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Thermal decomposition of natural dolomite

Article in Inorganic Materials · December 2011

DOI: 10.1134/S0020168511120156

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National Academy of Sciences of Belarus Institute of General and Inorganic Chemistry, Minsk, Belarus
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ISSN 00201685, Inorganic Materials, 2011, Vol. 47, No. 12, pp. 1372–1377. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.I. Rat’ko, A.I. Ivanets, A.I. Kulak, E.A. Morozov, I.O. Sakhar, 2011, published in Neorganicheskie Materialy, 2011, Vol. 47, No. 12, pp. 1502–1507.

Thermal Decomposition of Natural Dolomite

A. I. Rat’ko, A. I. Ivanets, A. I. Kulak, E. A. Morozov, and I. O. Sakhar
Institute of General and Inorganic Chemistry, Belarussian Academy of Sciences, ul. Surganova 9/1, Minsk, 220072 Belarus
email: [email protected]
Received December 22, 2010

Abstract—We have studied thermal modification of natural dolomite chips, which has allowed us to optimize
conditions for the preparation of supports for manganese oxide catalysts with appropriate physicochemical
properties (elevated carbon dioxide partial pressure and calcination temperature no higher than 800°C).
DOI: 10.1134/S0020168511120156

INTRODUCTION EXPERIMENTAL
1
To remove iron, manganese, and hydrogen sulfide We used dolomite chips from Ruba in different
from water, use is made of a process that involves water size ranges: <0.2, 0.63–1.6, and 1.6–2.5 mm. Heat
saturation with atmospheric oxygen. Next, the water is treatment was performed in an SNOL 7.2/1300 elec
passed through filter beds, typically quartz sand or tric furnace at temperatures from 700 to 900°C at 50°C
intervals. The heating rate was 5°C/min. Since one of
granite chippings. This approach is not very effective the thermal decomposition products of dolomite is
and requires bulky equipment and large amounts of carbon dioxide, to assess its effect on dolomite decom
filter materials [1]. For this reason, preference is now position, heat treatment was carried out in air and
given to modular water purification systems with man flowing argon.
ganesedioxidebased granular catalyst beds (Birm, Xray diffraction (XRD) patterns were collected on
Pyrolox, and others), which ensure stable removal of a DRON3 powder diffractometer (CuKα radiation,
iron, manganese, and hydrogen sulfide from water in 2θ = 10°–60°). IR reflection spectra were measured on
a Midac M2000 Fourier transform IR spectrometer.
conformity with sanitary regulations at a considerably Lowtemperature (77 K) nitrogen physisorption–des
higher throughput in comparison with conventional orption was studied by a static volume method using a
systems [2]. The use of catalytic beds is however lim Micromeritics ASAP 2020 MP surface/porosity ana
ited by their high cost and, in some cases, by their lyzer.
insufficient catalytic activity. Thermal analysis was carried out at temperatures
from 20 to 1000°C (heating rates of 5 and 10°C/min)
One approach proposed to resolve this problem is with Paulik–Paulik–Erdey (400mg samples) and
to produce catalytically active manganese oxide NETZSCH STA 409 PC/PG (50mg samples) ther
phases on the surface of supports [3]. Dolomite is a moanalytical systems. Thermogravimetry (TG) data
potentially attractive catalyst support because it has a were used to evaluate conversion (α) and reaction rate
basic surface, which is favorable for deposition of (dα/dT). Kinetic curves were plotted using the equa
tion
manganese dioxide precursors, and offers high
mechanical strength. To increase the specific surface dα/dT E
ln  = ln A – a , (1)
area of catalytic coatings based on transition metal f(α) RT
oxides and improve their adhesion to support surfaces, where Ea is the activation energy of the chemical reac
we proposed that dolomite should be heattreated. tion, A is the preexponential factor in the Arrhenius
The purpose of this work was to study the effect of equation, R is the gas constant, T is the absolute tem
key heattreatment parameters (temperature, heating perature, and f(α) is a mathematical representation of
the reaction rate in the form of a known formal kinet
rate, and atmosphere) on the chemical and phase
dα/dT
ics' function selected so that the plot of ln 
compositions and physicochemical properties of dolo
f(α)
mite. Our results make it possible to substantiate opti against 1/T gives a best fit straight line. Given that
mal conditions for the preparation of dolomite sup
1 Vitebsk oblast, Belarus.
ports for manganese oxide catalysts.

1372
 THERMAL DECOMPOSITION OF NATURAL DOLOMITE 1373

Table 1. Correlation coefficients (R2) obtained by fitting to formal kinetic equations in the first and second decomposition
steps at a constant heating rate of 10°C/min

Size range, heattreatment R2

Step
conditions F1 F2 R3 A1.5 A2 B1 D1 D2
<0.2 mm 1 0.88 0.87 0.88 0.85 0.82 0.62 0.92 0.92
(flowing argon) 2 0.94 0.90 0.85 0.86 0.82 0.81 0.82 0.90
0.63–1.6 mm 1 0.89 0.88 0.89 0.87 0.86 0.74 0.92 0.92
(flowing argon) 2 0.94 0.90 0.85 0.85 0.82 0.80 0.83 0.90
0.63–1.6 mm 1 0.45 0.46 0.44 0.40 0.38 0.30 0.54 0.53
(static air atmosphere) 2 0.99 0.98 0.99 0.99 0.99 0.99 0.96 0.99
1.6–2.5 mm 1 0.35 0.41 0.32 0.17 0.09 – 0.65 0.64
(flowing argon) 2 0.99 0.99 0.99 0.99 0.99 0.99 0.97 0.99

DTG and DTA peaks due to particular reaction steps a(1 – α)b/2, where a = 2 and b = 1 in a “contracting
may overlap, to assess the overlap of DTG peaks we surface” model and a = 3 and b = 2 in the contracting
calculated the resolution parameter volume model (R2 and R3 in what follows);
II I Avrami–Erofeev equation a(1 – α)(–ln(1 – α))n,
T max – T max where a = 1.5, 2, 3, or 4 and n = 1/3, 1/2, 2/3, or 3/4
R s = 2 
I II
. (2)
W +W (A1.5, A2, A3, and A4 in what follows);
I II
Prout–Tompkins equation α(1 – α);
Here, Rs is the degree of resolution; T max and T max are equations that take into account onedimensional
maxima in the DTG curve that correspond to the tem (1/2α), twodimensional (–(ln(1 – α))–1), and three
perature of the fastest decomposition reaction rate in dimensional diffusion: Jander (1.5(1 – (1 – α)1/3)–1(1 –
the corresponding step, and W I and W II are the widths α)2/3) and Gistling–Brounshtein (1.5(1 – (1 – α)1/3)–1)
of the respective peaks at the baseline level. equations (D1, D2, D3, and D4, respectively).
The compressive strength of the samples (size range Table 1 lists the correlation coefficients (R 2)
2.5–2.8 mm) was determined on an ING1M obtained by fitting to equations of formal kinetic
machine (Unikhim). curves obtained in the temperature range from the
Water absorption was evaluated from the relative dolomite decomposition onset to the temperature of
weight gain of the sample. the first DTG peak. The correlation coefficients for
The pH of aqueous extracts of dolomite was mea equations F0, R2, A3, A4, D3, and D4 are not given in
sured with a Hanna Instruments 221 pH meter at Table 1 because they are small, suggesting that these
room temperature. The dolomite : water volume ratio equations are inapplicable to formalkinetic descrip
was 1 : 10, and the residence time in water was 24 h. tion of the process under consideration.
The data in Table 1 and the temperature maxima in
decomposition curves (tmax) (Table 2) lead us to con
RESULTS AND DISCUSSION clude that the first step of dolomite decomposition is
Analysis of XRD (Fig. 1) and TG (Fig. 2) data leads an essentially irreversible, diffusioncontrolled pro
us to conclude that dolomite decomposition is a two cess, whereas the second step is a reversible process
step process. In the first step, at temperatures from 600 (depends on the carbon dioxide concentration) that
to 800°C, dolomite dissociates and the magnesium obeys a firstorder formal kinetic law. All of the above
carbonate decomposes. The second step, between 740 agrees well with earlier results [6, 7].
and 880°C, is calcium carbonate decomposition. Both The size range, dolomite sample weight, and heat
processes are endothermic. The present results are in ing rate also influence the position and overlap of DTA
excellent agreement with previous data [4, 5]. and DTG peaks. Increasing the heating rate, sample
Because the thermal decomposition of calcium weight, and particle size increases the tmax of the first
carbonate is a reversible process, it was of interest to step only slightly because of the influence of deceler
examine the effect of heat treatment atmosphere (air ated heat transport. A reduction in particle size and, to
or argon) on dolomite decomposition. From TG data a considerably greater extent, an increase in sample
for dolomite decomposition in flowing argon, we weight impede the removal of the carbon dioxide from
derived kinetic curves, which were then fitted to the the reaction zone, which leads to an increase in the tmax
most typical formal kinetic equations for f(α): of the second step and better resolution of the peaks.
(1 – α)n, where n = 0, 1, or 2 is the order of reaction The enthalpies of dolomite decomposition in
(F0, F1, and F2 in what follows); Table 3 have high positive values (100–130 kJ/mol).

INORGANIC MATERIALS Vol. 47 No. 12 2011

1374 RAT’KO et al.

(а) 1 1

1
1
1
1 1
1 1 1 11 1
1 1

1
2

(b)
2, 3
2 1 11
21
2
3 1 22 23 1 2
3
2 3

2
(c)

2, 3
Intensity

3
2 2 22
2
3 23 2 2

2
(d)

2, 3
1 2, 4
2, 4 3
2 4 2
1 4 2
1 31 4 22 1 2 2

4
(e)

3
4
4
3
4 4

10 20 30 40 50 60 70
2θ, deg

Fig. 1. XRD patterns of (a) unheattreated and (b–e) calcined dolomite samples: (b) 750°C, air; (c) 800°C, air; (d) 800°C, flow
ing argon; (e) 950°C, air; (1) dolomite, CaMg(CO3)2; (2) calcite, CaCO3; (3) periclase, MgO; (4) CaO.

Note that the activation energy in the first step of the 0.76 g/cm3, an increase in water absorption from 6 to
reaction considerably exceeds that in the second step: 53 wt %, and a rise in the pH of aqueous extracts of
180 and 130 kJ/mol, respectively. With increasing cal dolomite from 9.4 to 12.9.
cination temperature, the degree of dolomite decom The reduction in bulk density and increase in the
position increases, which is accompanied by a reduc porosity of the material upon calcination are due to
tion in the bulk density of the material from 1.42 to carbon dioxide release. Clearly, this leads to an

INORGANIC MATERIALS Vol. 47 No. 12 2011

 THERMAL DECOMPOSITION OF NATURAL DOLOMITE 1375

increase in water absorption, which eventually has an 100 0 4

advantageous effect on subsequent deposition of cata 2
lytically active oxides on the support. –2
90 3

DTA, mW/mg
DTG, %/min
The increase in water absorption is due not only to –4

TG, %
physical pore filling but also to chemical binding of the 80 –6 2
3
water. Dolomite decomposition gives magnesium and
calcium oxides. As a result of hydration, the oxides 70 –8 1
convert to poorly soluble hydroxides, which is respon –10
sible for the alkaline medium of aqueous extracts. This 60 0
is supported by the peaks of a free hydroxide in IR 1 –12
spectra in the range 3692–3694 cm–1 (Fig. 4). The rise 50 –14 –1
in the pH of aqueous extracts also has an advantageous 500 600 700 800 900 1000
effect on both the deposition of the catalytically active Temperature, °C
oxide phase and its subsequent attachment to the sur
face of the dolomite support. Fig. 2. Dolomite decomposition: (1) TG, (2) DTG, and
(3) DTA curves.
Figure 5 shows nitrogen adsorption–desorption
isotherms for dolomite before and after heat treatment
at 800°C in air. The isotherms of the two dolomite ment increases the BET surface area of dolomite from
samples belong to the fourth type of physisorption iso 1.0 to 2.5 m2/g.
therm, characterized by polymolecular adsorption, It is worth pointing out that heat treatment reduces
complicated by capillary condensation. Heat treat the mechanical strength of dolomite grains (Table 3),

Table 2. Effect of heattreatment conditions and heating rate (dt/dτ) on the peaks in decomposition curves (tmax), activation
energy (Ea), enthalpy (ΔrH), and resolution of peaks in the TG curve (Rs) during the thermal decomposition of dolomite

Size range, dt/dt, tmax,°C Ea, kJ/mol ΔrH,

Heattreatment conditions Rs
mm °C/min step 1 step 2 step 1 step 2 kJ/mol

<0.2 Flowing argon 10 808 848 180 (D1) 130 (F1) 130 0.67
0.63–1.6 Flowing argon 5 799 845 – – 120 0.84
0.63–1.6 Flowing argon 10 808 844 180 (D1) 130 (F1) 110 0.61
190 (D2)
0.63–1.6 Static air atmosphere 10 808 873 190 (D1) –* 100 1.2
180 (D2)
1.6–2.5 Flowing argon 10 809 834 –* 130 (F1) 120 0.44
120 (F2)
0.63–1.6 Static air atmosphere 10 805 925 – – – 1.4
0.63–1.6 Static air atmosphere 10 815 926 – – – 1.3
1.6–2.5 Static air atmosphere 10 817 924 – – – 1.3
* Data derived from the plot of ln((dα/dτ)/f(α)) against inverse temperature are not given because of their low reliability (correlation
coefficient well below 0.9).

Table 3. Weight loss (Δm), pH of aqueous extracts, bulk density (d), water absorption (W), and strength of the grains (S)
before and after heat treatment of dolomite at different temperatures with forced CO2 removal (by flowing argon) and in
static atmosphere
Heattreatment conditions Δm, % pH d, g/cm3 W, wt % S, N/grain
– 0 9.4 ± 0.2 1.42 ± 0.02 6±4 106 ± 14
700°C (static atmosphere) 18 ± 2 11.4 ± 0.2 1.14 ± 0.02 16 ± 3 44 ± 8
700°C (flowing argon) 18 ± 2 11.5 ± 0.2 1.13 ± 0.02 17 ± 3 41 ± 8
800°C (static atmosphere) 25 ± 3 12.5 ± 0.2 1.09 ± 0.02 19 ± 4 28 ± 6
800°C (flowing argon) 33 ± 4 12.7 ± 0.3 0.92 ± 0.03 34 ± 6 12 ± 4
900°C (static atmosphere) 47 ± 1 12.9 ± 0.3 0.76 ± 0.05 53 ± 9 –

INORGANIC MATERIALS Vol. 47 No. 12 2011

1376 RAT’KO et al.

ln((dα/dτ)/f(α)) 5

Adsorbate volume (st. conditions),

Adsorption
3.70 2
Desorption
3.20 4

2.70 3
2.20

cm3/g
1.70 2

1.20
1
0.70 1

0.20
9.20 9.70 10.20 10.70 11.20 11.70 12.20 12.70 0 0.2 0.4 0.6 0.8 1.0
p/p0
104/T, K–1
Fig. 3. Plot of ln((dα/dτ)/f(α)) against inverse tempera
ture for a dolomite sample (0.63–1.6 mm, flowing argon, Fig. 5. Nitrogen adsorption–desorption isotherms for
10°C/min, first step). The data correspond to mecha dolomite (1) before and (2) after calcination at 800°C
nism D1. in air.

nied by an almost complete, spontaneous disintegra

90 tion of dolomite grains.
The reason for these distinctions is that, during cal
80 1 cination in flowing argon, dolomite decomposes to
Transmission, %

give predominantly magnesium and calcium oxides,

70 which leads to an almost complete breakdown of the
parent structure. Dolomite decomposition in air at
60 temperatures no higher than 800°C leads to the forma
tion, in addition to magnesium oxide, of calcium car
2 bonate, which then acts as the key structureforming
50
component. Its formation is not accompanied by rad
40
ical structural changes.
Thus, the optimal temperature for the preparation
4000 3000 2000 1000 of a dolomitebased support is 780–800°C, and heat
Wavenumber, cm–1 treatment should be performed at an increased carbon
dioxide concentration. The heating rate should be
limited by the constraint that local overheating of
Fig. 4. IR spectra of dolomite (800°C, air) (1) before and dolomite should be minimized.
(2) after soaking in water (followed by drying at 200°C).

CONCLUSIONS
which somewhat limits the service time of the catalyst
in water deironing plants. Heating dolomite to 700°C We have studied thermal decomposition of dolo
is accompanied by a gradual decrease in the mechani mite by TG, XRD, and adsorption measurements and
cal strength of the grains from 106 to 44 N, which is assessed the influence of temperature, heating rate,
probably due to lattice defect accumulation. and heattreatment atmosphere on the chemical and
Further changes in the strength of grains depend on phase compositions and physicochemical properties
calcination conditions. When dolomite is calcined in of dolomite.
flowing argon (and the two decomposition steps Our results demonstrate that, to produce a support
almost fully overlap), the mechanical strength sharply for manganese oxide catalysts, dolomite should be
drops in the temperature range 700–850°C, to the decomposed at a temperature no higher than 800°C
point of complete grain disintegration even without and a high carbon dioxide concentration.
compression load. By contrast, during dolomite calci
nation in air at temperatures from 700 to 800°C, the The material thus obtained offers a necessary
mechanical strength of the grains decreases gradually, combination of water absorption (19 wt %), pH of
from 44 to 28 N, and only heating to above 800°C aqueous extracts (12.5), and mechanical strength of
causes a sharp drop in mechanical strength, accompa grains (28 N).

INORGANIC MATERIALS Vol. 47 No. 12 2011

 THERMAL DECOMPOSITION OF NATURAL DOLOMITE 1377

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INORGANIC MATERIALS Vol. 47 No. 12 2011

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