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Cytec Solutions: For Solvent Extraction, Mineral Processing and Alumina Processing
Cytec Solutions: For Solvent Extraction, Mineral Processing and Alumina Processing
IN PROCESS SEPARATION
Volume 17
CYTEC SOLUTIONS
for Solvent Extraction, Mineral Processing
and Alumina Processing
Michael Radossich
Vice President, In Process Separation
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
IN PROCESS SEPARATION
03
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
FIGURE 2:
ACORGA CB 1000 Mixing
and Settling
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
IN PROCESS SEPARATION
05
FIGURE 3:
TSS of Standard Filter Press and
CRUD BUSTER Process
using the crud buster process than the process using only
mechanical separation.
40
Plant Organic
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
30
29.2
27.6
34.9
Sample 2
Sample 3
Sample 4
39
FIGURE 5:
27
0
33.5.9
29.2
51
229
63
66
50
191
0%
61.2%
Organic Entertainment
34% decrease
Aqueous Entertainment
18% decrease
1032
645
IFT (dynes/cm)
IN PROCESS SEPARATION
07
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.
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.
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
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08
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.
OH
R1 + NO2+
R2
OH
O2N
H
OH
R1
R2
OH
O2N
OH
R1
R2
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
Extractant
Lix 84I
89.23
77.51
NR10
95.21
87.33
10
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
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
The results presented in Figure 1 show that there was a
strongest resistance to nitration when using the ACORGA
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
0.45
0.40
0.35
0.30
0.25
0.20
0.15
FIGURE 1:
0.10
0.05
IN PROCESS SEPARATION
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
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
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
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
As shown in the graph above higher stage efficiencies were achieved with the ACORGA NR reagent.
12
MODIFIED PLS
Acidity
g/L
5.7
NO3-
g/L
58.8
FeT
g/L
3.08
Cl-
g/L
10.38
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
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
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
IN PROCESS SEPARATION
Extractant
HEAP Extraction
Efficiency
(%)
ROM Extraction
Efficiency
(%)
Ketoxime
89.44
67.24
ACORGA NR 20
95.28
76.05
13
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
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.
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
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14
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%
Bulk Circuit
Flotation
Cu-Mo Bulk Concentrate (28% Cu, 1% Mo)
Mo Circuit
Roasting Steam
Cl2, O3, H2O2,etc
Pre-Treatment (Optional)
Cu Depressants
Tails
Cu Conc
FIGURE 1:
Conc
Mo Ro Conc
Mo Cleaner Circuit
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
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
Applicability and Other Advantages
Eliminates the need for N2 or covered cells.
Does not require extended conditioning time.
100
Cu
Mo
Recovery (%)
80
60
40
FIGURE 2:
20
0
NaSH 7.5 kg/T
IN PROCESS SEPARATION
17
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
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%
90
80
80.9
Mo
81.3
Cu
70
Recovery (%)
60
50
40
30
20
19.8
11.8
10
0
Na2S 44 kg /T
18
FIGURE 3:
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
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
98.8
92
NaSH 55 kg/T
90
NaSH 11 kg/T
80
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
Fe
Clearly, the benefits of adding AERO 7260 HFP are observed by the improved metallurgical performance and substantially
reduced dosage of NaSH.
IN PROCESS SEPARATION
19
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
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
.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
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
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
IN PROCESS SEPARATION
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers
NaSH, Nokes, Na2S, and Cyanide
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
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.
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.
22
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
23
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
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, %
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
Conditions
Ore-1
Ore-2
Ore-3
Machine
Agitair L500
Denver
Wemco
pH
10.5
9.5
9.5
% Solids
34
34
30
10
15
12
Grinding
30% + 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).
IN PROCESS SEPARATION
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
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
std
Test
FIGURE 2:
Evaluation of
selective versus non-selective
collectors 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
100
90
Cu
Cu-FC Grade =
Fe
Mo
80
Recovery (%)
70
60
50
40
30
FIGURE 3:
20
10
0
Rougher
Final
ST
Rougher
Final
Rougher
AP-
IN PROCESS SEPARATION
Final
AP-
100
90
Cu
Cu-FC Grade =
Fe
Mo
80
Recovery (%)
70
60
50
40
30
FIGURE 4:
20
10
0
Rougher
ST
Final
Rougher
Final
Coll-STD /
A-7260; 50
Rougher
Final
Coll-STD /
A-7260; 100
28
Rougher
Final
Coll-STD /
MBS-Na; 300
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.
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.
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.
IN PROCESS SEPARATION
29
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
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
Without Antiscalant
With Antiscalant
2700
2500
y = -8.325x + 1981.8
2300
2100
1900
1700
1500
1300
1100
900
FIGURE 4:
700
500
0
10
20
30
40
50
60
70
80
Hours
IN PROCESS SEPARATION
31
2300
2100
y = -0.4267x + 1744.1
1900
1700
1500
1300
1100
FIGURE 5:
900
700
500
1
11
21
31
41
51
61
71
81
91
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
Energy (Gj)
0.26 1.3
13 92
0.9 2.7
11 56 million
38 116 million
25 128 million
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.
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).
IN PROCESS SEPARATION
33
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.
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.
34
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.
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
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.
30
CYFLOC HX-3000
CYFLOC Ultra HX-5300 (Lab. Lot)
25
FIGURE 1:
150
200
250
300
350
400
600
CYFLOC HX-3000
CYFLOC Ultra HX-5300 (Lab. Lot)
500
Overflow Solids (mg/L)
FIGURE 2:
100
0
100
150
200
250
Total Dose (g/T)
36
300
350
400
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
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
IN PROCESS SEPARATION
37
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
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
5/2/12
Date
HX-3000 ULTRA HX-5300
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
MR = 8.77
FIGURE 4:
LCL = 0
5/2/12
Date
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
9/2/12
Date
HX-3000 ULTRA HX-5300
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
9/2/12
MR = 0.344
FIGURE 5:
LCL = 0
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
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
9/2/12
Date
HX-3000 ULTRA HX-5300
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
9/2/12
Date
IN PROCESS SEPARATION
39
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
HX-3000 ULTRA HX-5300
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
9/2/12
Date
HX-3000 ULTRA HX-5300
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
MR = 0.0381
FIGURE 7:
LCL = 0
9/2/12
Date
40
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant
Applied in CBA (Companhia Brasileira de Aluminio)
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
9/2/12
Date
HX-3000 ULTRA HX-5300
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
MR = 14.4
FIGURE 8:
LCL = 0
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.
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.
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.
IN PROCESS SEPARATION
41
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
(%)
4 weeks
250
3125
3.0
5 weeks
300
3750
3.6
6 weeks
333
4167
4.0
42
IN PROCESS SEPARATION
43
100
200
300
Cycle Time (hours)
400
650
600
550
500
450
400
FIGURE 2:
350
300
250
200
0
100
200
300
Cycle Time (hours)
400
100
200
300
Cycle Time (hours)
400
100
80
60
40
20
100
80
60
FIGURE 3:
40
20
0
44
100
200
300
Cycle Time (hours)
400
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
51.0
50.5
50.0
0
100
200
300
Cycle Time (hours)
400
100
200
300
Cycle Time (hours)
400
55
50
45
40
35
30
25
20
55
50
45
40
35
FIGURE 5:
30
25
20
100
IN PROCESS SEPARATION
200
300
Cycle Time (hours)
400
45
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
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
20
0
46
200
400
600
Cycle Time (hours)
800
1000
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
50
45
40
FIGURE 7:
35
30
25
20
0
200
400
600
Cycle Time (hours)
800
1000
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.
IN PROCESS SEPARATION
47
3.5
Regular Process
with PHOSFLOW
6.8
with PHOSFLOW
15.0
2.0
+94%
-87%
18
-88%
66
-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
48
[3]
[4]
[1]
[2]
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.
IN PROCESS SEPARATION
49
Contact Us
Bradford, UK
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Collectors, Extractants
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Emulsions
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Extractants
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Manufacturing Sites
Research Centers
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Cytec Industries Inc.
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Woodland Park, NJ 07424 USA
Tel: +1 973 357-3193
US Toll Free: +1 800 652-6013
Fax: +1 973 357-3117
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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
1905
1910
1925
1937
AERO brand
Cyanide in leadzinc flotation
Mercaptobenzothiozole
chemistry (AERO 400
series) as flotation
collector
1915
1920
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1930
Sulfonates
for non sulfide
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Cyanide in gold
and silver
cyanidization
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AEROFLOAT for
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Alumina hydrate flocculant
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1990
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extractant
(nitration resistant)
1999
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IN PROCESS SEPARATION
1994
New pyrite
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1987
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for Mg silicate minerals
2007
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1980
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1965
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process for coal
and other minerals
2005
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(Aldoxime) Cu extractant
1950
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1955
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and polyglycol
frothers
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(molybdenum
extractant)
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1000 reagent
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51
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