CATALYSIS, KINETICS AND REACTION ENGINEERING

Chinese Journal of Chemical Engineering, 21(7) 736—741 (2013)

DOI: 10.1016/S1004-9541(13)60533-9

Apparent Dissolution Kinetics of Diatomite in Alkaline Solution*

DU Gaoxiang (杜高翔)1,**, LÜ Guocheng (吕国诚)1 and HE Xuwen (何绪文)2

1
School of Materials Science and Technology, China University of Geosciences, Beijing 100083, China
2
School of Chemical & Environmental Engineering, China University of Mining & Technology, Beijing 100083, China

Abstract The dissolution kinetics of diatomite in alkaline solution is the theoretical basis for the process optimi-
zation of alkali-diatomite reaction and its applications. In this study, the dissolution kinetics of diatomite in NaOH
solution is investigated. The results indicate that the dissolution reaction fits well the unreacted shrinking core
model for solid-liquid heterogeneous reactions. The apparent reaction order for NaOH is 2 and the apparent activa-
tion energy for the reaction (Ea) is 28.06 kJ·mol−1. The intra-particle diffusion through the sodium silicate layer is
the rate-controlling step. When the dissolution reaction occurs at the interface of unreacted diatomite solid core, the
diffusion in the trans-layer (the liquid film around the wetted particle) reduces the rate of whole dissolution process.
Keywords diatomite, sodium hydroxide, dissolution kinetics

1 INTRODUCTION amorphous silica in the alkaline solution under mild

Sodium silicate is usually prepared by reaction of
quartz sands (SiO2) and sodium carbonates or sodium
sulfates (Na2CO3 or Na2SO4) at high temperatures
(above 1250 °C), in which high energy-consumption
and the pollution are the main disadvantages in those
conventional techniques [1]. In recent years, many
new methods have been developed to produce sodium
silicate by the reaction between amorphous silica ma-
terials, such as diatomite or opal, and alkaline solution,
such as sodium hydroxide, to avoid the environmental
and energy-consumption problems [2].
The modulus, which is the molar ratio of SiO2 to
Na2O in sodium silicate, changes with the amounts of
NaOH to SiO2 used and other reaction parameters. For
different applications such as mould sands, adhesives,
cementing materials, detergents and the preparation of
precipitated silica, the demand on the modulus of so-
dium silicate varies [3-6].
The dissolution kinetics of diatomite in alkaline
solutions is the theoretical basis for the process opti-
mization of alkali-diatomite reactions and applications.
The kinetic behavior between sodium hydroxide and
quartz materials in aqueous solutions under different
conditions has been reported by several groups. The
kinetic order for OH− and the kinetic constant under
hydrothermal conditions are 0.470±0.013 and
3.933×10−6 g·m2·s−1, respectively, when the reaction
temperature, pressure and molar ratio of SiO2/Na2O
are 220 °C, 2.7 MPa and 2, respectively [7-9]. The
dissolution and precipitation kinetics of quartz or
conditions with pH of 11-12 and temperature of
23-70 °C have been examined [10]. The kinetic model
for dissolution of silica aerosol in NaOH solution have
been investigated, with the concentration of silica
aerosol in NaOH solution being 0.05-0.79 mol·L−1 at
15-56 °C [11], the dissolution activation energy is
(80±6) kJ·mol−1 and the interfacial energy of coarsely-
and finely-dispersed samples are 0.09 and 0.24 J·m−2,
respectively [12, 13].
Most studies on the topic focus on the dissolution
kinetics of pure SiO2, such as quartz, in the alkaline
solution. Here, we investigate the kinetics of diatomite
dissolution in NaOH solution, propose a new dissolu-
tion model based on the analysis of experimental data,
and obtain reaction rate equation under certain reac-
tion conditions, in which the apparent reaction order
and the apparent activation energy are evaluated and
the main rate-controlling factors are to be determined.
2 EXPERIMENTAL
2.1 Materials
Diatomite is obtained from Jilin Yuantong Mining
Co., Ltd. (with particle size distribution of d50 = 7.73 μm
and d97 = 17.57 μm), the chemical composition and
mineral composition of which are shown in Table 1 and
Fig. 1, respectively. XRD results show that the diato-
mite material consists of a large quantity of diatomite
and a small quantity of quartz and clay. NaOH (solid,
A.R.) is purchased from Beijing Chemical Plant.

Table 1 Chemical composition of diatomite (%, by mass)

SiO2 Al2O3 Fe2O3 TiO2 CaO MgO K2 O Na2O MnO2 P2O5 SO3 L.O.I
90.30 3.48 0.95 0.26 0.28 0.26 0.32 0.16 0.002 0.072 0.036 4.28

Received 2012-01-06, accepted 2012-09-07.

* Supported by the National Natural Science Foundation of China (50674080).
** To whom correspondence should be addressed. E-mail: dgx@cugb.edu.cn
 Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013
Figure 1 XRD pattern of diatomite
2.2 Assumptions for the reaction
(1) Reactants diffuse uniformly in the reaction
system. Thus the solid content in the solution is low
and the system is rigorously stirred throughout [14].
(2) The reaction stops as soon as the sample is
removed from the reaction system. In order to quench
the reaction, the removed samples are diluted with a
quintuple volume of distilled water immediately at low
temperature, then filtrated and washed under vacuum.
(3) The chemical composition of the diatomite
material is that of pure SiO2 since it consists mainly of
SiO2 phase (Fig. 1). Thus the term “SiO2” instead of
“diatomite” is used here as the analysis and calcula-
tion “variable” in most cases.
2.3 Method
In a typical reaction, 120 g of diatomite, 35 g of
solid sodium hydroxide (in order to obtain completely
reacted product, the modulus of sodium hydroxide is
set to 4, a little larger than its theoretical modulus, 3)
and 360 ml distilled water were mixed in a 1000 ml
three-neck flask. All flasks were sealed by polytetra-
fluoroethylene plugs to prevent the solution from
evaporation. The three-neck flask was immersed into a
water bath at pre-set temperature and the system was
kept stirring for 3 h. 30 ml of sample was transferred
into a beaker with 150 ml of cold distilled water added
every 25 min. The resultant mixture was filtrated on a
piece of filter paper and then washed with distilled
water until sodium ions can not be detected in the so-
lution. The concentration of Na+ in the filtrate and the
amount of the SiO2 precipitate obtained were analyzed.
The apparent reaction order and apparent activation
energy were calculated and the kinetic equation was
established based on these data.
737
2.4 Instrument
DZK-4 thermostat water bath (Beijing Zhongx-
ingweiye Instrument Co., Ltd.), 0.5 L vacuum pump
(Beijing Zhongxingweiye Instrument Co., Ltd.), JB-300D
type electronic stirrer (Shanghai Standard Model Plant),
and S-3500N type Scanning Electron Microscope
(Hitachi Corporation) were used in the experiments.
3 RESULTS AND DISCUSSION
3.1 Reaction mechanism
The reaction between diatomite and sodium hy-
droxide is a liquid-solid multiphase reaction. This re-
action can be expressed as
nSiO2(s) + 2NaOH(l) Na2O·nSiO2+H2O (1)
where n is the modulus of sodium silicate, which is
the molar ratio of SiO2 to Na2O, ranging from 1 to 4.
The molar ratio used in the experiment is generally set
between 3.0 and 3.4 for preparing precipitated amor-
phous silica with large specific area, and at about 2.0 in
the cases of mould sand binders and detergents [15, 16].
Naturally, diatomite is the debris of diatoms with
regularly structured pore arrangement (Fig. 2). The di-
atomite particles have disc-like appearance with many
holes inside as shown in Fig. 2 (a). The pore structure
can be observed more clearly in Fig. 2 (b) and the pore
diameter usually ranges from 100 nm to 200 nm. The
diatomite particles are considered as solid particles in
this paper since the resultant sodium silicate film is too
viscous to allow the flowing of the reactant solution.
In the dissolution, the surface of diatomite particles
is gradually covered by a newly produced sodium sili-
cate layer, which is so concentrated and viscous that it
reduces the diffusion of sodium hydroxide species
significantly. Hence, for a solid diatomite particle, the
738 Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013
(a) Morphology in low magnification
Figure 2 SEM images of diatomite particles
reaction process can be divided into several steps: the
diffusion of sodium hydroxide from solution to the ex-
ternal surface of a wetted particle, referred to trans-layer
diffusion; intra-particle diffusion (the diffusion through
the sodium silicate layer) to the reaction interface; the
chemical reaction at the interface and the diffusion of
sodium silicate species into the main body of the solu-
tion, etc. Since the overall reaction rate is usually con-
trolled by the slowest step, a crucial task is to find the
rate-controlling factors. The shrinking unreacted core
model is one of readily accessible theories to describe
such solid-liquid multi-phase reaction. This model is
used here to describe the diatomite dissolution in the
alkaline solution, in which the total particle size is
invariable while the reaction interface moves inward
gradually. That is to say, the reaction proceeds gradu-
ally with the decrease of the solid core size and the
increase of the thickness of resultant sodium silicate
layer, with the diameter of the particle unchanged
(Scheme 1).
Scheme 1 Dissolution model of a diatomite particle in
NaOH solution
The diffusion rate of sodium hydroxide through
the liquid (newly-formed sodium silicate) film to the
diatomite surface is related to the diffusion resistance
and the concentration gradient of sodium hydroxide in
the hydraulic diameter of a wetted diatomite particle,
which can be described by Fick’s first law [17],
−dnNaOH /( S ⋅ dt ) = k1 ( cNaOH,L − cNaOH,S ) (2)
where dnNaOH/dt is the moles of NaOH passing
through the liquid film around the wetted particle in a
(b) Microstructure in high magnification
time interval, S is the surface area of a diatomite parti-
cle, k1 is the diffusion rate constant, cNaOH,L and cNaOH,S
are the molar concentrations of sodium hydroxide in
the external and internal surfaces of the liquid film
layer around a wetted diatomite particle (mol·L−1),
respectively. However, the actual chemical reaction
rate depends on the concentration of sodium hydroxide
at the reaction interface, the concentration of the resulted
sodium silicate and the reaction temperature, etc.
The temperature effect on the dissolution rate is
expressed by Arrhenius equation
K = K 0 ⋅ e − E / RT (3)
where K is a reaction rate constant, K0 represents the
rate constant when E = 0, and E is the reaction activa-
tion energy.
3.2 Apparent reaction order
Due to the high viscosity of sodium silicate at
low temperatures, the reaction is carried out at 70 °C
and 90 °C. Samples were collected at 70 °C and 90 °C
at an interval of 25 min and then the SiO2 content and
Na+ concentration of the collected samples were meas-
ured. The experimental results are shown in Table 2.
The modulus of sodium silicate varies with reac-
tion time. The actual modulus of sodium silicate can
be calculated by the amount of the residual sodium
hydroxide. For the sake of convenience, all moduli are
set to 4.0 in the calculation. The amounts of the re-
acted silica and sodium hydroxide at time t, denoted
by subscript t, can be calculated as follows.
mSiO2 ,t = cSiO2 ,filtrate,t ⋅ Vfiltrate,t ⋅ Vtotal / Va,t (4)
where mSiO2 ,t is the mass of the reacted silica (g),
cSiO2 ,filtrate,t is the concentration of SiO2 in the sample
suspension (g·L−1), Vfiltrate,t is the volume of filtrate
collected(L), Vtotal and Va,t are the total volume of the
reaction mixture and the volume of the sample col-
lected at time t, which are 0.552 L and 0.025 L, re-
spectively.
 Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013 739

Table 2 ex situ sample composition analysis

Reaction time Accumulative filtrated volume/ml Content of SiO2/g·L−1 Concentration of Na2O in filtrate/g·L−1
/min 70°C 90°C 70°C 90°C 70°C 90°C
25 448 452 1.79 3.52 2.88 2.36
50 420 375 3.28 6.78 3.25 2.96
75 389 370 4.68 7.62 3.88 2.91
100 470 355 4.43 8.09 3.00 2.90
125 430 384 3.55 7.59 3.50 2.61
150 425 392 5.99 8.24 3.63 2.75

Table 3 The relationship between concentration of unreacted NaOH and reaction time

Reaction cNaOH,t/mol·L−1 ln(cNaOH,t) (cNaOH,t)−1

time/min 70 °C 90 °C 70 °C 90 °C 70 °C 90 °C
0 1.54529 1.54529 0.43521 0.46068 0.64713 0.64713
25 1.27798 1.05420 0.24528 0.05278 0.78248 0.94859
50 1.08609 0.73727 0.08258 −0.30480 0.92073 1.35636
75 0.93845 0.64535 −0.0635 −0.43797 1.06559 1.54955
100 0.85126 0.57364 −0.16104 −0.55575 1.17474 1.74325
125 0.76842 0.52254 −0.26341 −0.64905 1.30137 1.91373
150 0.69671 0.50767 −0.36139 −0.67793 1.43533 1.96978

mNaOH,t = 2M NaOH ⋅ mSiO2 ,t ( 4M SiO ) 2

(5)

where mNaOH,t is the mass of sodium hydroxide con-

sumed (g), MNaOH and M SiO2 are molecular mass of
NaOH and SiO2, which are 39.997 and 60.0835 g·mol−1,
respectively.
The concentration (mol·L−1) of the remaining
silica and sodium hydroxide in the residual reaction
mixture at time t can be calculated as follows.
cSiO2 ,t = ( mSiO2 ,0 − mSiO2 ,t ) (Vtotal ⋅ M SiO2 ) (6)

cNaOH,t = ( mNaOH,0 − mNaOH,t ) (Vtotal ⋅ M NaOH ) (7)

where subscript 0 refers to the initial value.
The relation between lncNaOH,t and reaction time t
is linear when the apparent reaction order is 1, and the
relation between (cNaOH)−1 and reaction time t is linear
when the apparent reaction order is 2. The analysis
results for the alkali-diatomite reaction are shown in
Table 3.The relationship between the concentration of
the remaining NaOH and reaction time is readily de-
termined according to the data in Table 3.
As shown in Fig. 3, the apparent reaction order
for NaOH is 2. The apparent reaction rate is
2
−dcNaOH / dt = k ⋅ cNaOH, t
where k is a reaction rate constant, and cNaOH,t is the
concentration of the unreacted NaOH in the solution at
time t.
Figure 3 Determination of reaction order by data fitting
◇ 70 °C first order; △ 90 °C first order; ▲ 70 °C second order;
■ 90 °C second order; liner 90 °C second order;
liner 70 °C second order
The value of k is 0.1306 at 70 °C and 0.2245 at
90 °C, determined by the slope of the fitting straight
line as shown in Fig. 3. The apparent activation energy
for this reaction (Ea) is from the following equation:
ln ( KT2 / KT1 ) = Ea ⋅ (T2 − T1 ) ( RT2T1 ) (9)
The value of Ea is calculated to be 28.06 kJ·mol−1.
(8) 3.3 Controlling factors and kinetic equation for the
dissolution reaction
The alkali-diatomite particle reaction is explained
740 Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013

Table 4 Analysis on rate-controlling factor

x [1 − (1 − x)1/3] [1+3(1 − x)2/3 − 2(1 − x)]
Reaction time/min
70 °C 90 °C 70 °C 90 °C 70 °C 90 °C
25 0.18355 0.36458 0.06536 0.14029 1.98775 1.94646
50 0.31531 0.58220 0.11861 0.25242 1.96117 1.84102
75 0.41669 0.64532 0.16446 0.29214 1.92779 1.79380
100 0.47656 0.69436 0.19409 0.32640 1.90159 1.74994
125 0.53344 0.72945 0.22440 0.35323 1.87150 1.71384
150 0.58268 0.73985 0.25271 0.36163 1.84069 1.70225

by the unreacted shrinking core model. If the diffusion

of trans-liquid film is the rate-controlling factor, the
kinetic equation [18] can be expressed as
t =k⋅x (10)
where t is the reaction time, x is the conversion of di-
atomite (SiO2) (%), and k is a constant, related to
many factors such as surface area and diameter of par-
ticle, diffusion coefficient, and concentration of OH−
in the system.
If the dissolution reaction is the rate-controlling
factor, the kinetic equation [18] can be written as
t = k ⋅ [1 − (1 − x)1/ 3 ] (11)
where k is a reaction rate constant related to particle
surface area and concentration of OH− on the reaction Figure 4 Relationship between the conversion of SiO2 and
interface of particle. reaction time (1)
◇ 70 °C reaction rate; ■ 90 °C reaction rate; 70 °C liquid film
If the intra-particle diffusion rate, the diffusion diffusion rate; ▲ 90 °C liquid film diffusion rate; liner 90 °C
rate of OH− passing through the sodium silicate layer, liquid film diffusion rate; liner 70 °C liquid film diffusion
is the controlling factor, following equation [18] is rate; liner 90 °C reaction rate; liner 70 °C reaction rate
obtained
t = k ⋅ [1 + 3(1 − x) 2 / 3 − 2(1 − x)] (12)
where k is the reaction rate constant.
The rate-controlling factor and the apparent kinetic
equation for the diatomite dissolution in the NaOH
solution can be determined by comparing the linear
relationship between functions x, [1 − (1 − x)1/ 3 ] and
[1 + 3(1 − x)2 / 3 − 2(1 − x)] and reaction time t (the
analyses are taken separately at 70 °C and 90 °C), as
shown in Table 4, Figs. 4 and 5. The correlation coef-
ficients indicate that the intra-particle diffusion and
chemical reaction have almost the same influence on
the apparent reaction rate, but the linear dependence Figure 5 Relationship between the conversion of SiO2 and
of the former on reaction time t is better than that of reaction time (2)
later, so the intra-particle diffusion through the sodium ▲ 70 °C inner diffusion rate; ■ 90 °C inner diffusion rate;
liner 70 °C inner diffusion rate; liner 90 °C inner dif-
silicate layer is the most significant rate-controlling fusion rate
factor in the reaction.
Furthermore, the slopes of the regressed lines at
70 °C and 90 °C (Fig. 5) are −0.029 and −0.047, re- ⎡1 + 3 (1 − xSiO ) − 2 (1 − xSiO ) ⎤ = k ⋅ t
2/3
(13)
spectively, indicating that temperature also has obvi- ⎣ 2 2 ⎦

ous influence on the apparent reaction rate. where xSiO2 is the conversion of diatomite (SiO2) at
From the above analysis, the kinetic equation of reaction time t, k is a dimensionless constant for the
the diatomite dissolution in the NaOH solution can be apparent reaction rate equation and related to reaction
written as temperature, particle size, shape, etc.
 Chin. J. Chem. Eng., Vol. 21, No. 7, July 2013
4 CONCLUSIONS
The diatomite dissolution behavior in the NaOH
solution fits the unreacted shrinking core model for
the solid-liquid multiphase reaction under the mild
conditions (ambient pressure and low temperature) in
diluted, uniformly stirred solutions. The apparent re-
action order for this reaction is 2, its apparent reaction
2
rate can be expressed as −dcNaOH / dt = k ⋅ cNaOH, t , and
its apparent activation energy (Ea) is 28.06 kJ·mol−1.
The intra-particle diffusion of NaOH species
through the sodium silicate film on the surface of a wet-
ted diatomite particle and the chemical reaction at the
interface of unreacted solid core control the overall rate
of the dissolution reaction. However, the intra-particle
diffusion rate is the most significant rate-controlling
factor. The dissolution rate equation for the conversion
of diatomite (SiO2) (or the yield of sodium silicate) is
⎡1 + 3 (1 − xSiO )2 / 3 − 2 (1 − xSiO ) ⎤ = k ⋅ t , where k is a
⎣ 2 2 ⎦
dimensionless constant related to particle size, shape
and reaction temperature.
ACKNOWLEDGEMENTS
The authors are grateful to Prof. Libing Liao and
Prof. Shuilin Zheng for their proofreading and advice
on the manuscript.
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