Outotec Fluidization technology

Innovative solutions for fine grained materials

nn Calcination nn Roasting nn Reduction nn Gasification nn Combustion nn Decarbonization nn Oxidation nn Gas cleaning nn Heat recovery nn Cooling nn Drying nn Spray granulation

002 Fluidization technology

Alumina CFB calciner, Worsley Alumina, Australia.

50 years of technology evolution

For over 50 years Outotec has developed and commercialized fluidized bed technology for a variety of industrial applications.

Lurgi constructed the first reactor for roasting of sulfur bearing materials in 1950, based on the principles of fluidized bed technology. The new system was quickly adopted by industry; multiple hearth furnaces and rotary kilns were increasingly replaced by fluidized bed roasters, thereby ensuring enhanced product quality and significantly reduced plant emissions. Fluidized bed combined with efficient heat recovery and offgas treatment, including the process of converting the offgas to sulfuric acid, became state-of-the-art technology for processing sulfur bearing ores. We have delivered more than 260 plants to date. Significant process improvements have been achieved by using fluidization technology, for example in the production of alumina. The circulating fluidized bed (CFB) was developed over 40 years ago for the high temperature treatment of fine and light particles. A whole variety of other CFB applications followed, with more than 170 industrial plants worldwide. The CFB has been successfully applied for coal combustion, roasting of gold containing ores, direct reduction of iron ore fines and other uses. In the early 1990s we introduced a new variation of fluidization technology, the annular fluidized bed (AFB).

With the aquisition of Lurgi Metallurgie in 2001, Lurgi's fluidization know-how was transferred to Outotec. The development of fluidized bed technology continues and we are working on new processes utilizing solid mixtures, such as ore and coal, with different properties for industrial application.

Early FB pyrite roasting plant, BASF, Germany.

Fluidization technology 003

Fluidized bed types

Bubbling fluidized bed (FB) The classical bubbling fluidized bed is operated at relatively low gas velocities with the particles kept in balance against their own gravity. Most of the particles do not leave the surface of the fluidized bed, typically characterized by a defined surface between gas and solids. The surface may show a behavior similar to a boiling liquid, depending on size and density of the particles. From the mixing point of view, the FB is a continuously stirred tank reactor with a defined solids residence time distribution. The mean solid velocity is close to zero with the slip velocity almost identical to the gas velocity. Circulating fluidized bed (CFB) At higher gas velocities the slip velocity increases and the fluidized bed changes its behavior. The defined boiling surface disappears with the expansion of the fluidized solids. The fluidization gas has enough energy to entrain solids particles. The entrained particles are separated from the gas by a cyclone and recirculated via an external loop back into the fluidized bed reactor. In addition an internal recirculation of the solids in the fluidized bed reactor takes place. Both internal and external circulation results in a homogenous temperature distribution in the CFB system. Transport or flash reactor (FR) With further increase of the gas velocity, the solids are approaching the velocity of the gas. In the flash (transport) reactor the slip velocity between gas and solids is considerably decreased compared to the circulating fluidized bed. At the same time the advantages of homogeneous temperature distribution and ideal heat and mass transfer are decreased. This type of reactor is used in selected applications where low gas and solid retention times are sufficient.

Velocity

"Slip velocity"

Gas

Increasing solids density

Solids

Increasing expansion

Annular fluidized bed (AFB ) This new type of fluidized bed improves the introduction and mixing of hot dust laden process gases. These gases enter the reactor through a large central nozzle, with additional fluidization gas introduced through an annular nozzle ring. As a result, a very intense mixing zone is achieved within the reactor above the central nozzle, comparable to the conditions achieved by an external loop of a CFB. Further advantages are excellent process control and improved mass transfer conditions. The AFB can be combined with any other fluidized bed type.

004 Fluidization technology

Milestones in fluidized bed development

Bubbling fluidized bed 01 1950 First pyrite roaster, BASF, Germany, 40 tpd 02 1956 First zinc roaster, Nikon Kogyo, Japan, 40 tpd 03 1958 Sulfate decomposition roaster, Imperial Smelting, UK, 140 tpd 04 1962 First sulfating roaster for copper ores, Chambishi, Zambia, 118 tpd 05 1965 Hydrogen based reduction plant for NiO, Inco, Canada, 150 tpd 06 1965 First single-stage dearsenifying pyrite roaster, Boliden, Sweden, 350 tpd 07 1968 First double-stage dearsenifying pyrite roaster, Bayer, Germany, 450 tpd 08 1969 First slurry feed to pyrite roaster, Gold Fields, South Africa, 2 x 125 tpd 09 1971 First partial roaster for copper ore, Noranda, Canada, 900 tpd 10 1973 First 123 m 2 zinc roaster, Pasminco, Australia, 800 tpd 11 1994 Largest coarse pyrite roaster, Wengfu, China, 2 x 1,200 tpd 12 1996 Circored direct reduction plant, CAL, Trinidad, 1,500 tpd 13 1999 Largest zinc roaster, Asturiana de Zinc SA, Spain, 1,000 tpd 14 2004 Largest pyrite concentrate roaster, Tongling, China, 1,130 tpd 15 2005 Ni chloride pyrohydrolysis roaster, Goro Nickel, New Caledonia, 3 x 380 tpd Circulating fluidized bed 16 1959 First laboratory CFB plant at Metallgesellschaft, Germany, 0.5 tpd 17 1961 First pilot plant for alumina calcination, VAW Lnen, Germany, 24 tpd 18 1968 First industrial alumina calciner, VAW Lnen, Germany, 500 tpd 19 1973 First laboratory tests for iron ore reduction using CFB technology, R&D Center, Germany 20 1979 Significant capacity increase of alumina calciners, Interalumina, Venezuela, 3 x 1,400 tpd 21 1982 First coal combustion plant, VAW Lnen, Germany, 84 MW 22 1987 First gold ore roasting plant, KCGM, Australia, 575 tpd 23 1990 First alumina calciner with hydrate bypass, Worsley Alumina, Australia, 1,850 tpd 24 1991 Circodust demonstration plant, Thyssen, Germany, 120 tpd 25 1992 Largest roaster for gold ore, Newmont, USA, 2 x 3,800 tpd 26 1993 Largest CFB (11.5 x 14.7 m) based power plant, Soprolif, France, 650 MW 27 1996 Circored direct reduction plant, CAL, Trinidad, 1,500 tpd 28 2001 Oxidizing ilmenite roaster, Iscor, South Africa, 1,000 tpd 29 2002 Ore preheater, HIsmelt Corporation, Australia, 4,000 tpd 30 2003 Significant capacity increase of alumina calciners, Alunorte, Brazil, 2 x 3,300 tpd 31 2005 Reducing ilmenite roaster, Kenmare Resources plc, Mozambique, 1,200 tpd 32 2005 First preassembled module supply of alumina calciners, Alcan Gove, Australia, 2 x 3,500 tpd Flash reactor 33 1985 Flash reactor for high temperature alumina production, VAW Schwandorf, Germany, 250 tpd 34 1993 Flash reactor for ilmenite preheating, Namakwa Sands, South Africa, 625 tpd 35 1996 Circored direct reduction plant, CAL, Trinidad, 1,500 tpd Annular fluidized bed 36 1992 Waste heat boiler pilot plant, 1 tpd 37 1996 Circored direct reduction plant, CAL, Trinidad, 1,500 tpd 38 2002 Ore preheater, HIsmelt Corporation, Australia, 4,000 tpd 39 2005 Reducing ilmenite roaster, Kenmare Resources plc, Mozambique, 1,200 tpd Development in the Lurgi and Outotec companies, indicating the year of order.

Fluidization technology 005

Numbers refer to the development stages of the list of milestones.

References Bubbling fluidized bed

nn Zinc roasters 74 nn Pyrite, copper, gold, nickel concentrate roasters Total 190 264

Flash reactors
nn Ilmenite preheating 2 nn Circored, Trinidad 1 Total 3

Annular fluidized bed Circulating fluidized bed

nn Alumina calcining plants nn Gold ore roasting plants nn Sulphur adsorption nn Calcining of clay/lime nn Fluorine adsorption nn Coal based reduction (Elred) nn Gas based reduction (Circored) nn Ore preheating (Circoheat) nn Circodust (demonstration plant) nn AlF 3 synthesis (demonstration) 51 5 16 3 10 1 1 1 1 1 * No longer part of Outotec's offering nn Power plants* 82 nn Boiler pilot plant nn Circoheat, Kwinana nn Ilmenite roaster, Mozambique 1 1 1 nn Circored, Trinidad 1

Total 4

Total 172

006 More Fluidization out of ore! technology

Fundamentals
Fluidization systems are ideal for the treatment of fine grained materials. For processing ultra fine materials, Outotec has developed and patented a microgranulation process. The treatment of oversized material has to be evaluated depending on its behavior during processing.

Flexibility in feed particle size

Fluidized bed phase diagram

The so-called Reh* diagram illustrates the different phase behavior of gas-solids interactions. The yellow region represents the fixed bed operating domain. The blue region indicates the domain of the bubbling fluidized bed where gravity and drag forces on the particles are in balance. The grey section represents the pneumatic transport domain. The orange triangular region represents the area of the circulating fluidized bed. As the diagram is calculated for ideal spherical homogeneous particles it provides an indication only. However, coupled with experience from industrial plants the CFB operating range can be extended to area a of the diagram. This knowledge gained from operational experience is applied to the design of new plants and processes.

Important design criteria

Particle size and density Decrepitation behaviour Retention time Process temperature Process energy requirement Production rate Demand on product quality

Particle Froude Number

, d P] f [v G

Particle Reynolds Number

Re P

* Diagram developed by Prof. Dr.-Ing. Lothar Reh

Fluidization technology 007

Application in exothermic and endothermic processes Chemical reactions occurring between the solid particles and the fluidization gas can either be endothermic or exothermic. Endothermic processes require energy input, provided either directly by the combustion of fuels or indirectly by the introduction of hot gases and/or preheated solids. All types of fluidized bed systems can be used for both endothermic and exothermic processes. A typical example of an exothermic process is the roasting of sulfide ores. An example of an endothermic process is the calcination of alumina. Whether the process is endothermic or exothermic, tight control of temperature in a fluidized bed reactor is more easily achievable. Fluidized bed based plants may include heat recovery systems, which allow for the effective utilization of heat from offgas and solids streams to decrease operating costs and emissions.

Use of 3D design tools Outotec uses modern 3D design systems as planning and design tools also for fluidized bed based plants. The main advantages of such systems are: nn High planning reliability nn Improved drawing quality nn Reduced modification work on site nn Shorter job execution time nn Reduction in overall cost

AFB of ilmenite roaster, Kenmare Resources plc, Mozambique.

008 Fluidization technology

R&D and scale up competence

Outotec's pursuit of new fluidized bed applications for customer needs is supported by experimental work in the company's in-house R&D Center. For example development of neural networks, in-situ monitoring systems and modern mathematical methods, including computational fluid dynamics modeling, are key elements of research.

Outotec has developed theoretical models of fluidized bed systems and specialist scale up know-how over many decades. A unique set of pilot plants, suitable for processing of feeds in the range of 100 g batches up to 1,000 kg/h continuously, is available to develop and improve existing technologies for customer applications. These pilot plants are designed to be flexible with respect to temperature, pressure, gas and fluidization conditions and can be configured either as single or multistage units. However, the data gained in laboratory scale fluidized bed systems are not sufficient to provide design and performance criteria of industrial plants without the experience of operating facilities. Outotec's largest CFB based test facility is the Circofer demonstration plant at the R&D Center in Frankfurt. This plant is equipped with a 700 mm diameter CFB, recycle cyclone, integrated heat generator, char separator, magnetic separator, gas cleaning system, and all necessary ancillary equipment.

700 mm Circofer demonstration plant, R&D Center, Germany.

Scale up experience
With Outotec's experience in many state-of-the-art fluidized bed technologies the customers do not need a large scale demonstration plant as an expensive interim step. Examples of the scale up figures: Process, year Alumina calcination, 1970 Coal combustion, 1982 Gold ore roasting, 1990 Circored, 1999 From pilot plant size D=1,000 mm/24 tpd D=360 mm/20 kg/h D=200 mm/22 kg/h D=200 mm/8 kg/h To industrial plant size D=3,600 mm/500 tpd D=5,000 mm/500 tpd D=3,800 mm/2,000 tpd D=5,000 mm/1,500 tpd Scale up factor 1:20 1:1,000 1:4,000 1:3,500

Fluidization technology 009

Applications
Outotec's portfolio related to fluidized bed technology can be classified as follows.

Diagram for fluidized bed applications.

Reducing conditions
nn Dearsenifying pyrite roasting nn Circored (gas based fine ore reduction) nn Circofer (coal based fine ore reduction) nn Circodust (processing of steel plant residues) nn Circosmelt (prereduction and smelting of ilmenite) nn Reducing ilmenite roasting nn Heat recovery by fluidized bed cooling and Circotherm nn Circoheat (preheating of ore fines) nn Circochar (coal charring) nn Circonickel (prereduction of lateritic nickel ore) nn Partial roasting of copper concentrate

Oxidizing conditions
nn Alumina calcining nn Roasting of pyrite, copper and zinc concentrates nn Roasting of gold ore nn Oxidizing ilmenite roasting nn Heat recovery by fluidized bed cooling and Circotherm nn Circoheat (preheating of ore fines) nn Circoroast (improved pyrite roasting system)

010 Fluidization technology

Alumina calcination
The first industrial plant for the calcination of alumina was designed in 1968. Calcination is the final stage of the Bayer process, in which bauxite is digested with caustic soda to first extract and then precipitate a pure aluminum hydroxide (hydrate). The hydrate from the Bayer process is then calcined to alumina in a CFB. This step was earlier carried out in rotary kilns, but today all new capacity is installed as fluidized bed calciners.
Calcining stage Fuel Secondary air Primary air Cooling water Fluidized bed cooler CFB reactor Hydrate bypass Cooling water Alumina Hydrate Preheating stage II Preheating stage I Electrostatic precipitator Waste gas

Cooling stage I

Cooling stage II

CFB calcination process The CFB calciner uses a two-stage venturi preheating system to recover the waste gas heat by preheating and de-watering the hydrate. Final calcination to alumina (Al 2 O 3) is accomplished in the CFB reactor in which the energy is provided by direct combustion of fuel (oil or gas). The energy of the hot alumina is recovered to the incoming air in a multistage cooling system including cyclones and a fluidized bed alumina cooler.

Alumina calcination in the CFB.

Some energy of the hot alumina is also used for direct calcination of incoming hydrate in a so-called hydrate by-pass. This efficient heat recovery system leads to an overall fuel energy consumption of less than 3 GJ/t of alumina for the calcination process. CFB calciners operate in a range from 900 to 1,000 C depending on product quality demands.

Due to the homogeneous temperature in the CFB reactor, product qualities regarding specific surface area, loss on ignition and alpha content in the alumina can fulfill the demands of todays aluminium smelters. We have installed more than 50 CFB calciner units worldwide, which represents approximately one third of the world's production of smelter grade alumina.

Outotec's preassembled module (PAM) technology reduces capital cost and meets the challenges of plant construction in remote areas. The first PAM delivery of two large calciners took place in 2006 to the Northern Territory in Australia. The calcining units were preassembled in South East Asia and transported by ship to Alcan's Gove operation.

3,500 tpd preassembled calciner module being delivered to Alcan Gove, Australia.

006 More out of ore!

Fluidization technology 011

Roasting of sulfide ores

The roasting of sulfide ores and concentrates is an important process step in the production of metals and chemicals. Sulfides of iron, zinc, copper and other metals are oxidized with air at temperatures between 600 and 1,000 C into metal oxides and gaseous sulfur dioxide. After cleaning and cooling, the sulfur dioxide contained in the roasting gas is further processed to sulfuric acid. Both FB and CFB types of fluidized bed reactors are commonly used depending on the material properties and specific process requirements. Pyrite roasting in the FB The optimum reactor for roasting of extremely fine flotation concentrates of copper, pyrite and zinc is a highly stable FB. These reactors, characterized by relatively low fluidization velocities, are well suited to treat such fine materials with grain sizes down to approximately 20 microns. The established concept of a roasting plant consists of a FB roaster, waste heat boiler, gas cleaning and calcine handling systems. Dry feed throughput rates of over 350,000 tpa per unit are achievable. The generated SO 2 gas is recovered in a dedicated sulfuric acid plant.
Pyrite roasting plant, ETI Holding, Turkey.

Gold ore roasting in the CFB

Gold ore roasting in the CFB.

The CFB roaster is the appropriate

Gold ore CFB ore preheater Waste heat boiler CFB reactor

reactor
Hot electrostatic precipitator Gas cleaning + sulfuric acid plant

for

special

roasting

processes or higher throughput rates of over one million tpa. An example is the gold refractory ore roasting process, where sulfur and carbon removal are essential to obtain acceptable gold recoveries

Pyrite

Sulfur Fuel Fuel 02 make up Fuel

Fluidized bed cooler Quench tank

in the subsequent calcine leaching steps.

Calcine slurry Tailgas acid plant

012 Fluidization technology

Iron ore preheating and direct reduction

Circored The drivers for the development of the Circored process in the early 1990s were the growing demand for direct reduced iron (DRI) coupled with the advantages of using iron ore fines directly in the steelmaking value chain, avoiding the agglomeration step. The Circored process, using hydrogen as the only reductant, applies a two-stage
Air Preheating system CFB preheater Fuel Bucket elevator Natural gas
Steam reforming

Offgas scrubber To thickener Iron ore Suspension preheater Feed system

Recycle cyclone

Process gas heat exchanger CFB Reduction stage system I

Process gas compressor Process gas scrubber To thickener Bleed as fuel

Multiclone

FB stage II

Cyclone Product handling DRI system discharge Flash heater Hydrogen make up Hot briquetting option Hot charging option

CFB/FB reactor configuration for reduction. In addition, a single CFB is utilized for ore preheating and an AFB based flash heater is used to achieve the DRI briquetting temperature. The first commercial Circored plant, with an annual capacity of 500,000 t of hot briquetted iron (HBI), commenced operations in 1999 in Trinidad.

Fuel Air Process gas heater Fuel Air HBI

EAF Steel

Circored direct reduction in the CFB/FB.

Circoheat
Ore preheater, HIsmelt Corporation, Australia.

The first commercial Circoheat plant, operating at HIsmelt's Kwinana facility in Western Australia is capable of preheating approximately 1,300,000 tpa of iron ore fines to 850 C using offgas from the HIsmelt smelt reduction vessel (SRV). In the Circoheat process, wet iron ore fines are fed to a suspension preheater system where they are preheated to approximately 500 C prior to introduction into a CFB reactor. Hot combustible SRV offgas at a temperature of 1,000 C is introduced into the CFB reactor via an AFB system. The offgas is partially combusted with air to generate the necessary energy for preheating the iron ore. Since the SRV gas is not completely combusted, a reduction of the iron ore to the magnetite/wuestite stage is achieved. The preheated material is subsequently pressurized in a lock hopper system and injected at high temperature into the SRV via a new pneumatic hot ore conveying system.

Fluidization technology 013

Latest developments
Based on the wealth of experience gained in the field of fluidization technology, Outotec is continuously working on improving existing processes and developing new processes and applications to meet the demands of an industry pursuing sustainable solutions.

Circofer The Circofer to process reduce has iron been ore

developed

fines utilizing coal as reductant. Similar to the Circored process, Circofer CFB/FB uses reactor a two-stage to configuration

obtain a highly metallized product. A heat generator is integrated into the CFB prereduction circuit to provide the energy necessary for the endothermic reduction reaction by partially combusting the introduced coal with oxygen. The process operates at reduction temperatures of approximately 950 C in a closed gas circuit without the production of export gas.
Circored plant, CAL, Trinidad.

Circofer CFB prereduction step for HIsmelt.

Dolomite Iron ore

One possible application of Circofer

Char Multiclone Stand pipe Stage I Process gas scrubber

Coal

is as a single stage prereduction step for the HIsmelt process, replacing the Circoheat ore preheater. This leads to a significant increase in the throughput of the HIsmelt SRV.

Ore dryer

Preheating Stage II Reduction

CO2 Thickener Smelting Hot air CO2 absorber Steam Offgas

Hot air Coal crushing

Prereduced CFB iron and reactor Recycle char char Heat generator O2 Hot injection

Coal

Pneumatic coal feeding

Slag Char separator Hlsmelt SRV Hot metal with 4% C

Process gas heater Air

Process gas compressor Bleed gas

014 Fluidization technology

Circosmelt The combination of ilmenite prereduction in a single stage Circofer CFB unit with an electric smelting furnace allows for the production of a high quality TiO 2 slag and pig iron, resulting in significant energy savings.

Circoroast The next generation of sulfide ore roasting processes will have an environmental and maintenance friendly reactor design. The compact combination of roaster reactor, recycle cyclone, waste heat boiler and fluidized bed cooler provides maximum efficiency in heat recovery and reduced investment and operating costs.

Circochar The CFB based Circochar process, a spin-off from the circofer development, produces metallurgical char and a valuable fuel gas from fine grained high volatile coals. The gas quality can be adjusted to meet the requirements for power generation by adding steam or oxygen to the process.

Clay calcination Calcined clay can be mixed in a ratio of up to 40% with Portland cement to supplement production whilst maintaining quality. The calcination temperature for the clay is significantly lower than the production of equivalent Portland cement leading to considerable energy savings. Using the CFB calcination process, organic and inorganic compounds are removed to achieve a homogenous high quality intermediate product for further downstream processing.

Goal Char Ilmenite

Multiclone Stage I Preheating Dust Stage II Gas lift

Venturi scrubber

Hot Thickener magnetic CO2 separation Recyle char

CO2

Prereduced Steam Ilmenite

absorber

CFB Pneumatic transport Heat generator

Process gas Offgas compressor

O2

Smelting furnace

Process gas heater Titania slag Air

Pig iron

Circosmelt: Ilmenite preheating, prereduction and smelting.

Fluidization technology 015

Circotherm Where applications require intensive mixing between solids and hot dust laden gases, a special reactor design is needed. Circotherm is ideally suited for the quenching of hot offgases with solids, as well as condensing vapors contained in offgas streams that are difficult to handle. The core system comprises an AFB with integrated heat recovery systems and a solids recovery cyclone. Circonickel Outotec has developed a process where the calcination and reduction of lateritic nickel ores to the wuestite/metallic state is performed in a combination of a CFB and a FB system. Coal and natural gas can be used as reductants. Through improved process control of the prereduction, considerable energy savings in smelting of lateric nickel ores to ferro-nickel can be achieved. The new process avoids the production of excessive fine dust as currently generated in existing production plants. Furthermore, dust deposits of existing plants can be processed recovering its nickel content.

Circotherm pilot plant, R&D Center, Germany.

Outotec develops and provides technology solutions for the sustainable use of Earths natural resources. As the global leader in minerals and metals processing technology, Outotec has developed over decades several breakthrough technologies. The company also offers innovative solutions for the chemical industry, industrial water treatment and the utilization of alternative energy sources. Outotec shares are listed on the NASDAQ OMX Helsinki.

ferrous@outotec.com www.outotec.com Copyright 2011 Outotec Oyj. All rights reserved.

Finland, December 2011.