified simulated and experimental data is less than 5%, which means
the content of TMAH is significantly increased. Therefore, lower flow
the modification is feasible and successful. As shown in Fig. 8a, the error

Fig. 6. Comparison between the experimental and simulated results using f at 500 Pa (a) and 100 Pa (b).

5
W. Deng et al. Separation and Purification Technology 288 (2022) 120701

Fig. 7. The linear dependence relation between Ts and Te at 500 Pa (a) and 100 Pa (b).

Fig. 8. Comparison between experimental and modified model results at 500 Pa (a) and 100 Pa (b).

Table 2 Table 3
Values and codes of the independent variables in the Box-Behnken design. Box-Behnken design and experiment results.
Independent variables Code Variable levels Run X1 X2 X3 Water (%)
− 1 0 1
1 − 1 − 1 0 0.99
Operating pressure (Pa) X1 100 450 800 2 1 − 1 0 1.09
Heating temperature (oC) X2 65 75 85 3 − 1 1 0 0.54
Feed flow rate (g/min) X3 36 54 72 4 1 1 0 0.7
5 − 1 0 − 1 0.8
6 1 0 − 1 0.85
in the percentage of water content between the modified model and 7 − 1 0 1 0.73
8 1 0 1 1.31
experimental data is maximal at 80 ◦ C when the pressure is 500 Pa,
9 0 − 1 − 1 1.24
0.04% for PR, 0.03% for NRTL, respectively. Fig. 8b shows that the 10 0 1 − 1 0.78
maximal difference is at 75 ◦ C when the pressure is 100 Pa, 0.04% for 11 0 − 1 1 1.71
PR, 0.03% for NRTL, respectively. Coupled with the comparison with 12 0 1 1 1.27
Fig. 6 and Fig. 8, it indicates that the model modified using linear fitting 13 0 0 0 1.11
14 0 0 0 1.08
is suitable and accurate for the dehydration process. The reliability and
15 0 0 0 1.26
validity of the modified model would be further verified by experiment. 16 0 0 0 1.28
17 0 0 0 1.18

4.3. Optimization of the process

The RSM analysis was used to optimize the conditions of the dehy­
dration process, including the heating temperature, pressure and feed
flow rate. In this work, the effects of these variables on the response (Y)
of water content in the product were investigated. A form of RSM, i.e.
Box-Behnken design with three variables at three levels, was designed
and the code levels and real values of each parameter are listed in
Table 2. The base settings are the rolling speed 220 rpm, the condenser
temperature 8 ◦ C, the feed temperature 25 ◦ C and the initial water
content of the solution 5.82%, the water contents for the response are
given in Table 3.
The statistical significance of the regression model was checked by
the F test, and the analysis of variance (ANOVA) for the response surface
quadratic model which is shown in Table 4. The equation

6
W. Deng et al. Separation and Purification Technology 288 (2022) 120701

Table 4
ANOVA of the quadratic model a.
Source SS DF MS F-value p-value significant

Model 1.26 9 0.14 12.57 0.0015 significant

X1 0.099 1 0.099 8.90 0.0204 *
**
X2 0.38 1 0.38 34.03 0.0006
**
X3 0.23 1 0.23 20.48 0.0027
X1X2 9.0 × 10-4 1 9.0 × 10-4 0.081 0.7843
X1X3 0.070 1 0.070 6.31 0.0402 *
X2X3 1.0 × 10-4 1 1.0 × 10-4 8.991 × 10-3 0.9271
X12 0.46 1 0.46 41.16 0.0004 **

X22 2.132 × 10-4 1 2.132 × 10-4 1.917 × 10-3 0.9663

X32 0.034 1 0.034 3.08 0.1225
Residual 0.078 7 0.011
Lack of fit 0.058 3 0.019 3.94 0.1092 NS
Pure error 0.020 4 4.920 × 10-4
Correlated Total 1.34 16
a
Coefficient of determination (R2) = 0.95; SS, sum of squares; DF, degree of freedom; MS, mean square;
*
p < 0.05, significant;
**
p < 0.01, highly significant.

Fig. 9. Response surface (a) and contour plot (b) for the effects of operating pressure (X1) and heating temperature (X2) on water content (R) at a constant feed flow
rate of 54 g/min.

Fig. 10. Response surface (a) and contour plot (b) for the effects of operating pressure (X1) and feed flow rate (X3) on water content (R) at a constant temperature
of 75 ◦ C.

7
W. Deng et al. Separation and Purification Technology 288 (2022) 120701

Fig. 11. Response surface (a) and Contour plot (b) for the effects of heating temperature (X2) and feed flow rate (X3) on water content (R) at a constant pressure of
450 Pa.

Y = 1.14 +0.11X1 − 0.22X2 +0.17X3 +0.015X1 X2 +0.13X1 X3 − 0.32X12 ­

Table 5
+0.011X22 +0.10X32 was obtained using the quadratic polynomial The comparison between the predicted and the verified experiment results.
regression analysis based on the regression model established in Table 4,
Name RSM predicted Experiment
where the confidence interval is 95%. The equation presents that the
dehydration process model could be used to predict the response for P (Pa) 100 100
T (oC) 85 85
different variables. The model F-value of 12.57 and p-value of 0.0015
Feed flow rate (g/min) 54 54
(<0.01) indicates that the model terms are significant. In this case, X1, Initial water content (%) 5.82 5.82
X2, X3, X1X3, X12 are significant model terms (p < 0.05), which means Water content (%) 0.48 0.43
that the linear effects of T, p, feed flow rate, the interaction effect of T Removal rate (%) 91.75 92.35
and feed flow rate, the quadratic effect of T are the determining factors
for the response. A P-value greater than 0.100 indicates that the model
Fig. 11 shows the mutual effect of feed flow rate and heating tem­
terms are not significant. The p-value of lack-of-fit is 10.92%, it implies
perature on the water content. As shown in Fig. 11a, the 3D surface
that the lack-of-fit is not significant, which means the model is signifi­
inclines to the direction of low flow rate and high temperature, which
cant. The coefficient of determination (R2) is 0.95, indicating that the
demonstrates that high temperature and low feed flow rate leads to the
statistical model explains 95% of the variability in the response. Hence,
better separation. As shown in Fig. 11b, the value of the contour lines
the model predicted for the response is adequate as the model is stable
also decreases in the direction of low flow rate and high temperature,
and has only a small error, which is suitable for predicting the response
and the lowest water content is obtained at 85 ◦ C and 36 g/min. As
value.
discussed in 4.1.1 and 4.1.3, the solution is fully heated and the evap­
The response surfaces and contour plots describing the complex re­
oration rate increases at a lower feed flow rate. Therefore, reducing the
lationships between the variables and the responses are shown in Figs. 9-
flow rate and increasing the temperature have the same effect, and the
11, showing the mutual effect of each two variables on water content in
two variables form mutual promotion, so the operating condition at
the product.
higher temperature and lower feed flow rate would be preferable.
Fig. 9 shows the mutual effect of operating pressure and heating
The RSM analysis shows that mutual effect must be considered, when
temperature on water content. It can be observed from the 3D surface
the initial water content of the solution was 5.82%, the optimal condi­
that the dehydration is more favorable at higher temperature and lower
tion was 85 ◦ C, 100 Pa and 54 g/min feed flow rate, and the quadratic
pressure, where there is a tendency for the water content to decrease as
model predicted a minimum water content of 0.48% in the product.
the temperature increases and the pressure decreases. Combining with
the single factor experiments, it can be seen that high temperature and
4.4. Verification of the optimal condition
low pressure promotes the dehydration process synergistically, and the
lowest water content was obtained at 85 ◦ C and 100 Pa.
Table 5 shows the comparison between the predicted and the verified
Fig. 10 shows the mutual effect of operating pressure and heating
experimental results, which are carried out under the conditions of the
temperature on water content, Fig. 10a shows that lower feed flow rate
initial water content of the solution 5.82%, 85 ◦ C, 100 Pa and 54 g/min
results in lower water content. However, Fig. 10b shows that lower
feed flow rate. The water content in the product is 0.43 %, which is
water content is obtained at 100 Pa and 800 Pa, combining with that the
lower than the RSM predicted water content (0.48%), and the water
p-value of model terms X1X3 is < 0.05, it indicates that pressure and flow
removal rate in the verification experiment is 92.35%, which is higher
rate interact to influence the dehydration process. It can be seen from
than the RSM predicted (91.75%). In summary, although slight errors
the trend in Fig. 10a, to obtain lower water content, the flow rate needs
exist between the predicted and the verified experiment results, the
to decrease continuously while the pressure increases. When the pres­
model developed in this study is feasible for the prediction of the
sure decreases, a lower water content will be obtained while the flow
dehydration of TMAH solution using the molecular distillation process
rate approaches 54 g/min. As discussed in 4.1.3, a low flow rate leads to
with high accuracy.
a large evaporation of the solvent, resulting in a high cost in the solvent
recovery, so the dehydration process should preferably be carried out at
the flow rate of 54 g/min.

8
W. Deng et al.
5. Conclusion
The experiment and simulation of the dehydration of TMAH solution
using the molecular distillation process was proposed in this work,
where the heating temperature, pressure and feed flow rate are the three
main variables. The single factor experiments showed that molecular
distillation was able to dehydrate TMAH solution, which prevented the
thermal decomposition of TMAH. A modified model of Aspen Plus Flash
module was developed to simulate the dehydration process. The modi­
fication was carried out using a fitting factor and a linear fitting, and it is
found that the modified model data fits the experiment results well. The
RSM analysis was used to optimize the conditions of the dehydration
process based on the experiment and simulation, and the mutual effect
of each two variables on the water content in the product was analyzed,
it was found that the optimal conditions for the minimum water content
(0.48%) were 85 ◦ C, 100 Pa, and 54 g/min. The verification experiment
was also carried out at the optimal conditions, and the water content in
the product was 0.43%, which is close to the prediction. The dehydra­
tion of TMAH solution was successfully conducted, and the model
developed in this study would be a useful tool for the design of industrial
dehydration processes.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
Financial support from the National Natural Science Foundation of
China (Nos. 22178121, 21908254) is greatly appreciated.
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