Electrochemistry Encyclopedia --- Aluminum production

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ELECTROLYTIC PRODUCTION OF ALUMINUM
Theodore R. Beck Electrochemical Technology Corp. Seattle, WA 98125, USA (October, 2001, Last revision: May, 2008) Rare over 100 years ago, aluminum, made by an electrolytic process, is now ubiquitous in transportation, packaging, building construction and electrical transmission. Metallic aluminum was first made by H. C. Oersted in Copenhagen in 1825. He gently heated potassium amalgam (an alloy of potassium and mercury) with aluminum chloride and distilled the mercury from the resultant aluminum amalgam. A small lump of metal having the luster of tin remained behind. In 1845 Fredrick Wohler, at the University of Gottingen, made pinhead size particles of aluminum by reduction of aluminum chloride with potassium. He was not able to fuse them together but he measured their specific gravity and obtained values of 2.50 and 2.67 (g/cm3), quite accurate compared to the current value of 2.702. The low specific gravity, the ductility and the stability in air presaged the future utility of the metal, if it could be made cheaply. H. SainteClaire Deville announced an improvement in the process in 1854, that is reduction of aluminum chloride by sodium. The resulting sodium chloride-aluminum chloride melt acted as a flux and allowed the aluminum pin heads to fuse into marble-size globules. Subsequently a plant was built near Paris. Sodium was made by carbothermal reduction. Many others entered the field, in England, Germany, and the United States and improvements were made in the process, but the metal was still expensive. In 1884 a 100ounce (~2.8-kg) pyramid was cast to cap the Washington Monument, one of the largest pieces ever made at the time. The real breakthrough came in 1886 when Charles Martin Hall in Ohio and Paul L. T . Heroult of Paris independently applied for patents for the electrolytic process in molten salt for manufacturing aluminum. Both electrolyzed alumina (aluminum oxide) dissolved in molten Greenland cryolite (sodium-aluminum fluoride) at about 1000oC (1832oF). The electric dynamo, which came into use about 15 years earlier, allowed this new electrolytic industry to grow and prosper. Aluminum has many remarkable properties, which have driven it to be second in production to iron and steel. Aluminum has a low density, and many strong alloys are produced that contain relatively small percentages of copper, manganese, silicon, magnesium, or zinc. It has a high thermal and electrical conductivity, is non-magnetic, and is highly ductile. Aluminum and its alloys can be cast, rolled, extruded, forged, drawn, and machined. It is commercially available in many forms: plates, sheet, bars, angle- and Ibeams, pipe, wire, and foil. Although it is high on the electromotive series and should be an active metal, it is highly corrosion resistant under usual conditions in the atmosphere and in water because it rapidly forms a protective oxide film. Corrosion resistance is enhanced for many applications by producing a thicker aluminum oxide film by anodizing in an electrolyte such as 15% sulfuric acid.

The Bayer process for alumina production
Alumina (aluminum oxide) powder, fed to the electrolytic process, is produced by the Bayer process from bauxite ore. Bauxites contain 40-60% alumina, combined with silica (silicon oxide), iron oxide, and titanium dioxide. Bauxite is mined in many places worldwide, for example, Guinea, Jamaica, Brazil, Australia, and Africa. In the Bayer process, the alumina is dissolved in hot sodium hydroxide solution and the iron oxide and other oxides are removed as insoluble "red mud." Aluminum hydroxide is precipitated from the clarified solution by cooling and seeding with aluminum hydroxide crystals. The washed precipitate is calcined at up to 1200oC (2192oF) to produce anhydrous alumina. The particle size of the alumina is about 100 µm (µm = millionth of a meter) and is called "ore" in the electrolytic reduction plants.

The Hall-Heroult process for aluminum production

http://electrochem.cwru.edu/ed/encycl/art-a01-al-prod.htm

15/01/2009

were suspended in the electrolyte (bath) from a copper busbar above. which later became part of Aluminum Company of Canada. and the off gases are more difficult to collect. Aluminum is siphoned out of the cells on a daily basis into vacuum crucibles and sent to the cast house. Prebaked anodes are baked in brick-lined pits and the hydrocarbon off gases can be captured and burned. the cell through steel collector bars to the cathode bus and on to the next cell. or "pots. Soderberg anodes are baked by the heat generated in the cells.cwru. Both types of anodes are made of baked petroleum coke and coal-tar or petroleum pitch. A carbon lining contains the bath and a pool of molten aluminum on the bottom. producing 50 lb/day (~23 kg/day). Anode rods carry the current from the anode bus through steel stubs cast with iron Fig. with a 3-inch (~8-cm) baked carbon lining.Aluminum production Page 2 of 5 Fig. of cryolite bath in which alumina was dissolved. The cell line was powered by two steam-powered dynamos in parallel. The Pittsburgh Reduction Company's first cell room. Germany. and Norway early in the 20th century where water power was available.htm 15/01/2009 . In 1901 a plant was built in Canada. http://electrochem. The components of a prebake anode cell are described as follows. The pots were arranged so that they could be heated from below by a gas flame. Plants were built at Niagara Falls and other places where inexpensive water power was available. The carbon lining is contained in a steel shell with a thermal insulation of alumina or insulating brick. They had two electrolytic cells in series. Meanwhile the Heroult process was commercialized in France and Switzerland. Environmental restrictions in more advanced countries have halted construction of Soderberg cell plants. now known as Alcoa. Current is conducted out of reduction cell. In 1907 the company changed its name to Aluminum Company of America. operating at about 1750 amperes and 16 volts across the two cells. Modern cell rooms with prebaked and with Soderberg anodes are shown in Figures 3 and 4. Alcan. The overall cell reaction is: alumina + carbon = aluminum + carbon dioxide Aluminum reduction cells today are of two types: those with prebaked anodes and those with baked-in-place anodes (Soderberg). 2.Electrochemistry Encyclopedia --. Hall and several associates started the Pittsburgh Reduction Company in 1888 in Pittsburgh. The plant was enlarged to 475 lb/day (~215 kg/day) in 1890 and in 1891 a new plant was built at New Kensington. Carbon anodes suspended from an anode bus conduct current into the cell. Six to ten carbon anodes. 16 inches (~41 cm) wide and 20 inches (~51 cm) deep. The new plant produced 1000 lb/day (~453 kg/day) in 1893 and 2000 lb/day (~906 kg/day) in 1894. Oxygen from the alumina dissolved in the bath combines with the bottom surface of the carbon anode to form carbon dioxide. The anode butts are sent back to the anode plant to be ground and mixed into new anode paste to be pressed and baked. but it was found that they were self sustaining by the electrical heat generated. rated at 1000 amperes and 25 volts each. Italy. Hall's first electrolytic cells. near Pittsburgh (Figure 1). 1. The aluminum metal pad is the cathode where aluminum is deposited from the bath. The anodes are consumed in the process and replacements are added at individual locations on a regular schedule. 24 inches (~61 cm) long. Cross section of a modern prebake anode aluminum into holes in the tops of the anodes. A new industry was born. It is interesting that present-day cells are qualitatively of the same design. although considerably larger and under more precise quality control (Figure 2). 3 inches (~8 cm) in diameter and 15 inches (~38 cm) long when new. Other plants were built in England." were of cast iron.edu/ed/encycl/art-a01-al-prod. The pots held 300 to 400 lbs (~136 to ~181 kg).

Energy efficiency is approaching about 50% based on the heat of reaction for the cell reaction. Alumina is fed to the bath through holes punched in the crust.Kaiser Chalmette plant (Courtesy of Jon H. Magnussson. consumable anodes. Cells now run a day or longer between anode effects. As cells have become larger. This effect has limited the minimum anode-cathode distance (ACD) to about 4. 4. On the average. The carbon dioxide and air leaking in is now ducted to dry scrubbers which remove fluorides from the gas stream.5 cm because of spurious short circuits by metal contacting the anodes. this effect limits energy efficiency. A light bulb connected across the cell lights up with increased cell voltage as a signal for the operators to feed the cell with alumina and kill the anode effect. Reykjavik. Altech. Iceland). cryolite freezes on the sidewalls of the cells forming a "ledge" which protects the sidelining from severe attack by aluminum and molten cryolite. cell size has doubled about every 18 years in the 20th century. Fig. Titanium diboride is a material with good electrical conductivity. The cell voltage then rises and some fluorocarbons are generated. returns fluoride to the cells. cyanides. The hydrogen fluoride comes from residual hydrocarbons in the anodes and trace water in the alumina and air humidity reacting with the fluoride bath. The ratio of sodium fluoride to aluminum fluoride in the cryolite bath changes over time and corrective additions are added based on laboratory analyses. Electrolytic cell for 300 kA prebaked carbon anode technology in the cell room (Courtesy of Jon H. and other materials. Control of alumina concentration in the cells is accomplished by a slight underfeeding. Iceland). Altech. aluminum carbide. and nonwith time. Since a major voltage drop in the cell is caused by bath resistance. cells in new plants have increased with time as illustrated in Figure 5.edu/ed/encycl/art-a01-al-prod.Electrochemistry Encyclopedia --. A small part is ground and added to cement kilns as a source of fluoride. Significant further improvements in energy efficiency may be hard to achieve with the existing cell design.htm 15/01/2009 . but most now still end in landfills. 3. When the alumina reaches a critical level the cell goes on anode effect. Fresh alumina contacting the gases removes the hydrogen fluoride and evaporated fluoride particulate. Two improvements to Fig. The carbon dioxide exits through holes in the crust and is collected under the hoods. fed to the cells. Magnussson. 5. Soderberg electrolytic cell line . In operation. Cryolite also freezes over the top of the bath and forms a "crust" to support a top layer of alumina thermal insulation. is wetted by aluminum and is highly-resistant to corrosion by http://electrochem. The industry has largely solved the fluoride emission problem with dry scrubbing but economical disposal of used carbon cell linings remains a problem. As a result of increasing cell size and better process control. The linings contain highly alkaline bath. electromagnetic effects caused by interaction of the current through the cell with the magnetic field of the bus work have resulted in swirling of the metal pad and vertical distortions in the metal-bath interface. This alumina. caused by a limiting rate of diffusion of alumina to the anode surfaces. This increase is driven by a need to reduce labor costs and to increase energy efficiency. Reykjavik.Aluminum production Page 3 of 5 Fig.cwru. Development of increasing new cell size the Hall-Heroult process have been under development for many decades but have not reached commercial application yet: wetted cathodes. energy consumption has improved with time as shown in Figure 6. Since inception of the process.

The Toth Company in the same period did a carbothermal chlorination of clay and reduced the aluminum chloride produced with manganese. Production and uses of aluminum Worldwide aluminum capacity in December 1997 was 24. Brazil. By combining titanium diboride cathodes and non-consumable anodes as vertical electrodes the anode-cathode spacing could be further decreased and cell voltage could be less than for the conventional Hall-Heroult cells. The distribution of consumption of aluminum in the United States in 1999 is shown in Figure 7. Thus the Hall-Heroult process remains to be displaced.cwru. Bauxite or low-grade ores were reduced with carbon and the resulting impure aluminum was purified with an aluminum sub-chloride process. but this is partially offset by a lower anode overvoltage. Alternative processes In the past half century there have been a number of attempts at alternatives to the Hall-Heroult process. U. Alcoa had a large-scale development program in the 1970s for an aluminum chloride (aluminum trichloride) process.900 tons/yr was shut down.861.S.edu/ed/encycl/art-a01-al-prod. It turned out that the energy costs were higher than for the Hall-Heroult process and severe corrosion problems were encountered. The United States capacity was 4. carbon dioxide and fluorocarbons in the cells. Fig. of which 654. with lower bath voltage loss. By coating a slightly-sloping carbon cell bottom with titanium diboride and providing a sump to collect aluminum. of which 1. The manganese chloride formed was converted to manganese oxide and chlorine with air. such as hematite (an oxide of iron).302. The United States once had a more dominant position but new reduction plants have been moving to countries with less expensive hydro and coal power such as Norway. The cell reaction would then be: alumina = aluminum + oxygen Energetically this reaction requires a one-volt increase in the cell. 6. The chlorine was recycled and the manganese oxide carbothermally reduced to manganese and recycled. It was said that the cells worked well but there were technical problems with the plant to produce aluminum chloride. Many materials have been tested as non-consumable anodes. 7.000 tons/yr was shut down.Electrochemistry Encyclopedia --. Fig. Improvement in energy efficiency. the electromagnetic problem is eliminated and a smaller ACD (anode-cathode distance) can be used. would be eliminated. then abandoned because of technical problems and lack of overall economic advantage over the Hall-Heroult process. Related articles Extracting metals from sulfide ores Metal powder production by electrolysis Space resource processing For other industrial electrolytic processes see: Brine electrolysis http://electrochem. In the 1960s Alcan developed a carbothermic subhalide (aluminum monochloride) process.000 metric tons/yr. tin oxide and a cermet of nickel ferrite and copper.000 metric tons/yr. Alumina was carbothermally chlorinated to aluminum chloride which was electrolytically decomposed to aluminum and chlorine in bipolar cells with graphite electrodes. and Australia. consumption of aluminum in 1999. Venezuela.215.Aluminum production Page 4 of 5 aluminum and bath if kept cathodic. The saving would be in eliminating the manufacture and changing carbon anodes.htm 15/01/2009 . Several alternatives have been developed almost to industrial scale. A manganese-aluminum alloy formed that was uneconomical to separate. The production of greenhouse gases.

Malinovsky. Aluminum Electrolysis (2nd Edition). Ohio.Dictionary --ESTIR Home Page --.YCES Home Page http://electrochem.Electrochemistry Encyclopedia --.Encyclopedia Home Page --. 1982. Dusseldorf. February 1998. (http://electrochem.cwru.Subject Index --. Aluminum and its Production.htm 15/01/2009 .Aluminum production Page 5 of 5 Industrial organics Further reading z Aluminum the Magic Metal. Matiasovsky. C. F. Thonstad.edu/ed/encycl/art-a01-al-prod. J. K. and J. Case Western Reserve University . K. R. Edwards. Return to: Top --. M. 1930. T. Edited by Zoltan Nagy ( nagyz@email. and proceedings volumes are also available in the Electrochemistry Science and Technology Information Resource (ESTIR). Frary and Z. Aluminium-Verlag. Grjotheim.cwru. Pawlek. C. "National Geographic" August 1978. P. Y. McGraw-Hill. Copyright Notice.unc. Canby. z z Listings of electrochemistry books. Department of Chemistry .Table of Contents --. Krohn.edu ).Search --.edu/estir/) The Encyclopedia is hosted by the Ernest B. The University of North Carolina at Chapel Hill . New York. D. review chapters. Cleveland.Author Index --. Yeager Center for Electrochemical Sciences (YCES) and the Chemical Engineering Department . Bibliography z The Primary Aluminum Industry at the Turn of the Year 1997/98. "Light Metals Age" p 8. Jeffries.

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