Article

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Kinetic Study on Sodium Sulfate Synthesis by Reactive Crystallization

Juan Carlos Ojeda Toro,†,‡ Izabela Dobrosz-Gómez,†,§ and Miguel Á ngel Gómez García*,†,‡
†
Grupo de Investigación en Procesos Reactivos Intensificados con Separación y Materiales AvanzadosPRISMA. ‡Departamento de
Ingeniería Química, Facultad de Ingeniería y Arquitectura, and §Departamento de Física y Química, Facultad de Ciencias Exactas y
Naturales. Universidad Nacional de Colombia, Sede Manizales, Campus La Nubia, Km 9 Vía al Aeropuerto la Nubia, Apartado Aéreo
127, Manizales, Caldas, Colombia

ABSTRACT: In this work, the kinetics of the reaction between sodium chloride and sulfuric acid, in aqueous solution and in the
presence of ethanol as antisolvent, was studied as a function of each reactant concentration and temperature. The thermometric
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method was implemented to fit the experimental data obtained in an adiabatic batch reactor. The initial reaction rate
methodology was applied to determine the order of reaction as well as the specific reaction rate constants. The reaction rate
corresponded to an elementary reaction. Good agreement between experimental and simulation temperature profiles was
achieved (absolute average deviation (AAD) of ∼1.15%). The reactive crystallization process was found to be very selective to
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anhydrous Na2SO4, with yields higher than 95 wt %.

1. INTRODUCTION This paper is focused on the determination of a kinetic

Sodium sulfate is the sodium salt of sulfuric acid. It is a white
crystalline solid. When anhydrous, it is known as the mineral
thenardite. Its decahydrate form, Na2SO4·10H2O, can be found
naturally as the mineral mirabilite, also known as Glaubert salt
in synthetic form. The heptahydrate one, Na2SO4·7H2O, can be
transformed to mirabelite when cooled. Sodium sulfate is
mainly used for the manufacture of detergents and in the Kraft
process of paper pulping.1
With an annual production of ∼10 million tonnes, it is a
major commodity chemical product. The total value of natural
and synthetic sodium sulfate sold worldwide was estimated as
$42 million in 2012. China remains the leading exporter and
producer of natural and synthetic sodium sulfate in the world.
About two-thirds of the world’s production is from mirabilite
and the remainder from byproducts of chemical processes such
as hydrochloric acid production.2 Other chemical processes
where sodium sulfate is the principal product include (i) the
Mannheim process, which involves the direct reaction of
sodium chloride and sulfuric acid in a rotary furnace at 840 °C,
leading to high purity sodium sulfate and hydrogen chloride
gas; (ii) the Hargreaves process, which comprises sodium
chloride, sulfur dioxide, oxygen, and water in a gas reaction at
high temperatures; and (iii) the acid−base neutralization of
sodium hydroxide and sulfuric acid to produce sodium sulfate
and water. All these processes implicate high energy
consumption in both reaction and separation steps.3
The results of our previous work4 have indicated that sodium
sulfate can be obtained by reactive crystallization, a low energy
consumption and environmentally friendly process. In this case,
the reaction is carried out while the solid−liquid equilibrium of
system (solubility) is altered by antisolvent agent addition.5−7
Subsequently, a supersaturation driving force is generated and
the product (sodium sulfate) is precipitated in the reactive
solution. Consequently, the reaction and separation can be
performed in a single stage, and the high yield purity salt can be
separated at low energy costs, in a simple and faster operation.8
expression for the simultaneous sodium sulfate and hydro-
chloric acid production by sodium chloride and sulfuric acid
reaction in aqueous solution, in the presence of an antisolvent.
Considering the exothermic nature of this reaction, a
thermometric experimental methodology was defined basing
on the proposition of Nguyen et al.9 It allows to correlate the
increase in temperature with the reactive consumption and the
process of solid crystal formation. To ensure that the measured
change in temperature is provoked by all heat effects, an
adiabatic close system was used. The determined kinetic
expression rate shows the relationship between the temperature
variation and the reactive concentration changes, when the
material and energy balances are coupled.
2. REACTION KINETIC FRAMEWORK
2.1. Antisolvent Selection. Sodium sulfate and hydro-
chloric acid can be obtained by sodium chloride and sulfuric
acid reaction in aqueous phase (homogeneous), in the presence
of an antisolvent, as follows:
antisolvent
2NaCl(soln) + H 2SO4(soln) ⎯⎯⎯⎯⎯⎯⎯⎯⎯→ Na 2SO4(s) + 2HCl(soln)
(1)
High solubility of sodium chloride (reactant) and low solubility
of sodium sulfate (product) are the key features for antisolvent
selection. On the basis of experimental data reported in the
literature,4,10−12 it was found that ethanol and methanol present
good properties as antisolvent for the case under study.
However, for work security, health, and trade reasons, ethanol
was selected.
2.2. Adiabatic Batch Reactor Model. For an adiabatic
batch reactor, the material balance can be presented in the
following way:
Received: December 9, 2014
Revised: February 6, 2015
Accepted: February 9, 2015
Published: February 9, 2015

© 2015 American Chemical Society 2311 DOI: 10.1021/ie504763q

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Industrial & Engineering Chemistry Research Article

dNi Table 1. Chemicals Used in the Reactive System (NaCl−

= νi( −rA )VR H2SO4−EtOH−H2O)
dt (2)
where Ni is the number moles of species i, t is the time, νi is the initial mass final mass
chemical fraction purification fraction analysis
stoichiometric coefficient of species i, VR is the reactor volume, name source purity method purity method
and −rA is the rate of disappearance of A (sodium chloride), sodium Merck 0.995 none
which identify our specie basis of calculation. chloride
Similarly, the energy balance can be expressed as follows: sulfuric Merck 0.97 none
acid
dT ( −ΔHrxn,A(T ))( −rAVR ) ethanol Merck 0.998 none
=
dt ∑ NCi p ,i (3)
where ΔHrxn,A is the heat of reaction per mol of A and Cp,i is the
heat capacity of each species.
The rate of disappearance of A, −rA, in the sodium chloride
and sulfuric acid (B) reaction, might be given by a rate law as
follows:
−rA = kCAαC Bβ (4)
Thus, in eq 4, the reaction is α and β order with respect to Figure 1. Experimental scheme to obtain sodium sulfate by reactive
reactant A and B, respectively. crystallization.
Combining the material and energy balances, it is possible to
obtain

dT −ΔHrxn,A(T ) ⎛ k(T )CAαC Bβ ⎞

= ⎜⎜ ⎟⎟
dt Cp ,soln ⎝ CA0 ⎠ (5)
For the electrolytic system under study, the rate constant, k,
must be expressed as a function of the temperature and feed
concentration (sodium chloride):
⎛ −E ⎞
k(T ,C A 0) = A 0 exp⎜ ⎟
⎝ RT ⎠ (6)

A 0 = kc1 ln(C A 0) + kc2 (7)

where E is the activation energy and kc1 and kc2 are the kinetic
constants.
Considering that the energy generated by the reaction equals
the sensible energy absorbed by reactive mixture, it is possible
to say that Figure 2. NaCl and Na2SO4 solubilities4,13,14 in water−ethanol
mixtures at 25 °C.
Tf
Msoln ∫T Cp ,soln dT = MA0 ( −ΔHrxn,A )
(8)
0 Merck (Table 1). Deionized water (H2O) and ethanol
where Msoln and MA0
represent the mass of the solution and (C2H6O) were used as solvent and antisolvent, respectively.
initial mass of A, respectively. This equation can be expressed as 3.2. Apparatus. The experimental scheme, shown in Figure
follows: 1, was prepared for kinetic studies. It allows obtaining
temperature vs time data (in digital form). The experimental
MsolnCp ,solnΔT = MA0 ( −ΔHrxn,A ) (9) device includes a jacketed injector which contains the sulfuric
acid solution, an adiabatic batch reactor, a stir plate, a
assuming constant or mean heat capacities and heat of reaction. temperature sensor LM35-LabJack board U12, and a computer.
Finally, reorganizing eq 9, it is possible to obtain A homemade interface, programmed in MatLab software, was
( −ΔHrxn,A ) used to read and store the experimental data.
MsolnΔT
= 3.3. Procedure. On the basis of sodium chloride and
Cp ,soln MA0 (10) sodium sulfate solid−liquid phase equilibria at room temper-
ature in water−ethanol solution (Figure 2), the ethanol−water
Thus, the ratio between reaction enthalpy and heat capacity can mixture containing 50 wt % was selected to perform the
be calculated from experimental data (Msoln, M0A, and ΔT of thermometric tests. At such composition of ethanol−water
reaction). mixture, the solubility of NaCl is still relatively high and that of
Na2SO4 extremely low (Figure 2).
3. EXPERIMENTAL SECTION The experiments were performed according to the conditions
3.1. Chemicals. Sodium chloride (NaCl) and sulfuric acid presented in Table 2. Thus, each time, sodium chloride and
(H2SO4) were used as reactants. All chemicals were supplied by sulfuric acid solutions were prepared and stored in a
2312 DOI: 10.1021/ie504763q
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Industrial & Engineering Chemistry Research Article

Table 2. Experimental Design for the Kinetic Study on thermostatic bath at selected temperature. Subsequently, they
Sodium Sulfate Synthesis by Reactive Crystallizationa were fed to the adiabatic reactor and the jacketed injector,
respectively. After a significant time needed for temperature
experiment CA0, M CB0, M T0, °C data type
stability in the reactor (delay time of at least 100 s), the sulfuric
I.1 0.50 1.50 25 T vs t at different CA0
acid solution, at the same temperature as the temperature of the
I.2 0.75 reactor, was injected to the sodium chloride solution, starting
I.3 1.00 the reaction. As a result, a thermogram (temperature vs time
I.4 1.25
data) was obtained. Each test was carried out in triplicate in
II.1 1.47 1.00 25 T vs t at different CB0
order to avoid systematic errors and to determine the
II.2 1.50
reproducibility of results.
II.3 2.00
II.4 3.00
III.1 1.47 1.50 16 T vs t at different T0 4. RESULTS AND DISCUSSION
III.2 20 4.1. Reactivity Tests. The typical temperature−time
III.3 25 variations obtained from batch experiments are shown in
III.4 30 Figure 3. An increase in temperature was observed immediately
a
Experiments I and III were performed at sodium chloride saturation after the H2SO4 injection into the reactor, reaching a maximum
conditions (in ethanol/water mixed solvent at 25 °C). A = NaCl and B
temperature and remaining stable for a considerable time. In all
 H2SO4. Standard uncertainties (u) are u(T0) = 0.1 °C, u(CA0) =
cases, the temperature rise was ∼3 °C. However, it slightly
0.01, u(CB0) = 0.01. depended on the specific experimental conditions. All temper-
ature data have a deviation of approximately ±5% (thermo-
grams).

Figure 3. Representative thermograms obtained in triplicate for the following experiments: (a) experiment I.4, (b) experiment II.1, and (c)
experiment III.2.

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Ind. Eng. Chem. Res. 2015, 54, 2311−2316
Industrial & Engineering Chemistry Research
Figure 4. Sodium sulfate mass and yield obtained in each experiment
(the experiment conditions correspond to these presented in Table 2).
The solid products, synthesized in each experiment, were
characterized by X-ray diffraction (XRD) using a RIGAKU-
MINIFLEX II diffractometer. Sample diffractograms were
compared to the available patterns from the Joint Committee
on Powder Diffraction Standards (JCPDS).15,16 The following
salts were included in the analysis: NaCl, Na2SO4, Na3H(SO4)2,
NaHSO 4 , NaHSO 3 . NaH 3 (SO 4 ) 2 , Na 2 S 2 O 5 , Na 2 S, and
Na2S2O3. In all cases, the four main diffraction peaks
corresponded only to the diffraction pattern of anhydrous
Na2SO4 (thenardite, JCPDS 37-1465), confirming the high
selectivity of the reactive crystallization process. The product
yield was measured for each test. It was defined as the percent
relation between the mass of sodium sulfate obtained
experimentally and that expected stoichiometrically for a
certain amount of sodium chloride fed. The experimental
mass (average value) and calculated yields are shown in Figure
4. In all cases, the obtained yields were higher than 95%.
Furthermore, the tests carried out at sodium sulfate saturation
conditions (experiments II.1 and III.1) presented the highest
Figure 5. (a) Plot of temperature vs time to define the initial and final temperatures of sodium sulfate synthesis. (b) Plot of the derivative of
temperature with respect to time (dT/dt) vs time to apply the initial rate method. The MatLab function spline was used to fit experimental data.
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Table 3. Kinetic Parameters Values Fitted for the Rate Law
Expression of Sodium Sulfate Synthesis
parameter value
α 2.0 ± 0.01
β 1.0 ± 0.05
kc1 (L2/(mol2 s)) 1.54495 × 10−5 ± 7.73 × 10−7
kc2 (L2/(mol2 s)) 5.93663 × 10−2 ± 2.97 × 10−4
−E/R (K) 1.96809 ± 0.098
−ΔHrxn,A/Cp,soln (K) 7.93729 ± 0.397
sodium sulfate yields. The yields reached in II.2. and III.3
experiments were identical. All yield measurement data have a
deviation of approximately ±3%.
4.2. Numerical Data Analysis. To determine the precise
value of initial and final temperature (ΔT = Tfinal − Tinitial) of
reaction, for each experimental test of sodium sulfate synthesis,
the initial rate method was used.17,18 Figure 5 shows the
analysis of three representative experimental thermograms
(experimental raw data are presented as circle markers in Figure
5a). It should be noted that only the rising part of each curve
temperature vs time corresponds to the chemical reaction.
Thus, at first, the condition at which first derivate of
temperature vs time (dT/dt) equals zero (prior to the
maximum rate of temperature change, triangle markers in
Figure 5b) allows definition of the precise value of initial
reaction temperature for each test (triangle markers in Figure
5a). Next, the maximum rate of temperature change can be
determined as the maximum value of dT/dt vs time curve (star
marker in Figure 5b). Assuming that the initial rate of
temperature change equals its maximum rate, a straight line
can be traced between the initial and maximum temperature
rate points (triangle and stars markers in Figure 5a,
respectively). Then the final reaction temperature value (square
points in Figure 5a) will correspond to the intercept point
between the extrapolation of the previously traced straight line
(dotted line in Figure 5a) and the temperature profile.
Consequently, the absolute initial and final temperatures were
determined by calculating the average value of each of them
DOI: 10.1021/ie504763q
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Industrial & Engineering Chemistry Research
Figure 6. Comparison between simulation and experimental temperature profiles obtained for the following. (a) Experiments I: change in the NaCl
concentration fed. (b) Experiments II: Change in the H2SO4 concentration fed. (c) Experiments III: Change in feed temperature. All experimental
conditions correspond to these included in Table 2.
from three performed experiments. Thus, the temperature
change, expressed as ΔT = Tfinal − Tinitial, for each experiment
was determined, and the ratio −ΔHrxn,A/Cp,soln for each
experiment was calculated using eq 10.
By use of a nonlinear data fitting procedure (lsqnonlin
available in MatLab), the kinetic parameters in eq 5 were
adjusted numerically. The obtained results are presented in
Table 3. Thus, it is possible to say that the reaction order with
respect to NaCl (α) and H2SO4 (β) corresponds with the
stoichiometric coefficient of each species in the elementary
reaction (as written). It is important to clarify that the fitted
value of the parameter (−ΔHrxn,A/Cp,soln) includes all the heat
effects (enthalpy of reaction and heat of crystallization)
responsible for the detected increase in temperature. The fitted
value is in good agreement with the calculated one, based on
data reported in the literature.19,20 The relative error between
the values estimated by us (7.93729 K) and the calculated one
(7.7880 K) is 1.88%.
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The quality of the correlation was calculated from the
absolute average deviation (AAD) as follows:
NTD
100
AAD = ∑ |(xicalc − xiexp)/xiexp|
NTD i=1 (11)
where xi represents the temperature datum and NTD is the total
number of temperature experimental points. For a total of 103
experimental data, the AAD was ∼1.15%, confirming the
goodness of fit. Similar conclusions can also be made based on
the analysis of Figure 6, where calculated and experimental data
are compared (reactor batch calculations were performed using
eqs 2 and 3 and the adjusted kinetic parameters). The
simulated temperature vs time variations follow a similar
tendency as that observed from the experimental data.
However, one can see that at lower temperatures (16 and 20
°C) curve-fitting to experimental data presents more significant
deviations (probably due to the presence of some phase
nonidealities related to the crystallization process at low
temperatures). The reaction mechanism and kinetics will be
DOI: 10.1021/ie504763q
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Industrial & Engineering Chemistry Research Article

studied further as a function of the activities of the reactants
(including the activities model previously determined by us for
this system4) in order to involve intermediates and transitions
states. This will lead to a greater understanding of how and why
the reactive crystallization occurs, reducing the model deviation
at low temperatures and giving insights of better ways to
perform the reaction.
5. CONCLUSIONS
The feasibility of synthetizing sodium sulfate by reactive
crystallization was demonstrated in an adiabatic laboratory
batch reactor. The kinetics of the reaction was studied in a wide
range of reactant concentrations and temperatures. The rate of
reaction was monitored by measuring the temperature change
as a function of time. The reaction rate corresponded to an
elementary reaction. An excellent agreement between simu-
lation and experimental results in the adiabatic batch reactor
was achieved, with an absolute average deviation of ∼1.15%. A
high product yield was obtained during all experiments (>95 wt
%). The characterization test (XRD) of the obtained salt
confirmed its anhydrous nature and high purity.
(8) Tóth, J.; Kardos-Fodor, A.; Halász-Péterfi, S. The formation of
fine particles by salting-out precipitation. Chem. Eng. Process. 2005, 44,
193.
(9) Nguyen, D.; Fogler, H.; Chavadej, S. Fused Chemical Reactions.
2. Encapsulation: Application to Remediation of Paraffin Plugged
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(10) Iliuta, M.; Thomsen, K.; Rasmussen, P. Extended UNIQUAC
model for correlation and prediction of vapour-liquid-solid equilibria
in aqueous salt systems containing non-electrolytes. Part A. Methanol-
water-salt systems. Chem. Eng. Sci. 2000, 55, 2673.
(11) Li, M.; Wang, L.; Jiang, B.; Gmehling, J. Generalized LIQUAC
model for the single- and mixed-solvent strong electrolyte systems.
AIChE J. 2011, 57, 2535.
(12) Thomsen, K.; Iliuta, M.; Rasmussen, P. Extended UNIQUAC
model for correlation and prediction of vapor−liquid−liquid−solid
equilibria in aqueous salt systems containing non-electrolytes. Part B.
Alcohol (ethanol, propanols, butanols)−water−salt systems. Chem.
Eng. Sci. 2004, 59, 3631.
(13) Pinho, S.; Macedo, E. Representation of salt solubility in mixed
solvents: a comparison of thermodynamic models. Fluid Phase Equilib.
1996, 116, 209.
(14) Seidell, A. Solubilities of Inorganic and Organic Compounds; D.
Van Nostrand Company, Inc.: New York, 1919.
(15) Linnow, K.; Zeunert, A.; Steiger, M. Investigation of sodium

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sulfate phase transitions in a porous material using humidity- and
AUTHOR INFORMATION temperature-controlled X-ray diffraction. Anal. Chem. 2006, 78, 4683.
(16) Crystallography Open Database. http://www.crystallography.
Corresponding Author net/new.html.
*E-mail: magomez@unal.edu.co. Tel/Fax: (57) 6 8879300 - (17) Fogler, H. S. Elements of Chemical Reaction Engineering, 4th ed.;
55210/55129. Prentice Hall Professional Technical Reference: Upper Saddle River,
NJ, 2005.
Notes (18) Shoemaker, D.; Garland, C.; Nibler, J. Experiments in Physical
The authors declare no competing financial interest. Chemistry, 5th ed.; McGraw Hill: New York, NY, 1989.

■
(19) Green, D.; Perry, R. Perry’s Chemical Engineers’ Handbook, 8th
ACKNOWLEDGMENTS ed.; McGraw Hill: New York, 2007.
(20) Marliacy, P.; Solimando, R.; Bouroukba, M.; Schuffenecker, L.
The authors acknowledge the financial support of DIMA Thermodynamics of crystallization of sodium sulfate decahydrate in
(Programa para la Financiación de Semilleros de Investigación H2O-NaCl-Na2SO4: application to Na2SO4·10H2O-based latent heat
en Emprendimiento en la Universidad Nacional de Colombia storage materials. Thermochim. Acta 2000, 344, 85.
Sede Manizales2012Código 17037) and COLCIENCIAS
(Programa Jóvenes Investigadores e Innovadores Convocatoria
566 de 2012, Convenio Especial de Cooperación No. 0729 de
2012). The Laboratorio de Materiales Nanoestructurados y
Funcionales from Universidad Nacional de Colombia, Sede
Manizales, is also aknowledged for its help in XDR measure-
ments.

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