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THE IMPACT OF MAGNESIUM ON TRICALCIUM ALUMINATE (TCA)

FILTER AID PROPERTIES


Suss A*, Panov A, Kuznetzova N, Kuvyrkina A, Damaskin A, Damaskina A and Shmigidin Y
RUSAL VAMI, St. Petersburg, Russia
Abstract
It is known that addition of lime to the Bayer circuit promotes improvement of unit processes such as digestion, thickening,
desilication, filtration, etc. The lime is also required for generation of tricalcium aluminate hexahydrate (TCA) which is used
as a filter-bed in polishing filtration of pregnant liquor.
Lime prepared from different limestone deposits differs considerably in chemical composition. With the aim of determining
the applicability of using magnesian limestone in the Bayer process, investigations were conducted into the impact of
magnesium salts on TCA – production, structure and filtration properties, as well as the behaviour of the processed TCA
in the digestion circuit.
To examine the influence of composition, materials with MgO content from 0.75 % to 44.0 % were used as initial substances.
These raw materials included limestone, magnesium limestone, dolomite and a hydrated magnesium carbonate –
magnesium hydroxide double salt, MgCO3∙Mg(OH)2∙3H2O. All compounds were processed in three stages:
1. Roasting at temperature, either 1150 or 1200 ºС;
2. Water slaking;
3. Reaction with caustic-aluminate liquor.
The products obtained were compared by chemical and phase analysis. The influence of magnesium content on the
particle size distribution (PSD) of the corresponding TCA and specific resistance of the resultant filter-beds also were
investigated. In the course of this research, the basic possibility of using TCA prepared from magnesium limestone as a
pre-coat for polishing filtration was confirmed. Additionally, the optimal conditions for TCA production, such as roasting
temperature and condensate dosage, were also defined.
Further to this work, the influence of magnesium salts in the digestion of Sredny Timan bauxite, was studied using a variety
of additives (burnt limestone, burnt magnesium limestone and TCA batches prepared from both of these materials). Major
beneficial impacts associated with the use of magnesium in high-temperature digestion were identified and are presented
in this paper.

Notation

Na2Ot - titratable alkali (total);


Na2Ocarb - sodium carbonate (Na2СO3);
Na2Oc - caustic alkali (NaOН + NaAl(OH)4);
Na2O × 1,645 
α = - caustic ratio of liquor – molar ratio of Na2O to Al2O3;
Al2O3

Al2 O3 
μ Si = - silica ratio of bauxite (liquor) – weight ratio of Al2O3 to SiO2;
SiO2

C3AH6 - tricalcium aluminate hexahydrate, 3CaO∙Al2O3∙6H2O (TCA)

3CaO·Al2O3∙xSiO2∙(6-2x)H2O - the hydrogarnet series (where x = 0, 1, 2 or 3)

1. Introduction 1. MgAl2O4;
2. Mg(OH)2;
It is well known that lime, produced by limestone burning, is used
3. MgCO3;
in the Bayer circuit for many purposes. These include:
4. Mg6Al2CO3(OH)16·4H2O;
a) raising alumina recovery during bauxite digestion; 5. NaCa2Mg5Si7AlO23;
b) enhancing of desilication; 6. Mg2Al4Si5O18;
c) removal of harmful impurities such as phosphorus, titanium 7. (Ca, Mg) titanates;
and organic species from plant liquors; 8. MgTiO3.
d) causticisation;
Literature shows that formation of magnesium-aluminosilicates
e) recovery of soda from red mud during digestion of high-silica
during digestion reduces the Na2O loss, but doubles the alumina
bauxites.
loss associated with SiO2 removal [1].
Lime is also used to produce tricalcium aluminate hexahydrate
As part of investigations to determine the applicability of using
(TCA) that is applied as a filter-bed in polishing filtration.
magnesium limestone as a source of lime for the Bayer process,
On the basis of previous studies [1], it is known that if magnesium the influence of magnesium on generation of TCA and on the
content in lime exceeds 3 %, a number of components can be subsequent use of TCA for alumina production was investigated.
formed in caustic-aluminate liquors, in particular:

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2. Influence of magnesium on generation of Table 2. Calcia and magnesia contents of roasted materials
tricalcium aluminate hexahydrate Roasting temperature: 1150 ºС and 1200 ºС
Studies were carried out using magnesian limestone, commercial Roasted Product
Raw Material
limestone with an insignificant content of MgO, natural dolomite CaO (%) MgO (%)
and a hydrated magnesium carbonate, magnesium hydroxide
Limestone 96.3 0.4
double salt, as starting materials. The chemical analyses of
Magnesian limestone 91.5 6.0
these raw materials are presented in Table 1.
Dolomite 58.0 36.0
Table 1. Raw materials analysis
Reactant 3MgCO3∙Mg (OH)2∙3H2O 0.4 99.5
Raw materials LOI SiO2 Al2O3 Fe2O3 CaO MgO
In the previous studies it has been revealed that with use of
Limestone 43.5 0.76 0.3 0.04 54.3 0.77
slaked lime (solid powdery substance) instead of lime milk
Magnesian limestone 43.7 0.3 0.25 0.39 52.5 2.9 (slurry, suspension) for preparation TCA, larger monocrystals of
Dolomite 44.8 3.4 0.76 0.68 30.1 20.5 a filter-bed are produced. Therefore in this work slaked lime was
Reactant received. The burnt products were slaked with distilled water at
55.8 - - - 0.2 44.0
3MgCO3∙Mg(OH)2∙3H2O 60 ºС according to a standardised procedure and then analysed
for phase components using XRD Spectrometry. The results from
2.1. Roasting of raw materials and subsequent slaking of the this work are presented in Table 3.
produced compounds
In previous studies concerning TCA production [2], the influence After processing of the roasted samples by condensate at
of limestone roasting temperature was examined on the quality a temperature of 1150 ºС, its dosage corresponds to the
of the burnt lime produced. Temperatures below 1150 ºС led stoichiometric ratio of reaction of conversion of metal oxides into
to the under burning of material, whilst temperatures above hydroxides. With increase of the temperature up to 1200 ºС, the
1200 ºС resulted in over burning. Therefore, in studying the stoichiometric dose of the condensate led to formation of the
influence of roasting temperature on the chemical and phase pasty-like sample.

Table 3. X-ray diffraction analysis of the slaked materials

The phase content in cake, mass %

Mg6Al2(OH)18∙ ∙4,5H2O,7,8Å
L:S
Initial substance
mass

α-quartz
Mg(OH)2
Ca(OH)2

MgCO3
2,10Å
2,63Å

2,36Å

3,34Å
2,74Å
MgO

Roasting Temperature: 1150 °C

Limestone 0.42 96.5 - - - - -

Magnesian limestone 0.50 89.9 5.3 - - - -

Dolomite 0.40 56.8 26.8 - - 6.9 5.2

Reactant 0.41 - 16.4 79.4 3.8 - -

Roasting Temperature: 1200 °C

Limestone 0.38 92.5 - - - - -

Magnesian limestone 0.54 95.1 4.0 - - - -

Dolomite 0.38 56.8 24.6 - - 6.9 5.1

Reactant 0.46 - 15.9 78.9 4.8 - -

Note: L:S (liquid to solid ratio) means the ratio of the liquid phase mass (hot distilled water) to the mass of the solid phase (burnt products). X-ray diffraction analysis was
conducted with a DRON-6 (Co-radiation).

composition of TCA produced from magnesium compounds, all As a result of analysis of the experimental data, it is possible to
raw materials were roasted at either of these two temperatures, draw the following conclusions:
1200 ºС or 1150 ºС.
• At increase in temperature of roasting from 1150 to
Subsequent analysis of the calcined products showed their 1200 ºС reactivity of the roasted samples decreases due to
chemical composition to be independent of roasting temperature, the formation of less active CaO;
with the following results for CaO and MgO obtained (Table 2). • Slaking of burnt lime, produced from natural limestone, was
exhaustive in that СаО was not detected and appears to
have been completely converted into Са(OH)2;
• Magnesium oxide present in the product derived from
roasting magnesian limestone does not react with water.
Slaking of burnt dolomite resulted in essentially complete
conversion of СаО to Са(OH)2. MgO practically does not
enter into the reaction with water;

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• The MgO component in the calcined product derived Table 4. Analysis of plant green liquor used to produce TCA
from 3MgCO3∙Mg(OH)2∙3H2O partially reacts with water to batches
form Mg(OH)2, although the conversion is not complete / Na2Ot
quantitative. Na2Ocarb Na2Oc Al2O3 SiO2
αc
g/dm3
g/dm3 g/dm3 g/dm3 g/dm3
2.2. Synthesis of TCA (≡g/L)

The slaked materials described above were reacted with plant 232 29 203 124 1.1 2.7
green liquor for 2 hours at 95 ºС. The analysis of the plant green
The samples of TCA produced by this procedure were studied by
liquor used to prepare the various TCA / filter aids is shown in
x-ray phase and spectral methods, yielding the results presented
Table 4.
in Table 5.

Table 5. X- ray diffraction analysis of samples of the filter aid produced at temperature 95 °С

Intensity of peaks on the x-ray diagram, imp-sec

4CaO∙Al2O3∙0,5CO2∙10,6H2O,7,60Å
Mg6Al2(OH)16∙СО3∙
Mg (OH)2,2,34Å

Ca(OH)2,2,63Å

CaCO3,3,035Å

MgCO3,2,74Å
C3AH6,5,13Å
MgO, 2,10Å

4H2O,7,8 Å
Initial raw materials

Roasting Temperature: 1150 ºС

Limestone - - 225 - 50 Traces - -

Possibly
Magnesian Limestone 15 - 260 10 30 - -
traces

Possibly
Dolomite 210 - 140 70 10 - -
traces

Reactant 235 95 - 415 - - - -

Roasting Temperature: 1200 ºС

Limestone - - 175 - 30 5 - 5

Magnesian Limestone 15 - 200 5 60 5 - -

Possibly
Dolomite 160 - 145 55 Traces - -
traces

Reactant 400 - - 375 - - - -

Note: С3АН6 – 3СаО·Al2O3·6H2O – tricalcium aluminate hexahydrate.

On the basis of the experimental data it is possible to draw the


following conclusions:

• Magnesium oxide produced by thermal decomposition of


magnesian limestone, dolomite and 3MgCO3∙Mg(OH)2∙3H2O
reacts with green liquor to form magnesium hydrocarbo-
aluminate (Mg6Al2(OH)16CO3·4H2O) (with a structure similar
to hydrotalcite);
• Tricalcium aluminate hexahydrate produced from magnesian
limestone, burnt at 1150 °С, has greater crystallinity
(intensity of peaks – 260 imp./seconds) than TCA produced
from limestone containing minimal MgO, burnt at the same
temperature (intensity of peaks – 225 imp./seconds);
• Raising the roasting temperature of the raw materials to
1200 °С leads to a decrease in TCA quality for all types of
limestones and is characterised by lower crystallinity.

2.3 Particle size, crystallinity and filtration properties of


synthesized TCA
To review the impact of PSD and particle structure on the filtration
parameters, TCA / filter aid batches were synthesised at reaction
temperatures of 60 ºС, 80 ºС and 95 ºС. On the basis of the
optical microscopy it is known [2] that the synthesis temperature
essentially impacts PSD and crystallinity of TCA particles. Thus, at
a temperature of 95 ºС, crystals were obtained with more perfect
surface, better crystallinity and having stronger structure, with
positive effects in the filtration process (see Figure 1).
Figure 1. Filtration rate and specific resistance of a layer of TCA deposit versus
pressure drop

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The filtration rate is highly influenced by the size of TCA crystals in On the basis of PSD analysis (refer to Table 6), it can be seen that
a filter-bed: the larger the size of hydrogarnet crystals, the higher for all raw materials roasted at 1200 °С, some increase in the
the filtration speed [4]. In the literature [3], it is shown that under -20 / +10 micron fraction occurs. However, optical microscopy
plant conditions the polishing filtration of the green liquor is most on the samples shows that this is connected with the formation
effective when the TCA particles in a filter-bed are predominantly of agglomerates, rather than the monocrystals which result from
between -20 / +10 microns, with a minimum content of fraction roasting at 1150 °С.
-5 microns.

Table 6. Physical characteristics of samples of the filtering products produced at the temperature 95 °С
Roasting temperature, °С

The initial 1150 1200


raw materials
Average -5 -20 / +10 Average -5 -20 / +10
Diameter, Micron Micron Micron Diameter, Micron Micron Micron

Limestone 22.69 8.78 31.85 16.40 13.39 41.22

Magnesian Limestone 15.84 13.89 41.83 12.62 15.69 45.17

Dolomite 28.16 11.69 23.56 26.90 14.27 19.33

Reactant 99.69 1.64 1.84 79.92 4.33 3.92

Note: The grain size analysis was conducted with a CILAS 1180 laser analyser.

Figure 2 presents PSD plots of the the filter aids produced by


reaction with plant green liquor.

Limestone Magnesian limestone

Dolomite Reactant

Figure 2. PSD of filter aids produced from limestone, magnesian limestone, dolomite and a 3MgCO3∙Mg(OH)2∙3H2O reactant roasted at 1150 ºС

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The laser PSD analyses (Figure 2) indicates that an increase 9–10 microns, there were also insignificant quantities of calcium
in the magnesium oxide content in the initial roasted samples hydrocarboaluminate, CaO and MgO present.
is associated with a shift to a larger grain size in the resulting
filtering product. For the compounds produced from a reactant The initial and final deposits from the green liquor treatment
of magnesium, the particles size reaches 300 microns. The were studied by crystal optical analysis (Figures 3 and 4).
filter-bed produced from magnesian limestone (as a whole) is Analysis of the filter-bed material after processing at 70 ºС revealed
comprised of larger particles than the filter-bed produced from that the TCA monocrystals became more crystalline, the calcium
limestone, their maximum size reaches ~ 90–100 microns. hydrocarboaluminate content increased, the CaCO3 content rose

Figure 3. The compounds formed in TCA of magnesian limestone after filtering green liquor for a period of 2 hours at temperature 102 °C: a) calcium
hydrocarboaluminate 4CaO∙Al2O3∙0.5CO2∙10.6H2O; b) silica SiO2.

Figure 4. TCA, synthesised from the magnesian limestone after filtering green liquor for a period of 2 hours: a) at temperature 102 ºС; b) at temperature 70 ºС.

The optical microscopy also revealed that the average size of to 5 % and amorphous silicon oxide appeared (to 0.5 %); CaO and
monocrystals of TCA produced from magnesian limestone is MgO remained in insignificant quantities. By comparison, green
about 9–10 microns, whereas for the corresponding material liquor processing at 102 ºС resulted in the formation of a greater
produced from limestone it is only 5 microns. The composition quantity of large monocrystals (the average size increased up to
of TCA from magnesian limestone comprises ~ 10 % of a mix of 10–12 microns); well crystalline calcium hydrocarboaluminate
calcium hydrocarboaluminate, 4CaO∙Al2O3∙0,5CO2∙10,6H2O, and was found; CaCO3 content was ~ 3 %; CaO and MgO remained in
magnesium hydrocarboaluminate with hydrotalcite structure, insignificant quantities; and amorphous silicon oxide appeared.
6MgO∙Al2O3∙CO2∙12H2O (or Mg6Al2(OH)16CO3·4H2O). By comparison, This is consistent with the TCA undergoing transformation to
the composition of TCA generated from limestone includes about hydrogarnet as it is “aged” with green liquor.
50 % of calcium hydrocarboaluminate. This suggests that calcium
hydrocarboaluminate and magnesium hydrocarboaluminate As previously shown in Figure 1, large and well crystalline TCA
have a cementing effect on TCA monocrystals. monocrystals provide conditions for higher strength and lower
compressibility of the filter-bed. Therefore, it is concluded that
2.4 Impacts from ageing TCA on crystallinity the use of TCA, produced from magnesian limestone, positively
To reveal the structural changes occurring with TCA in the course affects the filtration process under production conditions.
of filtration, a number of experiments were conducted. The filtering
3. Influence of TCA type on bauxite digestion
material produced from magnesian limestone was treated with
green liquor maintained at temperatures of 70 and 102 ºС for a TCA contains СаО and Al2O3, therefore the possibility of applying
period of two hours. The initial TCA consisted of monocrystals of the prepared filter aids as a digestion additive was studied. In

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so far as the TCA produced from magnesian limestone also
Roasted magnesian
contains MgO, this study covers the influence of the magnesium limestone
compounds on high-temperature bauxite digestion.
Roasted limestone

Digestion trials were conducted at 260 ºС for 20 minutes using TCA from magnesian
Russian boehmitic bauxite from Sredny Timan and a synthetic limestone

liquor. The analyses of the bauxite and liquor are shown in the TCA from limestone
following Tables 7 and 8.
without additives
Table 7. Analysis of Sredny Timan bauxite
0 0,02 0,04 0,06 0,08 0,1 0,12 0,14
SiO2 Al2O3 Fe2O3 CaO MgO Р2O5 TiO2 LOI μSi Phosphorus content, g/dm 3

(wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) (wt %)

7.0 49.4 28.0 0.3 0.4 0.24 3.1 11.1 7.06 Figure 6. Phosphorus oxide in the digested liquor versus additive composition

An additional benefit observed when digesting Timan bauxite with


Table 8. Analysis of synthetic liquor used for digestion trials TCA as an additive is that the losses of caustic alkali (refer Figure
Na2Ot Na2Ocarb Na2Oc Al2O3 Density
7) are reduced. A possible explanation for this is that in the alkali
αc systems with high concentration of carbonateions (CO32-), the
g/dm3 (≡g/L) g/dm3 g/dm3 g/dm3 g/cm3
processes of anion exchange of type 2mOH- ↔ mCO32 – starts with
155 17 138 82 1.239 2.77
the production of solid solutions of carbonate groups [5] in the
To obtain more detailed data concerning behaviour of magnesium crystal lattice of TCA. As a result calcium hydro-carboaluminate,
salts during bauxite digestion, a series of experiments were (CHCA) 4CaO∙Al2O3∙0,5CO2∙10,6H2O, is formed, which due to the
conducted: developed active surface adsorbs SiO2 from solution. The process
results in the solid-phase transition of the metastable CHCA with
• Bauxite digestion without additives; hexagonal structures into the stable cubic phase – the calcium
• Bauxite digestion with various additives at a charge level of hydrogarnet. As a consequence, desilication of the liquor occurs
2 % (СаО + MgO) of the dry bauxite weight, including: partially via formation of calcium hydrogarnet, instead of solely
via sodium hydroaluminosilicate (DSP), leading to a reduction in
- TCA from limestone (СаО – 48 %; Al2O3 – 23.1 %);
caustic loss.
- TCA from magnesian limestone (СаО – 44 %; MgO –
2.6 %; Al2O3 – 22.8 %); Reduction in soda losses is especially appreciable when additives
- Roasted limestone (СаО – 96 %); containing magnesium oxide are employed (Figure 7). It is
- Roasted magnesian limestone(СаО – 92 %; MgO – 6.8 %); probable that magnesium hydrocarboaluminate also adsorbs SiO2
on the surface, forming hydrogarnet of magnesium with variable
The data obtained as a result of these laboratory experiments
structure and general formula 3MgO∙Al2O3∙xSiO2∙(6-2x)H2O that is
are presented in Figures 5, 6, 7.
an additional source for reduction of caustic losses.

Roasted magnesian
limestone Roasted magnesian
limestone

Roasted limestone
Roasted limestone

TCA from magnesian


TCA from magnesian
limestone limestone

TCA from limestone TCA from limestone

without additives without additives

82,5 83 83,5 84 84,5 85 85,5 95,0 100,0 105,0 110,0 115,0 120,0
Alumina recovery, % Losses of NaOH, kg/t

Figure 5. Alumina recovery at digestion of Timan Bauxite versus additive Figure 7. Caustic losses at Timan bauxite digestion versus additive composition
composition
The mechanism of soda loss reduction postulated above is further
Analysing the obtained results (Figure 5) it is revealed that: supported by a series of experiments that were conducted to
• Alumina recovery from the “additive free” digestion was investigate structural changes in TCA occurring under digestion
85.1 %, which is somewhat higher than for the tests in which conditions. X-ray analysis of TCA portions, produced from the
the additives were present. However, plant experience has various types of limestones and exposed to liquor held at digestion
shown that the lack of lime at digestion as a whole adversely temperature, evinced a transformation in crystal structure over
affects Timan bauxite processing. time. The TCA structure basically collapsed at digestion, with
• Dosage of TCA prepared from limestone (taking into account formation of phases such as calcium hydrocarboaluminate and
Al2O3 content) leads to an increase in alumina recovery from calcium hydrogarnet (3CaO∙Al2O3∙xSiO2∙(6-2x)H2О). These data give
bauxite, as compared to digestion with roasted limestone, the chance to draw a conclusion that the TCA dosage positively
from 84.06 to 84.31 %. influences the process of desilication and promotes a reduction
• The recovery with TCA addition, produced from magnesian in caustic loss.
limestone is also higher at 84.35 %, compared to 83.66 % 4. Conclusions
recovery using burnt magnesium lime.
MgO content in limestone up to 10 % positively impacts the
It was found during this course of experimentation (see Figure 6) characteristics of the produced filter-bed. The use of limestone
that addition of magnesium components in the digestion process with MgO content 10–12 % for production of TCA does not render
also reduces phosphorus content in the digested liquor. a negative influence on the filtration process and is comparable
with the use of “regular” limestone.

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MgO content up to 3 % in magnesian limestone does not have a
negative influence on subsequent application of the used TCA in
the digestion process.

Magnesium oxide reacts with green liquor forming magnesium


hydrocarboaluminate (Mg6Al2(OH)16CO3·4H2O).

The possibility of replacing the СаО added to bauxite digestion


with spent filter-bed from polishing filtration is experimentally
confirmed.

Application of TCA as an additive for digestion promotes alumina


recovery, whilst decreasing caustic losses.

TCA produced from a magnesian limestone parent material


gives monocrystals that are more crystalline, with larger sizes
that improves the characteristics of the filtration process (i.e.
compared to limestone).

Acknowledgements
Authors are expressing acknowledgement to L. Popkova and
M. Tzvetkova who carried out optical microscopic analyses for
this work.

References
1. R.A. Johnson, W.F. Scott. “Limestone usage in Bayer process with linkages in other industries” Tranaux du comite international pour l’etude des
bauxites, de l’alumine et de l’aluminium, 1979 №15. CMS ICSOBA Conference. Kingston, Jamaica, Aug 14/201977. Edite per l’academie yougostove
des Selences et des Arts 1978.
2. A.G. Suss, A.V. Damaskin. The technology of filter-bed preparation for new equipment on the NAP. JSC “RUSAL VAMI”. T. 1, Saint-Petersburg, 2007.
3. О.D. Linnikov, V.А. Nikulin, M.А. Perestoronina, V.S. Tchernoskutov. Generation of macrocrystalline TCA. Light Metals (in Russian), № 2, 2006.
4. L.J. Andermann, G.J. Pollet. The manufacture of tricalcium aluminate. Light Metals 2003 as held at the 132nd TMS Annual Meeting; San Diego, CA;
USA; 2–6 Mar. 2003.
5. V.М. Sizyakov, V.О. Zaharzhevskaya, О.А. Borzenko. Formation particularities and metastable stability of hydrocarboaluminates in the Na2O-Al2O3-
CaO-CO2-H2O system. Magazine of Applied Chemistry (in Russian), 1998 Т.71 Issue. 8, Saint-Petersburg, 1997.

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