See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/274377125

Crud Formation and Its Control in Solvent

Extraction

Conference Paper · September 2005

CITATIONS READS

2 177

1 author:

Cheng-yan Wang
Science and Technology University Beijing
65 PUBLICATIONS 152 CITATIONS

SEE PROFILE

All content following this page was uploaded by Cheng-yan Wang on 31 December 2015.

The user has requested enhancement of the downloaded file.

 CRUD FORMATION AND ITS CONTROL IN SOLVENT EXTRACTION

WANG Chengyan

Beijing General Research Institute of Mining & Metallurgy, Beijing 100044, China

All commercial solvent extraction plants suffer from crud, which mainly caused by solids. The
crud can influence phase continuity, emulsion stability, aqueous solution and air distribution.
The problems of crud formation, its control and disposition have been discussed from organic
phase, aqueous phase, solid particles and air in this paper.

INTRODUCTION

As an important section of hydrometallurgy, solvent extraction is paid attention for the

properties of less pollution, less energy loss, lower cost, and higher efficiency. However, all
commercial solvent extraction (SX) plants, inevitable, suffer from stable multi-phase
emulsions, which mainly caused by solid particles. We generally call those stable multi-phase
emulsions as crud, or gunk. The crud is made of organic, aqueous, air, and solid phases, and
is often found to distribute itself randomly throughout the separating phases, and sometimes
floating on top of the organic, causing floating crud, or “fish eyes”. It can influence phase
continuity, emulsion stability, and air distribution during SX. In extreme cases, it can cause
phase inversion, which the operating can’t run smoothly. It not only increases the loss of
organic with entrainment, but also increases the cost. The effecting elements on the crud
formation is complex, however, up to now, the mechanism of this is not clearly understood. In
this paper, based on the practices of the author in recently years, the reasons of crud
formation and its control during SE are discussed preliminarily.

REASONS OF CRUD FORMATION

Mineralogy studies indicate that the solid particles, which form stable multi-phase emulsions,
are typically less than 1 micron in size and average 0.16-0.37 micron. Major elements present
are Si, Al, and Fe, and crystalline mineral species found include alpha-quartz, micas, clays,

1066
jarosites and gypsum. Chemical composition of the crud, which was obtained from a copper
SX plant in China, is shown in Tab. 1.

Tab. 1 Chemical composition of crud

SiO2 Al2O3 Fe2O3 CaO MgO MnO2 S C Cu As

1 48.52 13.43 6.87 0.94 2.09 0.20 0.30 15.89 0.008 0.035
2 35.58 18.26 7.88 1.42 1.85 0.43 0.22 10.53 0.015 0.023

Usually, the crud is made of organic, aqueous, and solid phases. Sometimes, it floats on the
surface of the organic with air, causing floating crud, or “fish eyes”. So, the questions of crud
formation can be considered from four aspects: organic phase, aqueous phase, air and solid
particles.

Effect of organic phase

The organic phase during SX is made of extractant and diluent (usually is kerosene). The
quality of them has a great effect on crud formation. For example the extractantes of P204
and P507, made of China, which were used to separate nickel and cobalt, usually contain a
little lower carbon-carbon chain hydrocarbon compounds because of the backward
equipments of fractional distillation during their synthesis. The lower carbon-carbon chain
hydrocarbon compound will tend to induce the crud formation and lengthen the mixed phase
separation during SX. In extreme cases, the operating will total loss of control.

Because the sulfonated kerosene is expensive, most of the SX plants in China use civil
kerosene being the diluent. The civil kerosene is impure, and often contains unsaturated
hydrocarbons in it. These impurities and unsaturated hydrocarbons also have a great effect
on the crud formation and the mixed phase separation.

Effect of aqueous phase

The soluble organic acids and organic substances in the pregnant leach solution are the main
reasons for the aqueous phases to urge the crud formation. Information from operating SX
plants shows that these soluble organic acids and organic substances are introduced by three
main methods: (1) Dead animals and vegetables. For example, during the heap leaching of
low grade copper mineral, an amount of soluble humic acid in mineral will go into the organic
phase with pregnant leach solution; (2) Soluble composition of the corrosion preventive
coating. Economic considered, some SX plants usually use pitch as the anticorrosion material
to preserve the storage cells or ponds, the soluble organic acids and organic substances in
pitch, inevitable also, will dissolve in solution. (3) Organic substances carried by minerals
(such as the used catalyst and waste electroplate solution etc.) themselves. During SX, these
soluble organic acids and organic substances will combine with extractant to form organosol,
and results in the crud formation at last. In addition, the aqueous pH value also has a great
effect on the crud formation.

Effcet of solid particles

1067
As the key factor of crud formation during SX, solid particles can be introduced via five main
ways: (1) Suspension in pregnant leach solution; (2) Dusts from environment; (3) Precipitates
as aqueous pH value increases; (4) Solid impurities in industrial chemicals; (5) Solid particles
from recovery organic phase. Moreover, during the copper L-SX-EW, the powdery dropper
from anode is another way of solid particles introduced.

The ways of solid particles introduced are different with the technologies. When using P204
and P507 extractantes to separate Co from Ni, suspension in pregnant leach solution maybe
is the main way of solid particles introduced. When using heap leaching, dusts from
environment will be the main way. In order to reducing the organic loss, major plants recovery
organic from buffer cells and return them to the circuit, solid particles in the recovered organic,
inevitable, will be introduced. In the smelter acid being added as make-up, somehow these
solid impurities were finding their way from the acid into the organic phase in the strip settler.

Solid particles, which exhibit both hydrophilic and hydrophobic tendencies, are particularly
likely to give problems. High specific gravity particles are not believed to cause much of a
problem, as they tend to settle fairly quickly to the bottom of the settler unit where they
accumulate and removed at intervals. However, the smaller particles, especially the
precipitates as aqueous pH value increases can be a major problem and is often associated
with the presence of soluble silica, or with calcium in the feed leading to precipitation of
gypsum. In the rainy season, considerable amounts of clays and other solids would be
washed into the pregnant leach solution storage ponds. In extreme cases, it would cause
phase inversion, a phenomenon known in the industry as a “gunk run”.

During the electro-winning of copper, the powdery droppers from anode are particularly to
give attention. These droppers are mainly made of PbO2 that have high oxidation. If they are
carried by the strip solution into the strip stage, the extractant will be oxidized, and lose the
capacity of extraction, a phenomenon known in the industry as an “extractant poisoning”. In
extreme cases, the operating will total loss of control.

Effect of air
The effect of air on the crud is shown in the adsorption between solid particle and gas. If a
solid particle carried in the pregnant leach solution is only partly water-wetted, the
hydrophobic portion of its surface will most probably have a tin layer of air adsorbed on it. If
sufficient air is trapped and coalesced within the interfacial layer it can result in the local
average specific gravity falling below that of the upper organic layer. Thus the
air/mineral/organic/water crud complex can rise through the organic layer to the surface,
causing floating crud, or “fish eyes”.

Other sources of air occlusion in composite crud particles are caused by excessive vortex of
mixers, by allowing the mixed phase to exit too vigorously from the mixer unit into the settler
unit, by lack of attention to solution levels in overflow weirs, and by carried air of pipes.

1068
 CRUD CONTROL

As is seen from above that the crud formation is connected tightly with organic phase,
aqueous phase, solid particles, and air. So, the ways to minimize the crud also should focus
on the four aspects.

Organic phase control

Practices from operating SX plants show that using high concentration HCl to wash the
organic phase beforehand can take off its major impurities, such as lower carbon-carbon
chain hydrocarbon, unsaturated hydrocarbons etc. For example again the extractantes of
P204 and P507, if using 6Mol/L HCl to wash them beforehand, not only the phase separation
time is short largely, but also the crud is less.

Aqueous phase control

Removing trees, shrubs, and other vegetation from the immediate areas surrounding storage
ponds can help to eliminate the bacterial growth, and lower the soluble organic acids and
organic substances. If possible, using the pyrometallurgy beforehand to treat those solid
wastes, which contain organic substances such as the used catalyst, can largely eliminate
organosol formation. In addition, using neutralization precipitation, and washing with water to
treat the waste electroplate solution beforehand also can help to eliminate organosol
formation.

Solid particles control

Roofing settler and buffer cells can largely eliminate ingress of dust. Also, ingress of clay,
which carried by rain, can be largely eliminated by retaining wall around the storage ponds. In
addition, adding a little vegetable glue (a kind of flocforming agent and surfactant) in the
pregnant leach solution storage ponds can have great help to eliminate the suspension in
pregnant leach solution. The vegetable glue can ensure complete wetting of the solid particle
surfaces, including the hydrophobic regions, and can adsorb strongly onto the hydrophobic
surfaces to displace any adsorbed air. At the same time, those solid particles, such as SiO2,
Al(OH)3, and Fe(OH)3 etc. will be adsorbed together by the vegetable glue and being a big
particles to settle quickly to the bottom of the storage ponds.

As is mentioned above, during the electro-winning of copper, the droppers from anode are
particularly to give attention. If the anode is made of Pb-Ca-Sn or Pb-Ca-Sn-Sr, the droppers
are usually being a thin piece to settle to the bottom of the electrolytic cell, where they
accumulate and can’t be carried by the strip solution, are no longer capable of causing much
of a problem. If the anode is made of pure lead or Pb-Sb, the droppers are usually being
powdery and can be carried into the strip stage with the electrolytic solution, where they
would react with extractant. Up to now, the “extractant poisoning” had taken place, at least, at
two copper plants in China by lack of attention to anode materials.

Another problem about the copper L-SX-EW plants is the reclaim of organic phase in
electrolytic cells. Major SX plants in China, economic considered, reuse the recovered

1069
organic phase. However, this is very unsuitable. During the copper electro-winning, O2, which
has high oxidation, will be produced on anode. So, most of the extractant in electrolytic cells
has been oxidized and hydrolytic degradation, and has lost the capacity of extraction. If return
them to the circuit, they are no use beside trouble only.

Air control
Extraction tank, as the key equipment of SX, its design is very important for air control,
especially the design of the mixer’s rotational speed and its diameter. When the mixer’s
diameter is determined, the slower the rotational speed, the smaller the suction power; and
the flow of solution can’t get to the project. On the contrary, if with excessive rotational speed,
it not only causes excessive vortex, but also sucks an amount of air from pipe into mixer unit.
It is very disadvantage for the mixed phase separation. In addition, paying attention to
solution levels in overflow weirs, and keeping the mixed phase to flow gently from the mixer
unit into the settler unit is very important also.

The pipes connected with the extraction tank, should be as short as possible, if possible, don’t
use U type bend. It can help to lower the solution resistance and eliminate air carried.

Conditions of SX
Practices from operating SX plants show that with the organic phase as the continuous, or
external phase can compact the crud into the aqueous phase, where they can be resisted by
the hurdles in settler, and removed at intervals. Whereas under aqueous continuous
conditions, the crud tends to become less well compacted, distributed throughout the organic
phase, and is less easily removed from the system.

CRUD DISPOSAL

Typical crud handling methods in SE plants in foreign involve removing crud by suction from
the interface, allowing primary separation by gravity in storage tanks, returning the
supernatant organic to the circuit, and centrifuging the remainder to recover additional organic.
In China, because major SX plants is small, and moreover the centrifuge is expensive,
economic considered, most of them use natural separation by gravity method to disposal the
crud. However, in recently years, some of them have begun to use bentonite to treat the crud.
Studies indicate that if solid particles are hydrophilic, and preferential wetting by the aqueous
phase will tend to accelerate the separation of mixed phase, whereas if solid particles are
preferential wetted by the organic phase will tend to stabilize the mixed phase. At this
condition, the separation of mixed phase will become very difficult. So, using bentonite to treat
the crud is based on its hydrophilic property, expansibility, adherence, thixotropy, and
adsorption property to impel the crud demulsification. The solid particles, such as SiO2,
Al(OH)3, Fe(OH)3, and others colloid particles in crud, are adsorbed by bentonite to precipitate
with bentonite together, and then the organic is reclaim.

Another method to disposal the crud is using steam to raise the temperature of the crud to

1070
 about 45℃ to impel the crud demulsification. Suitable temperature in here must be attention.
Excessive temperature can give harm to the extractant and bring about the hydrolytic
degradation of the extractant.

CONCLUSION

The crud during SX is made of organic, aqueous, solid phases and air. Its formation is
connected tightly with organic phase, aqueous phase, solid particles, and air, and with many
effecting elements. The mechanism of this is not clearly understood. The crud can influence
phase continuity, emulsion stability, aqueous solution and air distribution. In extreme cases,
the operating will total loss of control. Solid particles are the key factor of crud formation, and
suspension in pregnant leach solution is the main way of solid particles introduced. So, to
eliminate the suspension in pregnant leach solution as being as possibly is very important for
the crud control. A well designed of extraction equipments and well-run conditions all can help
to the crud control.

REFERENCES

1. WANG Chengyan, MINING AND METALLURGY (in Chinese), Vol.10, No.1,68-71.

2. Tom Burniston, et al. E & MJ, 1992, 1, 32-35.

1071

View publication stats