PRECIPITATION

DONE BY : ZVIKOMBORERO DONGONDA N0188161W

ANDRIES NYAMANDI N0182697Y
TAPUWANASHE CHIMHUYA N01888181Y
NKOSIPHILE SIBANDA N0188416L
PISIRAI SADDAM N0189384G
RUMBIDZAI CHIWESHE N0181787P
TICHAONASHE MANHIBI N0174482Q
HUBERT KUDEJIRA N0188967G
DARLINGTON MWAONECHIRI N0173489Y
RUMBIDZAI MUNGUNI N0188216J
JASPER MUNAKA N0171628X
BRANDON MATANHIRE N0172869P
MARIA KAMALA N0182565M
Introduction
 Precipitation is a unit operation used for precious metal recovery in the final stages of
hydrometallurgical processes
 The principle technology to recover or remove metals from a solution is by chemical
precipitation where a mineral forms by crystallization from a solution.
 Once the precipitate (solids) forms, they can be removed easily by filtration.
 Although precipitation constitutes the concluding part of the hydrometallurgical process
flowsheet, the process is also put to use as a purification step in order to separate
impurities.
 Chemical precipitation is one of the most widely adopted methodologies that have been
employed for heavy metal removal from inorganic effluents in industries.
 Once the heavy metals precipitate to form solids, they can be removed easily.
 Precipitation is used to:
•selectively recover metals and compounds of the metal
• removal of contaminants from aqueous solutions (Precipitation, A. E. Nielsen, 1970).
Principle of Operation

 It principally involves the transformation of a soluble compound into an

insoluble form (insoluble precipitates of heavy metals as hydroxide, sulphide,
carbonate, and phosphate) through the addition of chemicals (precipitants).
 Certain chemicals like sulphides, hydroxides and carbonates when added to a
polymetallic solution, could change the ionic equilibrium of the system and
precipitate the metals as respective salts e.g. metal-sulphides or metal-
carbonate or metal-hydroxide (Precipitation, A. Nielsen, 1970). pH and
concentration of the metals are two important factors that affect the metal
precipitation.
Example of Precipitation Reaction
 Pb(NO3)2(aq) + 2NaI(aq) 2NaNO3 (aq) + PbI2 (s)
Principle of Operation

 Natural waters like lakes, oceans and groundwater contain dissolved

minerals such as salt or iron.
 Water can only hold a certain amount of dissolved minerals before it
becomes saturated.
 When the amount is too great to stay dissolved in the water
(supersaturated) the particles come together to form mineral solids and
precipitate out.
 For example, when water evaporates from a lake or ocean, it leaves
behind a solid “precipitate” of minerals.
 When minerals precipitate below earth’s surface it is because hot water
(hydrothermal fluid) changes temperature, pressure or composition,
such that the fluid becomes supersaturated and deposits the dissolved
minerals. If the water is flowing through cracks, the precipitated minerals
Mineral Precipitation Examples
Principle of Operation
Solubility Product Principle

 Precipitation of a compound from solution takes

place if its solubility product constant (Ksp) is
exceeded. The solubility product constant for a
given temperature is a measure of ion
concentration and applies to saturated solutions
of a salt.
Factors affecting Precipitation

 Precipitation of solid compound from solution is affected by

1. CO2 content
2. pH
3. Temperature
4. Type of precipitants
5. concentration
Effect of Carbon Dioxide content and pH of aqueous media

 Increasing CO2 content of natural waters results in

lowering of pH, and consequent greater solubility of
carbonate phases present;
 This in turn aids mineral (solid) formation
 Conversely, decreasing CO2 content in aqueous
environments causes a rise in pH and an increase of
carbonate ion concentration
Cont.…

 It is known that great changes of CO2 partial pressure cause relatively small
changes of pH and would not affect the carbonate ion concentration very
much;
 This is especially true of sea water, which has a self-contained buffering
system. The CO2 content of natural waters may be increased or decreased as
follows:
Effect of Temperature

 It is generally accepted that a higher temperature favours the

precipitation of metal recovery
 A higher temperature could affect an aqueous environment in
two ways, either of which would aid the precipitation of the
metal
 Initially, increased evaporation would result in an increase in
salinity
 Secondly, at higher temperature an aqueous medium would
tend to hold less CO2 and there would be a rise in pH and
carbonate ion concentration
Effect of pH

 After leaching, the solution containing dissolved earth metals, such as Fe3+,
Al3+, and Ca2+, is subjected to precipitation after the pH of the solution is
raised to >3–4 to remove the impurity ions.
 This is followed by the precipitation of these metals using an appropriate
precipitant.
 Unfortunately, during the first precipitation of impurities, including Fe3+ and
Al3+, earth metals are also co-precipitated or adsorbed on the surface of the
precipitated products, resulting in the loss of valuable metals.
 To prevent this loss, it would be desirable to be able to preferentially
precipitate these metals at low pH values where impurities
are still present in the solution.
Types of Precipitants

1. phosphate,
2. oxalate,
3. sulphate
4. fluoride/carbonate systems

 anions such as Cl-, NO3-, and SO42- play an important role in the
precipitation behavior, particularly through complexation with the dissolved
earth elements.
 In general, the effectiveness of precipitation follows the order of sodium
double salt, a hydrated form of sulfate, and anhydrous sulfate.
Stages of Precipitation

 Precipitation is not possible unless the solution is supersaturated. A saturated

solution can be made supersaturated by temperature change or by
fractionation through evaporation or crystallization of the solvent.
 Another way of making a supersaturated solution is to mix two solutions or
liquids which react chemically (e.g., electrolyte precipitation from aqueous
solution) or otherwise (salting out; addition of a poor solvent to a solution in a
good solvent). In theory precipitation process has two steps i.e.,
 1. Nucleation
 2. Particle or Crystal Growth (Hydrometallurgy Fundamentals and
Applications, L. Michael)
PRECIPITATION FLOW DIAGRAM
Nucleation
 1) Nucleation
 Precipitation does not start at any supersaturation, no matter how small,
because small crystals have a higher equilibrium concentration than large
crystals.
 Although it is almost impossible to measure the interfacial tension between a
crystal and a solution, there is no doubt that the interface contributes to the
Gibbs free energy of the system, approximately proportional to the area of
the interface (Hydrometallurgy Fundamentals and Applications, L. Michael).
 If a crystal in a solution is divided into a number of small crystals the
interface is increased. If the original crystal was in solubility equilibrium with
the solution the small crystals cannot be so.
 Actually, they will begin to dissolve, even at a small finite supersaturation.
The smaller a particle is, the higher is the supersaturation required for the
particle to be in equilibrium with the solution.
Cont.…

 This may be demonstrated by blowing bubbles in water by means of straws,

or glass capillaries, of diff3erent diameters.
 The narrower the tube is, the smaller are the bubbles, and the harder one has
to blow in order to produce the bubbles.
 It follows those crystals smaller than a certain critical size will dissolve if they
are brought into contact with a solution of moderate supersaturation the
critical size depends on the ratio of the concentration to the solubility,
whereas crystals larger than the critical size start growing and grow more and
more rapidly, as they get larger if the solute concentration is kept constant.
 But we know that crystals often appear from a moderately supersaturated
solution. How can that be explained? This can happen in two ways
(Hydrometallurgy Fundamentals and Applications, L. Michael).
Heterogeneous nucleation

 Any solution which has not been extremely well cleaned contains a vast
number of invisible solid particles. 100 particles per cubic millimeters is quite
normal even in filtered liquids. In fact, it is impossible to remove these
particles completely.
 They may act as hetero-nuclei, i.e., catalysts for the initiation of precipitate
crystals, the solute being adsorbed on the particles to form a layer which is
larger than a face of a crystal of the critical size, and thus able to grow in the
solution (Hydrometallurgy Fundamentals and Applications, L. Michael).
Homogeneous nucleation

 Even at a moderate supersaturation there is an appreciable number of

embryos, i.e., subcritical associates of crystal-like structure in equilibrium
with the solution, and a small fraction of these reaches the critical size by
thermal fluctuations.
 When this happens the chance that the associate will grow further is larger
than the chance that it will dissolve again. The critically sized embryos thus
play a role similar to the activated complex of chemical reaction kinetics.
Cont..…
 The method has been used in the study of homogeneous nucleation from
liquid metals (emulgated in oil). A similar technique is the study of a fog of
droplets crystallizing in a carrier gas.
 In the other type of experiments a very high supersaturation is produced very
rapidly so that the number of homogeneously nucleated particles is much
larger than the number of heteronuclei present.
 This was the method used in the classical work on homogeneous nucleation of
vapours of volatile liquids like ethanol and water.
Cont.…

 It has also been applied to the precipitation of sparingly soluble electrolytes

from solution.
 In case of heterogeneous nucleation, the number of particles is roughly
constant during the precipitation process, and the particles are of nearly the
same size.
 When homogeneous nucleation takes place the number of crystals increases
with time. The rate of nucleation is strongly dependent on the concentration,
and approaches zero as soon as the concentration has decreased by a
relatively small amount (Chemical Metallurgy, C. Gupta, 2003).
Particle or Crystal growth

 The nuclei cannot be observed until they have been developed through
growth.
 Crystals grow by the continued addition of one layer of molecular units on
another.
 The units arrive at the crystal surface by diffusion, sometimes aided by
convection, and are fitted to the crystal lattice.
 The details of adsorption of the units, and of their finding the right place and
orientation, are not accurately known.
Chemical precipitation processes
 Hydroxide precipitation.
 Strong bases like sodium hydroxide (NaOH), and lime or hydrated lime (Ca(OH) 2) are the
commonly applied chemicals for the precipitation of metal hydroxides.
 Weak bases (e.g. ammonia solution) can also be used to precipitate metal hydroxides,
however at higher pH it can form stable complexes because of the dissolution of metal
hydroxides (Contestabile, Panero, & Scrosati, 2001).
 A generalized equation for the metal hydroxide precipitation can be written as follows
 M2+ + 2(OH-) → M(OH)2
 where M is a divalent metal ion.
 Metal removal by hydroxide are widely used because of its relatively simple operation
and low capital cost (Huisman, Boks, & Stevels, 2003).
 A major disadvantage of this process is the high solubility of the metal hydroxide
complexes precipitated, when the pH is not optimum. A soluble metal complex M(OH) +
will be formed with respect to the change in the pH.
Sulphide precipitation

Ferrous sulphide (FeS), calcium sulphide (CaS), sodium sulphide

(Na2S), sodium hydrosulphide (NaHS), ammonium
sulphide((NH4)2S), hydrogen sulphide (H2S) are the major
chemicals used for the metals sulphides precipitation (MSP).
Sulphide Precipitation has various advantages over other methods
including the metal sulphide precipitates are less soluble, selective
metal precipitation can be done, reaction rates are fast, settling
properties are far better and sulphide precipitates can be reused
(Lewis, 2010).
 In addition to that, Sulphide Precipitation also offers selective
metal precipitation and can successfully be applied to extremely
low concentration (ppb) of metals (Kim, Kim, Lee, & Pandey,
2011).
Cont.…

 Operating pH plays an important role in the precipitation of metal sulphide and also various
metal sulphides have the tendency of solubility with respect to pH (Lewis, 2010; Sethurajan,
Lens, Horn, Figueiredo & van Hullebusch, 2017).
 Concentration of the sulphide is the key factor in the MSP, if it exceeds or depletes either
sulphides or metals will remain in the solution (Veeken, Akoto, Pol, & Weijma, 2003).
 Also, metal removal by Sulphide Precipitation has other various barriers (Lewis & Van Hille,
2006) to overcome such as:
 •formation of poly sulphides due to the localization of supplied sulphides, which results in
excessive consumption of sulphide and low metal removal and
 •low solubility of metal sulphides and higher super saturation which resulted in the formation
of fine particles with unfavorable solid-liquid separation difficulties.
 Optimization of sulphide dosage is the limiting parameter for its less known commercial
applications, as the metal sulphides have very less which will have an impact in the process
sensitivity (Veeken, Akoto, Pol, & Weijma, 2003; Lewis, 2010). Lewis and Van Hille (2006).
Carbonate precipitation

 Carbonates precipitation is also used to precipitate the metals as metal

carbonates, in which straight precipitation by chemicals such as calcium
carbonate is used or conversion of hydroxides to carbonates is applied for the
precipitation of metals (Wang, yung-tse, &Shammas, 2005).
 Carbonates precipitation can also be applied in combination with hydroxide
precipitations.
 Operation at low pH, faster settling and good metal removal were some of
the merits of carbonates precipitation.
 Sometimes oxalate precipitation was also used to precipitate
 Precipitation of Aluminum.
DESCRIPTION OF THE PRECIPITATION PROCESS FOR ALUMINIUM.

 Aluminate mother liquor is supersaturated with dissolved Aluminum. The

crystallization of Aluminum hydroxide from this liquor is the slowest part of
the Bayer cycle.
 The kinetics of the overall reaction are controlled by chemical steps, not by
mass transfer. Therefore, long holding times are required, and it is necessary
to provide a large recirculating mass of hydrate seed to accelerate the
reaction.
 The seed provides a catalytic surface to encourage the formation of Aluminum
hydroxide and a surface on which it can grow. It is very important that the
crystals produced are of the right form and structure to ensure that they pass
through the calcination stage to form ALUMINA.
A diagram showing precipitation process
of Aluminum.
Cont.….

 Hydrate seed, previously screened from the precipitation step is added to the
first precipitator. The Aluminum hydroxide crystallizes onto the seeds in a
controlled way. The precipitator is a large vertical tank (typical dimensions
are 30m high and 15m diameter with volume about 4.5 ML) with some form of
agitation to maintain the suspension of the solids in the liquor.
 Earlier forms of tank had cone bottom with air injections to provide the
agitation, these tanks were called POCHUCAS (originally deviced in New
Zealand, but first practically introduced in Pachuca, Mexico).
 Modern refineries have flat bottomed precipitation tanks with agitation via a
stirred propeller to maintain suspension of the solids in the liquor.
A portrait showing precipitation building
with Pachuca tanks
Simplified diagram showing what
happens during precipitation.
Diagram showing tanks in series during
the precipitation process.
Cont.….

 Precipitation takes place over at least 24 hours as the hydrate slurry passes
through up to 10 precipitators in a train. The number and size of the vessels
are necessary to accommodate the slow precipitation step in the Bayer cycle.
All other unit operation are much faster.
 As the hydrate slurry (typically 500g solid/l) passes down a precipitator bank
the temperature is carefully reduced to provide a greater driving force for
crystallization.
 The liquor (termed spent) leaving precipitation is still somewhat saturated in
dissolved aluminium.
Cont....

 The yield of hydrate through the precipitator train is an important efficiency

parameter. The greater the yield, the more efficient the refinery. Typically
the green liquor entering precipitation at 78-80 degrees Celsius will have an
Aluminum content of 140g/l and the spent liquor exiting precipitation at 55
degrees Celsius a value of 50g/l, giving a yield of 90g/l.
 The mechanism of precipitation involves a combination of agglomeration and
growth. The first stage of precipitation involves the sticking together of small
seed particles to form agglomerates. This is a relatively rapid process, which
is favored by high Aluminum supersaturations and high temperatures it
therefore is the predominant mechanism in the first stage of precipitation.
Cont.…

 The agglomerates so formed are of random shapes, and the overall strengths
of the agglomerated particles are low. This is also a step in which most of the
chemically included soda is incorporated into hydrate crystals. It is therefore
essential that the high yielding agglomeration stage is followed by a period of
controlled growth. In this growth stage, as well as increasing in size the
particles are strengthened and their shapes are regularized.
 In addition, the overall soda content of the particles is diluted. Depending on
the precipitation conditions, temperature and impurities in the liquor stream
the final hydrate particles may display a predominantly radial or mosaic
nature. The radial particles tend to be tougher and less prone to break up
into smaller particles compared to the mosaic particles when transported and
calcined, and so are preferred.
Scanning electron microscopy images
illustrating the two types of hydrate particle.
Cont....

 The optimum particle size distribution in the precipitation product ranges

typically from 45-150 micro meters in diameter with less than 5% in the -45 micro
meter fraction and no more than 10% greater than 150 micro meters. Exiting last
precipitator, the hydrate particles are screened from the spent liquor and
washed with good quality water to ensure as much entrained liquor is removed.
The moist filter cake is transported to calcination. The precipitation step in the
Bayer cycle is the most critical one. Two criteria:
 1) aim to maximize product recovery in the minimum time to increase efficiency
and
 2)aim to grow sufficiently large particles in a slow, controlled way to ensure the
product hydrate meets size and toughness specifications are essentially in
conflict.
 So good control of precipitation in a refinery is most important.
Case Study: General Uranium Extraction Process Flow
Diagram
Mil l Feed

Ore sorti ng Waste

3'' Screen

Grinding

Flotation

Thickener Repulping Ta ilings

Heat Exchanger Filtra tion

Water Evaporator

Ca(OH)2 Lime Plant CaCO3

NaOH Precipita tion

Carbona tion
Filtra tion

Na2U2O7
Drying Packing
To refin ery
PRECIPITATION OF URANIUM FROM
ALKALINE SOLUTIONS
 INTRODUCTION 
 Precipitation is the process whereby a dissolved mineral is freed from a
pregnant solution resulting in a mineral deposit and a barren solution.
 In the precipitation of uranium from alkaline solution process, the pregnant
solution is precipitated using NaOH resulting in 95-99% extraction of uranium
oxide U3O8 from the pregnant solution.
 This section is going to be focusing on the precipitation of uranium from
alkaline solutions, this then involves Direct precipitation from alkaline
solutions and Precipitation from alkaline stripping solutions.
Factors affecting choice of Precipitating
Reagent
 The type of precipitating reagent chosen is influenced by factors such as:
1. The purity of the feed solution to the precipitation
2. The product specifications required
3. The relative reagent cost
4. The possible environmental impact of the reagent.
Direct precipitation from alkaline solutions

 Leaching in an alkaline medium often leads to fairly pure liquors suitable for
direct precipitation with sodium hydroxide. The operation is performed at
temperatures ranging from 50 to 80°C for fairly extended periods (6-12 h).
 A portion of the precipitate is normally recycled to the next precipitation
batch or stage in order to maximize the surface area for precipitate growth.
Some 5 to 6 kg of NaOH are required for each kilogram of U3O8.
 In alkaline leach systems it is more important to conserve the carbonate
reagent for recycling to the leaching operation than to achieve complete
precipitation of the uranium
Cont..…

Pregnant solution
2-3g/l U
Barren Solution
0.1g/l U.

U3O8. Precipitate
(Yellow cake)

Reseeding cone
Precipitation from alkaline stripping solutions.

 Precipitation from alkaline stripping solutions can be carried out with sodium
hydroxide [2] according to the following reaction:
 2Na4U02(C03)3 + 6NaOH - Na2U207 + 6Na2C03 + 3H20
 This precipitation is carried out at ambient temperature with a fairly short
retention time of about two to four hours. The terminal pH value is 12. About
3 to 4 kg of NaOH are required for each kilogram of U308 precipitated
 If the use of sodium hydroxide is not desirable magnesium hydroxide can be
used as the precipitant. Peroxide precipitation is sometimes required to
prevent co-precipitation of other metals. In this case the alkaline stripping
solutions must be acidified prior to precipitation.
Thank You