Light Metals 2010 Edited by: John A.

Johnson TMS (The Minerals, Metals & Materials Society), 2010

Improvement of Product Quality in Circulating Fluidized Bed Calcination

Cornelis Klett1, Michael Missalla1, Roger Bligh2 Outotec GmbH, Ludwig-Erhard-Str. 21, 61440 Oberursel, Germany 2 Outotec (Australasia) Pty Ltd, Unit 1/25 Frenchs Forest Rd, Frenchs Forest, NSW 2070, Australia
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Keywords: Circulating Fluidized Bed, Calcination, Product Quality, Particle Breakage Abstract Until the introduction of Circulating Fluidized Bed (CFB) Calciners by Outotec (formerly Lurgi) in 1961, rotary kilns were the standard technology for the calcination of alumina. Since then, stationary calciners such as CFBs are the preferred technology for new installations due to their superior energy efficiency and uniform product quality. Over the last years Outotec has researched ways to minimize particle breakage in its CFB calciners. Although particle breakage is strongly dependent on the properties of the hydrate such as particle agglomeration and shrinking behavior, other major influences like mechanical stress are a direct function of calcining technology. Measurements for recently installed calciners have shown that Outotec has made a significant leap forward to reduce the particle breakage close to the level of rotary kilns whilst maintaining their enhanced operating performance and energy efficiency. The results of the recent achievements will be presented in this paper. Introduction Product quality is always a major focus for every industrial operation, with only production safety being more important. The production of Aluminium Hydroxide and its calcination to alumina is no exception. The calcination step is the last step in the chain of process steps to produce alumina from bauxite. Until the 1960s the calcination reaction was always performed in rotary kilns until 1961, when Outotec (then known as Lurgi) invented the circulating fluidized bed technology and applied it to the calcination of alumina in Circulating Fluid (CFB) Bed Calciners. With this new technology, energy consumption for alumina calcination was instantly cut by 30% and fluidized bed has been the technology of choice ever since. The new technology had quite some impact on product quality. While criteria such as LOI, BET, pick-up of iron and silica kept constant, the production of alpha alumina was significantly decreased while fines generation was increased. Although reduction of alpha alumina is basically considered to be an improvement in quality, increased fines is not. The mass fraction of particles smaller than 45m is a common measure of fines content and should be as low as possible but certainly within the limits specified by the smelter customers. To achieve the much lower energy consumption than rotary kilns CFB Calciners utilize much more energetic means of gas-solids contact (such as cyclones) with significantly higher velocities and hence strong mechanical stress on the particles. This leads to higher generation of fines in the process as compared to the calination in rotary kilns and has the result that the hydrate produced by the alumina refinery must be stronger and contain less fines in order to meet the final product quality specification. While this has certainly been achieved in many refineries, nevertheless, there are additional constraints placed on refinery performance indicators (e.g. yield).. Since the introduction of CFB Calciners, a major part of Outotecs calcination research has been dedicated to reducing fines generation without compromising on energy consumption or other aspects of on product quality (e.g. attrition index). While Outotec has been steadily improving its technology to reduce fines generation for many years, the latest installations represent a significant step improvement, with the result that the particle breakage in CFB Calciners has been reduced to only marginally higher than in rotary kilns and much lower than in earlier installations. The following areas have been improved and modified to achieve this: Decrease of mechanical stress on the alumina particles Optimization of reaction environment to produce less brittle alumina particles Optimization of process stability for stable operating conditions Particle Breakage In calcination the generation of fines is caused by Particle Breakage (PB). PB is defined generally as follows: PB = (Fraction < 45m)Alumina - (Fraction < 45m)Hydrate Where (Fraction < 45m)Hydrate is the mass fraction of the feed material to the calciner smaller than 45m and (Fraction < 45m)Alumina is the corresponding mass fraction in the alumina discharged from the calciner. It represents the increase of fines during the calcination process. However, PB consist of a few different effects and can further be split up according to the following contributions: PB = PBHydrate-attr. + PBtherm. + PBshrink. + PBmech. PBHydrate-attr. is the generation of fines due to attrition or abrasion of the uncalcined hydrate particles. Research has shown, that hydrate particles are very stable and the generation of fines from hydrate particles is not caused by breakage, but by surface abrasion. The amount of fines generated by this mechanism is fairly small compared with other mechanisms and can be neglected in the first instance.

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PBtherm. is breakage caused by thermal shock. In the various stages in the calcination process the hydrate particles undergo several stages of very rapid heating and temperature changes with fast generation of vapor. It has been investigated whether this can cause thermal stress in the particles or inner pressure due to vapor generation and lead to the fracture of the particles. For a few hydrates that seems to be possible, but for the majority of hydrates this effect could not be observed [1]. Whereas the first two contributions to PB can be neglected they have been named here to be complete and correct. The last two effects are the dominating ones and need to be considered carefully to assess the issue of PB in calcination. PBshrink.: During the reaction from hydrate to alumina the particle undergoes a shrinkage effect. The water is not just released from the crystal, but the crystal also gets restructured and contracts. Particles, which were just slightly larger than 45m, can shrink enough to be after the reaction smaller than 45m and will be recognized as PB as defined above. The amount of PB caused by PBshrink. depends on the morphology of the hydrate particles and on the mass fraction of particles just slightly larger than 45m. Hence it depends on the feed material to the calciner. Figure 1 shows the obtained PBshrink. for various industrial hydrates. The PBshrink. was obtained by calcining the material in a muffle furnace up to 1000C and then calculating the difference of the mass fraction smaller than 45m before and after the calcination. The values of PBshrink. varies some percentage points between the hydrates of different qualities. As the mass fractions smaller than 45m was obtained by air jet sieving sometimes the determination of shrinkage can also lead to an apparent growth of particles. This effect can be caused by the non-spherical shapes of the particles.

Figure 2: Typical CFB Calciner Flowsheet stream. In the feeding point and also in the cyclones they are exposed to mechanical stress. Gas cyclones are operating with fairly high inlet velocities between 10 to 30m/s. When the particles enter the cyclone they cannot follow the gas stream and due to their inertia they are exposed to particle-wall collisions at the inlet region of the cyclone [2]. Attrition tests have shown, that this effect is unfortunately barely influenced by the inlet geometry (tangential or volute). Outotec has investigated in detail the particle breakage of smelter grade alumina particles in gas cyclones. Besides the gas velocity also the solids concentration in the gas stream is of significant influence. In test cyclones the breakage is investigated by treating the material at various inlet velocities and concentrations. The development of the particle size distribution is monitored and the generation of fines in the smaller 45m class can be obtained. Figure 3 shows for one alumina the dependency of fines generation in a cyclone over the solids concentration at the cyclone inlet. It is clearly shown that at low inlet solids concentration, PB is significantly higher than at higher concentrations. This effect is known from other industries as the cushioning effect. The higher densities of particles lead to a dispersion of the impact energy over a larger number of particles. The higher density also leads to much shorter free traveling distances for particles to re-accelerate after a collision before they experience the next hit.

Figure 1: Particle Breakage due to shrinkage for various industrial hydrates. PBmech. is the last contributor to the overall breakage and also the most dominant one. It is most important to understand the PBmech since it can be influenced by the design of the calcination plant. Particle Breakage by Mechanical Stress In CFB calciners as shown in figure 2, the particles have to pass through several stages of heat recovery and reaction. In these stages they are exposed to mechanical stress due to particleparticle and particle-wallcollisions. The calciner in figure 2 consists of two preheating stages, the calcination stage in form of the CFB and two cooling stages and finally the fluid bed cooler. In the preheating stages and the cooling stages the particles are mixed with hot or cold air at the feed point. From there they travel to a gas cyclone, where they are separated again from the gas

Figure 3: Particle Breakage in Cyclones vs. Solids Inlet Concentration (typical)

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In CFB calciners as well as in flash calciners the typical solid loading in the preheating and cooling cyclones inlets can be found in the left half of the curve, whereas, in the recycle cyclone of a CFB, the solids loading is of significantly higher order of magnitude, and well beyond the right end of the curve. Due to the very high solids concentration in the CFB the contribution to overall particle breakage breakage from this process stage is reduced. In addition to the breakage in gas cyclones also breakage in the vicinity of fluidizing nozzles and fuel injection lances needs to be considered. The breakage in the dense fluid bed, such as the bottom zone of the CFB or the fluid bed cooler has been found to be significantly lower than in cyclones by one or two order of magnitudes. Due to the high solids densities and the comparatively low impact speed during collisions, attritions seem to be the more dominant mechanism here than actual breakage.
20 18 t=1.1h t=4.7h t=57.0h t=77.1h t=88.4h

The normal residence time of the material in the calciner is in the order of 30 minutes, hence more than ten times less than the test period. The observed breakage in the fluidized bed is less than 0.03% in a period of 30 minutes and can be neglected in further investigations. Breakage Behavior of Material Besides the conditions under which the alumina particles are exposed to mechanical stress also their breakage behavior and properties are of importance. In 2004 Outotec has presented a method of investigating the general strength of alumina particles originated from different hydrates [2]. The investigation has shown that the quality of the hydrate has significant influence on the strength of the alumina particles produced from it. During the breakage test work, the breakage behavior or characteristic of the material can also be assessed. When exposing the material to mechanical stress under various conditions, the change of the particle size distribution can be observed. Figure 5 shows the results of such tests for different aluminas originating from different hydrates. The chart on the left shows the behavior for an alumina produced from a strong hydrate. Whereas the chart on the right shows the behavior of a weak alumina. During breakage the particles undergo several subsequent breakages. It can be seen for the strong alumina (left), that the particles are very resistant to breakage and two distinct peaks are observed. The peak of the fine particles is formed by the fragments of the mother particles. The peak for the fragments is lower than for the mother particles and the general shape of the coarse fraction does not change too much. The weak Alumina does show only a very narrow peak for the fines with a very wide lower peak for the mother particles. Further it has been observed that weak hydrates typically also contains a high proportion of particles around the sizes of 50m, which will firstly likely to shrink into the fines below 45m, but also break very fast into the fraction below 45m. When defining the particle breakage at 45m the strong alumina does show as much increase in the sub 45m class since most of their fragments are still larger than 45m. By contrast, fragments broken from weak alumina tend to report to the sub 45m class and will significantly contribute to the Particle Breakage of the calciner.

Mass Fraction, % Q3,%

16 14 12 10 8 6 4 2 0 0 20 40 60 80 100 120 140

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180

particle diameter, m Particle size, m

Figure 4: Breakage in Fluidized Bed under typical fluidization conditions as in Fluid Bed Cooler Figure 4 shows the development of particle size distributions in a 50mm test fluidized bed over a period of 88 hours. The material was fluidized with velocities similar to the velocity in the fluid bed cooler of a modern CFB calciner. In frequent time intervals samples have been taken and the current bed particle size distribution has been measured. Over the period of 88 hours, no significant breakage could be observed.

Figure 5: Change of particle size distribution during breakage test [2]. Left a strong alumina and right a weak alumina.

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Influence of Calcination Temperature on Particle Breakage Although most of the influence on particle breakage is imbedded in the properties of the feed hydrate, a influences are present in the calcinations process, which can be controlled. Using the characterization technique developed by Outotec [2] the influence of temperature on the friability of alumina has been investigated. Figure 6 shows the results of this investigation for one hydrate. Hydrate samples have been taken and calcined in a muffle furnace at different temperatures (x-axis), then treated in the apparatus described in [2] and the increase of fines smaller than 45m determined. It shows, that at low calcination temperatures the increase of friability is low as the fines generated during the subsequent breakage test is low. Between 500 and 800C the slope is moderate and between 800 and 1000C the breakage increases rapidly.

equalize giving the particle a homogeneous temperature distribution. This could make the surface more brittle than the calcination temperature in figure 6 would suggest. In CFB Calcination the environment for the particles is significantly different. Due to the recirculation and the high solids concentration the heat is dissipated over a much larger number of particles and an overheating of surfaces does not occur. The energy needed for the hydrate particle to be calcined is not transferred once, but fed to the particle in a nearly constant manner by transferring heat from the recirculated particles, which have been taken on latent heat. The particles are heated slower and continuously. The temperature gradient within a single particle is low, which will then correspond close to the conditions of the data in figure 6. Operating Stability In order to achieve the best results for low particle breakage the operating stability of the process becomes more and more important. The findings presented above demonstrate not only the importance of proper design, but also operation of the calciner. Over the last years, [3] [4]the stable operation of CFB calciners have been in focus and great improvements have been made up to the point of complete automation of the plants. Figure 7 shows the ability to maintain calcination temperature in the furnace under all circumstances. The modern automation approaches enable the operators to change the load of the plant in a flexible manner and also to keep the furnace temperature within a range of +/- 10 to 15C. From Figure 6, the particle breakage changes between 800 and 1000C approx. 1.2% for every 10C increase. With a value of 40% in the Saatci Test [2] at 1000C this means a ratio of 3% on the actual breakage. For a plant with a normal PB of 3.5% this would correspond to a variation of 0.1% for each temperature variation of 10C. To control the particle breakage means to control the stability of furnace temperature. However the dependency could also be more than proportional, which would mean an over-proportional increase of breakage with increasing temperatures. In this case the fluctuations of calcination temperature around the set-point would be a disadvantage to the overall breakage as every increment of temperature would cause more damage than a decrease could compensate.
1050 400

Figure 6: Friability of alumina calcined at different calcining temperature. Modern calciners operate at temperatures between 950C (for CFB calciners) and 1050C (for flash calciners). This is the range with the highest impact on the strength of the calcined particles. It is very likely, that the curve increases even further beyond 1000C. The way the test is set up means, that nearly all coarse particles will break down to a natural minimum size. For weak material such as the one calcined at more than 1000C it means that after the normal test period no material is left to further break down into the lower 45m class and no increase in this class will be observed. A refinement of this procedure can elaborate on this question and will be included in the future work. This behavior shows the importance of controlling the calcination temperature very carefully and to avoid any hot spots, for example, in the vicinity of fuel lances and burners. However, the temperatures and conditions used in the test work do not absolutely represent the conditions in a calciner. The temperature profile within the calcination stage is not uniform and particles do not always experience the same temperature. Furthermore, the temperature profile within a particle does not need to be homogeneous either. For example, in the case of flash calcination, the solids concentration is relatively low and the majority of the material passes only once through the furnace. This means that all the energy needed for calcination needs to be transported from the combustion gas into the particle in an extremely short time. This can lead to very high temperature gradients within the particle and the surface has to be significantly overheated to more than the equilibrium calcination temperature. Only later will the heat

Furnace Temperature Setpoint

1000 Furnace Temperature, C

Furnace Temperature

350 Calciner Feed, t/h (wet) 300

950

250 235 200 150 100

900

850

800

50

Calciner Feed
750 0:00 6:00 12:00 18:00 0:00 6:00 Time 12:00 18:00 0:00 6:00 0 12:00

Figure 7: Operation stability of CFB calciners during rapid load changes

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At the refinery of Rio Tinto Alcan in Gove the unique opportunity existed, that rotary kilns, older CFB Calciner from 2000 and the latest CFB technology of Outotec operate at the same time with the same hydrate and hence hydrate quality. This enabled Outotec to demonstrate and test their latest technology against well known technologies with respect to their particle breakage performance. Figure 9 shows the results of the last 18 months of operation and indicates the percentage of particle breakage in old and new calciners as compared to the breakage in the rotary kilns at similar loads. As expected the existing CFB Calciner from 2000 produces up to 200% or 3 times more fines than the rotary kilns. The old calciner has maximum breakage at around 60% load, which is caused by excessive specific air flows at the low loads. As with fixed duct diameters a minimum flow needs to be established to maintain sufficient transport velocities. Furthermore, it is hard to separate stable operating data at these conditions from transient conditions such as start-up and shut down. Between 70% and 90% load the breakage is then the lowest as the unit can operate at its optimum ratios of air to fuel and air to solids flow. Then towards 100% load and beyond a slight increase in breakage can be observed as here the units are operated closer to their maximum, but still the breakage is only increased minimally. For the new CFB Calciners, the development of the breakage with plant operating load is qualitatively the same. However the breakage is significantly lower than for the older CFB unit and only slightly higher than for the rotary kilns. The breakage of the new CFB Calciners from 2007 are rarely higher than 50% or 1.5 times higher than for the rotary kilns. Future Developments With the gained knowledge and approach towards understanding particle breakage it is now also possible to investigate the consequences for new CFB Calciner flowsheets, such as the new configuration presented in a previous Outotec paper[6]. Figure 10 shows one of the latest flowsheets of Outotec. With the new flowsheet the energy efficiency of the CFB Calcination will be reduced significantly. The new process consist of the introduction of a hydrate dryer which is utilizing heat from the fluid bed cooler to dry hydrate prior to feed into the calciner from its free surface moisture.

Figure 8: Modern CFB Calciner flowsheet Latest Performance In 2007 Outotec commissioned their most recent CFB Calciners at Rio Tinto Alcans refinery in Gove. The flowsheet is shown in figure 8. These units have now been in operation for more than 18 months. In parallel an older version CFB Calciner from 2005 and a few rotary kilns were in operation. The new calciners have been specifically designed by Outotec to perform with very low particle breakage. As is typically the case when existing rotary kilns are replaced with new calcination technology, particle breakage becomes an issue for the refinery. This was especially the case in Gove because the older CFB calciner built in 2000 was producing only marginally acceptable fines content. Therefore, Outotec had to ensure a much lower breakage for the two new units, than for the older CFB Calciner. Outotec applied its recent research results to the new units. The main measures taken were Optimization of velocity profile Optimization of fluidization technology (SF Nozzle and improved bubble caps) Improved position for fuel injection Reduction in calcination temperature Improved automation for stable operation

Many of these improvements have been presented in the recent years [3], [4] and [5]. Up till now PB in CFB or flash calciners is typically about 5% (even up to 8%) higher than in rotary kilns. This is because rotary kilns rely on very long residence times and gentle heating rates. This ensures that no overheating is applied to th eparticles. The alumina particles are transported in a very dense bed and with low velocities. Hence the calcination in rotary kilns is typically more gentle. In CFB and flash calciners, the particles are mixed with gases, separated and further transported more vigorously than in rotary kilns, leading to a much higher mechanical stress imposed on the particles.

Figure 9: Particle Breakage of CFB Calciners compared to rotary kilns

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Now when the new configuration is installed as in figure 10, but with no by-pass in operation the additional stages have the potential to increase the breakage 3.7% if nothing else is modified. However, the by-pass is a major part of the energy saving methodology and can operate to up to 15% of the total dry hydrate flow. As a result, a few effects happen simultaneously. Firstly, only the remaining part of the hydrate flow will actually pass through the CFB and undergoes breakage there. Secondly the recombined flows of alumina originating from the furnace material and from the by-pass material has now been calcined at different temperatures. According to the temperature effect from above, the by-pass material is significantly less brittle and will lead to a reduction of breakage in the cooling stages. This effect is even large enough to compensate for any temperature increase in the furnace to achieve the target LOI. Figure 10: New low fuel consumption CFB Calciner As a result of the dry hydrate feed the temperature in the preheating stage 1 would increase as the heat of the gas flow is not needed anymore for evaporation of water. To recover the heat a third preheating stage can be introduced. As a further measure, a hydrate by-pass around the furnace is installed to bypass a small stream of dried hydrate past the furnace and mix it with the alumina discharge from the furnace. The by-passed material is then calcined with the heat from the alumina discharged from the furnace. As a further improvement a third cooling stage could be installed to improve the heat recovery from the alumina. With the introduction of a new calcination flowsheet or configuration, the question of the probable particle breakage also needs to be answered. Based on the findings above this question can be tackled. In figure 11 a few scenarios are investigated. The figure shows the expected particle breakage compared to a typical breakage of 3.5% for a Base Case CFB Calciner like the one shown in Figure 8. In case the furnace temperature is increased by 10C the particle breakage is likely to increase to 3.6% as described in the sections above.
3.8

With a by-pass ratio between 10 and 15% the particle breakage can be decreased to the same amount as in the Base Case configuration despite using more stages and more mechanical stress. Conclusions With the recent research activities and developments Outotec has made a significant effort to understand particle breakage in CFB Calciners. The recent success with the latest CFB Calciners generating particle breakage only slightly above the bench mark for particle breakage in rotary kilns demonstrate Outotecs capabilities to design optimum calcination technology for product quality. References [1] J. D. Zwicker, The Generation of Fines due to Heating of Alumina Trihydrate, TMS Light Metals (1985) [2] S. Saatci, H.W.Schmidt, W. Stockhausen, M.Strder, P.Sturm, Attrition behaviour of Laboratory calcined Alumina from various Hydrates and its influence on SG Alumina Quality and Calcination Design, TMS Light Metals pp 81-86 (2004)

3.7 Particle Breakage, %

[3] P. Hiltunen, R. Bligh, C. Klett, M. Missalla, H.-W. Schmidt, How to achieve high availability with large calciners and avoid unforeseen downtime, TMS Light Metals pp 63 68, (2008) [4] M. Missalla, J. Jarzembowski, R. Bligh, H.-W. Schmidt, Increased availability and optimization of calciner performance due to automation, TMS Light Metals , (2009) [5] M.Missalla, C.Klett, R.Bligh, Design Developments for Fast Ramp-up Easy Operation of New Large Calciners TMS Light Metals pp 79 85, (2007) [6] C. Klett, M. Missalla, R. Bligh, M. Stroeder, P. Hiltunen, M. Graham, Outokumpu Technologys State-of-the-Art CFB Calciners A Review, Proceedings to EMC (2007)

3.6

3.5

3.4

3.3

3.2 Base Case Furnace Temp. +10C Without Bypass Bypass 10 % Bypass 15 %

Figure 11: Particle breakage for different Calciner configurations

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