Alumina Process

Bauxite and Alumina

Alumina (aluminium oxide Al2O3) is a fine white material similar in appearance to salt. While alumina is also used in abrasive, ceramics and refectory industries, Queensland Alumina Limited produces only smelter-grade alumina for the owners reduction plants in Australia and overseas. The QAL process was designed to refine bauxite located at Weipa in North Queensland. The extensive deposits of this ore were formed by weathering of sands and rocks millions of years ago, increasing the alumina content as other more soluble elements were removed. Bauxite occurs close to the surface in seams varying from one meter to nine meters, formed as small reddish pebbles (pisolites). The ore is shipped to Gladstone following "beneficiation" to remove low-grade material, and blending to provide a consistent grade. The Bayer Process

The Bayer Process - an economical method of producing aluminium oxide - was discovered by an Austrian chemist Karl Bayer and patented in 1887. The process dissolves the aluminium component of bauxite ore in sodium hydroxide (caustic soda); removes impurities from the solution; and precipitates alumina tri hydrate which is then calcined to aluminium oxide. A Bayer Process plant is principally a device for heating and cooling a large re circulating stream of caustic soda solution. Bauxite is added at the high temperature point, red mud is separated at an intermediate temperature, and alumina is precipitated at the low temperature point in the cycle. Bauxite usually consist of two forms of alumina - a mon hydrate form Boehmite (Al2O3.H2O) and a tri hydrate form Gibbsite (Al2O3.3H2O). QAL uses the Bayer Process to refine two grades of Weipa bauxite, the bulk of which is "monohydrate" grade bauxite.

Boehmite requires elevated temperatures (above 200C) to dissolve readily in 10% sodium hydroxide solution. The tri hydrate grade bauxite is mainly Gibbsite which dissolves readily in 10% sodium hydroxide solution at temperatures below 150C. Consequently, monohydrate bauxite undergoes high temperature extraction under pressure in digesters, while tri hydrate grade material is added as a "sweetening bauxite" to the flash tanks where temperatures are less than 200C. The design of the plant meets the requirement of smelters of coarse or sandy alumina for reduction to aluminium. The recovery rate is about one tonne of alumina per 2.2 tonnes of bauxite. From the plants, million-tonne bauxite stockpile to the A-frame alumina storage sheds is a processing journey of about 2.5 days. The QAL plant circulates some 550 million liters of caustic soda solution through four distinct stages, the functions of which are detailed in this process description.

Process: 1. DIGESTION OF BAUXITE Grinding: Pisolitic, monohydrate-grade bauxite sized to a maximum of 20mm, is ground in 10 mills (each with one compartment of rods and one of balls) to allow better solid liquid contact during digestion. Recycled caustic soda solution is added to produce a pump able slurry, and lime is introduced for phosphate control and mud conditioning. Desilication: The silica component of the bauxite is chemically attacked by caustic soda, causing alumina and soda losses by combining to form solid desilication products. To de silicate the slurry prior to digestion, it is heated and held at atmospheric pressure in pre-treatment tanks, reducing the buildup of scale in tanks and pipes. Most desilication products pass out with the mud waste as sodium aluminium silicate compounds. Digestion: The plant has three digestion units. The monohydrate slurry is pumped by high pressure pumps through two agitated, vertical digester vessels operating in series. Mixed with steam and caustic solution, alumina in the bauxite forms a concentrated sodium aluminate solution leaving un dissolved impurities, principally inert iron and titanium oxides and silica compounds. Reaction conditions to extract the monohydrate alumina are about 250C and a pressure about 3500 kPa, achieved by steam generated at 5000 kPa in coal-fired boilers.

Under these conditions, the chemical reactions are rapid:-

2NaOH + Al2O3.3H2O 2NaOH + Al2O3.H2O --> 2NaAlO2 + 2H2O

-->

2NaAlO2

4H2O

By sizing the vessel to optimum holding time, about 97% of the total available alumina is extracted and the silica content of liquor is reduced. Heat Recovery:

After digestion about 30% of the bauxite mass remains in suspension as a thin red mud slurry of silicates, and oxides of iron and titanium. The mud-laden liquor leaving the digestion vessel is

flash-cooled to atmospheric boiling point by flowing through a series of flash vessels which operate at successively lower pressures. The flash steam generated is used to preheat incoming caustic liquor in tubular heat exchangers located parallel to the flash tank line. Condensate from the heat exchangers is used for boiler feed water and washing waste mud. Sweetening: The tri hydrate bauxite has separate grinding and pre-treatment facilities. During the pass through the flash tanks, this additional bauxite slurry with high tri hydrate alumina content is injected to maximise the alumina content of the liquor stream. This occurs in the appropriate flash vessels when the slurry from the digesters has been cooled to less than 200C. 2. Settlers: Most red mud waste solids are settled from the liquor stream in single deck 40 meter diameter settling tanks. Flocculants are added to the settler feed stream to improve the rate of mud settling and achieve good clarity in the overflow liquor. Washers: The mud is washed with fresh water in counter-current washing trains to recover the soda and alumina content in the mud before being pumped to large disposal dams on Boyne Island. CLARIFICATION OF THE LIQUOR STREAM

Slaked lime is added to dilute caustic liquor in the washing process to remove carbonate (Na2CO3) which forms by reaction with compounds in bauxite and also from the atmosphere and which reduces the effectiveness of liquor to dissolve alumina. Lime regenerates caustic soda, allowing the insoluble calcium carbonate to be removed with the waste mud.

Na2CO3 + Ca(OH)2 --> CaCO3 + 2NaOH Filters: Settlers overflow liquor containing traces of fine mud is filtered in Kelly-type constant pressure filters using polypropylene filter cloth. Slaked lime slurry is used to produce a filter cake. Mud particles are held on the filter leaves for removal and treatment in the mud washers when filters are sequentially taken off line. Heat Interchange:

With all solids removed, the pregnant liquor leaving the filter area, contains alumina in clear

supersaturated solution. It is cooled by flash evaporation, the steam given off being used to heat spent liquor returning to digestion. 3. PRECIPITATION OF ALUMINA HYDRATE

Crystallisation: Dissolved alumina is recovered from the liquor by precipitation of crystals. Alumina precipitates as the tri hydrate Al2O3 .3H2O in a reaction which is the reverse of the digestion of tri hydrate 2NaAlO2 + 4H2O --> Al2O3.3H2O + 2 NaOH

The cooled pregnant liquor flows to rows of precipitation tanks which are seeded with crystalline tri hydrate alumina, usually of an intermediate or fine particle size to promote crystal growth. Each precipitation tank is agitated, with a holding time of about three hours. During the 25-30 hours pass through precipitation, alumina of various crystal sizes is produced. The entry temperature and the temperature gradient across the row, seed rate and caustic concentration are control variables used to achieve the required particle size distribution in the product. As correct particle size is important to smelter operations, sizing is carefully controlled. The QAL precipitation plant was designed to operate on a continuous basis to produce "sandy" or coarse alumina. Classification: The finished mix of crystal sizes is settled from the liquor stream and separated into three size ranges in three stages "gravity" classification tanks. The primary classifiers collect the coarse fraction which becomes the product hydrate. The intermediate and fine crystals from the secondary and tertiary classifiers are washed and returned to the precipitation tanks as seed. Spent Liquor: Spent caustic liquor essentially free from solid overflows from the tertiary classifiers and is returned through an evaporation stage where it is re concentrated, heated and recycled to dissolve more alumina in the digesters. Fresh caustic soda is added to the stream to make up for process losses. 4. CALCINATION OF ALUMINA

Washing: A slurry of coarse hydrate (Al2O3.3H2O) from the primary thickeners is pumped to hydrate storage tanks and is filtered and washed on horizontal-table vacuum filters to remove process liquor.

Calcining:

The resulting filter cake is fed to a series of calcining units - an 1800 tonnes a day circulating fluidised bed calciner or one of nine rotary kilns each 100m long and 4m in diameter. The feed material is calcined to remove both free moisture and chemically-combined water. Firing-zone temperatures above 1100C are used, achieved by firing with natural gas. The circulating fluidised bed calciner is more energy efficient than the older rotary kilns. Product sandy alumina particles are 90%+ 45 m (microns) in size. Cooling: Rotary or satellite coolers are used to cool the calcined alumina from the rotary kilns, and to preheat secondary combustion air for the kilns. Fluidised-bed coolers further reduce alumina temperature to less than 90C before it is discharged on to conveyor belts which carry it to storage buildings where it is stockpiled for shipment. Reference: Web Back

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All about Aluminium and its processing

Strengthening Mechanisms: Introduction

Pure, untreated aluminium is a soft metal with insufficient strength for most engineering applications. In order to take advantage of its low density, aluminium has to be strengthened by one or more mechanisms. These are considered in det The 4 mechanisms

In general, four different strengthening mechanisms are used to strengthen aluminium. These are summarised below: Mechanism Strain hardening Description Plastic deformation, or work hardening, of metals increases the dislocation density. Dislocation barrier Other dislocations

Dense dislocation 'tangles' can form, obstructing the movement of other dislocations. Solute hardening Precipitation hardening Grain size hardening Softening Alloy elements, such as Mg, Mn and Cu can 'pin' dislocations, thereby strengthening Solute atoms the material. Small, finely dispersed precipitates can significantly increase the strength of aluminium alloys. Precipitates

Reducing the grain size increases the alloy Grain strength according to the Hall-Petch boundaries relationship. Mechanisms in Aluminium Alloys

Alloys that develop their shape and properties by cold-working often have to be re-softened at regular intervals before further deformation can take place. Other examples of softening include the re-solution of second phases in age-hardening alloys, and the controlled grain growth of alloys with small grain sizes. An interesting exception is provided by solute-hardened materials which cannot be softened since this strengthening mechanism is determined solely by composition and not by thermal or mechanical processing. Strengthening Mechanism Associated Softening Mechanism(s) Strain Hardening Age hardening Grain Size hardening Solute hardening Recovery, Recrystallisation, Grain growth Solution heat treatment Grain growth NONE

Aluminium

Processing

From bauxite extraction to the final aluminium products, several processes are needed. Firstly, alumina is extracted from bauxite through the Bayer process. Then, alumina is reduced by electrolysis into molten metallic aluminium through the Hall-Heroult process. This molten aluminium (also called primary aluminium) is then cast into ingots for subsequent remelting or more usually into cylindrical extrusion billets or rectangular rolling slabs. Besides primary production, aluminium recycling is also an important source of aluminium, especially for ingot production. Ingots are used to produce cast products like engine blocks. Extrusion billets are pushed through shape dies to give extruded profile used, for example, in structures while rolling slabs are hot rolled and usually cold rolled into sheet, plate or foil used, for example, for facade panels or packaging applications. Extruded profiles and sheets, frequently called wrought products, as well as cast products usually need subsequent transformations and treatments to become useful components or products.

Those transformations (like surface treatment, forming, joining, etc.), frequently called enabling technologies, are gathered as downstream processes. Rolling: Introduction

Rolled products, i.e. sheet, plate and foil constitute almost 50% of all aluminium alloys used.

In North America and Western Europe, the packaging industry consumes the majority of the sheet and foil for making beverage cans, foil containers and foil wrapping. Sheet is also used extensively in building for roofing and siding, in transport for airframes, road and rail vehicles, in marine applications, including offshore platforms, and superstructures and hulls of boats. Also, while relatively little is currently used in the manufacture of high volume production automobiles, it is expected that the next decade will see an increase of aluminium sheet used for body panels. The starting stock for most rolled products is the DC (Direct Chill semi-continuous cast) ingot. The size of the ingot depends on the size of the DC unit available, the hot rolling mill capacity, volume required for a particular end use and to some extent the alloys being cast. Ingots up to over 20 tons in weight, 500-600 mm thick, 2000 mm wide and 8000 mm long are produced. The DC ingot is usually cooled after casting to room temperature and then re-heated to around 500 C prior to successive passes through a hot rolling mill where it is reduced in thickness to about 4 - 6 mm The strip from the hot rolling mill is coiled for transport to the cold mill which might be on the same site or elsewhere. Cold mills, in a wide range of types and sizes are available; some are single stand, others 3 stands and some 5 stand. Cold rolling speeds vary but modern mills operate at exit speeds as high as 3000 m per minute and alloys may be cold rolled to thickness of around 0.05 mm. Applications of Rolled Products

Here are some typical applications of rolled aluminium sheet and plate alloys. Strain-hardening alloys 1060 Chemical equipment, Tankers 1100 Cooking utensils, Decorative panels 3003, 3004 Chemical equipment, Storage tanks, Beverage can bodies 5005, 5050, 5052, 5657 Automotive trim, Architectural applications 5085, 5086 Marine structures, Storage tanks, Rail cars 5454, 5456 Pressure vessels, Armour plate 5182, 5356 Cryogenic tanks, Beverage can ends

Heat-treatable alloys 2219 High temperature (e.g. supersonic aircraft) 2014, 2024 Airframes, Auto body sheet 6061, 6063, 6082, 6351, 6009, 6010 Marine structures, Heavy road transport, Rail cars, Auto body sheet 7004, 7005, 7019, 7010 Missiles, Armour plate, Military bridges 7075, 7079, 7050, 7010, 7150 Airframes, Tooling plate Heat treatment

Different aluminium alloys can be subjected to a range of heat treatments: Homogenisation: after casting, alloys are heated to remove any segregation, i.e. to obtain a homogenous composition throughout the alloy. Annealing: strain-hardening alloys (1xxx, 3xxx and 5xxx) can be softened after cold working. Precipitation or age hardening: 2xxx, 6xxx and 7xxx alloys can be strengthened by precipitation hardening, or 'ageing'. Solution heat treatment of precipitation hardening alloys prior to ageing in order to take alloy elements into solution. Stoving (e.g. to 'cure' a paint or lacquer coating) Process Routes

Although we often tend to consider processes such as casting, rolling, extruding and heat treatment as separate processes, it is very important also to think in terms of entire process routes. A process route will be developed for a given application in order that all the required properties are achieved or optimised.On the following pages, you can see some different process routes for different semi-finished products.

Recycling Aluminium has been recycled since the days it was first commercially produced and today recycled aluminium accounts for one-third of global aluminium consumption world-wide.

Recycling is an essential part of the aluminium industry and makes sense economically, technically and ecologically. At the end of their useful life, all aluminium products retain some worth which guarantees that it is possible to create value by recycling them into new products. Efficiency of aluminium recycling thus translates into high recycling rates for the various applications. ail in this section. Applications The main properties which make aluminium a valuable material are its low density, strength, recyclability, corrosion resistance, durability, ductility, formability and conductivity. Due to this unique combination of properties, the variety of applications of aluminium continues to increase. It is essential in our daily lives. We cannot fly, go by high speed train, high performance car or fast ferry without it. We cannot get heat and light into our homes and offices without it. We depend on it to preserve our food, our medicine and to provide electronic components for our computers. Reference Web Back

site:

http://aluminium.matter.org.uk/

Aluminum - Production and Transformation

From Bauxite Aluminium is the earth's most abundant metallic element, making up approximately eight per cent of the planet's crust. While aluminium never occurs naturally in its pure form, it is commonly found in the form of oxides. The most commercially viable source of aluminium is bauxite, which is predominantly found in tropical and sub-tropical regions of the world. Bauxite can be found as granules or rocks and it can vary in color, depending on its exact composition. While the ore is generally easy to mine, the process to extract the aluminium from the bauxite is quite complex. The process of making metallic aluminium is carried out in two successive stages: a chemical process to extract alumina or anhydrous aluminium oxide (A12O3) from the bauxite, and an electrolytic process to reduce the alumina to aluminium. To Alumina

The bauxite, which contains about 75 per cent hydrated alumina (A12O3 3H2O and A12O3 H2O) is crushed and grounded into a powder and mixed with a solution of caustic soda. 1. This paste is mixed with further amounts of caustic soda solution in autoclaves or digesters. 2. There, under pressure and at a high temperature, the caustic soda combines with the hydrated alumina to leave a solution called sodium aluminate. Any impurities remain as undissolved residue. 2NaOH + bauxite --- > Na2OAl2O3 + 4H2O + residues The residue or "red mud", mainly the oxides of iron, silicon and titanium, is removed by sedimentation and filtration. 3. 4. The inert red mud is washed to recover the chemicals and is disposed of by a "wet stacking" technique over a specially prepared land area. The sodium aluminate solution is then pumped into precipitator tanks where very fine and pure alumina trihydrate is added as "seed". Under agitation and with gradual cooling the alumina trihydrate contained in the solution precipitates on the "seed". 5. The trihydrate solids are then separated from the caustic soda solution by settling and vacuum filtering. The caustic soda solution is recovered and returned to the start of the process to be reused in autoclaves. The trihydrate solids are then passed through high-temperature (900-1100C) calciners that extract the chemically combined water that they contain. 6. Al2O3 3H2O + heat -- > Al2O3+ 3H2O ^ The aluminium oxide (Al2O3) that results is a white powder, like table salt in appearance, known as calcined alumina. Four to five tonnes of bauxite are required to produce approximately two tonnes of alumina which, in turn, yield one tonne of aluminium. On to Aluminium Electrolysis is the transformation of alumina into aluminium. An aluminium smelter comprises three main sectors: Carbon, Potlines and Casthouse. CARBON SECTOR

This is where anodes are produced. Anodes are designed to be hung over electrolytic pots to carry the required electrical current. These anodes are a mixture of coke and petroleum pitch. Coke is crushed to a very precise granulometry, mixed with pitch to form a paste which is molded in vibro-compactors to produce raw anodes or "green" anodes. Raw anodes are then transferred to gas or oil-fired furnaces where they are baked for several days at high temperature (1100 C). Once baked, anodes are rodded, that is attached to aluminium stems from which they will hang over electrolytic pots. Anodes burn and must be replaced about every twenty days; the carbon sector is also responsible for the recovery of carbon content in spent anodes (or butts) for recycling as well as for the cleanup of stems which will be reused. The smoke given off by the anode baking process is thoroughly treated in highly sophisticated systems. Production:

POTLINES Aluminium is obtained from alumina by electrolytic reduction - a chemical term meaning the removal of oxygen atoms from aluminium oxide. The calcined alumina is reduced to aluminium metal in electrolytic cells, or "pots", connected in series to a direct current power source. The cells are rectangular steel pots lined with refractory bricks and carbon blocks acting as the cathode.

The pot contains a molten electrolyte, called "bath" in which alumina is dissolved. The electrolyte is a mixture of cryolite (Na3AlF6), a molten salt, and certain additives to give it appropriate density, conductivity and viscosity. The principal additive is aluminium fluoride (AlF3) which must be replaced from time to time due to losses through evaporation and a chemical reaction converting it into more cryolite. The emitted fluorides are collected and treated. Suspended in the electrolyte are a number of anodes (positive electrodes) which act as electrical conductors for a high intensity direct current. Electrical current passing from the anode through the electrolyte to the pot, which acts as a cathode, reduces the alumina molecules into aluminium and oxygen at a temperature of approximately 950C. This process is called electrolysis. The oxygen is released on the carbon anode, where it combines with the carbon to form carbon monoxide and carbon dioxide (CO and CO2). The aluminium, being heavier than the bath, settles to the bottom of the pot. Considerable electrical energy, between 13 and 17 kilowatt-hours per kilogram of aluminium, is consumed in the process. Each pot is tightly closed to achieve greater energy efficiency and to capture the pollutants emitted; gas treatment centers provide a very effective environmental protection. At regular intervals, the molten aluminium is tapped from the bottom of the pot into large laddles and transferred to holding furnaces for casting. CASTHOUSE Molten metal from potlines is transferred to huge holding furnaces with a capacity of up to 60 tonnes, where it is refined and optionally mixed with metal additives to produce aluminium alloys. While aluminium is sometimes used as is in its commercially pure form, most applications involve the addition of small quantities of other metals to create alloys with special properties. Certain alloying elements will increase strength or corrosion resistance, while others enhance such properties as machinability, ductility, weldability and strength at high temperature. Recyclable aluminium beverage cans, for example, are made from an alloy containing manganese and magnesium that provide strength and formability. Magnesium is added to aluminium to create an alloy that provides the added strength required for the can top. Alloys containing magnesium and silicon are very corrosion-resistant and suitable for use in window frames, doors and pleasure boats. Copper and zinc are added to produce alloys of the highest strength, while chromium, manganese or titanium are added for grain-size control. Recent research with metal matrix composite, a combination of aluminium and ceramic particles, promises stronger materials that are more cost-effective, stiffer and provide better resistance to wear. Aircraft components are made from high-strength alloys containing copper, magnesium, silicon and zinc as the principal alloying elements. The aerospace industry employs the new aluminium-lithium alloys which provide significant weight savings over alloys of similar strength. Aluminiummagnesium-silicon alloys are used in architectural applications where pleasing, corrosion-resistant surface finishes are required. Automotive castings, strong and machinable, are made from aluminium-copper-silicon alloys. Once the exact content of the molten aluminium has been analyzed, it is either cast into ingots, slabs or billets using the DC casting (direct chill) method, or cast directly into semi-finished products.Aluminium is cast into shapes that vary depending upon the type of equipment that will be used to process the metal. For example, very large ingots of rectangular shape, also called slabs,

are intended for hot-rolling to produce plate, sheet and foil. Cylindrical ingots, also called billets, are for extrusion while metal for remelting can be cast into large blocks called sows, as well as tri-lock shapes or T-ingots, depending upon the shape. Each ingot can weigh up to 25 tonnes. Transformation ROLLING The process of flattening the ingot or slab is carried out by either hot- or cold-rolling the metal. In hot-rolling, the ingot is preheated so as to soften and/or homogenize it, and is then passed back and forth through massive rolls that reduce the ingot's thickness while increasing its length. The width remains unchanged. Hot-rolling improves the metallurgical qualities of the metal without appreciable work-hardening. Subsequent cold-rolling gives the strength characteristics that result from work-hardening, and the metal can be rolled to tighter dimensional tolerances. Plate, which is hot-rolled, is 6.30 millimeters or more in thickness, while sheet, which is hot-andcold-rolled, varies in thickness from 6.30 down to 0.15 millimeters. Foil is also cold-rolled to gauges below 6 microns. A continuous length of foil, 450 kilometers long, could be rolled from a single slab. The aluminium beverage can market is the primary end-user for aluminium sheet. EXTRUDING The extrusion process consists of pushing a pre-heated cylindrical aluminium ingot through a steel die. The ingot is formed into a continuous length of uniform cross-section by forced flow through the steel die. The outline of the die opening is reproduced in the extruded aluminium in much the same way as decorative icing is forced from a pastry pouch. Extruded tubing and hollow shapes are formed by placing a steel mandrel inside the die opening. The aluminium is forced to flow between the mandrel and the die, reproducing the shape of the mandrel on the inside of the section and the shape of the die on the outside. Extruded tubing is used in the manufacture of such items as doors, window frames, building wall cladding, highway lighting standards and garden furniture. Larger extrusions are also used in the manufacture of railcars, truck trailers, aircraft and ship super-structures. OTHER METHODS Aluminium may be cast into various shapes by pouring molten metal into molds. The methods used are die casting, permanent mold casting or sand casting. Forging - In this process, the desired part is formed in a confined die from a hot metal slug. This is achieved by applying force which causes the metal to flow and fill the die cavity. Drawing - All aluminium wire and some tubing and rod products are manufactured by a coldrolling process called drawing; a starter stock is pulled through a die in which it is both shaped and reduced. In the production of tubing, lengths of extruded, thick-walled tube are drawn through progressively smaller dies until reduced to the desired diameter. Impacting - Also known as impact extruding, impacting is a combination of both extruding and forging. A disc-shaped slug of metal is placed in a die and struck by a punch; part of it is forged into a base, flange or hub, and the remainder is extruded upwards, downwards or sideways from the forged section. Anodizing - Aluminium, particularly when intended for architectural purposes, may be anodized. Anodizing is an electro-chemical process whereby the natural oxide film on aluminium is

thickened by passing an electric current through certain acid electrolytes with the aluminium part as the anode. Anodizing also provides a means of coloring the metal with dyes. This process also increases aluminium's hardness and corrosion resistance. Reference: Web Back

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