1. Introduction
After crushing and grinding of bauxite, the Bayer process moves from predominantly physical preparation to its first major chemical control operation called pre-desilication. For a gibbsitic bauxite refinery, this operation is particularly important because the reactive silica in bauxite principally associated with kaolinite and other reactive aluminosilicates is attacked by caustic liquor. If this silica is allowed to remain in solution and travel into digestion, it subsequently participates in DSP formation at locations where its presence is undesirable.
The objective of pre-desilication is therefore not simply to “Remove silica.” The real objective is to Convert reactive silica into a controlled, crystalline desilication product (DSP), while minimizing the associated losses of Na₂O and Al₂O₃ and discharge that DSP with the residue (Red mud). This makes desilication a chemical control point, soda-loss control point, equipment-protection point and ultimately an alumina-quality control point.
As per Industrial Experts, properly operated pre-desilication can convert approximately 90% of reactive silica into DSP, although the achievable value is strongly dependent on bauxite mineralogy, liquor chemistry, temperature, residence time and available DSP surface area.
2. Is Reactive Silica same as Total Silica?
This distinction is fundamental. Bauxite silica can broadly be considered as:
- Reactive silica (R. SiO₂): Mainly kaolinite and other caustic-reactive silicate minerals.
- Non-reactive silica: Principally quartz under normal low-temperature conditions.
Reactive silica is the silica that creates the major Bayer-process chemical burden. For example, kaolinite can react with caustic liquor according to the simplified reaction. Thus, a mineral originally presents as a solid in bauxite becomes soluble silicate and aluminate species. The soluble silicate must then be removed from solution.
3. Formation of DSP
The dissolved silicate does not remain indefinitely in Bayer liquor. It reacts with sodium aluminate and other liquor species and precipitates as desilication product (DSP).
The DSP family principally includes the following:
- Bayer sodalite
- Bayer cancrinite
- Sodium aluminosilicate phases
- Calcium-containing DSP phases where Ca is available.
For conventional low-temperature gibbsitic Bayer refining, sodalite-type DSP is particularly important. The actual DSP composition therefore changes with liquor chemistry.
4. The DSP Formation Mechanism
DSP formation should not be regarded as an instantaneous single chemical reaction.
The actual crystallization sequence depends on following parameters:
- temperature
- residence time
- caustic concentration
- aluminate concentration
- silica concentration
- carbonate
- sulphate
- chloride
- calcium
- seed surface
- liquor supersaturation.
This has an important plant implication as “Desilication is a kinetic operation of chemical-equilibrium operation.” Simply providing a large tank volume is not sufficient. The system must provide the correct temperature–time–chemistry–solids-surface-area combination.
5. Why Pre-Desilication Is Necessary
If reactive silica is not substantially removed before
digestion, several undesirable phenomena occur as Without adequate
pre-desilication, it causes following negative results:
- higher caustic soda consumption;
- higher alumina loss;
- increased DSP generation;
- greater red-mud soda loading;
- silica remaining in pregnant liquor;
- heat-exchanger scaling;
- reduced heat-transfer coefficient;
- increased cleaning frequency;
- possible silica contamination of hydrate/alumina;
- deterioration of overall refinery recovery.
Incomplete desilication is specifically associated with silicate scaling and potential alumina-product contamination.
6. Soda Loss — The Economic Penalty of Reactive Silica
This is one of the most important aspects of desilication.DSP does not consist only of silica. It incorporates:
- SiO₂
- Al₂O₃
- Na₂O
- water
- anions such as carbonate, sulphate, chloride and hydroxide.
Since DSP leaves the circuit with red mud, the soda and alumina incorporated in it are effectively removed from the active Bayer liquor circuit. Literature consistently identifies DSP formation as a major source of caustic and alumina.
7. The “Sodalite Factor” : A Practical Plant Concept
There is an important distinction between the stoichiometric composition of an ideal DSP phase and the plant sodalite factor used for estimating actual chemical soda loss. The actual DSP generated in an operating refinery is not necessarily a pure theoretical mineral. Its composition changes with:
- liquor chemistry,
- temperature,
- residence time,
- sulphate,
- carbonate,
- chloride,
- calcium,
- DSP phase transformation,
- digestion condition.
Therefore, for plant calculations, a soda to reactive silica ratio factor is normally established from laboratory test work of bauxite at established process conditions. Stoichiometric number are only used by Bayer Process Experts based on their rich experience with similar bauxite.
Sodalite factor of approximately 0.70 (Na₂O/R.SiO₂) is adopted as an empirical / theoretical design sodalite factor which has been observed close to actual operating sodalite factor of Alumina refinery. Therefore, one can use “sodalite factor = 0.70” in a design calculation with clear understanding of the numerator, denominator, analytical basis and explicitly defined units in order to have accurate results.
8. Recommended Method for Steady Control of g/l SiO₂
This is one of the most important practical recommendations. Do not control desilication only by:
- temperature;
- residence time;
- tank level;
- operator experience.
Instead establish a closed-loop silica control system by measuring feed silica, outlet silica, silica saturation, silica removal and then arrive at equilibrium silica.
9. Desilication Control Philosophy
A robust desilication control philosophy is developed purely based on outlet dissolved SiO2.
10. What Happens When Desilication Is Insufficient?
If sufficient desilication is not done then residual reactive silica enters digestion circuit causing following consequences:
10.1 At
digestion temperature, it may cause
- higher soda loss;
- higher alumina loss;
- more DSP;
- increased residue volume/load.
High-temperature digestion can also increase silica dissolution from minerals such as quartz, particularly where the digestion temperature is high.
10.2 Impact on Digester Heat-Transfer Equipment
Residual silica can subsequently precipitate as sodium aluminosilicate causing scale formation in:
- heaters;
- heat exchangers;
- liquor lines;
- digestion equipment.
Scale reduces the overall heat-transfer coefficient causing high steam demand.
10.3 Impact on Clarification
Higher DSP loading affects the residue system. Potential effects include:
- increased mud solids;
- altered particle-size distribution;
- changed settling behavior;
- increased liquor entrainment;
- higher filtration/washing load;
- increased soda loss with residue.
The actual impact is refinery-specific because settling depends on the complete residue mineralogy and flocculation system.
1 10.4 Impact
on Precipitation
The most dangerous consequence of inadequate desilication is allowing excessive dissolved silica to reach the pregnant liquor ultimately increasing the silica impurity in product ATH and alumina.
10.5 Impact on Evaporation
The evaporator circuit is particularly sensitive to impurities and scaling. If silica-bearing liquor enters the evaporation system:
- liquor concentration increases;
- silica supersaturation may increase;
- DSP/silicate scale may form;
- heat-transfer coefficient decreases;
- circulation becomes more difficult.
Thus, insufficient desilication indirectly affects the refinery's steam economy.
10.6 Recommended Daily Desilication Dashboard
|
|
Unit |
|
|
Bauxite R.SiO₂ |
% |
Feed-forward control |
|
Bauxite total SiO₂ |
% |
Mineral balance |
|
Bauxite moisture |
% |
Slurry control |
|
Slurry density |
t/m³ |
Solids control |
|
PDS temperature |
°C |
Reaction kinetics |
|
Residence time |
h |
Reaction completion |
|
Na₂O |
g/L |
Liquor chemistry |
|
Al₂O₃ |
g/L |
Liquor chemistry |
|
RP |
— |
Liquor balance |
|
Feed SiO₂ |
g/L |
Silica load |
|
Outlet SiO₂ |
g/L |
Primary KPI |
|
Equilibrium SiO₂ |
g/L |
Thermodynamic reference |
|
Silica ratio |
— |
Degree of saturation |
|
Silica supersaturation |
g/L |
Process control |
|
DSP concentration |
g/L |
Seed inventory |
|
DSP bleed |
t/day |
Solids balance |
|
Soda loss |
kg/t ATH |
Economics |
|
Mud soda |
% Na₂O |
Residue loss |
|
Heat exchanger ΔT |
°C |
Scaling indicator |
|
Heat-transfer coefficient |
W/m²K |
Equipment health |
11. Key Technical Takeaway
For gibbsitic bauxite, It is always recommend that the desilication section be treated as the first formal chemical control point of the refinery. The key philosophy for Alumina Refinery is highlighted below:
“Know the reactive
silica entering the refinery, predict the silica entering desilication, control
the temperature, residence-time, DSP environment, continuously measure
dissolved SiO₂ leaving desilication, calculate silica ratio/supersaturation and
prevent the silica problem from being transferred to digestion, heat
exchangers, precipitation and evaporation circuits.”
Trust, our Engineers are enriching their knowledgebase through Bayer Process Masterclass. So far, we have published BM-001 to BM-005 and BM-006 is under preparation which will be published shortly. If you wish to learn on any specific aspects of Alumina production, please feel free to interact with us.
Rajendra Kunwar
Bayer Process Expert.
CETI Enterprises,
India.
www.ceti.co.in