Outokumpu Lurgi Metallurgie has developed a process for the calcination and reduction of laterite nickel ore fines where the reduction of iron and nickel to the wustite/metallic states respectively, is performed in a fluidized bed reactor using reduction gas generated very cost effectively from natural gas in an autothermal catalytic reactor. As an option coal can be used as reductant as well as additional fuel. The process of reduction and calcination is very energy optimized. It uses the offgas from the fluidized bed reduction reactor, which still contains energy, to dry and calcine the nickel ore fines in a primary stage circulating fluidized bed (CFB) reactor. The product shows high metallisation of nickel and iron oxides reduced to the wustite stage. This results in considerable energy savings in smelting the prereduced product to ferro-nickel. Alternatively the product can be leached to produce nickel. Laboratory tests showed very high recovery of nickel and cobalt.
Introduction
The principle of different fluidized bed reactor systems has been progressively developed and widely used by Lurgi Metallurgie over a period of almost fifty years for a multitude of process applications. Its versatility has manifested itself in the treatment of minerals including solid fuels and for metallurgical processes both in the ferrous and non-ferrous fields. Process applications have ranged from calcining, roasting, combustion and charring of coals as well as for offgas treatment. The more recent developments are ore preheating / prereduction as well as direct reduction of ore fines using natural gas or coal as reductant.
Laterite nickel ores usually contain considerable amounts of moisture and combined water [1]. Therefore, they have to be dried and calcined prior to smelting in an electric furnace or prior to a hydrometallurgical winning process. In the electric furnace nickel is reduced to the metallic state. Iron is reduced simultaneously to the wustite state in which, with other oxides, it forms a slag, which is separated from the metal. Performing the reduction in the electric furnace consumes a high amount of electrical energy. Lurgi Metallurgie has developed a process where the reduction of iron and nickel to the wustite / metallic state, is performed in a fluidized bed reactor using synthetic reduction gas, as energy source. The synthetic gas can be generated very cost effectively from natural gas in a catalytic process.
Comparison of Different Reactors Based on Type of Movement of Solids
The application of reactors for processing solid material can be systematically ordered as shown in the following table:
Moving Bed Fluidized Bed Pneumatic Transport Typical reactors Rotary hearth furnace Rotary kiln Travelling grate Shaft furnace Fluidized bed Circulating fluidized bed Suspension preheater Flash heater Type of driving force Mechanical / Gravity Gravity / Gas flow Gravity / Gas flow Type of solids/gas movement Counter current Co-current Cross flow Once through Counter current in stages Cross flow in stages Co-current Once through Particle Size 6- 50 mm 0.1 2 mm (<0.1 with micro- granulation) 0.01 1 mm Solid retention time Hours Days Minutes - Hours < Seconds Gas retention time Seconds Seconds << Seconds Heat and mass transfer Low / Very low High / Very high High Temperature control Bad / Sufficient Good / Very good Sufficient Solids behaviour Wide range of change for particle size and behaviour Limited application for agglomerative and sticking particles Space/time yield Very low / Low High Very high
Fluidized Bed Systems
It is known that in fluidized reactor systems particle concentrations can reach several kilograms per cubic meter of fluidization gas. This high solids concentration leads to large surface areas and enables direct contact of gas molecules with particle surface molecules. Excellent conditions for enhanced heat and mass transfer are thus provided which leads to achieving nearly ideal isothermal conditions and better reaction kinetics. The mechanism is further improved when the difference between particle and gas velocity, the slip velocity, is high as in Circulating Fluidized Beds (CFB). The different conditions of gas velocities and solids concentrations allow the classification of fluidization reactor systems into four categories. For the calcinations and reduction of nickel ore fines a combination of a bubbling fluidized bed (FB) and a CFB is used. Therefore, only these two configurations are described below. For a more comprehensive description refer [2].
The Classical Bubbling Fluidized Bed or Stationary Fluidized Bed:
The gas velocity is moderate (u = 0.4-1.5 m/s). There is a distinct transition between a high solids concentration volume (the bed with a clearly defined surface of moving particles) and a gas phase with low solids concentration (the freeboard) in the reactor. The fluidization gas tends to form bubbles with low solids concentration that increase in size with bed height. The industrial systems can reach quite large cross-sectional reactor areas but are limited in bed height due to bubble formation. The possibility of introduction of secondary gases is limited. The systems are generally used when very fine particle have to be handled and reaction times are in the range of hours, as in the case of slow diffusion-controlled reactions.
The Circulating Fluidized Bed:
High gas velocities (u = 3-9 m/s) increase particle concentrations also in the upper part of the reactor, but a particle concentration profile over the reactor height still exists. Particles rise in the middle of the reactor and flow back down with high velocities near the reactor walls. This boundary layer of particles with downstream velocity increases from the top to the bottom of the reactor. Horizontal mixing of particles is limited. It mostly occurs in the lower part of the reactor where the downstream particles turn direction to rise and go through a zero vertical velocity component. Large amounts of particles get entrained in the offgas and have to be recycled via recycling cyclones. Heat could be removed to cool the product and/or generate steam, which is advantageous for combustion processes. The difference in velocities between the gas phase and the particle (the slip-velocity) reaches a maximum, therefore heat and mass transfer rates are about 10 times higher than for classical fluidized bed systems.
Advantages and Limitations of Fluidized Bed Systems
A general advantage of fluidized bed systems, as in the case of shaft furnaces as well, is the absence of movable machinery parts within the reactor facilitating heat insulation. The systems can be refractory lined and temperatures 1100 C can be applied. The main advantage of fluidized beds over shaft furnaces is low refractory wear from abrasion resulting from limited direct contact of solids with the lining.
Limitations in the application of fluidized bed reactor systems could be due to the required fineness of particles. Ideal particle size is in the range of 0.05 1.0 mm (50 1,000 microns). Coarser particles - if they do not decrepitate from thermal or mechanical stress in the fluidized bed - can be ground before feeding to the process. Finer particles can be microgranulated prior to the process [3].
For particles, which tend to get weak or sticky during the process, fluidized bed systems can be applied if it is possible to use an inert bed material as a separator to dilute the bed of reactive particles and minimize particle impingement. A positive example is the direct reduction of iron ore fines with coal in a CFB reactor where the reduced iron particles, which tend to agglo- merate, are diluted by char formed by the reacted coal. A negative example is the failure in application of the CFB technology for the production of cement clinker.
In some cases particles are difficult to fluidize due to their shape or cohesive behavior. Efforts have been made to enable the processing of such material by using some surface coatings or other pre-treatment measures.
Substitution Process in Alumina Calcination
In the late 1960s the calcination of aluminum hydroxide (Al(OH) 3 ) to alumina (Al 2 O 3 ) was performed in large rotary kilns. The theoretical minimum of energy for this calcination process is about 2380 MJ/t Al 2 O 3 (assuming 8 wt.-% moisture in feed material and 300C product temperature). Old rotary kilns showed a consumption of 5400 MJ/t alumina. Rotary kilns with suspension preheaters decreased this number to 3900 MJ/t. The first CFB plant for calcination of alumina in 1970 (500 t/d) showed a consumption of 3150 MJ/t. [4]. Modern CFB plants (3100 t/d) reach numbers of 2850 MJ/t and below. Nowadays rotary kilns for alumina calcination are the exception. The advantages of CFB plants in alumina production are:
Moderate maintenance and repair costs of about 1 US$/t Al 2 O 3.
Low investment costs (especially for large production figures) of about 24 million US$ for a 3100 t/d alumina production plant. High availability of 92 % to 95 % Small plant foot print (about 45m x 19m for a 3000 t/d plant) Good product quality due to excellent temperature and combustion control Environmentally friendly through very low dust emission
Process Description of Calcination and Reduction in a Fluidized Bed
Figure 1 shows the typical flowsheet of the process.
Figure 1: Calcination and Reduction of Laterite Nickel Ore Fines
Gas and solid fines flow in counter-current directions. The fines are dried and preheated in a suspension preheater to make use of the sensible offgas heat. Depending on the moisture of the ore it may be advantageous to apply a second preheating stage where part of the L.O.I. is released. This feature will increase the energy efficiency but is only economically viable if the free moisture is below 15 wt.-%. In a CFB reactor the material is further heated up to the desired temperature (900 1000C) and combined water is released. Some additional fuel is required in the CFB to close the heat balance. This fuel can be of any type (oil, gas, coal) since the combustion in the CFB is very efficient.
The product from the CFB is discharged to a bubbling fluidized bed where hematite (Fe 2 O 3 ) is reduced to the wustite (FeO) state whereby simultaneously nickel oxide (NiO) is reduced to the metallic state (Ni). Both reactions have very high conversion rates reaching 80-90 % of the equilibrium within the retention time. The material discharged from the fluidized bed (FB) reactor can be transferred hot to an electric arc furnace to produce ferro-nickel or it can be used after cooling in a hydrometallurgical process for nickel winning.
The offgas from the CFB reactor will be dedusted in a bag house. The discharged fine dust can be mixed to the product from the FB reactor or recirculated to the feed after a microgranulation step. The offgas leaving the bag house contains only oxidized gaseous components that can be released to the atmosphere. Due to the isothermal combustion conditions in the CFB the NO x
emissions are usually below 50 ppm.
The reduction atmosphere in the fluidized bed can be generated by introducing a synthetic gas produced by means of autothermal catalytic natural gas decomposition. The reducing gas
leaving the bubbling fluidized bed is used as fuel in the CFB reactor. The Steamfree Autothermal Catalytic Reforming uses preheated air and natural gas and produces a synthetic gas with the following characteristics:
Process Parameters for Steamfree Syngas Production
Reaction Pressure bar 2 Reaction Temperature C 930 Consumption Air mol/mol Feed 3.06 Natural Gas Nm 3 /Nm 3
Syngas 1.33 Reformed Gas Analysis, dry CO 2 mol. % 1.3 CO mol. % 18.2 H 2 mol. % 33.6 CH 4 mol. % 0.02 H2O mol. % 1.0 N 2 mol. % 45.9 Calorific Value kJ/Nm 3 5910
The offgas leaving the reduction fluidized bed has approximately the following composition:
CO 2 mol.% 9.8 CO mol.% 9.8 H 2 mol.% 15.7 CH 4 mol.% 0.02 H 2 O mol.% 18.9 N 2 mol.% 45.8 Calorific Value kJ/Nm 3 2920
Energy Balance
As feed material, a laterite nickel ore with 35 wt.-% free moisture, 2 wt.-% (d.b.) Ni, 25 wt.-% (d.b.,) Fe, and 12 wt.-% (d.b.) L.O.I is assumed. The energy required for drying, calcination and heating to 900 C in a CFB with one suspension preheater is approximately 2600 MJ/t dry feed. The energy for prereduction (100 % NiO to Ni, 30 % oxygen removal from Fe 2 O 3 ) requires approximately 600 MJ/t dry feed. In total the theoretical energy requirement is 3200 MJ/t dry feed.
A combined drying/heating/prereduction plant based on fluidized bed technology will consume about 1500 MJ/t dry feed natural gas (reformed to synthetic gas) and 2500 MJ/t dry feed of another fuel (natural gas, oil, coal, etc.). The latter will be injected directly to the CFB and is combusted there. The total energy required for preheating and prereduction is therefore in the range of 4000 MJ/t of dry feed or 200 GJ per ton of nickel, resulting in an efficiency of 80 %.
Products
Product Use
The product obtained from the bubbling fluidized bed contains high contents of metallic nickel (>90 % of total nickel) and precisely adjusted contents of metallic iron (typically between 1 and 5 % of total iron). In the case of using coal instead of synthetic gas the remaining carbon content can be adjusted to be lower than 2 %.
The product can be used for:
The production of ferro-nickel in an electric arc furnace. Tests with fine grained DRI (0.1-1.0 mm) in a DC arc furnace to produce steel have shown that it is possible to feed fines to an electric furnace with minor dust losses. The use of a hollow electrode is not required.
The electrical energy required for an electric arc furnace to produce ferro-nickel with 25% nickel from an ore which has been dried, dehydrated and preheated to 850C is 6875 kWh/t FeNi [5]. Due to the prereduction of the feed the energy consumption in an electric arc furnace can be decreased by approximately 2100 kWh/t FeNi. Since the content of metallic iron can be adjusted, an optimum iron/nickel ratio can be achieved for the ferro-nickel product. For ferro-nickel production a high preheating temperature (1000C) is desirable which will further decrease electric energy consumption.
For electro winning of metallic nickel and cobalt after leaching. Because the process conditions can be adjusted very precisely a high yield for nickel and cobalt can be achieved. Especially low temperatures (<700C) can be adjusted in the fluidized bed quite accurate.
Product Quality
Temperature and retention time can be adjusted in wide ranges independent of throughput. The temperature can be controlled very accurate. In gold roasting plants a temperature accuracy of 10 K has been reached. Especially for a high yield in the leaching process it is ensured that no overheating occurs. Experience has shown that the quality can be ensured over long operating periods with only small deviations. The reduction degree of iron is controllable and adjustable. The formation of metallic iron should be avoided if the material is used in a leaching process. In the electric arc furnace the allowed content of metallic iron is depended on the iron and nickel content of the feed and the operation of the EAF. The higher the nickel content and the lower the iron content the more metallic iron is allowed to be formed during prereduction.
Test Work
Metallurgical processes use natural materials, which vary considerably in chemical and physical characteristics as well as in their fluidization and reaction behavior. Therefore, testing of materials is a pre-condition to determine their suitability for a particular process and obtain design parameters for an industrial plant prior to commencing preliminary engineering for establishing the economic feasibility of the project. The test results are subsequently used for final plant design.
Lurgi Metallurgie generally applies a phased program of testing, using bench scale and pilot plant fluidized bed testing facilities at its Research & Development Centre in Frankfurt. This enables the development of optimum customized processing procedures to select the appropriate reactor system and the respective flow sheet. The in-house material beneficiation department assists to optimize the raw material selection and preparation. The research and development possibilities are completed by facilities located in the central research center of Outokumpu located in Pori, Finland.
Preliminary Phase One tests are performed on a bench scale in a fluidized bed reactor with 50 mm inner diameter. Small quantities of material (100-200 g per test) are sufficient for investigation of principal process parameters that fundamentally also form the basis of further test work:
Temperature behavior: The reactor can be externally heated in a furnace to temperatures of up to 1100 C. Decrepitation, sticking or agglomeration behavior can be detected. Fluidization gas composition for a specific application. Solids retention time. Different materials can be compared, e.g. with regard to their reduction rate by analyzing the reduction degree after certain solids retention times. Specific reduction gas requirement per mass of solids.
Phase Two involves the testing of material under continuous operating conditions over several hours. A CFB pilot plant with 80 mm inner diameter and a reactor height of 1.5 m is used. It is provided with external electrical heating, achieving process temperatures of up to 1000 C. The material throughput can be varied from 0.8 kg/h to over 5 kg/h.
To obtain more reliable information for the design of an industrial plant it is necessary to operate longer test campaigns over several days on a pilot scale in a larger reactor. This constitutes Phase Three of the test program. For this purpose different pilot plants with 200, 350 and 700 mm respective inner diameters and respective heights of 6m, 10m and 10.5m, are available.
Test Results
Figure 2 shows reduction degrees of iron oxides as well as achieved yields of nickel and cobalt from an ammonia leaching procedure, after calcination and reduction in the 50mm fluidized bed reactor, with dependency on temperature. The CO/CO 2 ratio of the feed gas was kept constant at 1.0. From the test results it can be concluded that lower temperatures are better for high nickel and cobalt yields in the leaching process. The results also show that during the prereduction high amounts of nickel have been reduced to the metallic state because only metallic nickel is soluble during the leaching. The reduction degree of iron oxides is below 30% and the analyses on metallic iron show that the Fe 0 -content is below 0.8 wt.-%. The yield for nickel at 650C prereduction temperature varies between 84% and 93% for three different ores investigated under these conditions. Cobalt yield showed the same tendency with values between 66% and 84 %, respectively. Reduction of Latherite Nickel Ores in Fluidized Bed System 0 10 20 30 40 50 60 70 80 90 100 500 600 700 800 900 Temperature C R e d u c t i o n
D e g r e e
/
Y i e l d
% Reduction Degree Ni Yield Co Yield CO/CO2=1
Figure 2: Results of Test Work in 50mm Fluidized Bed Apparatus
Use of Ultrafines
In many nickel production plants dry ultrafines (<0.05mm) with relatively high amounts of nickel (>3%) and low contents of iron (<20%) are generated during the preheating and prereduction process. These ultrafines are disposed because they cannot be processed further. After microgranulation with addition of water (no further binder is required) the microgranules (0.1-1mm) can be fed to the CFB for hardening and calcination. Tests have shown that these granules are very stable and easy to reduce. Therefore, the presented process is able to make use of the disposed fines and its metal value content.
Industrial Plant
Lurgi Metallurgie has a long experience of developing new processes from the pilot stage to the industrial application. Examples are the substitution of rotary kilns for alumina calcining by CFB technology, the coal combustion in CFB boilers or the recent development of direct reduction for HBI production [6]. A CFB preheater for preheating of iron ores before injecting them into a HIsmelt [7] smelt reduction vessel is currently under construction in Kwinana, Western Australia and will go in operation in late 2004.
An estimation for a preheating and prereduction plant to treat 880,000 t/a feed material for the consequent production of nickel as ferro-nickel or metallic nickel results in an approximate investment cost of 20 million US$. This figure does not include any hot transportation and feeding system to the electric furnace because this is very site dependent. Also construction costs may vary significantly dependent on the location of the plant. The energy efficiency of such a plant will be in the range of 80%, which is comparable to alumina calcination plants.
Further Development
Development is going on to substitute the use of natural gas by coal, which is introduced into the bubbling fluidized bed reactor and partially combusted with air to generate a reducing atmosphere. Tests using very fine dust discharged from operating rotary kilns offgas and fine laterite ores have shown successful microgranulation and reduction behavior.
References
1. Canterford, J.H., Minerals Sci. Eng., vol.7, no.1, January, 1975 2. Orth et al, Proceedings of IFSA 2002 3. Husain R., Paper presented at ILAFA -39, Isla de Margerita, Venezuela October 1998 4. Schmidt, H.W., Advanced Circulating Fluid Bed Technology for Alumina Calcination, Proc. CFB VI, Wrzburg 1999 5. Roorda H.J., Hermans J.M.A., Erzmetall 34 (1981), Nr. 2 6. Husain R. et al, Coal and Gas Based Fine Ore Reduction: Circofer
and Circored
, 4 th European Coke and Ironmaking Congress, June 19-22, 2000, Paris La Dfense, France 7. www.hismelt.com.au
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