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IN PROCESS SEPARATION
VOLUME 17
CYTEC SOLUTIONS
for 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
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. 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.
04
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.
IN PROCESS SEPARATION
05
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.
40
35
34.4
34.6
30
29.1 27
29.3 27.6
29.2 26.8
30
25
22.3
FIGURE 4: IFT of Circuit Organic, Recovered Organic, and Clay Treated Organic
06
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.
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.
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.
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. 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. The nitration mechanism is shown below: NO3- + H2SO4 HNO3 + HSO4- (1) HNO3 + H2SO4 NO2+ + H2O + HSO4- (2)
OH N OH R1 + NO2+ R2 O2N H OH + R2 N OH R1 O2N OH N OH R1
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.
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
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
TabLE 2: Results of Simulations with Plant Solutions (23% extractant).
solutions. McCabe Thiele analysis was then used to calculate the expected recovery for the configuration. The results are presented in Table 2.
Efficiency [%] Train B 77.51 87.33 copper recovery than LIX 84I extractant, which was used in the plant.
The better extraction kinetics under high copper tenor and low pH conditions of ACORGA NR10 results in a 6% higher
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 NR10 reagent (approx. 50%) compared to LIX 84I, LIX 860 and Plant Organic.
2.0 1.8 1.6 1.4 Nitration (%) 1.2 1.0 0.8 0.6 0.4 0.2 0 03-10-2012 12-09-2012 19-09-2012 26-09-2012 10-10-2012 24-10-2012 31-10-2012 17-10-2012 07-11-2012 14-11-2012 21-11-2012 28-11-2012
0.50 0.45 Residual Copper, gpl Cu 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0 26-09-2012 10-10-2012 17-10-2012 24-10-2012 07-11-2012 14-11-2012 21-11-2012 12-09-2012 19-09-2012 03-10-2012 28-11-2012 31-10-2012
FIGURE 1: Results of the accelerated nitration tests based on residual copper and nitroxime
IN PROCESS SEPARATION
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 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 80 70 60 50 40 Acorga NR 20 HEAP LIX 84 IC HEAP Acorga NR 20 ROM LIX 84 IC ROM 80.1 79.5 90 85.9
As shown in the graph above higher stage efficiencies were achieved with the ACORGA NR reagent.
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.
12
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
60 50 40 30 20 10 0 0 1 2 3 4 Sample 5 6 7 8
Nitration (%)
FIGURE 3: Results of accelerated nitration tests based on residual copper and nitroxime
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
HEAP
Cu PLS pH / H2SO4 O/A E O/A S g/L - / g/L 1.97 2.08 0.95 1.24
ROM
1.63 1.81 0.95 1.24
Spent
42 175
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
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.
IN PROCESS SEPARATION
13
Use of ACORGA NR Reagents in the Presence of Nitrate Ions in SX: The State of the Art
30 25 20 Fe+3, ppm 15 10 5 0 0 10 20 30 40 50 60 70 80 90 100 Loaded Organic, % 30 25 20 Fe+3, ppm 15 10 5 0 0 10 20 30 40 50 60 70 80 90 100 Loaded Organic, % ROM-Ketoxime ROM-NR20
Heap-Ketoxime
Heap-NR20
FIGURE 4: Organic Fe Co-extraction as a function of copper loading for Heap and ROM solutions
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.
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.
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 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.
Cu-Mo ore
Cu ~ 0.5% Mo ~ 0.05%
Bulk Circuit Flotation Cu-Mo Bulk Concentrate (28% Cu, 1% Mo) Mo Circuit
Cu Conc
FIGURE 1:
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
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.
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.
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. 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.
100
Cu
Mo
80
Recovery (%)
60
40
20
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% 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 70 60 Recovery (%) 50 40 30 20 10 0 Na2S 44 kg /T Na2S 22 kg /T, AERO 7260 HFP 1.2 kg /T 19.8 11.8 80.9 81.3
Mo
Cu
18
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 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%.
a) 100
90 80 70 Recovery (%) 60 50 40 30 20 10 0 Cu 36.9 36.9 33
99.2
99
98.8 92 NaSH 55 kg/T NaSH 11 kg/T NaSH 11 kg/T + 0.25 kg /T 7260 68.4
47.2
Fe
B) 50
40
Grade (%)
30
20
FIGURE 4:
10 3.2 0 0.2 0.2 Cu 0.2 Mo Mo Concentrate Fe 4.2 2.4
2nd Cleaner Circuit Lab data of Cu, Mo and Fe a) recovery and b) grade
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 Average Mo in Scav Tail (%) .30 .25 .20 .15 .10 .05 0 Nokes Standard 50% Reduction 75% Reduction 100% Reduction
FIGURE 5: Plant data for Mo in scavenger tails as a function of Nokes dosages used
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
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.
20
AERO7260 HFP: Novel, Safe and Sustainable Alternative to Traditional Hazardous Modifiers NaSH, Nokes, Na2S, and Cyanide
% 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
Day 1 Day 2 Day 3
-60
-80
-100
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 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.
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 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
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). 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).
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.
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
TabLE 2: Laboratory Test Conditions for Each of the Ores
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.
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 92 90 Cu Recovery 88 86 84 82 80 15 20 25 30 35 40 45 50 55 60 Fe Recovery
DT
IPET
SMTC
FIGURE 1: Selectivity comparison for copper minerals vs. pyrite for 3 collector types
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 87.5 Cu Rec (%) 87 86.5 86 14.0 6.8 1 17.5 5.8 2 22.0 6.8 3 22.1 6.5 4 19.5 6.8 5 29.0 6.4 std Fe Rec (%) Mass Pull (weight %) Test
26
N 1 2 3 4 5 STD
Collector-1[M] AP-9950; 20 g/t XD-5002; 10 g/t AP-9950; 15 g/t MX-8522; 15 g/t MX-7017; 15 g/t PAX; 20 g/t
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). 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 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.
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
Cu-FC Grade =
Cu
Fe
Mo
FIGURE 3: Comparative study between a non-selective collector (SIPX) and two selective collectors
Rougher ST Final Rougher APFinal Rougher APFinal
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%).
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
IN PROCESS SEPARATION
Cu-FC Grade =
Cu
Fe
Mo
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%).
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.
28
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. 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. 3. G.I. Dvila-Pulido, A. Uribe-salas, R. Espinosaa-Gomez, International Journal of Mineral Processing, 101 (2011) 71-74. 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. 5. Maximiliano Zanin, Saeed Farrokhpay, Depression of Pyrite in Porphyry Copper Flotation, 8th International Mineral Processing Seminar (Procemin 2011), 135-143. 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.
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 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.
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
2700 2500 2300 2100 1900 1700 1500 1300 1100 900 700 500
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
y = -8.325x + 1981.8
FIGURE 4: Typical heat transfer decay during 160 hrs. without MAX HT
Hours
IN PROCESS SEPARATION
31
2300 2100 1900 1700 1500 1300 1100 900 700 500
1 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161
y = -0.4267x + 1744.1
FIGURE 5: Constant heat transfer coefficient resulting from the use of MAX HT
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.
TabLE 6. POtEntiaL and REaLiZEd BEnEfits Of MAX HT TEchnOLOgy Energy (Gj) CO2 Reduction (Kg) Waste Reduction (Kg)
Savings per ton of alumina produced Realized savings (20 commercial plants) Potential savings (All 73 plants)
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). 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. 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.
IN PROCESS SEPARATION
33
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
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. 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. 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. This paper describes the relative performance of CYFLOC ULTRA HX-5300 versus CYFLOC HX-3000 in the CBA alumina plant.
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 25 20 15 10 5 0 100 150 200 250 Total Dose (g/T) 300 350 400 CYFLOC Ultra HX-5300 (Lab. Lot) CYFLOC Ultra HX-5300 (Manuf. Lot) Settling Rate (m/h)
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.
600 CYFLOC HX-3000 500 Overflow Solids (mg/L) 400 300 200 100 0 100 150 200 250 Total Dose (g/T) 300 350 400 CYFLOC Ultra HX-5300 (Lab. Lot) CYFLOC Ultra HX-5300 (Manuf. Lot)
36
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 Flocculant Mud Settler TD 1 Mud Washer Mud Washer Mud Washer Filtrate (KM)
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
Date
HX-3000 ULTRA HX-5300
40 Moving Range 30 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 5/2/12
UCL = 28.65
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.
Date
HX-3000 ULTRA HX-5300
UCL = 1.125
38
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
UCL = 105.5
MR = 32.3
FIGURE 6:
LCL = 0 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.
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
Date
HX-3000 ULTRA HX-5300
UCL = 0.1246
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.
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.
40
Performance Evaluation of CYFLOC ULTRA HX-5300 A New HXPAM Red Mud Flocculant Applied in CBA (Companhia Brasileira de Aluminio)
350 Individual Value 300 250 200 150
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
HX-3000 ULTRA HX-5300
Date
HX-3000 ULTRA HX-5300
80 Moving Range 60 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 9/2/12
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.
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
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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
TabLE 1. Production Gain by Extending Cycle NEw shUt dOwn frEQUEncy (frOM 2 wEEks tO) 4 weeks 5 weeks 6 weeks PrOdUctiOn tiME savEd (hrs/yEar) 250 300 333 MErchant gradE acid prOdUctiOn incrEasE (T/yEar) 3125 3750 4167 (%) 3.0 3.6 4.0
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.
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
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.
42
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.
IN PROCESS SEPARATION
43
FIGURE 2: Data for heat transfer coefficient for (a) PHOSFLOW treated cycle and (b) control cycle
100 Valve Position (% Open) 80 60 40 20 0 100 Valve Position (% Open) 80 60 100 200 300 Cycle Time (hours) 400
FIGURE 3:
40 20 0 100 200 300 Cycle Time (hours) 400
Data for valve position for (a) PHOSFLOW treated cycle and (b) control cycle
44
FIGURE 4: Data for current load on recirculating pump for (a) PHOSFLOW treated cycle and (b) control cycle
55 50 Flow Rate (m3/hr) 45 40 35 30 25 20 0 55 50 Flow Rate (m3/hr) 45 40 35 30 25 20 0 100 200 300 Cycle Time (hours) 400 100 200 300 Cycle Time (hours) 400
FIGURE 5: Data for feed acid flow rate for (a) PHOSFLOW treated cycle and (b) control cycle
IN PROCESS SEPARATION
45
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.
FIGURE 6:
40 20 0 200 400 600 Cycle Time (hours) 800 1000
Data for heat transfer coefficient and valve position for extended evaluation of PHOSFLOW
46
FIGURE 7: Data for current load on recirculating pump and feed acid flow rate for extended evaluation of PHOSFLOW
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
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.
IN PROCESS SEPARATION
47
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
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. 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.
[3]
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.
[2]
[4]
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