ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 9, pp. 1447!1452. + Pleiades Publishing, Ltd.

, 2007.
Original Russian Text + A.R. Kobeleva, V.Z. Poilov, 2007, published in Zhurnal Prikladnoi Khimii, 2007, Vol. 80, No. 9, pp. 1409!1415.

INORGANIC SYNTHESIS
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
AND INDUSTRIAL INORGANIC CHEMISTRY

Technology for Production of Calcium Carbonate

with Prescribed Properties
A. R. Kobeleva and V. Z. Poilov
Perm State Technical University, Perm, Russia
Received October 30, 2006; in final form, March 2007

-
Abstract Physicochemical conditions for production of calcium carbonate with prescribed size and shape of
particles and crystal structure by reaction of CaCl2 and Na2CO3 solutions were studied. A technology for
manufacture of calcium carbonate with prescribed properties was developed.

DOI: 10.1134/S1070427207090017

Calcium carbonate and products obtained from this
compound are widely used in various fields of econ-
omy: in building, as a component of finishing materi-
als; for manufacture of cement, glass, and ceramics;
in pharmacology, to manufacture toothpastes and
antacid preparations; in cosmetics, to produce creams;
in water treatment, as filter materials; in paper in-
dustry, to manufacture cigarette, chalk-overlay, and
tracing paper; in production of plastics and artificial
leather; finely dispersed powdered chalk serves as
a filler or pigment in cable, paint-and-varnish, poly-
mer, rubber, and petrochemical industry; etc.
In all these fields, various requirements are im-
posed on calcium carbonate: on its chemical composi-
tion and size and shape of crystalline CaCO3 particles,
on which depend the commercial characteristics of
calcium carbonate and fields of its use (Table 1).
Technologies for production of precipitated calci-
um carbonate from various raw materials: natural car-
bonates and solid carbonate wastes and solutions,
have been and are being developed. Different proc-
esses are used, depending on a starting raw material
and requirements to the final product. A technology
widely used in Russia is that in which calcium carbo-
nate is produced by carbonation of a Ca(OH)2 suspen-
sion with carbon dioxide, with the subsequent separa-
tion of the precipitate from the solution and drying
and calcination of the resulting product [13 4]. A dis-
advantage of this technology is that it is difficult to
obtain the CaCO3 product with prescribed properties.
Of practical interest is development of a technique
based on CaCO3 precipitation in a chemical reaction
of technical soda Na2CO3 and a CaCl2 solution
produced from waste formed in manufacture of soda
ash (distiller fluid) or by dissolution of natural chalk.
The main development direction of this technology is
production of calcium carbonate with prescribed
physicochemical properties (definite particle size and
shape, crystal structure, impurity content).
The process of calcium carbonate synthesis in-
cludes the chemical reaction
CaCl2 + Na2CO3 = CaCO32 + 2NaCl.
In this study, we examined conditions in which
calcium carbonate is obtained in different reactant
supply modes, ion concentration ratios [Ca2+]/[CO233],
starting reactant concentrations, temperatures, and
hydrodynamic modes of chemical precipitation of
CaCO3 in the presence of various modifiers.
In the batch mode of chemical precipitation of
CaCO3, a certain amount of a calcium chloride or
soda solution was poured into the reactor and heated
to a certain temperature, after which the second reac-
tant was fed at a constant rate by a peristaltic pump.
In the continuous mode of CaCO3 synthesis, the reac-
tants were permanently fed by pumps at a constant
rate into the reactor filled to the stirrer blade level
with distilled water. The process was performed with
agitation during a certain time at a constant rate of
rabble rotation. The resulting CaCO3 precipitate was
filtered off and washed on the filter with distilled
water. The calcium carbonate paste was dried in
a drying box at 100oC. The dried calcium carbonate
was examined with a KS optical microscope at a
1500 0 magnification in transmitted light. Photo-
microscopic studies were performed by photographing
CaCO3 microcrystals with an Olympus C 500 digital

1447
1448 KOBELEVA, POILOV

Table 1. Application fields of calcium carbonate with different characteristics and physicochemical properties
ÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
Crystal ³ Density, ³ ³ Particle size, ³CaCO product characteristics³ Main application fields
structure ³ g cm!3 ³
Particle shape
³ mm ³ 3 ³
ÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
Calcite ³ 2.71 ³Cubic ³ 0.233.5 ³Developed surface ³Paper industry
³ ³Spindle-like ³ 0.233.5 ³High mechanical strength ³Plastics manufacture
³ ³Barrel-like ³ 0.233.5 ³Low caking ³Rubber industry
Vaterite ³ ³ 2.64 ³³Prismatic ³³ 235 ³³High purity, low caking ³³Pharmaceuticals
³ ³Spherical ³ 0.530.1 ³Developed surface ³Paper industry
³ ³Platelike ³ 235 ³High covering power ³Paint-and-varnish materials
Aragonite ³³ 2.94 ³³Needle-like ³³ (237) 0 0.5 ³³High purity, high whiteness ³³Pharmaceuticals
ÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
Table 2. Parameters of particles of calcium carbonate obtained at various ion concentration ratios [Ca2+]/[CO23!].
Simultaneous supply of reactants, T = 60oC, cCaCl = 116 g l!1, cNa CO = 230 g l!1, feed rate: vCaCl = 0.8 0 10!6 m3 s!1,
vNa CO = 0.4 0 10!6 m3 s!1, w = 11 rps
2 2 3 2

ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄ
2 3

Ion concentration ratio

³ ³ Particle size, mm ³ CaCO content,
2+ 2 ! !
[Ca ]/[CO3 ] [g l ] 1 ³ Shape of resulting particles ÃÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄ´ 3
wt %
³ ³ minimum ³ maximum ³ average ³
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄ
0.21 ³Squared, spherical ³ 1.5 ³ 8.0 ³ 3.5 ³ 99.11
0.26 ³Spherical ³ 1.5 ³ 9.0 ³ 3.5 ³ 99.08
0.32 ³Squared, spherical ³ 1.2 ³ 5.0 ³ 3.2 ³ 99.09
0.41 ³Spherical, rectangular ³ 1.2 ³ 6.0 ³ 3.0 ³ 99.10
0.63 ³Cubic, spherical ³ 1.2 ³ 6.0 ³ 3.0 ³ 99.07
0.73 ³Oblong, spherical, squared ³ 1.2 ³ 5.2 ³ 2.5 ³ 99.08
0.98 ³Oblong, squared ³ 1.0 ³ 4.0 ³ 2.0 ³ 99.09
1.22 ³Oblong ³ 1.0 ³ 4.0 ³ 1.8 ³ 99.10
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄ
camera. The information obtained was processed on varying the concentration of the reactants supplied
a computer, using Photoshop and Camedia software. (Table 3).
The maximum, average, and minimum sizes of CaCO3 In the stationary precipitation mode, the crystallite
crystals were measured and their shapes were deter- size decreases as the concentration of the reactant
mined. The particle sizes were found using a microm- solutions becomes higher. Because the reactant supply
eter grid scale. The error in determining the particle rate was maintained constant, an increase in the
sizes in the range 1330 mm did not exceed 7%. reagent concentrations results in higher flow rate of
The laboratory studies revealed that the parameters substances into the reactor.
of precipitate particles are strongly affected by the ion The flow rate Wi was calculated by the formula
concentration ratio [Ca2+]/[CO233] (Table 2).
Wi = vc/Vr,
It was found that finely dispersed calcium carbo-
nate particles of diameter d ; 133 mm are formed in
where v is the volumetric flow rate of a solution of ith
the stationary mode in the case of an excess of Ca2+
substance (m3 s31); c, concentration of ith substance
ions. If, however, CO233 ions are in excess, coarsely
(kg m33); and Vr, volume of the reaction medium in
dispersed particles of diameter d ; 23 6 mm are ob-
the reactor (m3).
tained. At an excess of CO233 anions, the solubility of
calcium carbonate increases because of the formation An increase in the flow rate of a substance into
of soluble complexes of the [Cax(CO3)y] type, which the reactor leads, in accordance with the mass action
makes lower the supersaturation and, accordingly, law, to a rise in the rate of the chemical reaction
the primary nucleation rate [5]. The size of the form- between Ca2+ and CO233 ions. As a result, the super-
ing CaCO3 crystallites can also be controlled by saturation created in the solution becomes higher,

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 TECHNOLOGY FOR PRODUCTION OF CALCIUM CARBONATE 1449

Table 3. Average diameter of CaCO3 particles at various concentrations of reactants and modes of their supply
ÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ Concentration, g l!1 ³ Average diameter of CaCO3 particles, mm, for indicated mode of reactant supply Q
Run ÃÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
no.* ³ ³ ³ ³ CaCl2 solution into a Na2CO3 ³ Na2CO3 solution into a CaCl2
³ Na2CO3 ³ CaCl2 ³ simultaneous ³ solution ³ solution
ÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
1 ³ 110 ³ 55 ³ 10 ³ 11 ³ 6
2 ³ 150 ³ 75 ³ 8 ³ 9 ³ 3
3 ³ 230 ³ 116 ³ 5 ³ 2 ³ 1.5
4 ³ 90 ³ 116 ³ 3 ³ 3.5 ³ 3
5 ³ 110 ³ 116 ³ 3 ³ 3 ³ 3
6 ³ 150 ³ 116 ³ 4 ³ 3 ³ 2.5
7 ³ 180 ³ 116 ³ 4 ³ 2.5 ³ 2
8 ³ 230 ³ 45 ³ 11 ³ 4 ³ 3
9 ³ 230 ³ 55 ³ 8 ³ 3 ³ 2
10 ³ 230 ³ 75 ³ 6 ³ 2.5 ³ 2
11 ³ 230 ³ 90 ³ 6 ³ 2 ³ 1.5
ÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
* Mode: run nos. 133, stationary; nos. 4 311, nonstationary.

which accelerates the nucleation process and gives rise can be obtained, which is predetermined by adsorption
to a large number of fine crystalline particles. of molecules on the surface of nucleating crystals and
by blocked growth of crystalline particles.
In the nonstationary (batch) precipitation mode,
the residence time of particles in the reactor exhibits Inorganic modifiers favor an increase in the size of
a wide scatter and the concentration ratio of reagent dav, mm
ions, [Ca2+]/[CO233], permanently changes, which
(a)
leads to size scatter and multitude of forms of calcium
carbonate particles.
An increase in temperature markedly accelerates
the chemical interaction between the ions, makes
faster the primary nucleation (which results in the
formation of finely dispersed precipitates), weakens
the strength of binding between microblocks in the
T, oC
forming crystalline agglomerates (which favors their dav, mm
disintegration), and, to a lesser extent, leads to an in- (b)
crease in the face growth rate of crystalline particles
(Fig. 1a).
The size of calcium carbonate particles is strongly
affected by the hydrodynamic operation mode of
the crystallizer (Fig. 1b). As the agitation rate in-
creases from 3.3 to 11 rps, the crystallite size de-
creases by a factor of nearly 2. The reason is that both
the primary nucleation rate and the disintegration rate
of the forming unstable agglomerates of CaCO3 par- w, rps
ticles increase. Fig. 1. Average diameter dav of CaCO3 particles vs.
The effect of organic and inorganic modifiers on (a) process temperature T at different reactant sypply
the size of CaCO3 crystalline particles was studied. modes and stirrer rotation rate w = 3 rps and (b) stirrer
rotation rate w at simultaneous delivery of reactants at T =
60oC. cCaCl = 116 g l!1, cNa CO = 230 g l!1; vCaCl =
For this purpose, a certain amount of an additive was
introduced into a calcium chloride solution (Table 4).
0.8 0 10!6 m3 s!1, and vNa CO = 0.4 0 10!6 m3 s!1.
2 2 3 2

Organic modifiers lead to a decrease in the size of 2 3

(a) Mode of reactant supply: (1) simultaneous, (2) CaCl2
CaCO3 particles. In the presence of additives of this solution into a Na2CO3 solution, and (3) Na2CO3 solution
type, calcium carbonate crystals less than 1 mm in size into a CaCl2 solution.

RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 80 No. 9 2007

1450 KOBELEVA, POILOV

Table 4. Effect of the type and concentration of modifies on the size and shape of CaCO3 particles
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄ
Modifier type ³ Modifier ³ Content, wt % ³Particle size, mm³ Particle shape
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄ
Organic: ³ ³ ³ ³
anion-active ³Carboxylic acids CnH2n + 1COOH³ 0.09313.04 ³ 1.3 ³Spherical
³Primary alcohols CnH2n + 1OH ³ 0.03313.04 ³ 1.2 ³Oblong
cation-active ³Aliphatic amines ³ 0.09313.04 ³ 1.0 ³Spherical
Inorganic ³NH4Cl ³ 0.0532.5 ³ 15.0 ³Hexagonal
³PbCl2 ³ 0.0731.25 ³ 5.0 ³Spherical, oblong
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄ
Table 5. Effect of modifiers on characteristics of washed CaCO3 precipitates
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ Diameter and shape of CaCO3 particles after indicated stage
ÃÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
Modifier, ³ chemical precipitation ³ 1st washing ³ 2nd washing ³ 3rd washing
wt % ÃÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄ
³ dav, ³ shape of ³ dav, ³ shape of ³ dav, ³ shape of ³ dav, ³ shape of
³ mm ³ crystals ³ mm ³ crystals ³ mm ³ crystals ³ mm ³ crystals
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄ
3 ³ 5 ³Various ³ 5 ³Various ³ 3 ³Various ³ 3 ³Various
NH4Cl, 10 ³ 15 ³Hexagonal ³ 10 ³Hexagonal ³ 8 ³Hexagonal ³ 10 ³Hexagonal
Soap, 2.5 ³ 4 ³Squared ³ 3 ³Rectangular ³ 3 ³Rectangular ³ 3 ³Squared
Paraffins, 10 ³ 4 ³Polygonal ³ 6 ³Squared ³ 4 ³Polygonal ³ 5 ³Squared
C4H9OH, 12 0 10!3 ³ 5 ³Oblong ³ 4 ³Various ³ 3 ³Various ³ 3 ³Various
SAA, 2 0 10!3 ³ 4 ³Rounded ³ 3 ³Rounded ³ 4 ³Rounded ³ 4 ³Oblong
Amines, 3 0 10!3 ³ 3 ³Rounded ³ 5 ³Rounded ³ 4 ³Various ³ 4 ³Various
ÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄ
CaCO3 crystals by a factor of 1.532. This effect of The effect of the ion concentration ratio [Ca2+]/
inorganic modifiers is possibly due to selective ad- [CO233] on the shape of CaCO3 particles is presumably
sorption of modifier ions and to a change in the charge due to the sign and amount of charges of excess ions
on crystal faces (Table 4). adsorbed on the surface of CaCO3 particles being
The shape of calcium carbonate particles (Fig. 2) is precipitated. For example, triangular, hexagonal, and
affected by the following parameters: ion concentra- rounded platelike particles are formed at a large ex-
tion ratio [Ca2+]/[CO233], process temperature, and cess of CO233 anions. In this case, the triangular shape
presence of a modifier. is the primary form, and the hexagonal and rounded
forms are derivative products of disintegration and
wear of triangular CaCO3 particles upon their colli-
sions with other particles, stirrer, and reactor walls.
If the excess of CO233 anions becomes less pronounced
and the ion concentration ratio [Ca2+]/[CO233] ap-
proaches the stoichiometry, the platelike shape tends
to pass to a three-dimensional, more compact shape of
CaCO3 particles: cubic and spherical [6].
A change in the precipitation temperature is
reflected in the shape of the resulting calcium carbo-
nate particles. At low temperatures, mostly particles
of three-dimensional shape are formed, whereas at
high temperatures (>90oC), CaCO3 particles become
Fig. 2. Types of crystal habits: (1) spheres, (2) rounded needle-like, which points to an unequal acceleration of
plates, (3) needles, (4) cubes, (5) hexagons, (6) rectangular the growth of different faces of CaCO3 particles
plates, (7) triangular plates, and (8) rhombic plates. (Fig. 3).

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 TECHNOLOGY FOR PRODUCTION OF CALCIUM CARBONATE 1451

Fig. 3. Photographs of CaCO3 particles obtained at (a) 23 and (b) 90oC. Magnification 1500 0.

To dump
Natural chalk
Hydrochloric acid
Water

Soda ash To sludge

Water collector
Steam
Steam

Steam Steam

To sludge collector

CaCO3
to drying

Fig. 4. Flowsheet for production of calcium carbonate. (1) Reactor for preparing a calcium chloride solution, (21!10) centrifugal
pumps, (31!5) vacuum filters, (4) collector for the calcium chloride solution, (5, 9) receiving tanks, (6) reactor for preparing
a soda solution, (7) plate-and-frame filter-press, (8) collector for the soda solution, (10, 11) heaters, (12) reactor for synthesis of
calcium carbonate, (13) water supply tank, and (141!3) repulpers.

Adsorption of modifiers on active centers of the
crystals can change the growth rate of their different
faces to different extents, which leads to a change in
the crystal habit. Inorganic modifiers (NH4Cl, PbCl2)
favor an increase in the number of forms of CaCO3
particles, with rounded, oblong, squared, and poly-
gonal shapes obtained.
Also, ways to control the crystal structure of cal-
cium carbonate and the possibility of obtaining prod-
ucts of different modifications were studied. The crys-
tal structure of CaCO3 was examined by X-ray dif-
fraction analysis. Calcium carbonate with a phase
composition of calcite can be obtained in continuous
chemical precipitation from solutions containing cal-

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1452 KOBELEVA, POILOV

cium and sodium ions in the presence of NH4Cl, urea, a calcium chloride solution from natural chalk, (2)
and amine hydrochloride additives. Depending on an clarification of the calcium chloride solution, (3) prep-
additive used, calcite crystals have different configura- aration of a soda solution, (4) chemical precipitation
tions: rhombic with NH4Cl, cubic with urea, oval with and filtering-off of the calcium carbonate precipitate,
the amine, and squared in the presence of surface- (5) separation of the precipitate from the solution and
active anions (SAA). desorption of impurities from the calcium carbonate
precipitate, and (6) drying of the precipitate.
Vaterite crystals are formed as spherulites or plates
in the case of a continuous chemical precipitation This procedure allows synthesis of CaCO3 products
from solutions containing calcium and sodium ions at with different properties on the same equipment unit.
60oC and concentrations of the starting solutions
equal to 116 and 180 g l31, respectively. In this case, CONCLUSIONS
CaCO3 crystals become platelike.
Calcium carbonate with a phase composition of (1) The technology developed enables control over
aragonite can be obtained in a continuous chemical the characteristics and consumer properties of the
precipitation from solutions containing calcium and product in a wide range.
sodium ions at 20oC and concentrations of starting (2) The properties of the CaCO3 product obtained
solutions equal to 116 and 230 g l31, in the presence upon precipitation can be controlled by changing the
of a minor amount of sucrose. precipitation mode (temperature, rate at which super-
saturation is created, and the rate and method of
Because CaCO3 particles are formed in the pres-
reactant supply), using complexing substances or
ence of a NaCl solution, there is a stage of washing to modifier additives affecting the shape and size of
obtain a purer product. The effect of washing on CaCO3 particles, and introducing a CaCO3 seed.
the size and shape of precipitated calcium carbonate
particles was studied. A multistage washing can lead (3) Finely dispersed and ultradispersed powders
both to an increase and a decrease in the average can be obtained in CaCO3 precipitation by using not
diameter of product particles (Table 5). This change in only aqueous, but also organic media and dispersing
the size and shape of the particles can be attributed to additives that prevent aggregation of CaCO3 particles.
occurrence of ripening processes in the suspension
(Ostwald phenomenon), with a simultaneous mech- REFERENCES
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as a result of agitation, which leads to a poorer uni- 1. GB Patent 9 600 488.
formity of particles, and the crystal habit takes a char- 2. EP Patent 0 812 300.
acteristic shape with rounded corners and edges. 3. GB Patent 441 223.
The results of the study were used to develop a 4. FR Patent 2 784 371.
process installation shown in Fig. 4. Calcium carbo- 5. RF Patent 2 218 305.
nate is produced in several stages: (1) preparation of 6. RF Patent 2 246 445.

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