Collectors Strength - Xanthate Family - Recovery Power Page 1 of 9

Collectors Strength – Xanthate Family –

Recovery Power
A little about collector strength and Xanthates: Some call it selectivity, I call it “how
much do you put on”. Even the most selective collector can be rendered un­selective it
you add enough.

In reverse order of strength (strongest to weakest):

1. PAX
2. SIBX
3. SIPX
4. SEX
5. Methyl Xanthate (uncommon)

Collector strength chart

More about the collecting power of xanthate and the Effect of pH on Pulp Potential
and Sulphide Mineral Flotation at http://www.scribd.com/doc/174126698/Effect­of­
pH­on­Flotation or http://journals.tubitak.gov.tr/engineering/issues/muh­02­26­
4/muh­26­4­2­0103­22.pdf

The decision about which xanthate to use is typically based on dosage and cost. We
tend to observed similar metallurgical performance using any of the xanthates, you

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just need a lower dosage as you go up in strength. What will change performance is
switching the family of reagent. i.e. dithiophosphinates (3418A) or carbimates (5100)
etc. These are more selective collectors and will exhibit different performance
regardless of dosage in our experience.

TYPES OF XANTHATES

Most zinc circuits use SIPX. In the lab, we need the weaker xanthate as PAX is too
strong and the dosages have to be so low that we have trouble accurately adding it.

There may be some minor differences in performance with different xanthates, but
they’re pretty minimal in our experience once you take out the effect of dosage.

There are two surface chemistry interactions taking place between particle, xanthate
molecule and the air bubble.

1. Particle surface – xanthate charged end

2. Xanthate molecule polar end – bubble surface

First interaction gets stronger as the mineral charge on the particle surface gets
stronger (if metallic mineral is more exposed – liberation – or if mineral surface is
influenced by properties of the pulp such as pH). OR/ AND if the xanthate ionic/

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charged end is more charged – e.g. stabilized by K+ vs. Na+ or when the structure of
the polar end is shorter and more branched, then hydrocarbon chains will create
stronger charge on the ionic end.
E.g. here is the theoretical order of affinity of xanthate molecule to the same mineral
surface from strongest to weakest: amyl > isobutyl > ethyl > propyl > butyl xanthate.

In case of the second interaction between xanthate and the air bubble surface, there
are two main factors at play – the stability or rigidity of the bubble surface (depends
on the frother used and its amounts). And the length of the hydrocarbon chain of the
xanthate: the longer or the more branched is the chain, better xanthate molecule will
stick to the air bubble surface. Order from strongest to weakest interaction between
xanthate molecule and air bubble is theoretically: butyl > propyl > isobutyl > ethyl >
amyl.

The longer chain xanthates can present good recoveries with well liberated particles,
because they will be able to attach pretty much anything to the air bubble. Selectivity
of long chain xanthates is usually poorer than with the shorter chain xanthates and
thus their consumption is relatively higher (up to 20­30% compared to one degree
shorter hydrocarbons). In case particles size is increased (liberation decreased), and
there are not enough of metallic species in the ore, recoveries with longer chain xan­
thates will be most vulnerable. For rougher recovery of particles with high content of
pyrite, pyrrhotite and other abundant species longer chain xanthates indeed do show
better recoveries.

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The Evaluation of Collectors in Sulfide Ore Flotation

The influence of pH on collector efficiency as related to recovery is veil known. How­

ever, the effect of pH on K can be equally important with increasing pH causing an
increase in K even in pH ranges where R is dropping in value. Figure V demonstrates
this type of pH interaction on two widely different copper sulfide ores using constant
dosages of DF­1012 and Z­200. The R curves for both copper and gangue have rather
pronounced maxima with the K curves increasingly monotonically with pH. It is inter­
esting to note that with different ore types the differences in K can be significantly
greater in influencing over­all plant performance than the differences corresponding
to the maximum R values achievable by proper pH control. This is consistent with
observed history of testing flotation reagents such as the Xanthates at many sulfide
flotation plants. Lab evaluations of these historical trials based on classical one time
point recovery tests (e.g. R alone) has simply not been enough to provide accurate lab
predictions of plant performance.

Figure VI summarizes a typical lab study of evaluating several collectors (Z­6 and Z­
200) on a given ore holding the frother (DF­1012) and pH constant. The effect of con­
centration between the two collectors is obvious with the maximum ultimate copper
recovery, R, achievable being about the same with either reagent. However, the rate
effect of the two reagents is significantly different which was shown to be important
in later plant scale testing as the plant was in a region of rate control. The use of Z­
200 over Z­6 gave increased plant recoveries of 2­3% with constant DF­1012 dosage.
The critical lab K was found to be 3.5. The pattern of R and K changes for both copper
and gangue are similar although use of high dosages of Z­6 lowered the grade com­
pared to Z­200 as indicated by the R trends of the gangue as shown in Figure VI. This
is one of several examples indicating the importance of optimizing flotation not only
for R but also K. In this example, without knowledge of the rate characteristics associ­
ated with the two chemical systems, the prediction of plant performance from lab
data would be strictly trial and error.

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Figure VII shows a similar test to those just discussed but on a different ore. This fig­
ure demonstrates that with some ores adding too much of some reagents can be
harmful on either R or K (e.g. the effect of 0.06 lb/ton of Z­200 at a pH of 9). The col­
lector Z­200 is particularly sensitive to pH with many ores and often requires a pH of
9 or lower to be economic. Also in this figure, at a given pH and frother concentration
the R and X trends with different reagents can be exactly the opposite. In this data
set, increasing collector concentration of Z­200 lowers R and increases K while
increasing Z­6 increases R and lowers K. This reverse pattern with different reagents
was demonstrated in the plant.

Figure VIII gives an example of a detailed lab analysis on a copper sulfide ore utilizing
cresylic acid, Z­200, and ammonium sulfide. This example is very typical of why a
good lab test can go bad in the plant trial. A simple factorial experiment on reagent
concentration was run with the concentration of each reagent being normalized so
that 1.0 part cresylic acid (CA), 1.0 part Z­200 collector, and 1.0 part of (NH4)2S (AS)
represents the optimal lab reagent combination. Inspection of Figure VIII shows why
the 1.0, 1.0, 1.0 combination was chosen.

The increase in the ultimate equilibrium recovery, R, with reagent addition is obvious
with the greatest increase being, in all cases, from a concentration of 0.75 to 1.0. One
goal of the plant trial was to achieve the 2% increase in R using increased Z­200 dos­
age from 1.0 to 1.5. As is often the case, however, this increase in recovery due to
increased reagent dosage is accompanied by a decrease in the K or rate of removal of
mass from the cell. With this ore, the rate decrease generally becomes more signifi­
cant as reagent addition increases. This was exactly what was observed in the plant as
plant recovery fell when the Z­200 dosage was increased from 1.0 to 1.5 – contrary to
what the classical lab tests indicated. Thus, having the information on the K’s clearly
pointed to the potential for trouble in the plant with increased collector dosage.
Therefore, the selection of optimal reagent combinations should be based on maximiz­
ing the ultimate recovery R while minimizing the loss in the rate of mass removal
from the cell (it was found that maintaining a lab K value of 1.5 was critical in the
above test). The importance of maintaining a sufficiently large value of K or R
depends on the plant economics, the mineral value, the flotation circuit configuration,
and the over­all cell capacity that exists in the plant. For example, if the rate of mass
removal from the cell is not limiting the observed recovery in the plant, then a loss in
X is not as important as maintaining or increasing R.

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The Evaluation of Xanthate Collectors

The examples presented to this point have emphasized the differences in R and K that
various reagent changes can cause. However, with some sulfide ores a rather amazing
insensitivity to changing collector type exists (especially with Xanthates). Figure IX
shows such a study on a copper ore run with a wide range of Xanthates utilizing MIBC
frother and a constant pH of 10.5. The implications of the data presented in this figure
as well as those of data collected from other tests with Xanthates on different ores are
important and somewhat unexpected. It is well known that the chemical structure dif­
ferences exhibited by the various Xanthates do exhibit differences in the equilibrium
recovery of a given ore that can be achieved with constant dosages of active material.
However, it has been found using the R­K analyses of this article that when it is possi­
ble to adjust the concentrations of different Xanthates on a given ore to give approxi­
mately the same target equilibrium recovery (hence the same R), the rate character
(the K value) associated with this target R is nearly always the same regardless of the
Xanthate used.

This is quite important for several reasons: first, the obvious chemical implication
that the structural differences between Xanthates do not significantly affect K (unlike,
for example, Z­ 200, a carbamate, versus Z­6, a Xanthate, in Figures VI and VII) and
second, the obvious, engineering implication that sometimes none of the Xanthates
are effective in improving a flotation that is under rate control as the Xanthates are
very often relatively poor in rate performance and indistinguishable from one another
with regard to rate. If one increases the target value of R desired by adjusting any of
the Xanthate concentrations, the associated K will automatically drop in value (e.g.
note Z­6 in Figure IX). Thus, it is important, when using any of the Xanthates on sul­
fide ores with a plant operation that potentially could be in rate control, to be aware
of the possible need to improve the rate character of the flotation by some means
other than increased amounts of Xanthate. In a few cases, this can be done mechani­
cally but most often is best done by using a frother capable of high rates of mass
removal (e.g. the glycol ethers which will be shown in the next section) or by blending
appropriate collectors (e.g. a Xanthate and Z­ 200 which is sometimes done in prac­
tice). If the plant can be shown to definitely not be in rate control, the implication is
to use the collector (e.g. Xanthate) which gives the target R and grade with the lowest
over­all cost.

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