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Notation
Al2 O3
μ Si = - silica ratio of bauxite (liquor) – weight ratio of Al2O3 to SiO2;
SiO2
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:
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
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;
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
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
Possibly
Magnesian Limestone 15 - 260 10 30 - -
traces
Possibly
Dolomite 210 - 140 70 10 - -
traces
Limestone - - 175 - 30 5 - 5
Possibly
Dolomite 160 - 145 55 Traces - -
traces
Table 6. Physical characteristics of samples of the filtering products produced at the temperature 95 °С
Roasting temperature, °С
Note: The grain size analysis was conducted with a CILAS 1180 laser analyser.
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
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
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
Roasted limestone
Roasted limestone
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.
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.