Cytec Solutions V17 2013 PDF

DELIVERING TECHNOLOGY BEYOND
OUR CUSTOMERS IMAGINATION
IN PROCESS SEPARATION
Volume 17
CYTEC SOLUTIONS
for Solvent Extraction, Mineral Processing
and Alumina Processing
Letter from the Vice President

To our Valued Customers,
Advancements in our new product development effort as well as mergers and acquisitions over
the past several years has transformed Cytecs business portfolio. These changes have created a
leading high growth specialty chemical business.
What does this mean for our mining customers? We continue to collaborate with you to address
challenges and meet them with our technology and products. With economic challenges,
changes in ore grades, and the demand for natural resources, Cytec is committed to finding
sustainable, quality solutions to help you keep up with these challenges.
To help meet the growing demand from our customers, Cytec has made significant investments
in our manufacturing assets to improve reliability and increase capacity. One of the most significant investments includes a
several hundred million dollar investment to expand our site in Niagara Falls, Canada. This site produces both mining products
and phosphine derivates. We are also investing in assets to increase R&D capabilities at other global sites.
We at Cytec want to help bring about solutions to your current and future operations success and we have a well balanced
portfolio of products and expertise that are unmatched. The major benefits of our products include increasing revenue
through improved production, reducing operating costs, and reducing capital expenditure to build new plants. We have a
significant focus on technology development and you can rely on Cytec to bring you the latest technology with our steady
stream of new products that ensures you always have the best option by partnering with Cytec.
In this edition, we highlight some of these new product advances. These include a scale controlling solution for phosphoric
acid product plants with our innovative PHOSFLOW technology, an alternative to traditional hazardous modifiers with our
AERO 7260 HFP, and nitration residence with our ACORGA NR series reagents. We are also pleased to share that our MAX HT
Bayer sodalite scale inhibitor was awarded the 2012 EPA Presidential Green Chemistry Challenge Award.
I have been with Cytec for over 18 years and in many roles that have helped prepare me for my new role to lead the In
Process Separation business. Now, I am excited to lead a business that is focused on our valued customers and partners in
the mining industry. I am dedicated along with my team to provide you with the service and solutions you are looking for
now and in the future.
Thank you for your interest and business,
Michael Radossich
Vice President, In Process Separation
Solvent Extraction, Mineral Processing and Alumina Processing
Table of Contents:
Solvent Extractions
Crud Processing Improvements Using ACORGA CB 1000
Crud Busting Reagent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX:
The State of the Art. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Mineral Processing
AERO7260 HFP Depressant: Novel, Safe and Sustainable Alternative to Traditional
Hazardous Modifiers NaSH, Nokes, Na2S, and Cyanide. . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Rejection of Pyrite: Challenges and Sustainable Chemical Solutions . . . . . . . . . . . . . . . . 23
Alumina Processing
MAX HT Bayer Sodalite Scale Inhibitor:
A Green Solution to Energy Consumption. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Performance Evaluation of CYFLOC ULTRA HX-5300
A New HXPAM Red Mud Flocculant Applied in CBA
(Companhia Brasileira de Aluminio). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Industrial Minerals
Scale Controlling Chemical Additives for Phosphoric Acid Production Plants. . . . . . . . . 42
03
Crud Processing Improvements Using Acorga

Cb 1000 Crud Busting Reagent
Tyler McCallum, Troy Bednarski, and Matthew Soderstrom
Cytec has developed a unique crud treatment process utilizing both chemical and mechanical
means to enhance the solid/liquid separation, improve recovered organic quality, and reduce
operational costs.
Crud (a complex solid stabilized emulsion of aqueous and
organic) is a common concern in most solvent extraction
processes[1,3]. If crud is allowed to build up in the circuit,
aqueous and organic velocities within the settlers will
increase, resulting in higher entrainments and operational
costs. Crud movement between stages can cause
continuities to flip and may require a significant reduction in
plant flows or a plant shutdown to stabilize the operation[2].
To prevent these events, interfacial pumping is typically
carried out to remove crud from the circuit and process it
for organic recovery[4]. Crud processing can be very time
consuming, and the recovered organic quality is often lower
than desired with current processing methods.
Cytec has developed a unique crud treatment process
utilizing both chemical and mechanical means to enhance
the solid/liquid separation, improve recovered organic
quality, and reduce operational costs. The use of ACORGA
CB 1000 crud busting reagent allows a rapid separation
of solids from the organic phase. ACORGA CB 1000 is an
SX qualified chemical additive, which aids in the recovery
of organic from crud. The process involves breaking the
stabilized crud emulsion, freeing the associated organic,
and settling the solids very rapidly. This process allows
operations to return clean organic back to the plant more
efficiently and may enable operations to process more crud.
In addition to the improvement in processing time, the crud
buster process enables more efficient clay treatment and
therefore can improve the quality of organic that is returned
to the SX circuit.
04
The crud buster process involves mixing the crud with

organic (under organic continuity) then breaking the crud
emulsion through the addition of hydrophilic solids (clay).
Once the emulsion has been temporarily broken, the
addition of ACORGA CB 1000 will bind to the solids causing
them to settle and preventing the emulsion from re-forming.
Following the clay and ACORGA CB 1000 addition, the
agitator may be stopped, allowing the phases to separate
and quickly recover the majority of the organic freed from
the crud emulsion. This organic can then be more efficiently
clay treated and returned to the process quickly without the
typical issues associated with filtration of an emulsion.
The solids remaining after the primary separation (containing
some residual organic and aqueous, which was freed from
the crud emulsion) can then be processed using typical
methods for a secondary solid/liquid separation and further
organic recovery. The volume of the secondary separation
is substantially less; therefore limited time is required for
processing. Any organic recovered from the secondary
separation should also be subjected to clay treatment.
The laboratory test shown in Figure 2 illustrates the effect of
ACORGA CB 1000 in breaking the crud emulsion and freeing
the associated organic. For this test, crud was dispersed in
an organic continuous mix of diluent. The picture on the
left is the organic continuous mix before clay addition; the
middle picture is after addition of clay and ACORGA CB
1000; and the picture on the right is the immediate result
after agitation was ended. As shown, a very clear organic
phase is evident using the process and recovery of this
organic can be quickly achieved.
Crud Processing Improvements Using ACORGA CB 1000 Crud Busting Reagent
FIGURE 2:
ACORGA CB 1000 Mixing
and Settling
Crud Buster Benefits

Crud processing using ACORGA CB 1000 can offer
significant time savings due to the rapid chemical separation
of organic from crud without requiring the initial step of
using a press or centrifuge to break the crud emulsion. The
organic that is quickly recovered is a very clean stream
largely free of suspended solids. This clean organic stream

can then be clay treated more efficiently producing a high
quality recovered organic. The small amount of ACORGA
CB 1000 remaining in the organic after the solid/liquid
separation is removed by the clay during clay treatment.
Time Savings
Eliminating the need of a press or centrifuge for the initial
rupturing of the crud emulsion to free organic allows
significant time savings. The crud emulsion can blind filter
cloths when using a plate and frame filter press (requiring
additional time to drop and recharge the press). Centrifuges

are limited by the flow rate and crud volume to be processed.
The crud buster process allows a rapid solid/liquid separation
without the additional steps/equipment.
Total Suspended Solids (TSS)

Current crud treatment methods (regardless if using a
centrifuge or filter press) are often inefficient and frequently
allow suspended solids to be left in the recovered organic.
The return of organic with these now finely dispersed solids
can be the cause of additional operational difficulties.
The amount of solids remaining in the organic following
mechanical processing can vary greatly and is dependent on
the equipment being utilized. High TSS in recovered organic

is common.
Figure 3 shows solids removed from the organic during
each step of processing. The top row of pictures gives an
indication of the TSS present in the organic phase after each
step using a traditional filter press process without ACORGA
CB 1000. The bottom row of pictures represents the crud
buster process after each step.
05
FIGURE 3:
TSS of Standard Filter Press and
CRUD BUSTER Process
Visually it is easy to see that the final organic product

returned to the circuit post clay treatment was much cleaner
using the crud buster process than the process using only
mechanical separation.
Interfacial Tension (IFT)

Mechanical rupturing of crud often results in surface active
species associated with crud being transferred to the organic,
lowering the IFT and organic quality. This is in addition to
the problem of solids often being redistributed.
the circuit organic. This reduction in organic IFT is true for

operations using plate and frame filter presses or centrifuges.
The figure also shows that both the plant organic and crud
processed organic have the potential to be of higher quality
with efficient clay treatment. Without clay treatment of the
recovered organic, the associated surface active species from
the crud are often returned to the circuit.
Figure 4 shows the interfacial tension of various organic

samples from operating plants. Traditional mechanical
rupturing processes return organic with a lower IFT than
40
Plant Organic
Interfacial Tension (dynes/cm)
Recovered Organic from Crud
30
34.6
34.4
35
29.1
29.3
27
35.3
26.8
25
22.3
FIGURE 4:
IFT of Circuit Organic, Recovered
Organic, and Clay Treated Organic
20
Sample 1
06
Clay Treated Organic
30
29.2
27.6
34.9
Sample 2
Sample 3
Sample 4

Operations that practice clay treatment of recovered organic
typically only utilize 0.1 0.3 wt% clay due to plugging
concerns. This is rarely sufficient to remove all surfactants
from the organic, and the clay is often deactivated by
aqueous remaining with the organic. As shown in Figure 5,

an excess of 2% clay is required to restore the organic IFT
(of this specific plant organic) to its maximum value.
39
Interfacial Tension Time (dynes/cm)
Recovery Organic Clay Treatment Curve

37
35
33
31
29
FIGURE 5:
27
0
Clay Treatment vs.

Interfacial Tension
Clay Concentration (wt%)
The use of ACORGA CB 1000 efficiently separates the

organic from the solids/aqueous emulsion, enabling the
organic to be treated with the appropriate clay dosage

without deactivation of the clay.
Benefits of Higher Organic Quality

Pilot plant testing was completed to compare organic
recovered by crud buster to organic recovered by
typical mechanical crud processing means. This work was

completed using a 2E + 1S configuration at 6 lpm feed flow
and results are shown in Table 1.
Table 1. Pilot Plant Comparison

CB Processed Organic
Typical Processed Organic
33.5.9
29.2
Extract PDT Org Cont. (seconds)
51
229
Extract PDT Aq Cont. (seconds)
63
66
Strip PDT Org Cont. (seconds)
50
191
Dispersion Band Org Cont. (% of org depth)
0%
61.2%
Organic Entertainment
34% decrease
Aqueous Entertainment
18% decrease
1032
645
IFT (dynes/cm)
Cu:Fe Transfer Ration
07

The crud buster process (enabling efficient clay treatment)
produced an organic with a higher IFT and better overall
organic quality. This resulted in a significant improvement in
phase disengagement times, dispersion band depth, organic
and aqueous entrainments, and Cu:Fe selectivity.
Note: Lower Fe transfer (along with reduced aqueous

entrainment) would be expected to result in a significant
reduction in operating costs through electrolyte bleed
reduction.
Conclusion
Current crud treatment and organic recovery practices
are often not efficient in producing a high quality organic
product. Use of mechanical equipment to break the crud
emulsion is effective, but often leaves suspended solids
and surfactants in the organic. It is critical to clay treat
recovered organic (although not always practiced). When
clay treatment is performed, the clay concentration used
is often lower than optimal because of concerns related to
plugging of the filtration equipment. The resulting organic
returned to the circuit leads to redistribution of solids,
poor phase disengagement, and higher entrainments.
Metallurgical performance can also be negatively impacted.
The crud buster process enables efficient clay treatment

and results in a high quality recovered organic in a timely
manner. Crud buster is expected to produce an organic with
a lower TSS and a higher IFT than current processes. These
improvements in organic quality have been shown to result
in improved SX performance (break times, entrainments,
kinetics, stage efficiency, Cu/Fe selectivity) and are expected
to bring operational cost savings.
References
1. R.F. Dalton, C.J. Maes, and K.J. Severs, Aspects of Crud Formation
in Solvent Extraction Systems, Arizona Conference of the AIME,
Tucson, AZ., 1983.
2. Cytec Industries Inc., Crud: How It Forms and Techniques for
Controlling It, Marketing Publication, 2006.
3. T. Burniston, J.N. Greenshields, and P.E. Tetlow, Crud control in

Copper SX Plants, E&MJ, 1992, (Jan) pp. 32-35.
4. M. Cox, Liquid-Liquid Extraction and Liquid Membranes in the
Perspective of the Twenty-First Century, Solvent Extraction and
Liquid Membranes, 2008, pp. 1-19.
For more information on this subject and other Cytec technologies, please visit our website at www.cytec.com.
TRADEMARK NOTICE: The indicates a Registered Trademark in the United States and the indicates a trademark in the United States. The mark
may also be registered, subject of an application for registration, or a trademark in other countries.
08
Use of ACORGA NR Reagents in the Presence of

Nitrate Ions in SX: The State of the Art
Rodrigo Zambra*, Alejandro Quilodran, Gonzalo Rivera, and Osvaldo Castro
Given the relevance of the nitration threat in Chile due to high nitrate containing ores in some
plants and the lack of an available practical solution for the industry, Cytec developed a superior
line of modified aldoxime extractants.
This work presents the results of studies of different solvent
extraction operations in the north of Chile where nitration
concerns are the greatest. While all copper solvent extraction
operations have some nitrates present, this paper is focused
on the four copper SX plants that have the potential for
appreciable levels of nitrate ions in their leach solutions.
Nitration is a phenomenon that initially attracted the
interest of the copper mining industry in the late 90s due
to the experience at Lomas Bayas where they experienced
significant nitration of the organic inventory. Since then
the industry developed the position that ketoxime-based
extractants were the best solution for operations with
nitration risk.
Nitrated oximes (ketoximes and aldoximes) form stable
Cu complexes that prevent the stripping of copper. Once
the oxime is nitrated, the oxime no longer works as an
extractant because that portion of the organic no longer
transfers copper.
Nitration is certainly a function of the nitrate concentration

in aqueous solutions, but it is also a function of the
acidity, temperature, redox potential, interfacial tension
and the reactivity of the aqueous and organic phases.
Nitration of oxime compounds leads not only to reduced
copper transference capacity, but also increased phase
disengagement times, reduced interfacial tension, increased
entrainment and hydrolytic degradation.
Given the relevance of the nitration threat in Chile due to
high nitrate containing ores in some plants and the lack
of an available practical solution for the industry, Cytec
developed a superior line of modified aldoxime extractants.
These products, known commercially as the ACORGA NR
series, provide nitration protection without reducing copper
production capacity.
Examples of the relative performance of ACORGA NR
series extractants and ketoxime-based extractants are
discussed next.
The nitration mechanism is shown below:

NO3- + H2SO4 HNO3 + HSO4- (1)
HNO3 + H2SO4 NO2+ + H2O + HSO4- (2)
OH
OH
R1 + NO2+
R2
OH
O2N
H
OH
R1
R2
OH
O2N
OH
R1
R2
R1 H or CH3 (aldoxime or ketoxime)

R2 C9H19 or C12H25 (nonylaldoxime or dodecylaldoxime)
09
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
Case 1, Plant A
The conditions at Plant A prior to substitution of the ketoxime extractant LIX 84I with the modified aldoxime ACORGA
NR10 are listed below:
Table 1: Characterization of the Solutions at Plant A
Element
Units
PLS
g/L
4.60
36
pH/H2SO4
-/g/L
1.60
180
NO3-
ppm
1,890
63
ORP
mV
470
500
Cu
Spent
Simulations
In order to compare the extraction efficiency of the reagents
LIX 84I and ACORGA NR10, the extraction and stripping
isotherms were created in the laboratory using real plant
solutions. McCabe Thiele analysis was then used to calculate

the expected recovery for the configuration. The results are
presented in Table 2.
Table 2: Results of Simulations with Plant Solutions (23% extractant).
Extractant
Efficiency [%] Train A
Efficiency [%] Train B
Lix 84I
89.23
77.51
NR10
95.21
87.33
The better extraction kinetics under high copper tenor and

low pH conditions of ACORGA NR10 results in a 6% higher
copper recovery than LIX 84I extractant, which was used in

the plant.
Accelerated Nitration Tests

Several tests were then carried out in order to evaluate the
behavior of the extractant in a possible nitration scenario.
The properties of the evaluated PLS feed (which had
adjusted values of pH and nitrate to make the solution more
aggressive) are shown in Table 3.
This PLS was mixed continuously in a 1:1 ratio at 40C
with three separate reagents prepared at 25 vol %: LIX
84I (ketoxime), LIX 860 (pure aldoxime), ACORGA NR10
(modified aldoxime) and Plant Organic (a blend of the
regents appointed previously).
10
Table 3: PLS Conditions for the Accelerated Nitration Tests.

Value
Units
Cu
2.50
g/L
NO3-
62.0
g/L
FeT
4.70
g/L
Cl-
10.30
g/L
P. Redox
752
mV
40
pH
1.10
The results presented in Figure 1 show that there was a
strongest resistance to nitration when using the ACORGA
NR10 reagent (approx. 50%) compared to LIX 84I, LIX 860

and Plant Organic.
2.0
Ketoxime
1.8
Unmodified Aldoxime
1.6
Plant Organic
Nitration (%)
1.4
NR10
1.2
1.0
0.8
0.6
0.4
0.2
28-11-2012
21-11-2012
14-11-2012
07-11-2012
31-10-2012
24-10-2012
17-10-2012
10-10-2012
03-10-2012
26-09-2012
19-09-2012
12-09-2012
0.50
Residual Copper, gpl Cu
0.45
0.40
0.35
0.30
0.25
0.20
0.15
FIGURE 1:
0.10
Results of the accelerated

nitration tests based on
residual copper and nitroxime
0.05
28-11-2012
21-11-2012
14-11-2012
07-11-2012
31-10-2012
24-10-2012
17-10-2012
10-10-2012
03-10-2012
26-09-2012
19-09-2012
12-09-2012
11
Case 2, Plant B
The second case shows the laboratory and piloting test to
compare the behavior of the ACORGA NR 20 extractant
and the reagent currently in use at the plant LIX 84I.
This plant has a complex SX configuration, with two
different PLS feeds: the heap leaching solution at 1.8 gpl
Cu and pH 2.0 and the ROM leaching solution at 1.6 gpl

Cu and pH 1.6. The stage efficiency was measured to
compare the performance of LIX 84I and ACORGA NR 20,
with both feeds.
100
90
90
80
85.9
80.1
79.5
70
60
50
FIGURE 2:
40
Acorga NR 20
HEAP
LIX 84 IC
HEAP
Acorga NR 20
ROM
LIX 84 IC
ROM
Stage efficiencies for PLS

HEAP and ROM
As shown in the graph above higher stage efficiencies were achieved with the ACORGA NR reagent.
Accelerated Nitration Tests

The following products were tested, LIX 84I, ACORGA
NR20 and a traditional aldoxime that is not nitration
resistant, unprotected reagent under aggressive nitrating
conditions. The evaluation took place over a period of 150
days. The PLS used in this study was modified to be highly
nitrating. Impurities were added to a real PLS (chloride,
iron, and nitrate) with a pH of 1.0, as shown in Table 5. The
extractants were mixed in a 1:1 ratio, and the solution was
submerged in a thermostatic bath at a temperature of 40C
with constant agitation.
12
Table 4: Characterization of the PLS

COMPOSITION
MODIFIED PLS
Acidity
g/L
5.7
NO3-
g/L
58.8
FeT
g/L
3.08
Cl-
g/L
10.38
It can be clearly seen in Figure 2 that both the ACORGA

NR20 and LIX 84I extractants had an appropriate resistance
to nitration but the unprotected extractant had significant
nitration before 80 days of mixing.
60
Acorga NR 20
Unprotected Reagent
50
Nitration (%)
LIX 84IC
40
30
20
FIGURE 3:
Results of accelerated
nitration tests based on
residual copper and nitroxime
10
0
0
Sample
Pilot Plant Evaluation

The ACORGA NR20 extractant was then evaluated in a 100
cm3/min pilot plant utilizing two PLS solutions (Heap and
ROM). The initial conditions for the pilot study are presented
in Table 5. The configuration of the pilot plant corresponded
to that of an industrial plant, and the extractant was added
at 26.30 % for LIX 84I and 24.94% for ACORGA NR 20. The
results of the tests are shown in Table 6.
that has favourable kinetics for mass transfer as compared

to those for extractants based on ketoxime chemistry. As
a result, a better mixing efficiency near the equilibrium
point is achieved. In addition, the ACORGA extractant
tolerates a wider pH range, maintaining good chemical and
metallurgical performance from pH 1.0 to 2.5.
Table 6: Extraction Efficiency, Pilot Plant Results
Table 5: Pilot Plant Test Initial Conditions
HEAP
ROM
Spent
g/L
1.97
1.63
42
- / g/L
2.08
1.81
175
O/A E
0.95
0.95
O/A S
1.24
1.24
Cu PLS
pH / H2SO4
The extraction efficiency results clearly show a better

metallurgical performance for the ACORGA NR20
extractant, resulting in a 5.8% increase in copper recovery
for the Heap and 8.8% increase for the ROM. Both
extraction efficiencies are enhanced using the ACORGA
NR20 extractant, which is based on a modified aldoxime
Extractant
HEAP Extraction
Efficiency
(%)
ROM Extraction
Efficiency
(%)
Ketoxime
89.44
67.24
ACORGA NR 20
95.28
76.05
In addition, the results for the selectivity of the ACORGA

NR20 extractant conclusively confirm that the new reagent
improves the plant selectivity by approximately 50%. The
organic Fe loading for both the Heap and the ROM PLS
streams are shown in Figure 4.
13
30
Heap-Ketoxime
Heap-NR20
ROM-Ketoxime
ROM-NR20
25
Fe+3, ppm
20
15
10
5
0
0
10
20
30
40
50
60
70
80
90
100
Loaded Organic, %
30
25
Fe+3, ppm
20
15
10
FIGURE 4:
Organic Fe Co-extraction
as a function of copper loading
for Heap and ROM solutions
5
0
0
10
20
30
40
50
60
70
80
90
100
Loaded Organic, %
CONCLUSION
Based on the results of the studies in the laboratory, and in
the pilot plant, the following conclusions can be made:
There is a great increase in the extraction efficiency and
transfer of copper when using the ACORGA NR extractant,
mainly because it provides better performance at low pH
and enhanced extraction kinetics, which help improve the
stage efficiency.
In all of the cases studied, the ACORGA NR reagent

performed better in terms of copper recovery by at least
two percentage points with a maximum difference of 8
percentage points.
Cu/Fe selectivity is also increased significantly (50%) by
use of ACORGA NR extractants rather than ketoxime.
The ACORGA NR extractant offers protection for the plant
organic inventory under nitration conditions, ensuring a
similar or better response than the LIX 84I extractant.
14
AERO7260 HFP Depressant : Novel, Safe and

Sustainable Alternative to Traditional Hazardous
Modifiers NaSH, Nokes, Na2S, and Cyanide
Mukund Vasudevan and D.R. Nagaraj
Cytec has developed AERO7260 HFP Depressant, a highly efficient and versatile sulfide mineral
depressant with wide applicability.
Introduction
NaSH/Nokes are commonly used modifiers in Cu-Mo
separation systems. However, these materials present
a significant safety and health hazard to humans and a
potential environment risk. After listening to the industrys
need for safer alternatives, Cytecs innovation laboratory
in Stamford, CT USA, focused its resources on finding a
solution which is described in this article.
Cu-Mo ore
Cu ~ 0.5%
Mo ~ 0.05%
Cu-Mo operations typically process ores rich in Cu sulfides

(head grade 0.1-2%) and molybdenite (MoS2, head grade
0.01- 0.05%) via an operation consisting of a) the bulk
flotation circuit, followed by b) Mo circuit as seen in
Figure 1.
Bulk Circuit
Flotation
Cu-Mo Bulk Concentrate (28% Cu, 1% Mo)
Mo Circuit
Roasting Steam
Cl2, O3, H2O2,etc
Pre-Treatment (Optional)
Cu Depressants
Conditioning with Cu Depressant

Mo Rougher
Tails
Cu Conc
FIGURE 1:
Conc
Mo Ro Conc
Mo Cleaner Circuit
The bulk flotation circuit is intended to produce a high grade

Cu concentrate containing molybdenite values along with
minor amounts of pyrite and some non-sulfide gangue. This
concentrate is then processed in the Mo circuit to selectively
A generic flow sheet for a

Cu-Mo circuit
float MoS2 while depressing Cu sulfides and pyrite. This

selective Cu-Mo separation is accomplished with the use of
depressants such NaSH, Nokes, and Na2S (and cyanide, in
some instances) with NaSH as the most widely used.
15
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
NaSH, Nokes and Na2S depressants generate significant
amounts of a toxic, lethal, and flammable gas, H2S. Cyanide,
which is also used as a depressant is both poisonous and has
the potential to generate HCN, a toxic and flammable gas.
In order to insure the safety of workers, the surrounding
communities and the environment, Cu-Mo plants require
several safety measures including H2S alarms and exhaust
hoods over flotation cells and other exposed areas. In
addition, H2S monitors are required on all personnel entering
these plants and workers must adhere to strict safety
protocols which involve rigorous training and evacuation
procedures. In spite of these measures, hazards still persist
and the industry is waiting for a safer, economically viable

depressant which will provide the same metallurgical
benefits.
In response, Cytec has developed AERO7260 HFP
Depressant, a highly efficient and versatile sulfide mineral
depressant with wide applicability as a selective depressant
for Cu sulfides and pyrite and a safer alternative to NaSH,
Na2S, and Nokes reagent.
The following sections discuss in greater detail the issues
with conventional depressants and benefits and application
guidelines for AERO 7260 HFP in Cu-Mo separation.
Problems with Current/Conventional Depressant Technology

NaSH has been the main Cu sulfide depressant used in
Cu-Mo separations for many decades. However, due to
the danger of generation of high concentrations of toxic,
flammable, hazardous, and lethal H2S gas, NaSH poses
significant issues in plant operations and poses a threat to
the local environment. Transportation of 20 to 40 tons
per day of 40% solution of NaSH present shipping and
logistics issues both in urban and remote areas. Metallurgical
performance with NaSH is also not robust, for instance,
plants can observe large performance swings with changes
in ore mineralogy, and often pyrite depression with NaSH is

inadequate even at very large dosages, creating a significant
challenge in flotation operations.
In the absence of a robust and economically viable
alternative, NaSH (Na2S and Nokes in some plants)
continues to be used extensively in Cu-Mo operations
globally despite the hazards and all the safety concerns
associated with it. AERO 7260 HFP is Cytecs innovative
solution to this challenging issue.
Advantages of AERO 7260 HFP

Depression Efficiency
AERO 7260 HFP is a highly efficient depressant for Cu
sulfides and pyrite which effectively replaces 50 to 90% of
NaSH depending on the process conditions.
Dosage-Performance
AERO 7260 HFP requires only 10% to 20% of the dosage
of NaSH, providing similar metallurgical performance.
Stability and Ease of Handling
Stable and chemically inert reagent in storage,
transportation, and under process conditions
Does not release H2S or other toxic gases, and is
non-hazardous
Classified as non-hazardous to the environment
16
No downstream or upstream effects to mineral

processing
Easy-to-handle aqueous solution
Completely miscible in water
pH
AERO 7260 HFP is effective in a wide pH range (6 to 12).
Staged Addition
AERO 7260 HFP is long lasting reagent eliminating the
necessity of staged addition down the bank in scavengers
and cleaner cells as with NaSH.
Bulk Concentrate Pretreatment
Eliminates pretreatment of bulk Cu-Mo concentrate with
steam, acid and CO2 conditioning, attrition conditioning, etc.
Applicability and Other Advantages
Eliminates the need for N2 or covered cells.
Does not require extended conditioning time.
Does not contain any phosphorous or arsenic, so is

suitable in many MoS2 operations.
Clearly, with such advantages, AERO7260 HFP offers a
significant technological step forward in minimizing human
and environmental hazards in Cu-Mo separations.
Proven Performance of AERO 7260 HFP Lab and Plant Data

The cumulative Cu and Mo recoveries from the concentrate
from a North American mine are shown in Figure 2. For
this concentrate sample, 7.5 kg/T of NaSH was required to
provide efficient Cu depression (Cu recovery ~ 10%) and
Mo recovery of greater than 95%. AERO 7260 HFP at 0.5

kg/T replaced approximately 65% of the NaSH dosage and
provided comparable Cu depression.
100
Cu
Mo
Recovery (%)
80
60
40
FIGURE 2:
20
Cumulative Cu and Mo recovery

from a Cu-Mo North American
concentrate
0
NaSH 7.5 kg/T
NaSH 7.5 kg/T + 7260 0.52 kg/T
17
In Figure 3, the Cu and Mo recoveries for a Cu-Mo
concentrate from an Asian mine are shown. Efficient Cu
depression was achieved only when 44 kg/T of Na2S was
used. Under these conditions, Cu recovery was about 20%
and Mo recovery was about 80%. The effect of 1.2 kg/T

AERO7260 HFP helped achieve even better Cu depression
and Mo selectivity with only half the dosage of Na2S.
90
80
80.9
Mo
81.3
Cu
70
Recovery (%)
60
50
40
30
20
19.8
11.8
10
Cumulative Cu and Mo recovery

from a Cu-Mo Asian concentrate
0
Na2S 44 kg /T
18
FIGURE 3:
Na2S 22 kg /T, AERO 7260 HFP 1.2 kg /T
Figures 4A and B show Cu, Mo, and Fe recoveries and
grades for lab data using AERO7260 HFP on another North
American mine Cu-Mo cleaner concentrate. In terms of
Cu depression, this concentrate required about 11 kg/T of
NaSH; however the Fe depression was not efficient at this
dosage. For efficient Cu and Fe depression, a higher dosage
99.2
a) 100
99
of 55 kg/T NaSH was required. The addition of 0.25 kg/T of

AERO 7260 HFP plus 11 kg/T of NaSH significantly enhanced
both Cu and Fe depression and Mo selectivity. This suggests
that AERO 7260 HFP is highly effective in the depression of
both Cu and Fe and enables mine operations to significantly
reduce NaSH consumption, in this case by over 80%.
98.8
92
NaSH 55 kg/T
90
NaSH 11 kg/T
80
NaSH 11 kg/T + 0.25 kg /T 7260

68.4
Recovery (%)
70
60
47.2
50
40
36.9 36.9
33
30
20
10
0
Cu
Mo
Mo Concentrate
50.7
49.2
B) 50
Fe
45.4
Grade (%)
40
30
20
FIGURE 4:
10
3.2
0
0.2
0.2
4.2
0.2
Cu
Mo
Mo Concentrate
2.4
2nd Cleaner Circuit

Lab data of Cu, Mo and Fe
a) recovery and
b) grade
Fe
Clearly, the benefits of adding AERO 7260 HFP are observed by the improved metallurgical performance and substantially
reduced dosage of NaSH.
19
Figure 5 provides the average Mo assay in the scavenger tails
from another Cu-Mo plant. The overall objective in this plant
was to significantly reduce or eliminate Nokes (1400 g/T)
usage in its Mo circuit, while maintaining Mo recovery
(Mo < 0.2% in scavenger tails). With only about 100 to 200
g/T of AERO7260 HFP, a significant volume of Nokes was
replaced, while the key specifications were maintained.
.40
Average Mo in Scav Tail (%)
.35
.30
.25
.20
.15
.10
FIGURE 5:
Plant data for Mo in
scavenger tails as a function
of Nokes dosages used
.05
0
Nokes
Standard
50% Reduction
75% Reduction
Figure 6 shows the plant data when using AERO 7260 HFP
in an on/off cycle on 3 consecutive days. The plot shows the
percentage difference in Cu, Mo and Fe grades in the cleaner
circuit with and without AERO 7260 HFP on any given day.
In the off-cycle, only NaSH was being used to control the
respective grades in order to meet production specifications.
With NaSH only, both Mo and Cu specifications were
achieved while Fe was above the specifications, i.e. sufficient
20
100% Reduction
pyrite depression was not achieved. With the addition of

AERO 7260 HFP (on-cycle), all the specifications were
achieved in addition to reducing the NaSH consumption
by over 60%. Further, it was observed that Mo grades were
significantly better in the on-cycle. This clearly suggests the
benefits of AERO 7260 HFP in such operations. Moreover,
through optimization, the NaSH dosage could be reduced by
80%, by adding only about 2 kg/T of AERO 7260 HFP.
% Difference between control and with AERO 7260 HFP (%)
20
Fe
Cu
Mo
-20
-40
FIGURE 6:
Three consecutive days of plant
data using AERO7260 HFP in an
on/off cycle in the cleaner
circuit. The % difference in Fe, Cu,
and Mo grades between control
(off cycle) and with AERO7260 HFP
(on cycle) is shown
-60
-80
-100
Day 1
Day 2
Day 3
General Guidelines for Application

The typical dosages to test AERO7260 HFP is around
250-1500 g/T, and needs to be adjusted depending on
the ore mineralogy and other process conditions. Higher
dosages may be evaluated as needed. Optimization should
be based upon Cu and pyrite depression, Mo selectivity,
and economics.
The performance of AERO 7260 HFP is best when air is
used. Note: N2 can be used, however the performance
advantages and benefits of AERO 7260 HFP may not be
fully realized.
Pretreatments are not required with AERO 7260 HFP.
AERO 7260 HFP should be added along with NaSH

(or Nokes/Na2S).
Recommended conditioning times are 5 to 15 minutes.
Longer conditioning times, e.g. 30 min or longer are not
required.
AERO 7260 HFP can be added in the roughers, scavenger
or cleaner stage, as needed. Usually, if the dosages are
optimized, stage addition is not required.
AERO 7260 HFP can be added as-is, or may be diluted as
needed.
Other Applications for AERO 7260 HFP

AERO 7260 HFP is an excellent depressant for a variety of
sulfide minerals, selectivity being dictated by dosage of
AERO 7260 HFP and process conditions. Products based on
AERO 7260 HFP have a wide range of applications including:
b) Depression of penalty/toxic elements in Cu and complex

sulfide ores.
a) Rejection of gangue from sulfide concentrates:

Depression of all sulfide minerals while floating Non
Sulfide Gangue E.g. Ni-talc separation.
d) Depression of iron sulfides in Cu-pyrite and Zn-pyrite

separations.
c) Enhancement of selectivity in Cu-Pb, Pb-Zn, Cu-Zn

separations.
e) Depression of Cu sulfides and pyrite in Cu-Mo,

Cu-graphite, Cu-F, Cu-Talc separations.
21
Conclusion
AERO7260 HFP is a novel, safer, versatile and highly
effective Cu sulfide and pyrite depressant with broad
applicability. This paper focuses on the application and
benefits of using AERO 7260 HFP in Cu-Mo separations.
The examples discussed in the paper include both lab and
plant data which highlight the effectiveness of AERO 7260
HFP in depressing Cu sulfides and pyrite and improving the

selectivity with respect to Mo. In addition to enhanced
selectively, dosages of hazardous reagents such as NaSH,
Nokes, and Na2S could be reduced by 60%-80% with
relatively small dosage of AERO 7260 HFP (0.5 to 2 kg/T).
References
D. R. Nagaraj, S. S. Wang, P. V. Avotins and E. Dowling, Structureactivity relationships for copper depressants, Trans. IMM, Sect C:
Vol 95, 1986, pp. 17-26.
D.R. Nagaraj, C.I. Basilio, R.-H. Yoon and C. Torres, The Mechanism
of Sulfide Depression with Functionalized Synthetic Polymers, Proc.
Symp. Electrochemistry in Mineral and Metals Processing, The
Electrochemical Society, Princeton, Proceedings Vol 92-17, 1992,
pp 108-128.
Chander, S. 1988. Inorganic depressants for sulfide minerals.
Chapter 14 in Reagents in Mineral Technology. Edited by P.
Somasundaran and B.M. Moudgil. New York: Marcel Dekker.
22
Rejection of Pyrite: Challenges and Sustainable

Chemical Solutions
Mario Palominos* and Carmina Quintanar
In recognition of the growing interest in meeting sustainability challenges, Cytec has been
focused on the creation of greener products (collectors, modifiers and frothers) and processes
using the FLOTATON MATRX 100 approach.
Abstract
The mining industry is currently facing significant
sustainability challenges in terms of dealing with difficultto-process low-grade resources. These ores are typically
characterized by complex mineralogy and the presence of
significant amounts of penalty gangue sulfide minerals and
toxic elements. Among them, pyrite is a common challenge
in many operations.
Three chemical strategies for dealing with gangue sulfides
and penalty elements include:
a) selective flotation of value minerals while rejecting
penalty minerals throughout the entire circuit;
b) rejecting penalty minerals in an appropriate part of the
circuit using selective depressants; and
c) using a combination of selective collectors and
depressants in appropriate parts of the circuit.
New products and application technologies have been
developed in recent years for implementing these strategies
as dictated by the particular needs of a given plant.
However, in recognition of the growing interest in meeting
sustainability challenges, Cytec has been focused on the
creation of greener products (collectors, modifiers and

frothers) and processes using the FLOTATON MATRX 100
approach.
Chemicals today play a critical role, not just in flotation, but
in almost all areas of mineral processing. They will play an
even greater role in tackling the challenges and achieving the
goals of sustainable mineral processing, particularly in the
areas of water efficiency and water resource management;
waste reduction and remediation; minimizing environmental
impact, safety and health risks (meeting and exceeding the
requirements of regulations); energy efficiency; and dealing
with difficult-to-process, low-grade mineral resources and
reserves. Together, these challenges are often termed greener
processing. There is also a growing desire to develop greener
chemicals, a major challenge in itself.
Different strategies for dealing with difficult-to-process
low-grade resources in a sustainable manner are evaluated
in order to determine the most efficient alternatives. The
discussion includes an overview of recent developments at
Cytec using case studies in which the application of selective
collectors and polymeric modifiers, including the newer,
greener chemistries, are demonstrated.
23
Rejection of Pyrite: Challenges and Sustainable Chemical Solutions
Introduction
In earlier years, pyrite content and other sulphide gangues
were less of a problem in the mineral processing of copper,
lead, zinc and other elements, mainly due to the lower
content of this mineralogical species, the high content of the
valuable minerals and the lower ecological sensitivity to gas
emissions (principally SO2) coming from the smelter.
The first goal was to achieve higher selectivity, which was
achieved through the development of dithiophosphate
alternatives to the well-known xanthates (introduced
to the market in 1923). Subsequently, it was found that
thionocarbamates (and most commonly the isopropyl
ethyl derivative, IPETC), generally have a higher selectivity
than the above-mentioned chemistries. A third stage in the
development of selective collectors focused on xanthate
esters and dithiocarbamates1.
In parallel, the use of high pH2 to depress pyrite was
implemented (particularly as a cleaning step). Lime (CaO)
was the depressant agent, and was used as a slurry (Ca(OH)2
in preference to caustic soda (NaOH) or soda ash (Na2CO3).
Hence, the solution used was based on flotation at high
pH (10-11) using a selective collector in the rougher stage
and a very high pH (> 11) in the cleaning step. The solution
was acceptable for the processing conditions at that time.
However, the use of lime negatively affected the recovery of
valuable secondary elements (e.g., molybdenum and gold).
Currently, use of seawater is an additional limiting factor for
the application of lime.
A second alternative, employed now for several years, is
based on the use of depressants for iron sulphides (mainly
pyrite and pyrrhotite). Sodium cyanide yields some good
results; however, secure handling and environmental issues
make its use unattractive. Thus, sulphoxy depressants have
been increasingly applied in recent years.
A factor not always considered is the degree of activation
of the pyrite, mainly by copper ions from altered or oxidized
minerals. When pyrite is unactivated, it is possible to obtain
good results using lime, sodium cyanide or sulphoxy species
(such as sodium or ammonium sulphite or metabisulphite3).
24
When pyrite is activated, however, lime is much less

effective, cyanide has its safety, health and environmental
(SHE) issues and the sulphoxy species have to be used at
high dosages. Furthermore, the degree of association of
pyrite, particularly in conjunction with valuable species
(copper, molybdenum, gold, lead, zinc etc.) must be
considered. Selectivity should be for liberated pyrite in order
to prevent the loss of any valuable species associated with
the pyrite.
Alternatives to inorganic depressants have also been
utilized, including organic products from natural sources4,5,6
(including quebracho, tannins and their derivatives) and
ethylene diamine tetraacetic acid. In recent years, polymeric
depressants have been developed that work effectively
for both active and non-activated pyrites. These products
are actually hydrophilic copolymers containing chemical
functionality that is able to adhere selectively to iron
sulphide species and lead to their depression. Importantly,
polymeric depressants do not have the toxicity problems
associated with the inorganic depressants, and they may be
used at significantly lower doses.
The need to process ores with higher iron sulphide content,
the generally lower grades of valuable elements and the
growing importance of secondary elements (molybdenum,
gold, etc.), are driving greater interest in the use of selective
collectors. In recent years, more selective reagents have
been developed for the rougher stage in order to achieve
selective flotation with high efficiency at this point, and thus
minimise the use of depressants in the cleaning step. The
compounds of interest have included structurally modified
dithiocarbamates and thionocarbamates. These collectors
have the advantage of being selective against liberated
pyrite, but effective for the valuable elements associated
with pyrite, such as copper, molybdenum, and others,
thereby avoiding the loss of these valuable species related to
the non-flotation of associated particles (middlings).
Methodology
Mineral ore samples from South America were used to evaluate the application of selective collectors and polymeric
depressants. The feed grades of the ores are listed in Table 1.
Table 1: Feed Grades of the Mineral Ores Used in the Evaluation of Selective Collectors.
Ore
Copper content, %
Iron content, %
Molybdenum content, ppm
Ore-1
0.74
2.1
98
Ore-2
0.33
4.73
107
Ore-3
1.05
4.40
300
Experimental Procedure
Laboratory flotation tests were conducted to simulate 1) just
the Rougher stage and 2) the different stages of the plant
(open cycle test). The flotation products were collected and
analysed for copper, iron and molybdenum using atomic
absorption analysis. These mass balance results allowed the
calculation of the metallurgical balance, and therefore the

metallurgical recoveries, for each test. The conditions for the
laboratory tests with the different mineral ores are described
in Table 2.
Table 2: Laboratory Test Conditions for Each of the Ores
Conditions
Ore-1
Ore-2
Ore-3
Machine
Agitair L500
Denver
Wemco
pH
10.5
9.5
9.5
% Solids
34
34
30
Flotation time (min)
10
15
12
Grinding
30% + 100#Ty
20% + 100 #Ty
20% +65#Ty
Note that with Ore-3, when the standard collector was used,
typical conditions for the cleaning stage were used (lime was
added) and the pH was 11.5. However, lime was not added in
the cleaning stage for the other collectors tested with Ore-3
(final pH=8.7).
Results and Discussion

The study with Ore-1 demonstrated the difference in
the selectivity for iron for the different types of selective
collectors: dithiophosphate (DTP),
isopropyl ethylthionocarbamate (IPETC) and a structurally

modified thionocarbamate (SMTC).
25
94
DT
IPET
SMTC
92
Cu Recovery
90
88
86
84
FIGURE 1:
Selectivity comparison for
copper minerals vs. pyrite for
3 collector types
82
80
15
20
25
30
35
40
45
50
55
60
Fe Recovery
The difference in the performance of DTP and IPETC, as

described above in the Introduction, can be readily seen
in Figure 1. IPETC, one of the first selective collectors to
replace the xanthates, provides good recoveries and better
selectivity. Importantly, though, it can also be seen in
Figure 1 that the structurally modified thionocarbamate
AERO XD-5002 promoter, which represents a new family
of collectors developed by Cytec, is clearly advantageous in
terms of its selectivity for copper minerals against pyrite (as
represented by the Fe assay).
A complementary study was then conducted with a second

ore (Ore-2) with different mineralogical characteristics.
Again, a series of selective collectors was evaluated,
including the structurally modified thionocarbamate AERO
9950 promoter, which provided the highest selectivity
against iron and also the best copper recovery among the
tested chemicals. The results of this study are presented in
Figure 2, while the different collectors and their dosage levels
used in the test are listed in Table 3. Collector-1 refers to
the main collector that was added to the grind. Collector-2,
when used, refers to a secondary collector added in the
conditioning stage prior to initiation of flotation.
88.5
88
Cu Rec (%)
87.5
87
86.5
86
26
14.0
17.5
22.0
22.1
19.5
29.0
Fe Rec (%)
6.8
5.8
6.8
6.5
6.8
6.4
Mass Pull (weight %)
std
Test
FIGURE 2:
Evaluation of
selective versus non-selective
collectors using Ore 2

at pH 11.5, the regular condition for depression when lime is
used. For the evaluated alternatives, however, lime was not
added in the cleaning stage, so that comparisons could be
made with results obtained for the subsequent study using
depressants (see below).
Table 3: Reagent Scheme for the Study Using Ore-2.
Collector-1[M]
Collector-2 [C]
AP-9950; 20 g/t
XD-5002; 10 g/t
AP-9950; 15 g/t
MX-945; 5 g/t
MX-8522; 15 g/t
MX-945; 5 g/t
MX-7017; 15 g/t
MX-945; 5 g/t
STD
PAX; 20 g/t
[M]: Grind mill; [C]: Conditioning
The selective collectors evaluated with Ore-3 included AERO

9950 promoter (structurally modified thionocarbamate)
and AERO 9955 promoter (a mix of thionocarbamate and
dithiocarbamate). Their performance was compared to
that of the non-selective collector SIPX (sodium isopropyl
xanthate), for which the standard conditions were used.
The third study included a cleaning stage (evaluated in an

open cycle test). As indicated in the Experimental section,
for the standard collector, the cleaning stage was conducted
The following figure (Figure 3) shows both the rougher and

global recoveries (considering an open cycle test with two
cleaning stages and a scavenger stage) conducted on Ore-3.
100
90
Cu
Cu-FC Grade =
Fe
Mo
80
Recovery (%)
70
60
50
40
30
FIGURE 3:
20
Comparative study between a

non-selective collector (SIPX)
and two selective collectors
10
0
Rougher
Final
ST
Rougher
Final
Rougher
AP-
It can be seen in the figure that similar copper rougher

recoveries were obtained for all three of the collectors,
while in the rougher stage, the xanthate and AERO 9950
promoter had similar molybdenum recoveries and the
AERO 9955 promoter provided a greater recovery. The iron
recoveries in the rougher stage were significantly different,
however. The xanthate had a high recovery (approximately
80%), followed by the AERO 9955 promoter (with a value
near 65%), but the AERO 9950 promoter was the most
selective (rougher Fe recovery of approximately 40%).
Final
AP-
The overall recovery of iron for the xanthate was calculated

to be 30% based on analysis of the final concentrate
after the two cleaning steps and considering the classical
cleaning at high pH. AERO 9955 promoter, meanwhile, had
an overall iron recovery of close to 20%, while that of AERO
9950 promoter (the most efficient in the rougher stage)
was approximately 15%. With these values, the grades
obtained for the final concentrate in terms of the copper
content were determined and are indicated in Figure 3.
With both AERO 9950 promoter and AERO 9955 promoter,
27

the final copper concentrates reached or exceeded the
requirements for commercial grade material. In addition,
due to the lower pH, there was limited loss during recovery
of the by-product molybdenum (Mo) in the cleaning stage

as compared to the reduction in the Mo recovery using the
standard collector (SIPX).
Comparative Study with Different Pyrite Depressants

Figure 4 shows the results using different depressants, such
as lime (for the standard condition), sodium metabisulphite
(MBS), which is currently used, particularly when seawater
is used for the processing, and new polymeric organic
depressants. The ore used in this work was the same as that
100
90
used to evaluate the selective collectors (Ore-3). In this

study, the standard collector (xanthate) was used in all of
the tests so that the effect of the different depressants could
be evaluated in the cleaning stage.
Cu
Cu-FC Grade =
Fe
Mo
80
Recovery (%)
70
60
50
40
30
FIGURE 4:
20
Inorganic and organic

depressants for pyrite
using Ore-3
10
0
Rougher
ST
Final
Rougher
Final
Coll-STD /
A-7260; 50
Rougher
Final
Coll-STD /
A-7260; 100
MBS and the polymeric depressant developed by Cytec,

AERO 7260 HFP depressant, were evaluated under similar
conditions (pH = 8.5). The standard test used only lime
as the depressant and was conducted at pH = 11.5. All
three depressants were added at the regrind mill stage.
Importantly, as can be seen in Figure 4, neither the standard
or the alternative depressants reached the values necessary
for commercial concentrate grades (Cu > 25%).
28
Rougher
Final
Coll-STD /
MBS-Na; 300
The addition of the depressant in the rougher stage

to simulate the effect of the selective collector was
also evaluated. However, low depression of iron was
observed. The most significant effect was that copper and
molybdenum species were depressed at high levels.
Conclusion
The results presented above demonstrate that there are
new alternatives available on the market that are even more
selective than the classic collectors commonly used for
pyrite and other sulphide mineral gangue and can address
the increasing levels of these contaminants that are present
in todays mineral deposits.
In addition, it was also shown that it is more efficient to

use highly selective collectors in the roughing stage, rather
than to use collectors with low or medium selectivity in
conjunction with depressants. In the latter case, high doses
are typically required, particularly when using organic
depressants, which were found to be inefficient and have
the potential to negatively affect the recovery of both the
main sulphide product and secondary products, such as
molybdenum and gold.
References
1. Klimpel R. Richard, A discussion of traditional and new reagent
Chemistries for a Flotation of Sulphide Minerals. Chapter 7,
Reagents for Better Metallurgy, Society for Mining Metallurgy
and Exploration Inc., Littleton, Colorado USA, 1964.
4. Pedro E. Sarquis, Adriana Moyano, Mercedes Gonzalez, Vanesa

Bazn, Organic Depressant Reagent Effect on pyrite in Copper
Minerals Flotation, 8th International Mineral Processing Seminar
(Procemin 2011), 109-116.
2. Yuqiong Li, Jianhua Chen, Duan Kang, Jin Guo, Depression of

Pyrite in alkaline medium and subsequent activation by copper,
Minerals Engineering 26 (2012) 64-69.
5. Maximiliano Zanin, Saeed Farrokhpay, Depression of Pyrite in

Porphyry Copper Flotation, 8th International Mineral Processing
Seminar (Procemin 2011), 135-143.
3. G.I. Dvila-Pulido, A. Uribe-salas, R. Espinosaa-Gomez,

International Journal of Mineral Processing, 101 (2011) 71-74.
6. Jianhua Chen, Yuqiong Li,Ye Chen , Cu-S Flotation Separation

via the combination of Sodium Humate and Lime in a low pH
Medium, Minerals Engineering, 24 (2011), 58-63.
29
MAX HT Bayer Sodalite Scale Inhibitor:

A Green Solution to Energy Consumption
Morris Lewellyn, Alan Rothenberg, Calvin Franz, Frank Ballentine, Frank Kula, Luis Soliz, Qi Dai, and
Scott Moffatt
As the premier advanced chemicals partner for the Alumina industry, Cytec specializes in
producing products with the breadth and depth to advance all stages in the Bayer Process. Our
product innovations have transformed the industrys expectations regarding their technology
suppliers and our strategy is to continue to develop solutions that will provide step changes in
the industry. Our MAX HT scale inhibitor, a revolutionary product that eliminates sodalite scale
from heat exchangers, recently received the 2012 Environmental Protection Agencys Presidential
Green Chemistry award.
The award recognizes companies that have pioneered
sustainable technologies that incorporate the principles of
green chemistry.
MAX HT was developed to reduce or eliminate scaling from
the evaporator and digester heaters in the Bayer process.
This product has been successfully applied in 20 Bayer
process plants worldwide, resulting in the significant benefits
of increased heat transfer, reduced energy consumption and
reduced acid waste from reduced heater cleanings. Based
on trial data from a number of plants, the estimated annual

savings per ton of alumina produced are 0.26-1.3 Gj energy,
resulting in 13-92 kg reduction in CO2 emissions, and
0.9-2.7 kg reduction in acid waste.* When these savings are
applied to the total alumina production from the 20 plants,
this leads to an estimated realized annual savings of 11-56
million Gj energy, 0.54-3.9 billion kg CO2 emissions, and
38-116 million kg of acid waste reduction.
* The range reflects the wide variety in the operation of Bayer plants around
the world.
Introduction
Cytec has developed a line of polymers for use as scale
inhibitors in evaporator and digester heaters used in the
Bayer process [1-8]. These products provide benefits by
reducing or eliminating the scale formation in the heaters
resulting in significantly higher heat transfer, reducing
energy consumption and waste. These products have been
successfully applied in a number of plants utilizing the
Bayer process throughout the world [9-11]. This technology
is also being assessed for sodalite scale elimination in the
evaporation process for the treatment of other types of
substrate [12].
The scale deposited in these heaters is sodium
aluminosilicate sodalite or DSP (desilication product).
30
This is a result of the silica that is present in bauxite ores as

silicates, primarily clay minerals, that dissolves quickly under
typical Bayer alumina digestion conditions. The Bayer liquor
remains supersaturated in silica and this supersaturation
is greatest after the alumina precipitation step, i.e. in the
spent liquor. As the alumina-depleted liquor is reheated,
the rate of silica precipitation in the form of sodalite
increases markedly with increasing temperature due to faster
kinetics[13]. This precipitation occurs as scaling on the inside
of the heat exchange tubes and a significant loss of heat
transfer occurs, leading to increased energy consumption,
increased caustic losses, reduced liquor flows, reduced
throughput, reduced evaporation, and reduced production.
MAX HT Bayer Sodalite Scale Inhibitor: A Green Solution to Energy Consumption

Without MAX HT, the method used to manage the sodalite
scale problem is to clean out the system whenever the heat
exchanger performance drops below a certain level, typically
about half the original heat transfer rate. This cleaning is
generally accomplished with the use of a 5-10% sulfuric
acid solution to dissolve the scale. The used acid constitutes
a waste stream requiring disposal. In addition to the acid
cleaning, much of the inter-stage piping is cleaned using
mechanical means, such as jackhammers, to remove the scale.
Cytec performed plant trials to research energy savings. See

Figures 4 & 5. For detail on the results of the trials please go
to www.cytec.com. The results of the trials show potential
energy and waste savings which was the basis for the
awarding Cytec the 2012 U.S. EPA (Environmental Protection
Agency) Presidential Green Chemistry Challenge Award for
MAX HT.

Without Antiscalant
With Antiscalant
The use of MAX HT is one way to make the Bayer process

greener in terms of energy use and waste generation. MAX
HT is commercial at twenty different plants across the globe,
and under evaluation at a number of other plants. Many of
these are double stream plants where the scale inhibitor can
be used on both evaporator and digester heaters, but there
are a number of single stream plants that find benefits from
just treating the evaporator heaters.
Dirty and clean heat exchangers from operating
without and with MAX HT antiscalant after 160 hrs.
of continuous operation, corresponding to the
heat transfer curves in Figs. 4 and 5, respectively.
2700
2500
y = -8.325x + 1981.8
2300
2100
1900
1700
1500
1300
1100
900
FIGURE 4:
700
Typical heat transfer decay

during 160 hrs. without MAX HT
500
0
10
20
30
40
50
60
70
80
90 100 110 120 130 140 150 160
Hours
31
2300
2100
y = -0.4267x + 1744.1
1900
1700
1500
1300
1100
FIGURE 5:
900
Constant heat transfer

coefficient resulting from
the use of MAX HT
700
500
1
11
21
31
41
51
61
71
81
91
101 111 121 131 141 151 161
Hours
Benefits of MAX HT
MAX HT sodalite scale inhibitor has been used successfully
in a number of Bayer process plants. Typically, the on-stream
time for a heater is increased from some 8-10 days to
45-60 days for digestion and 20-30 days to >150 days for
evaporators. This ability to maintain a high heat transfer over
a much longer life cycle between cleanings has resulted in a
number of benefits. These benefits are summarized below:
1. Increased evaporation when used in the evaporator
heaters. This leads to reduced caustic consumption and
improved mud washing in the washer circuit because
more water is available for efficient washing of the red
mud and gibbsite crystals. The annual realized reduction
of caustic is estimated to be 79,000-198,000 tons of 50%
caustic.
2. Increased production. This is a result of an increased
average flow due to being able to maintain the
outlet temperature without having to reduce flow to
accommodate a lower heat transfer rate.
3. Reduced energy consumption realized per annum.
Savings in the range of 4.4-22.0 million tons of steam
have been realized, which translates to 11-56 million Gj
energy, or 0.54-3.9 billion kg CO2.
32
4. Less direct steam to the digester when used in the

digester heaters. By being able to maintain the maximum
live steam heater outlet temperature, the need to add
steam by direct injection in the digesters is reduced or
eliminated, resulting in less extraneous dilution which
impacts soda recovery and therefore caustic consumption.
This also allows more mass in the digester in terms of
liquor and bauxite leading to higher production.
5. Reduced digester and evaporator heaters cleaning and
maintenance. This leads to a reduction in cost for the
acid, labor, tube changes, etc. There is also less exposure
of the workers to the associated hazards. The realized
annual reduction in hazardous acid waste is 38-116
million kg. The number of cleaning cycles can be reduced
from a range of 20-50 per year per heater train to less
than 10 per heater train.
6. Steadier plant operation.

The value of the MAX HT technology is to reduce energy
usage by 0.26-1.3 Gj, reduce CO2 emissions by 13-92 kg, and
reduce waste generation by 0.9-2.7 kg per ton of alumina
produced. There are about 73 operating Bayer plants
throughout the world, ranging in production capacity of
0.2 to 6 million tons of alumina annually, with the majority

being in the 1.5 to 3 million tons capacity. The estimated
annual environmental benefit for the 20 commercialized
plants is shown in Table 6 along with the estimated global
annual potential benefit based on 2011 figures.
Table 6. Potential and Realized Benefits of MAX HT Technology
Savings per ton of alumina produced

Realized savings (20 commercial plants)
Potential savings (All 73 plants)
Energy (Gj)
CO2 Reduction (Kg)
Waste Reduction (Kg)
0.26 1.3
13 92
0.9 2.7
11 56 million
0.54 3.9 billion
38 116 million
25 128 million
1.3 8.9 billion
86 263 million
Conclusion
1. MAX HT provides estimated annual savings per ton of
alumina produced of 0.26-1.3 Gj energy, resulting in 13-92
kg reduction in CO2 emissions and 0.9-2.7 kg reduction in
acid waste.
2. This more efficient use of energy results in increased
evaporation in the evaporator heaters, leading to reduced
caustic consumption and more efficient use of water.
3. The use of MAX HT leads to increased production due

to an increase in average flow and reduced direct steam
injection.
4. The use of MAX HT also results in reduced cleaning of
digester and evaporator heaters resulting in reduced
exposure of workers to the hazards and reduced acid
waste.
References
1. D. Spitzer, A. Rothenberg, H. Heitner, and F. Kula, Method of
preventing or reducing aluminosilicate scale in a Bayer process,
U.S. patent 6,814,873B2 (2004).
2. D. Spitzer, A. Rothenberg, H. Heitner, and F. Kula, Method and
compositions for preventing or reducing aluminosilicate scale in
alkaline industrial processes, U.S. patent 7,390,415B2 (2008).
3. H. Heitner, Silane substituted polyethylene oxide reagents and
method of using for preventing or reducing aluminosilicate scale
in industrial processes, U.S. patent 7,674,385B2 (2010).
4. H. Heitner and D. Spitzer, Hydrophobically modified polyamine
scale inhibitors, U.S. patent 7,999,065B2 (2011).
6. D. Spitzer, A. Rothenberg, H. Heitner, F. Kula, M. Lewellyn, O.

Chamberlain, Q. Dai, and C. Franz, A real solution to sodalite
scaling problems, Proceedings of the 7th International Alumina
Quality Workshop, 2005, 153-157.
7. D. Spitzer, O. Chamberlain, C. Franz, M. Lewellyn, and Q. Dai,
MAX HT Sodalite Scale Inhibitor: Plant experience and impact
on the process, Light Metals, 2008, 57-62.
8. M. Lewellyn, A. Patel, D. Spitzer, C. Franz, F. Ballentine, Q. Dai,
O. Chamberlain, F. Kula, and H. Chen, MAX HT Sodalite Scale
Inhibitor: Plant experience with first and second generation
products, Proceedings of the 8th International Alumina quality
Workshop, 2008, 121-124.
5. D. Spitzer, A. Rothenberg, H. Heitner, F. Kula, M. Lewellyn, O.

Chamberlain, Q. Dai, and C. Franz, Reagents for the elimination
of sodalite scaling, Light Metals, 2005, 183-188.
33

9. A. Oliveira, J. Dutra, J. Batista, J. Lima, R. Diniz, and E. Repetto,
Performance appraisal of evaporation system with scale
inhibitor application in Alunorte plant, Light Metals, 2008,
133-136.
10. L. Riffaud, P. James, E. Allen, and J. Murray, Evaluation
of sodalite scaling inhibitor A users perspective (Paper
presented at the International Symposium on Aluminum: From
Raw Materials to Applications Combining Light Metals 2006
and the 17th International ICSOBA Symposium, Montreal,
Quebec, Canada, 1-4 October 2006), Bauxite & Alumina
session, paper 29.7.
11. M. Kiriazis, J. Gill, and D. Stegink, Evaluation of MAX HT at
Queensland Alumina LTD, Proceedings of the 9th International
Alumina Quality Workshop, 2012, 88-92.
12. L.N. Oji, T.L. Fellinger, D.T. Hobbs, H.P. Badheka, W.R. Wilmarth,
M. Taylor, E.A. Kamenetsky, and M. Islam, Studies of potential
inhibitors of sodium aluminosilicate scales in high-level waste
evaporation, Separation Science and Technology, 43 (2008),
2917-2928.
13. J. Addai-Mensah, Fundamentals of sodium aluminosilicate
crystallization during process heat exchange, (Paper presented
at the World congress of Chemical Engineering, 7th, Glasgow,
United Kingdom, 10-14 July 2005), 86781/1-86781/10.
14. L. Perez, Mechanism of calcium phosphate scale formation and
inhibition in cooling systems, Calcium Phosphates in Biological
and Industrial Systems, ed. Z. Amjad (Boston, Kluwer, 1998),
395-415.
34
Performance Evaluation of CYFLOC ULTRA

HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
Luis Soliz, Renata Vinhas, Emiliano Repetto, Paulo Prado, Haunn-Lin T.Chen, Roberto Seno Junior,
Andre Arantes, Rodrigo Santos, and Rodrigo Moreno
In the late 1980s, Cytec Industries Inc. developed a series of hydroxamated polyacrylamide
products (HXPAM) to be used as high performance flocculants for treating red mud in the
Alumina Bayer Process1,2,3. This product family, known as CYFLOC HX Series, has since become
the most widely used flocculant on red mud settlers in the industry.
Introduction
The applications of several flocculants from CYFLOC HX
00 and 000 series have been evaluated in a variety of
alumina plants worldwide. Since then, the alumina industry
has realized a number of significant benefits from the use of
CYFLOC HX flocculants.
The replacement of CYFLOC ULTRA HX-5300 by CYFLOC

ULTRA HX-6000 series HX-6100, HX-6200, HX-6300,
and HX-6400 was due to further improvements in the
manufacturing process. The new series will be available in
the market in the near future.
After years of producing HXPAM emulsions, CYTEC

Industries Inc. has developed a family of new hydroxamated
polyacrylamide products5 CYFLOC ULTRA HXPAMS.
CYFLOC ULTRA HX-5300 was the first of a new series.
This paper describes the relative performance of CYFLOC

ULTRA HX-5300 versus CYFLOC HX-3000 in the CBA
alumina plant.
Background CBA Bauxites Characterization

There are two types of bauxites processed in CBA: Zona da
Mata and Pocos de Caldas. Both bauxites are commonly
blended and added into the process in different ratios
according to the production plan.
The Pocos de Caldas ore has shown to be more difficult to
process than Zona da Mata ore due to the higher content
of reactive silica as well as the lower amounts of iron and
available alumina content. Operational adjustments are

required in order to control instabilities in the clarification
stage when the blend contains more than 40% Pocos de
Caldas bauxite. These instabilities include: difficulties in red
mud settling, and a loss of compaction in the vessel, which
leads to reduced throughput and consequently reduced
production.
Benchmarking of CYFLOC ULTRA HX-5300 Performance

In December of 2011, settling tests were conducted at CBA
in order to determine the performance of CYFLOC ULTRA
HX-5300 relative to the CYFLOC HX-3000 sample applied in
the process used on the settlers and first washer at the time.
Samples of settler feed slurry were collected and tested in

CBAs laboratory. According to the process data, the blend
of Zona da Mata and Pocos de Caldas bauxite at the time of
testing was 71% and 29% respectively.
35
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Figure 1 indicates that the manufacturing and laboratory
samples of CYFLOC ULTRA HX-5300 provided a significant
improvement in the red mud settling rate and overflow
clarity. Approximately 238 g/T of CYFLOC HX-3000
was required in order to deliver a settling rate of 10 m/h.
Conversely, the same settling rate was achieved with
approximately 194 g/T of CYFLOC ULTRA HX-5300. Findings
from these tests showed that the dosage of flocculant
was reduced by approximately 18% when CYFLOC ULTRA
HX-5300 was applied versus CYFLOC HX-3000.
Similar to settling rate performance, samples of CYFLOC

ULTRA HX-5300 also outperformed CYFLOC HX-3000
in clarity, as indicated in Figure 2. At a dosage of 225 g/T,
CYFLOC ULTRA HX-5300 delivered supernatant clarity
of approximately 80mg/L versus 140 mg/L when CYFLOC
HX-3000 was applied. After positive results were achieved
in the laboratory a plant trial was recommended in order to
verify the product performance in the plant.
30
CYFLOC HX-3000
CYFLOC Ultra HX-5300 (Lab. Lot)
25
Settling Rate (m/h)
CYFLOC Ultra HX-5300 (Manuf. Lot)

20
15
10
5
FIGURE 1:
Settling Rate versus Total Dose

of Flocculant
100
150
200
250
300
350
400
Total Dose (g/T)
600
CYFLOC HX-3000
CYFLOC Ultra HX-5300 (Lab. Lot)
500
Overflow Solids (mg/L)
CYFLOC Ultra HX-5300 (Manuf. Lot)

400
300
200
FIGURE 2:
100
Supernatant Solids versus Total

Dose of Flocculant
0
100
150
200
250
Total Dose (g/T)
36
300
350
400
Plant Application of CYFLOC ULTRA HX-5300

In February 2012, a plant trial was conducted at CBA
for a period of ten days. The purpose of the trial was to
demonstrate that it is possible to control the settler stage
with the application of CYFLOC ULTRA HX-5300 while
achieving a dose reduction of approximately 18% versus
CYFLOC HX-3000. Based on historical data of two previous
months, the success criteria of the trial was to maintain
process conditions similar to the prior conditions when
CYFLOC HX-3000 was applied. These conditions included:
Maintain the overflow (O/F) solids equal to or less than,
80 mg/L
Maintain underflow (U/F) density equal to or higher than,

1450 g/L
Maintain the interphase level at approximately 4.5 meters
Maintain U/F density equal to or higher than 1450 g/L
Do not negatively impact filtration operation (carry over
measurements)
The plant trial was carried out on the TD1 settler according
to the diagram below:
Flocculant
Overflow
Settler Feed Slurry
Filtrate
(KM)
Flocculant
Mud Settler TD 1
Mud Washer
Mud Washer
Mud Washer
Mud Washer
Red Mud
Residue
FIGURE 3:
CBAs Clarification Flow Diagram
Results and Discussion

During the trial the target of Pocos de Caldas bauxite content
was 38% in the blend. However due to logistic issues, the
real content of Pocos bauxite in the blend varied from 27%
to 45%. That wide range of Pocos de Caldas bauxite charge
was an interesting aspect to be evaluated. Even when the
amount to Pocos bauxite increased from 27% to 45%, it
was possible to control the settler stage with the CYFLOC
ULTRA HX-5300 application. This observation suggested
that CYFLOC ULTRA HX-5300 has significant potential to
allow for flexibility in bauxite savings. However, a longer term
evaluation is required to confirm this hypothesis.
Figure 4 contains sixty days of overflow clarity data from

a period prior to the trial as well as overflow clarity data
that was collected during the ten day trial period. The
data indicates that the overflow clarity was maintained at
approximately 75mg/L in the TD 1 settler when CYFLOC
Ultra HX-5300 was applied. The mean and the standard
deviation in both periods were very similar. Over the last few
days of the trial the data suggested that the overflow clarity
increased to approximately 100 mg/L. This deterioration is
attributed to inefficient dispersion of the flocculant in the
vessel caused by a reduction of the feed rate.
37
HX-3000 ULTRA HX-5300
Individual Value
120
100
UCL = 98.72
80
X = 75.41
60
LCL = 52.09
40
1/12/11 8/12/11 15/12/11 25/12/11 1/1/12
8/1/12
15/1/12 22/1/12 29/1/12
5/2/12
Date
Moving Range
40
30
UCL = 28.65
20
10
0
1/12/11 8/12/11 15/12/11 25/12/11 1/1/12
8/1/12
15/1/12 22/1/12 29/1/12
MR = 8.77
FIGURE 4:
LCL = 0
Overflow Clarity Chart
5/2/12
Date
Specifically, the CBA measurement of the interphase level is

taken from the top of the settler. The data from the period
prior to the trial indicated that the interphase level
was approximately 4.2 meters. Figure 5 illustrates that the

interphase level remained stable and in some cases slightly
improved to 4.6 meters when the new flocculant was applied.
Individual Value
UCL = 5.483
5
X = 4.567
4
LCL = 3.651
3
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
9/2/12
Date
Moving Range
1.5
UCL = 1.125
1.0
0.5
0
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
Date
38
12/1/12 19/1/12 26/1/12 2/2/12
9/2/12
MR = 0.344
FIGURE 5:
LCL = 0
Interphase Level Chart
Similar to the overflow clarity and interphase level, the
underflow density also remained stable during the trial.
Figure 6 depicts the mud density data prior to the trial and
during the trial. The mean density prior to the trial and
during the trial was approximately 1515 g/L and 1521 g/L,
respectively.
UCL = 1607.0
Individual Value
1600
1550
X = 1521.1
1500
1450
LCL = 1435.2
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
9/2/12
Date
UCL = 105.5
Moving Range
100
75
50
MR = 32.3
25
FIGURE 6:
LCL = 0
0
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
Underflow Density Chart
9/2/12
Date
The Filtration Rate parameter was also monitored. Figure 7

showed that the filtration rate remained stable during the
trial. CYFLOC Ultra HX-5300 delivered a filtration rate of
approximately 0.97 m3/m2/h versus 0.94 m3/m2/h when
CYFLOC HX-3000 was applied.
The carry over was also monitored to ensure that no

flocculant was carried over to the filters. No problems or
issues were reported from the security filtration stage.
39
Individual Value
1.1
UCL = 1.0704
1.0
X = 0.969
0.9
LCL = 0.8676
0.8
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
9/2/12
Date
Moving Range
.20
.15
UCL = 0.1246
.10
.05
0
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
MR = 0.0381
FIGURE 7:
LCL = 0
Filtration Rate Chart
9/2/12
Date
Figure 8 illustrates the flocculant dosage usage in the plant

both prior to and during the trial. Statistical evaluation
indicated that CYFLOC HX-3000 dosage was approximately
252 g/T of mud, while CYFLOC Ultra HX-5300 was 208 g/T.
40
This represented a dosage reduction of approximately 18%

when CYFLOC Ultra HX-5300 was applied as opposed to
CYFLOC HX-3000, even during the time period in which
45% Pocos de Caldas bauxite was added the process.
Individual Value
350
300
250
UCL = 246.2
X = 207.9
200
LCL = 169.5
150
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
9/2/12
Date
Moving Range
80
60
UCL = 47.1
40
20
0
1/12/11 8/12/11 15/12/11 22/12/11 29/12/11 5/1/12
12/1/12 19/1/12 26/1/12 2/2/12
MR = 14.4
FIGURE 8:
LCL = 0
Flocculant Dosage Chart
9/2/12
Date
Conclusion
1. The test indicated that CYFLOC ULTRA HX-5300 had
equivalent settler performance as compared to CYFLOC
HX-3000.
2. It was possible to control the settler stage while applying
CYFLOC ULTRA HX-5300, even when the process had the
addition of 45% Pocos de Caldas bauxite.
3. There were no problems or issues reported by the security

filtration stage during the trial.
4. It was possible to reduce flocculant dosage by
approximately 18% with the application of CYFLOC
ULTRA HX-5300 relative to CYFLOC HX-3000.
References
1. Spitzer, D. P. and Yen, W. S., US 4,767,540 (1988)
2. Rothenberg, A. S., Spitzer, D. P., Lewellyn, M.E., and Heitner, H.
I. New reagents for alumina processing, Light Metals, (1989), pp
91-96.
3. Spitzer, D. P., Rothenberg, A. S., Heitner, H. I., Lewellyn, M.E.,
Laviolette, L. H., Foster, T., and Avotins, P. V., Development of
new Bayer process flocculants, Light Metals, (1991), pp 167-171.
4. Ryles, R. G. Avotins, P. V., SUPERFLOC HX, a new technology

for the alumina industry, Fourth International Alumina Quality
Workshop, (1996), pp 75-86.
5. Rothenberg, A. S., Lewellyn, M.E., Chen, H-L.T., Magliocco,
L., Sassi, T., Microdispersions of hydroxamated polymers and
method of making them, Patent Application Filed.
41
Scale Controlling Chemical Additives for

Phosphoric Acid Production Plants
John Carr, Lei Zhang, Matthew Davis, S.A. Ravishankar, and Greg Flieg
Cytec has developed a novel family of antiscalants, PHOSFLOW, that reduces the fluorosilicate,
calcium sulfate and aluminate scale formation in phosphoric acid operations allowing for longer
cycle times, increased production, and reduced maintenance time.
1. Introduction
Accumulation of scale is a perennial problem in phosphoric
acid production processes. The large quantities of dissolved
and un-dissolved species present during the digestion and
concentration process lead to the formation of scale deposits
on the filters, pipelines carrying the acid, evaporators,
heat exchangers and coolers [1-2]. Scale buildup can cause a
number of operational issues such as plugging of equipment,
inefficient feed rate to the evaporators, increased utility
costs, lost production due to downtime, and downgraded

products from lower concentration due to poor heat
transfer[3-4]. A rough calculation of potential production gain
from extending the operating cycle of a heat exchanger is
illustrated in Table 1 assuming 50 weeks/year operation with
a capacity of 300 T P2O5/day (i.e. 105 000 T/year or 12.5 T/h)
with a shutdown frequency of every 2 weeks and a shutdown
duration of 20 hours.
Table 1. Production Gain by Extending Cycle

New shut down frequency
(from 2 weeks to)
Production time saved

(hrs/year)
Merchant grade acid production increase

(T/year)
(%)
4 weeks
250
3125
3.0
5 weeks
300
3750
3.6
6 weeks
333
4167
4.0
Cytec has developed a novel family of antiscalants,

PHOSFLOW, that reduces the fluorosilicate, calcium sulfate
and aluminate scale formation in phosphoric acid operations
allowing for longer cycle times, increased production, and
reduced maintenance time. The technology has been
demonstrated via three commercial scale plant trials at
42
two distinct points in the phosphoric acid production

process. No negative downstream effects were observed.
The antiscalant is easily applied to the process through a
piston pump requiring minimal capital investment. This
article will summarize the application of this technology to a
commercial phosphoric acid heat exchanger and feed line.
Scale Controlling Chemical Additives for Phosphoric Acid Production Plants
2. Trial of PHOSFLOW Technology in Phosphoric Acid Plant Heat

Exchanger and Feed Acid Line
The customer identified the feed acid line to the heat
exchanger and the heat exchanger as areas that suffer from
scale buildup and requires periodic cleaning to maintain acid
flow. The typical cycle length of the heat exchanger was 3
weeks and a clean out of the feed acid line was necessary
approximately 10 days into the cycle. The cleanout time
for the feed acid line was 4 hours and 3 days for the
heat exchanger. Cleanout of the heat exchanger entails
mechanical cleaning with a high pressure water lance that
takes approximately 15 hours with an average of 150 tubes
visually plugged out of a bundle of 868 tubes. During a
cycle, the flow rate of acid to the evaporator decays from an
initial rate of approximately 50 m3/hr to less than 39 m3/hr.
A two-trial evaluation was proposed where the first trial of
the antiscalant would replicate their normal operating cycle
time of 3 weeks. The data generated from the trial would be
compared with historical data as well as data from a control
cycle run immediately after to ensure similar environmental
conditions and ore chemistry were encountered. If the
results looked promising, a second trial would be conducted
looking to extend the cycle beyond the typical 3 weeks. The

process parameters chosen as indicators of performance for
the feed line and heat exchanger are listed below:
Heat transfer coefficient Gives an indication as to the
efficiency of heat transfer. Values greater than 450 W/m2
K are considered sufficient.
Percent valve open reading the valve opening is
modulated to attain a set point flow rate. When the line
is scaled or a blockage develops, the valve will need to be
fully open (100%) to achieve the set point flow.
Current load on recirculation pump in the heat exchanger.
If the tubes in the heat exchanger become plugged, the
current load on the recirculation pump will increase.
The number of tubes plugged in the heat exchanger and
the time required for cleaning the heat exchanger.
The flow rate of acid through the system.
2.1. Results from Three Week Trial of PHOSFLOW Antiscalant

The antiscalant was dosed into the outlet side of the feed
line pump carrying 28% P2O5 acid from a storage tank to a
heat exchanger designed to increase the acid concentration
to 54% P2O5. The dose was set at 50 ppm (vol/vol) for the
duration of the trial and monitored regularly. Figures 2-5

below show a comparison of the process parameters for the
antiscalant treated cycle as well as the cycle immediately
after designated as a control cycle.
43
Heat Transfer Coefficient (W/m2 K)

650
600
550
500
450
400
350
300
250
200
100
200
300
Cycle Time (hours)
400
650
600
550
500
450
400
FIGURE 2:
350
Data for heat transfer

coefficient for
(a) PHOSFLOW treated cycle and
(b) control cycle
300
250
200
0
100
200
300
Cycle Time (hours)
400
100
200
300
Cycle Time (hours)
400
Valve Position (% Open)
100
80
60
40
20
100
80
60
FIGURE 3:
40
Data for valve position for

(b) control cycle
20
0
44
100
200
300
Cycle Time (hours)
400

54.0
Current Load (Amps)
53.5
53.0
52.5
52.0
51.5
51.0
50.5
50.0
0
100
200
300
Cycle Time (hours)
400
54.0
Current Load (Amps)
53.5
53.0
52.5
52.0
FIGURE 4:
51.5
Data for current load on

recirculating pump for
(b) control cycle
51.0
50.5
50.0
0
100
200
300
Cycle Time (hours)
400
100
200
300
Cycle Time (hours)
400
55
Flow Rate (m3/hr)
50
45
40
35
30
25
20
55
Flow Rate (m3/hr)
50
45
40
35
FIGURE 5:
30
Data for feed acid flow rate for

(b) control cycle
25
20
100
200
300
Cycle Time (hours)
400
45

With the exception of the valve position parameter, all
other data points indicated that the antiscalant effectively
controlled the scale buildup in the feed acid line and heat
exchanger, especially compared to the control cycle. It can
be observed that the flow rate, heat transfer coefficient
and current load were all maintained to a greater degree
than in the control cycle. With respect to the feed acid line,
it did require a washout as the data indicated a blockage
occurred however it should be noted that the slope of the
curve before jumping to 100% open and after the washout
(where it returned to baseline) was very low in contrast to
the control cycle. Additionally, the increase in valve position
was not accompanied by a large drop off in flow rate as in
the control cycle indicating a reduced scaling rate. Thus

a higher rate of production was realized in the antiscalant
treated cycle.
When the heat exchanger was opened and inspected, it was
observed that only 18 tubes were plugged compared to a
historical average of 150. Additionally, the cleanout using
a high pressure water lance took approximately one hour
compared with a historical average of 15 hours.
The data and visual inspection results showed great promise
for extending the cycle length of the heat exchanger, thus it
was decided to continue the evaluation with a trial aimed at
doubling the cycle time.
2.2. Results from Extended 6 Week Trial of PHOSFLOW Antiscalant
As with the 3 week trial, the antiscalant was dosed into the
outlet side of the feed line pump carrying 28% P2O5 acid
from a storage tank to a heat exchanger designed to increase
the acid concentration to 54% P2O5. The dose was set at
50 ppm (vol/vol) for the duration of the trial and monitored

regularly. Figures 6 and 7 show the data from the process
parameters of interest for the antiscalant treated cycle.
650
600
550
500
450
400
350
300
250
200
0
200
400
600
Cycle Time (hours)
800
1000
100
80
60
FIGURE 6:
40
Data for heat transfer coefficient

and valve position for extended
evaluation of PHOSFLOW
20
0
46
200
400
600
Cycle Time (hours)
800
1000

54.0
Current Load (Amps)
53.5
53.0
52.5
52.0
51.5
51.0
50.5
50.0
0
200
400
600
Cycle Time (hours)
800
1000
55
Flow Rate (m3/hr)
50
45
40
FIGURE 7:
35
Data for current load on

recirculating pump and feed
acid flow rate for extended
evaluation of PHOSFLOW
30
25
20
0
200
400
600
Cycle Time (hours)
800
The data for the process parameters show a successful

extension of the cycle time without as significant degradation
in heat transfer coefficient, feed acid flow rate, or increase
in pump current load. In the case of valve position, it can
be observed that the line was not cleaned out sufficiently
from the start and that it had already developed a blockage.
Nevertheless, the antiscalant allowed for production level
flow rates for a significant period of time before the line was
washed. No additional line cleanouts were necessary during
the remainder of the trial which lasted an additional 700
hours past the first cleanout. This is significantly more than
1000
their average cycle time from historical data of 486 hours so

a mid-cycle wash was effectively eliminated.
When the heat exchanger was opened and inspected, it
was observed that only 66 tubes were plugged compared
to a historical average of 150 tubes for a 3 week cycle.
Additionally, the cleanout time using a high pressure
water lance took approximately 2.5 hours compared with
a historical average of 15. The operators observed that
the scale was very soft and easy to remove from the heat
exchanger tube walls.
3. Conclusion
The plant trial results demonstrate that Cytec Industries
PHOSFLOW antiscalant technology provided a significant
benefit in terms of controlling scale buildup within process
pipelines and heat exchangers of a phosphoric acid plant.
Figures 8 and 9 summarize the results of the three trials and

new process option available by applying the antiscalant. The
trials were considered a success and are leading to further
evaluations of the technology at this customers plant and
others to help establish the robustness of the technology.
47
Total Cycle Time (weeks)

Regular Process
Hours Required to Clean Heat Exchanger
3.5
Regular Process
with PHOSFLOW
6.8
with PHOSFLOW
15.0
2.0
+94%
-87%
# of Heat Exchange Tubes Plugged

150
Regular Process 3+ weeks

with PHOSFLOW 3+ weeks
18
-88%
66
with PHOSFLOW 6+ weeks
-56%
FIGURE 8:
Compilation of plant trial results
for application of PHOSFLOW
antiscalant technology
Feed line
3 day
Feed line
wash boil-out wash
(4 hours)
(4 hours)
Baseline
Process
Process with
PHOSFLOW
3 weeks
3 weeks
Only one feed line wash / no 3 day boil-out 6+ weeks
Feed line wash (4 hours)

FIGURE 9:
Comparison of customers
historical process with one
using PHOSFLOW antiscalant
48

References
Theys, T, 2003. Influence of the Rock Impurities on the
Phosphoric Acid Process, Products and Some Downstream Uses,
presented at the IFA Meeting of the Technical Committee , Abu
Dhabi.
[3]
Behbahani R.M., Mller-Steinhagen, H., and Jamialahmadi M.,

2003. Heat Exchanger Fouling in Phosphoric Acid Evaporators
Evaluation of Field Data, Heat Exchanger Fouling and Cleaning:
Fundamentals and Application, Vol. 9, p. 60.
[4]
[1]
[2]
Behbahani R.M., Mller-Steinhagen, H., and Jamialahmadi M.,

2006. Investigation of Scale Formation in Heat Exchangers of
Phosphoric Acid Evaporator Plants, The Canadian Journal of
Chemical Engineering, Vol 84, p. 189.
Jamialahmadi, M., Mller-Steinhagen, H., 2007. Heat Exchanger
Fouling and Cleaning in the Dihydrate Process for the Production
of Phosphoric Acid, Chemical Engineering Research and Design,
Vol 85, p. 245.
49
Contact Us
Bradford, UK
Welland, Canada:
Collectors, Extractants
Longview, WA:
Emulsions
Botlek, Netherlands: Dewatering Aids

Werndorf, Austria: CGM
Mt Pleasant, TN:
Extractants
Stamford, CT
Willow Island, WV:
Collectors, Dewatering Aids
Atlanta, GA: CGM, Collectors
Mobile, AL:
Emulsions
Phoenix, AZ
Houston, TX: Collectors, Frothers
Atequiza, Mexico:
Collectors, Anti-Scale
Rayong, Thailand: Emulsions,

Flocculants, Blending
Antofogasta, Chile:
Collectors, Blending
& Warehousing
Australia:
Collectors,
Blending
So Paulo, Brazil
Australia: Emulsions
Santiago, Chile
Manufacturing Sites
Research Centers
Corporate Headquarters
Cytec Industries Inc.
Five Garret Mountain Plaza
Woodland Park, NJ 07424 USA
Tel: +1 973 357-3193
US Toll Free: +1 800 652-6013
Fax: +1 973 357-3117
North American
Regional Office
Cytec Industries Inc.
2085 E. Technology Circle
Suite 102
Tempe, AZ 85284 USA
Tel: +1 480 730-2000
Fax: +1 480 730-2245
50
South American
Regional Offices
Europe, Africa and the

Middle East Regional Office
Los Orfebres 305

La Reina, Santiago, Chile
Tel: +56 2-560-7901
Tel: +56 2-560-7900
Fax: +56 2-273-6423
Cytec Industries BV38,

Franko Str., Of. 4
Kiev, 01030
Ukraine
Tel: +380-44-2302093
Fax: +380-44-2386076
Cytec Comrcio de Materiais

Compostos e Produtos
Qumicos do Brasil Ltda.
Av. Dr. Cardoso de Melo,
1460-6 andar CJ 61-62 Ed Pillar
CEP 04548-005 Vila Olimpia
So Paulo SP, Brazil
Tel: 55-11-5033-2828
Asia Pacific Regional Office

Australia Regional Office
Cytec Australia Holdings Pty Ltd.
Suite 1, Level 1, Norwest Quay
21 Solent Circuit
Baulkham Hills, NSW 2153
AUSTRALIA
Tel: +61 2-9846-6200
Fax: + 61 2-9659-9776
China Regional Office

30A Junyao International Plaza
789 Zhao Jia Bang Road,
Xuhui District
Shanghai 200032
Tel: +86-21-6422-8920
Fax: +86-21-6422-8980
Delivering Innovative Technologies for the Mining Industry Since 1907

1951
1907
Calcium Cyanamide American Cyanamid
1905
1910
1925
1937
AERO brand
Cyanide in leadzinc flotation
Mercaptobenzothiozole
chemistry (AERO 400
series) as flotation
collector
1915
1920
1925
1930
Sulfonates
for non sulfide
flotation
1935
1940
1915
1930
AERO brand
Cyanide in gold
and silver
cyanidization
Dithiophosphates
AEROFLOAT for
sulfide flotation
1945
1975
1983
1965
Hydroxamated PAMs
for Bayer Process
1981
1989
SIMS
pioneered
for plant
troubleshooting
AEROPHINE
flotation products
1975
1980
1970
1978
New collector
formulations
for non-sulfide
flotation
Synthetic polymers
for Bayer liquor
washers
1985
2013
CYFLOC TF-9000
Alumina hydrate flocculant
AEROFLOAT MX 500
1990
1995
2000
2005
2010
2010
ACORGA NR
extractant
(nitration resistant)
1999
2001
Alkyl hydroxamate collectors

for oxides and clay
Chemical enhancement of magnetic

separation (MagSep) technology
1994
New pyrite
depressants
1987
Alumina hydrate flocculant

CYFLOC TF-8000
Polymeric depressants
for Mg silicate minerals
Ester modified aldoxime
First generation neutral

circuit promoters
2007
ACORGA OPT products
1988
Polymeric depressants
for flotation
Synthetic polymers
for flocculation
New chemistries AERO XD-5002 &

MAXGOLD series for sulfide flotation
CYTEC is spun off from

American Cyanamid
Selective gold collectors

introduced (MTP)
1980
1960
2008
MAX HT for scale control

in alumina refineries
1992
CYANEX 301
extractant
CYANEX 272
extractant
1970
2004
1984
CYANEX 923
extractant
1965
FLOTATION MATRIX 100

for improving metals recovery
1955
1952
Heavy media
process for coal
and other minerals
2005
Nonyl salicylaldoxine
(Aldoxime) Cu extractant
1950
1948
1976
Synthetic red mud flocculants
for Bayer Process
1955
Synthetic alcohol
and polyglycol
frothers
Cadmium removal agents for

phosphoric acid production
CYANEX 600
(molybdenum
extractant)
AERO 7260 HFP
mineral depressant
2011
2015
2020
2012
PHOSFLOW for scale control
in phosphoric acid plants
Chemical enhancement of
electrostatic separation
(AERO EZ reagents)
ACORGA Crud Buster
1000 reagent
CYANEX 572 solvent extraction
reagent for Rare Earths
Alumina CYFLOC HX Ultra flocculants

XR Series - Xanthuate replacement chemistries
ACORGA OR extractant (oxidative resistant)
51
DELIVERING TECHNOLOGY BEYOND

OUR CUSTOMERS IMAGINATION
cytec.com
TRADEMARK NOTICE:
The indicates a Registered Trademark in the United States and the
indicates a trademark in the United States. The mark may also be
registered, subject of an application for registration, or a trademark
in other countries.
2013 Cytec Industries Inc. All rights reserved
CYTECSOLUTIONS_V17

Cytec Solutions V17 2013 PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Cytec Solutions V17 2013 PDF

Uploaded by

Copyright:

Available Formats

DELIVERING TECHNOLOGY BEYOND

OUR CUSTOMERS IMAGINATION

Letter from the Vice President

Solvent Extraction, Mineral Processing and Alumina Processing

Crud Processing Improvements Using Acorga

The crud buster process involves mixing the crud with

Solvent Extraction, Mineral Processing and Alumina Processing

Crud Processing Improvements Using ACORGA CB 1000 Crud Busting Reagent

Crud Buster Benefits

largely free of suspended solids. This clean organic stream

additional time to drop and recharge the press). Centrifuges

Total Suspended Solids (TSS)

the equipment being utilized. High TSS in recovered organic

Crud Processing Improvements Using ACORGA CB 1000 Crud Busting Reagent

Visually it is easy to see that the final organic product

Interfacial Tension (IFT)

the circuit organic. This reduction in organic IFT is true for

Figure 4 shows the interfacial tension of various organic

Interfacial Tension (dynes/cm)

Recovered Organic from Crud

Clay Treated Organic

Solvent Extraction, Mineral Processing and Alumina Processing

Crud Processing Improvements Using ACORGA CB 1000 Crud Busting Reagent

aqueous remaining with the organic. As shown in Figure 5,

Interfacial Tension Time (dynes/cm)

Recovery Organic Clay Treatment Curve

Clay Treatment vs.

Clay Concentration (wt%)

The use of ACORGA CB 1000 efficiently separates the

organic to be treated with the appropriate clay dosage

Benefits of Higher Organic Quality

typical mechanical crud processing means. This work was

Table 1. Pilot Plant Comparison

Typical Processed Organic

Extract PDT Org Cont. (seconds)

Extract PDT Aq Cont. (seconds)

Strip PDT Org Cont. (seconds)

Dispersion Band Org Cont. (% of org depth)

Cu:Fe Transfer Ration

Crud Processing Improvements Using ACORGA CB 1000 Crud Busting Reagent

Note: Lower Fe transfer (along with reduced aqueous

The crud buster process enables efficient clay treatment

3. T. Burniston, J.N. Greenshields, and P.E. Tetlow, Crud control in

Use of ACORGA NR Reagents in the Presence of

Nitration is certainly a function of the nitrate concentration

The nitration mechanism is shown below:

R1 H or CH3 (aldoxime or ketoxime)

solutions. McCabe Thiele analysis was then used to calculate

Table 2: Results of Simulations with Plant Solutions (23% extractant).

Efficiency [%] Train A

Efficiency [%] Train B

The better extraction kinetics under high copper tenor and

copper recovery than LIX 84I extractant, which was used in

Accelerated Nitration Tests

Table 3: PLS Conditions for the Accelerated Nitration Tests.

Solvent Extraction, Mineral Processing and Alumina Processing

NR10 reagent (approx. 50%) compared to LIX 84I, LIX 860

Residual Copper, gpl Cu

Results of the accelerated

Cu and pH 2.0 and the ROM leaching solution at 1.6 gpl

Stage efficiencies for PLS

Accelerated Nitration Tests

Table 4: Characterization of the PLS