Red mud

Red mud, also known as bauxite residue, is an industrial waste generated during the refinement of bauxite into alumina using the Bayer process. It is composed of various oxide compounds, including the iron oxides which give its red color. Over 95% of the alumina produced globally is through the Bayer process; for every tonne of alumina produced, approximately 1 to 1.5 tonnes of red mud are also produced. Annual production of alumina in 2018 was approximately 126 million tonnes resulting in the generation of over 160 million tonnes of red mud.[1]

For the tannic for drilling mud, see Quebracho tree.
Red mud near Stade (Germany)
Bauxite, an aluminium ore (Hérault department, France). The reddish colour is due to iron oxides that make up the main part of the red mud.

Due to this high level of production and the material's high alkalinity, it can pose a significant environmental hazard and storage problem. As a result, significant effort is being invested in finding better methods for dealing with it.[2]

Less commonly, this material is also known as bauxite tailings, red sludge, or alumina refinery residues.

Production

Red mud is a side-product of the Bayer process, the principal means of refining bauxite en route to alumina. The resulting alumina is the raw material for producing aluminium by the Hall–Héroult process.[3] A typical bauxite plant produces one to two times as much red mud as alumina. This ratio is dependent on the type of bauxite used in the refining process and the extraction conditions.[4]

More than 60 manufacturing operations across the world using the Bayer process to make alumina from bauxite ore. Bauxite ore is mined, normally in open cast mines, and transferred to an alumina refinery for processing. The alumina is extracted using sodium hydroxide under conditions of high temperature and pressure. The insoluble part of the bauxite (the residue) is removed, giving rise to a solution of sodium aluminate, which is then seeded with an aluminium hydroxide crystal and allowed to cool which causes the remaining aluminium hydroxide to precipitate from the solution. Some of the aluminium hydroxide is used to seed the next batch, while the remainder is calcined (heated) at over 1000 °C in rotary kilns or fluid flash calciners to produce aluminium oxide (alumina).

The alumina content of the bauxite used is normally between 45 - 50%, but ores with a wide range of alumina contents can be used. The aluminium compound may be present as gibbsite (Al(OH)3), boehmite (γ-AlO(OH)) or diaspore (α-AlO(OH)). The residue invariably has a high concentration of iron oxide which gives the product a characteristic red colour. A small residual amount of the sodium hydroxide used in the process remains with the residue, causing the material to have a high pH/alkalinity, normally >12. Various stages in the solid/liquid separation process are introduced to recycle as much sodium hydroxide as possible from the residue back into the Bayer Process in order to make the process as efficient as possible and reduce production costs. This also lowers the final alkalinity of the residue making it easier and safer to handle and store.

Composition

Red mud is composed of a mixture of solid and metallic oxides. The red colour arises from iron oxides, which comprise up to 60% of the mass. The mud is highly basic with a pH ranging from 10 to 13.[3][4][5] In addition to iron, the other dominant components include silica, unleached residual alumina, and titanium oxide.[6]

The main constituents of the residue after the extraction of the aluminium component are insoluble metallic oxides. The percentage of these oxides produced by a particular alumina refinery will depend on the quality and nature of the bauxite ore and the extraction conditions. The table below shows the composition ranges for common chemical constituents, but the values vary widely:

ChemicalPercentage composition
Fe2O35–60%
Al2O35–30%
TiO20–15%
CaO2–14%
SiO23–50%
Na2O1–10%

Mineralogically expressed the components present are:

Chemical nameChemical formulaPercentage composition
Sodalite3Na2O⋅3Al2O3⋅6SiO2⋅Na2SO44–40%
CancriniteNa3⋅CaAl3⋅Si3⋅O12CO30–20%
Aluminous-goethite (aluminous iron oxide)α-(Fe,Al)OOH10–30%
Hematite (iron oxide)Fe2O310–30%
Silica (crystalline & amorphous)SiO25–20%
Tricalcium aluminate3CaO⋅Al2O3⋅6H2O2–20%
BoehmiteAlO(OH)0–20%
Titanium dioxideTiO20–10%
PerovskiteCaTiO30–15%
MuscoviteK2O⋅3Al2O3⋅6SiO2⋅2H2O0–15%
Calcium carbonateCaCO32–10%
GibbsiteAl(OH)30–5%
KaoliniteAl2O3⋅2SiO2⋅2H2O0–5%

In general, the composition of the residue reflects that of the non-aluminium components, with the exception of part of the silicon component: crystalline silica (quartz) will not react but some of the silica present, often termed, reactive silica, will react under the extraction conditions and form sodium aluminium silicate as well as other related compounds.

Environmental hazards

Discharge of red mud is hazardous environmentally because of its alkalinity and its toxic components.

In 1972 there was a red mud discharge off the coast of Corsica by the Italian company Montedison.[7] The case is important in international law governing the Mediterranean sea.[8]

In October 2010, approximately one million cubic meters of red mud from an alumina plant near Kolontár in Hungary was accidentally released into the surrounding countryside in the Ajka alumina plant accident, killing ten people and contaminating a large area.[9] All life in the Marcal river was said to have been "extinguished" by the red mud, and within days the mud had reached the Danube.[10] The long-term environmental effects of the spill have been minor after a €127 million remediation effort by the Hungarian government.[11]

Residue storage areas

Residue storage methods have changed substantially since the original plants were built. The practice in early years was to pump the slurry, at a concentration of about 20% solids, into lagoons or ponds sometimes created in former bauxite mines or depleted quarries. In other cases, impoundments were constructed with dams or levees, while for some operations valleys were dammed and the residue deposited in these holding areas.[12]

It was once common practice for the red mud to be discharged into rivers, estuaries, or the sea via pipelines or barges; in other instances the residue was shipped out to sea and disposed of in deep ocean trenches many kilometres offshore. Most disposal in the sea, estuaries and rivers has now stopped, and remaining producers that still maintain this practice are actively seeking alternatives due to increasingly stringent environmental legislation.[13]

As residue storage space ran out and concern increased over wet storage, since the mid-1980s dry stacking has been increasingly adopted.[14][15][16][17] In this method, residues are thickened to a high density slurry (48–55% solids or higher), and then deposited in a way that it consolidates and dries.[18]

An increasingly popular treatment process is filtration whereby a filter cake (typically resulting in 26–29% moisture) is produced. This cake can be washed with either water or steam to reduce alkalinity before being transported and stored as a semi-dried material.[19] Residue produced in this form is ideal for reuse as it has lower alkalinity, is cheaper to transport, and is easier to handle and process.

In 2013 Vedanta Aluminium, Ltd. commissioned a red mud powder-producing unit at its Lanjigarh refinery in Odisha, India, describing it as the first of its kind in the alumina industry, tackling major environmental hazards.[20]

Use

Since the Bayer process was first adopted industrially in 1894, the value of the remaining oxides has been recognized. Attempts have been made to recover the principal components – especially the iron. Since mining began, an enormous amount of research effort has been devoted to seeking uses for the residue.

Many studies have been conducted to develop uses of red mud.[21] An estimated 2 to 3 million tonnes are used annually in the production of cement,[22] road construction[23] and as a source for iron.[3][4][5] Potential applications include the production of low cost concrete,[24] application to sandy soils to improve phosphorus cycling, amelioration of soil acidity, landfill capping and carbon sequestration.[25][26]

Reviews describing the current use of bauxite residue in Portland cement clinker, supplementary cementious materials/blended cements and special calcium sulfo-aluminate cements have been extensively researched and well documented.[27]

  • Cement manufacture, use in concrete as a supplementary cementitious material. From 500,000 to 1,500,000 tonnes.[28][29]
  • Raw material recovery of specific components present in the residue: iron, titanium, steel and REE (rare-earth elements) production. From 400,000 to 1,500,000 tonnes;
  • Landfill capping/roads/soil amelioration – 200,000 to 500,000 tonnes;[23]
  • Use as a component in building or construction materials (bricks, tiles, ceramics etc.) – 100,000 to 300,000 tonnes;
  • Other (refractory, adsorbent, acid mine drainage (Virotec), catalyst etc.) – 100,000 tonnes.[30]
  • Use in building panels, bricks, foamed insulating bricks, tiles, gravel/railway ballast, calcium and silicon fertilizer, refuse tip capping/site restoration, lanthanides (rare earths) recovery, scandium recovery, gallium recovery, yttrium recovery, treatment of acid mine drainage, adsorbent of heavy metals, dyes, phosphates, fluoride, water treatment chemical, glass ceramics, ceramics, foamed glass, pigments, oil drilling or gas extraction, filler for PVC, wood substitute, geopolymers, catalysts, plasma spray coating of aluminium and copper, manufacture of aluminium titanate-Mullite composites for high temperature resistant coatings, desulfurisation of flue gas, arsenic removal, chromium removal.[31]

In 2015 a major initiative was launched in Europe with funds from the European Union to address the valorisation of red mud. Some 15 Ph.D. students were recruited as part the European Training Network (ETN) for Zero-Waste Valorisation of Bauxite Residue.[32] The key focus will be the recovery of iron, aluminium, titanium and rare-earth elements (including scandium) while valorising the residue into building materials.

See also

References
  1. Annual statistics collected and published by World Aluminium.
  2. Evans, K., "The History, Challenges and new developments in the management and use of Bauxite Residue", J. Sustain Metall. May 2016. doi:10.1007/s40831-016-00060-x.
  3. Schmitz, Christoph (2006). "Red Mud Disposal". Handbook of aluminium recycling. p. 18. ISBN 978-3-8027-2936-2.
  4. Chandra, Satish (1996-12-31). "Red Mud Utilization". Waste materials used in concrete manufacturing. pp. 292–295. ISBN 978-0-8155-1393-3.
  5. Society for Mining, Metallurgy, Exploration U.S (2006-03-05). "Bauxite". Industrial minerals & rocks: commodities, markets, and uses. pp. 258–259. ISBN 978-0-87335-233-8.
  6. Ayres, R. U., Holmberg, J., Andersson, B., "Materials and the global environment: Waste mining in the 21st century", MRS Bull. 2001, 26, 477. doi:10.1557/mrs2001.119
  7. Crozier, Jean. "Le long combat contre la pollution de la Méditerranée par la Montedison". France 3 Corse ViaStella (in French). Retrieved 4 January 2019.
  8. Huglo, Christian. "Le recours au juge est la garantie de conservation de l'intégralité de la règle environnementale". Actu-Environnement (in French). Retrieved 4 January 2019.
  9. Gura, David. "Toxic Red Sludge Spill From Hungarian Aluminum Plant 'An Ecological Disaster'". NPR.org. National Public Radio. Retrieved 5 January 2019.
  10. "Hungarian chemical sludge spill reaches Danube". BBC News. 7 October 2010. Retrieved 3 February 2021.
  11. "Hungarian red mud spill did little long-term damage". Retrieved 14 December 2018.
  12. Evans, Ken; Nordheim, Eirik; Tsesmelis, Katy (2012). "Bauxite Residue Management". Light Metals. John Wiley & Sons, Ltd. pp. 61–66. doi:10.1002/9781118359259.ch11. ISBN 9781118359259.
  13. Power, G.; Gräfe, M.; Klauber, C. (June 2011). "Bauxite residue issues: I. Current management, disposal and storage practices". Hydrometallurgy. 108 (1–2): 33–45. doi:10.1016/j.hydromet.2011.02.006.
  14. B. G. Purnell, “Mud Disposal at the Burntisland Alumina Plant”. Light Metals, 157–159. (1986).
  15. H. H. Pohland and A. J. Tielens, “Design and Operation on Non-decanted Red Mud Ponds in Ludwigshafen”, Proc. Int. Conf. Bauxite Tailings, Kingston, Jamaica (1986).
  16. E. I. Robinsky, “Current Status of the Sloped Thickened Tailings Disposal System”, Proc. Int. Conf. Bauxite Tailings, Kingston, Jamaica (1986).
  17. J. L. Chandler, “The Stacking and Solar Drying Process for disposal of bauxite tailings in Jamaica”, Proc. Int. Conf. Bauxite Tailings, Kingston, Jamaica (1986).
  18. "Bauxite Residue Management: Best Practice" (PDF). World Aluminum. Retrieved 5 January 2019.
  19. K. S. Sutherland, "Solid/Liquid Separation Equipment", Wiley-VCH, Weinheim (2005).
  20. "Vedanta commissions red mud powder plant in Odisha". Business Line. 19 November 2013.
  21. Kumar, Sanjay; Kumar, Rakesh; Bandopadhyay, Amitava (2006-10-01). "Innovative methodologies for the utilisation of wastes from metallurgical and allied industries". Resources, Conservation and Recycling. 48 (4): 301–314. doi:10.1016/j.resconrec.2006.03.003.
  22. Y. Pontikes and G. N. Angelopoulos "Bauxite residue in Cement and cementious materials", Resourc. Conserv. Recyl. 73, 53-63 (2013).
  23. W.K.Biswas and D. J. Cooling, "Sustainability Assessment of Red Sand as a substitute for Virgin Sand and Crushed Limestone", J. of Ind. Ecology, 17(5) 756-762 (2013).
  24. Liu, W., Yang, J., Xiao, B., "Review on treatment and utilization of bauxite residues in China", Int. J. Miner. Process. 2009, 93, 220. doi:10.1016/j.minpro.2009.08.005
  25. "Bauxite Residue Management". bauxite.world-aluminium.org. The International Aluminium Institute. Retrieved 9 August 2016.
  26. Si, Chunhua; Ma, Yingqun; Lin, Chuxia (2013). "Red mud as a carbon sink: Variability, affecting factors and environmental significance". Journal of Hazardous Materials. 244–245: 54–59. doi:10.1016/j.jhazmat.2012.11.024. PMID 23246940.
  27. "Mining and Refining – Bauxite Residue Utilisation". bauxite.world-aluminium.org. Retrieved 2019-10-04.
  28. Y. Pontikes and G. N. Angelopoulos "Bauxite residue in Cement and cementious materials", Resourc. Conserv. Recyl. 73, 53–63 (2013).
  29. Y. Pontikes, G. N. Angelopoulos, B. Blanpain, "Radioactive elements in Bayer’s process bauxite residue and their impact in valorization options", Transportation of NORM, NORM Measurements and Strategies, Building Materials, Advances in Sci. and Tech, 45, 2176–2181 (2006).
  30. H. Genc¸-Fuhrman, J. C. Tjell, D. McConchie, "Adsorption of arsenic from water using activated neutralized red mud", Environ. Sci. Technol. 38 (2004) 2428–2434.
  31. B. K. Parekh and W. M. Goldberger, "An assessment of technology for the possible utilisation of Bayer process muds", published by the U. S. Environmental Protection Agency, EPA 600/2-76-301.
  32. "Project | European Training Network for Zero-Waste Valorisation of Bauxite Residue (Red Mud)".

Additional references
  • M. B. Cooper, “Naturally Occurring Radioactive Material (NORM) in Australian Industries”, EnviroRad report ERS-006 prepared for the Australian Radiation Health and Safety Advisory Council (2005).
  • Agrawal, K. K. Sahu, B. D. Pandey, "Solid waste management in non-ferrous industries in India", Resources, Conservation and Recycling 42 (2004), 99–120.
  • Jongyeong Hyuna, Shigehisa Endoha, Kaoru Masudaa, Heeyoung Shinb, Hitoshi Ohyaa, "Reduction of chlorine in bauxite residue by fine particle separation", Int. J. Miner. Process., 76, 1–2, (2005), 13–20.
  • Claudia Brunori, Carlo Cremisini, Paolo Massanisso, Valentina Pinto, Leonardo Torricelli, "Reuse of a treated red mud bauxite waste: studies on environmental compatibility", Journal of Hazardous Materials, 117(1), (2005), 55–63.
  • H. Genc¸-Fuhrman, J. C. Tjell, D. McConchie, "Increasing the arsenate adsorption capacity of neutralized red mud (Bauxsol™)", J. Colloid Interface Sci. 271 (2004) 313–320.
  • H. Genc¸-Fuhrman, J. C. Tjell, D. McConchie, O. Schuiling, "Adsorption of arsenate from water using neutralized red mud", J. Colloid Interface Sci. 264 (2003) 327–334.
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