G.M. RITCEY
Extractive, Metallurgy Section, Ore Processing Laboratory, CANMET, Energy, Mines and
Resources Canada, Ottawa (Canada)
(Received May 3rd, 1979; accepted May 25th, 1979)
ABSTRACT
Ritcey, G.M., 1980. Crud in solvent extraction processing -- A review of causes and treat-
ment. Hydrometallurgy, 5: 97--107.
An overview is presented on the various aspects affecting solvent loss through crud
formation, encountered in many hydrometallurgical plants that employ solvent extraction
processing. This crud, or stable emulsion mixed with solids, can be caused by properties
of the feed solution, the solvent and its composition, the type of contactor selected and
the method of operation. Cruds differ between plants and therefore treatment schemes
and preventative measures are impossible to define without actual testing and evaluation.
A summary of items for consideration in solving crud problems is given.
INTRODUCTION
formation of stable emulsions and cruds, (7) spillage and (8) sampling. These
solvent losses, and particularly those losses attributed to emulsion and crud
formation, can in part be related to: (1) nature of feed, (2) reagent choice,
(3) equipment selection and (4) m e t h o d of operation, such as the droplet
size, continuous phase, excessive turbulence, etc. Additional details on solvent
losses are noted in a text co-authored by the writer [1].
Nature of feed
The nature of the feed composition can be a major determining factor as
to whether crud will be formed in the subsequent extractive operations.
Solids must be absent from most solvent extraction circuits, and clarification
is usually aimed at achieving about 10 ppm solids. One of the major causes
of crud is the lack of good clarification, with the result that solids get through
to the solvent extraction circuit. The presence of colloids, such as silica [2],
can produce stable emulsions and crud during the mixing of the phases to
achieve mass transfer. Aged feeds can constitute a greater potential crud
problem than fresh leach solutions [3]. In plants where bacteria have been
prevalent, due to favourable environmental conditions, crud has resulted and
expensive circuit modifications were subsequently required. The elimination
of air to such circuits is often necessary to minimize bacteria and fugal growth
[4]. Certain systems may have hydrolysed compounds precipitating out of
solution, and thus a crud results. In certain extraction systems the anionic
strength of the aqueous feed solution may be insufficient, so that stable
emulsions occur when the two phases are mixed. If sufficient agitation is ap-
plied over a period of time, then crud can result. One other important cause
of cruds in solvent extraction plants is the dust from the air, if permitted to
be drawn into the agitation in a mixer-settler circuit. Thus, vessels should be
covered to prevent dust accumulation. Organic matter in the feed, such as
lignin or humic acids, may also promote crud formation.
Nature of solvent
The choice of the extractant and solvent composition is an important
aspect in the successful solvent extraction operation, but the possibility of
crud due to the solvent composition must not be overlooked. Many systems
require a modifier, to improve phase disengagement, to assist in solubilizing
the metal-organic species and to reduce third phase and emulsion tendency.
If a solvent has the tendency to produce emulsions on mixing with the aque-
ous feed solution, which could cause cruds if colloids or suspended solids
are present in the aqueous feed, then the cause may be due to several factors.
Perhaps the system requires the addition of a modifier, a change to a different
modifier, or a higher modifier concentration is demanded. Also, possibly the
diluent type and composition may not be compatible with the system. An
aromatic diluent or an aliphatic diluent with some aromatic content may be
99
more desirable than a completely aliphatic diluent for that particular process.
Frequently, in the solvent makeup, there are unreacted chemicals from the
manufacturing process or, possibly, impurities from the containers used to
transport the solvent components. The problems associated with such im-
purities become particularly evident if their effects are not considered during
bench scale investigations [1]. Their presence in a solvent system can produce
cruds, good or poor phase separation and enhanced or poor loading character-
istics. Such effects could result in abandoning a particular solvent because of
its poor chemical and physical characteristics.
Degradation of the solvent, due to the presence of certain metals in the
feed solution, use of oxidizing agents during stripping, high temperature
processing, biodegradability, etc. may result in decomposition products
forming stable emulsions and cruds. Several uranium plants have reported the
degradation of the isodecanol modifier to isodecanoic acid in the amine-
isodecanol system. Naphthenic acid extraction of copper from leach liquors
also showed degradation to an insoluble crud composed of 23% of the ex-
tractant [4]. In the refining of uranium using tributyl phosphate in contact
with nitric acid, degradation products of mono- and dibutyl phosphates are
produced. Amines are susceptible to degradation in the presence of oxidizing
agents. Carboxylic acids and D2EHPA have been reported to withstand low-
pressure reductions in a process to produce metal powders [ 5]. The LIX
reagents containing LIX 63 (e.g., LIX 64, LIX 64N, LIX 70 and LIX 73) are
stable up to temperatures of 40C, while those not containing LIX 63 {e.g.,
LIX 65N, and LIX 71) can safely withstand higher temperatures.
Equipment selection
There is no universal contacting equipment suitable for all solvent ex-
traction operations. Even within a plant, it may be completely wrong to
select the same type of contactor for all stages of the extraction process. Each
plant, therefore, has to make a choice; the final selection is governed by the
t y p e of aqueous feed and composition, the solvent type and composition,
and how the respective physical characteristics affect the mixing process, flow
patterns and coalescence [6]. Naturally the mass transfer efficiency must also
be considered. With an adequate understanding of all physical--chemical
variables present in the process that will thus have an effect on the extraction
as well as the minimizing of emulsion and crud, then the right equipment for
that plant can be selected [1, 6 ] . That is, the type of equipment and the
method of agitation used to achieve mass transfer is of concern, if emulsion
tendency is to be minimized. Degradation of the solvent may have to be
considered in the equipment choice, due to the chemical system. In one
plant, centrifugal contactors were chosen over mixer-settlers because of lower
solvent degradation [ 7 ].
Method of operating
In the solvent extraction process, one of the major concerns should be the
100
technique by which mass transfer is achieved. That is, the physical design and
operation can contribute n o t only to high solvent losses, such as by entrain-
ment, b u t also to the formation of stable emulsions and cruds. The physical
aspects of the process are concerned with the dispersion of the two phases
on mixing, the t y p e of droplet formation and the rate and completeness of
coalescence. These are important aspects in the choice of suitable contacting
equipment and in the design and operation of the plant. Depending upon the
t y p e of contacting equipment selected and the energy input to the system,
different types of dispersion will be created for a particular system. Differ-
ences will be evidenced b y rates of mass transfer, drop size distribution,
wetting of surfaces, sedimentation and coalescence rates, and entrainment.
Depending upon the physical--chemical properties of the two phases being
dispersed, such as viscosity, surface tension, presence of solids, colloids, etc.,
then with increasing agitation and decrease in drop sizes, a region of instabili-
ty will be reached followed by a stable emulsion. If solids or colloids are also
present, then a crud will result. This is demonstrated in Fig. 1 showing the
operating regions of pulsed columns [ 8]. The information is readily related
to excessive turbulence in mixer-settlers, particularly of the pump--mix
design, and in certain agitated columns where backmixing is severe. Flow
patterns during mixing can influence emulsion tendency, which can be further
influenced b y the continuous phase.Thus, if solids are present in mixer-settler
operations, and excessive turbulence exists, it would be advisable to use a
t y p e of contactor more suited to the physical--chemical characteristics of
the system. Centrifugal contactors would also be an unwise choice if solids
are present or crud formation is likely. Equipment such as the Graesser
Contactor, pulse sieve-plate column, ARD contactor and possibly in-line
mixers could be considered. Pulse columns have been described in the ex-
traction of uranium from ore leach slurries and in the presence of crud [9, 10]
~0//
oJ
Flooding
Flooding ~%~/ Region
(insufficient ~/
pulse) ~/
D E S C R I P T I O N O F SOME C R U D S
The chemical and physical aspects of crud can differ for each separate
operation, and will vary in inorganic composition, organic content, color,
density, etc. The composition of many cruds appear to have in c o m m o n
such constituents as Si, A1, Fe, P, SO4, together with solvent, particles of
gypsum, clay and other fine particles, Often there is a direct relationship
between the feed liquor and the crud compositions, indicating possible
aqueous carry-over as well as inefficient clarification prior to solvent ex-
traction.
In some of the South African plants a tar-like substance is generated and
determined to be aliphatic carboxylic acids. There is evidence of the presence
of isodecanoic acid, resulting from the oxidation of the isodecanol modifier.
More than one plant in North America has experienced some crud problems
when greater than 3% isodecanol is present. Possibly the vortex created on
mixing is a contributing factor to the crud produced b y the break<lown of
the isodecanol. Ferric iron, as an oxidant, is also present. In one early plant,
the animal glue flocculent used for filtration of the leach pulp caused severe
fungal growth in the solvent extraction circuit. The addition of a solvent-
soluble fungicide (a derivative of benzo-thiozole) alleviated the crud due to
the fungus. Use of an aromatic diluent, instead of aliphatic, was also affective
in minimizing the crud problem due to bacteria.
In some scrub and strip circuits, the crud is mainly composed of silica, as
well as inorganic sulphates. Such crud may be treated with dilute sulphuric
102
acid, and recirculating through a pump results in the crud breaking down.
There is evidence in at least a few uranium circuits that the presence of
humic acids may be a possible cause of the crud problem. Lignin appears to
be another cause of crud formation.
Plants extracting uranium from phosphoric acid can also have excessive
crud formation, which is often a waxy material. This appears to be due to
the excessive agitation of the two phases in the presence of humic acids con-
rained in the phosphoric acid.
The presence of hydrolyzable compounds, which precipitate due to ex-
cessive agitation and high shear, can cause severe crud problems. Zirconium
presents a particular problem and is a major constituent of at least one crud
in a uranium processing circuit. Also, as stated earlier, zirconium will tend to
hydrolyze in a H N O 3 - T B P circuit given the right conditions of shear or energy
input (proximity to saturation of the solvent and the type and construction
of contactor, particularly in the coalescing zone). The use of Teflon plates
in columns for such an extraction process definitely increased coalescence and
decreased the tendency for hydrolysis and crud formation. [15].
Because crud originating in one plant is usually different from that ob-
tained in another, or in another circuit in the same plant, the treatment
scheme adapted for solvent recovery will, of necessity, be different. That is,
there is no universal treatment scheme that would be amenable to all cruds
because of the difference in the causes of crud formation. Some cruds are
broken down by settling and skimming [16], others by filtering [17], some
by acidification [16] or neutralization to an alkaline condition [9, 16], some
are broken by extreme agitation such as cycling through a centrifugal pump
[ 16], etc. After such treatment procedures, if successful, the solvent that is
released can be readily decanted for recovery. In some plants, a separate
solvent treatment stage is necessary, with a wash such as Na2COa being used
[16].
As an example of how different plant cruds react to treatment, CANMET
treated three by acid and alkali adjustment of a slurry-water mixture. None
of the three, one of which was from a stripping circuit, responded to alkali
treatment. In fact the stable emulsion and crud problem became greater.
With the first extraction crud containing a large a m o u n t of slimes from the
CCD circuit, 50% of the crud was dissolved at pH 1, and about 70% at pH
1. The second extraction crud, containing no slime solids from clarifica-
tion, when mixed with water, 50% of the organic was released. Acidification
to pH 0 released no further organic, and in strong H2SO4, 95% of the organic
was released but as a fine emulsion. A sample of crud from a stripping circuit
was determined to be composed of 60% organic, 30% solids (as a precipitate)
and 10% aqueous. Acidification to pH 1.2 dissolved 20%, while at pH 0.5,
85% of the solvent was released. Further acidification resulted in reforming
103
the crud. However, if the crud was slurried in the strip raffinate from that
circuit (initial pH 4.17), instead of water, only 50% of the crud dissolved at
pH 0.5, and only in strong acid was 90% of the solvent released.
Thus, with cruds differing in their chemical and physical-chemical history
of formation, treatment to break down the crud and recover the solvent is
only accomplished by the testing and evaluation of many possibilities. At
this time, only "trial and error" tests can be suggested to determine the best
treatment techniques.
CRUDPREVENTION
TABLE 1
Occasionally, the water used for solution makeup to scrub or strip cir-
cuits, because of impurities, can cause subsequent emulsions and cruds. At
one uranium plant in South Africa, deionized water was used to l~epare the
ammoniacal strip solution, rather than normal plant water which tended to
cause crud formation [ 2 2 ] .
Equipment selection is important, as is also the proper operation of the
contacting devices. It is generally recognized that high shear is the primary
cause of the droplet haze, and subsequent emulsion and crud formation.
TABLE 2
Possible items of information required for consideration in solving plant crud problems
(1) Ore
-- mineralogy and analysis
(2) Leach
-- oxidant and quantity added Possible effects on degradation as well as
-- any other chemicals added emulsion-production or crud-stabilization.
(3) Liquid--solids separation
-- type of separation (e.g., CCD)
-- type and quantity of surfactant added
- use of sand filters or other types of clarifiers (e.g., anthracite and frequency of
-
regeneration.
(4) Feed solution to solvent extraction
- suspended solids
-
- dissolved solids
-
-presence of lignin
-
-diluent-
- extractant
-
- vortex in mixer
-
-continuous phase
-
-presence of precipitates
-
(b) stripping
-mixer and settler operations as in " e x t r a c t i o n " above
-
- continuous phase
-
- stripping agent
-
- presence of precipitates
-
106
CONCLUSIONS
REFERENCES
18 Rossiter, G. Anamax Twin Buttes Oxide Plant Operating Experience -- First Year.
Presented at the Arizona Section, AIME, Hydrometallurgical Division, spring, 1976.
19 Abramo, J.A. and Lowings, S.W.H. Uranium processing at Exxon's Highland Operati-
on. Presented at Symposium on Solvent Ion Exchange, AIChE, Tucson, Arizona, May,
1973.
20 Hurst, F.J. Recovery of uranium from wet-process phosphoric acid by solvent ex-
traction. Presented at Annual AIME meeting, Las Vegas, February, 1976.
21 Reference 15, Davy-Power Gas, p. 59.
22 Meyburgh, R.G.J. South African Inst. Min. and Metall., Oct., 1970, pp. 54--66, and
April 1971, pp. 190--197.
23 Ryle, B.G. USAEC Report TID 5295, 1956.