The Solvay process or ammonia-soda process is the major industrial process for the production of soda ash (valued primarily for its content of sodium carbonate). The ammonia-soda process was developed into its modern form by Ernest Solvay during the 1860s. The ingredients for this process are readily available and inexpensive: salt brine (from inland sources or from the sea) and limestone (from mines). The worldwide production of soda ash in 2005 has been estimated at 42 billion kilograms (92 billion pounds), which is more than six kilograms per year (13 lb) for each person on Earth. Solvay-based chemical plants now produce roughly three-quarters of this supply, with the remainder being mined from natural deposits.
The Solvay process results in soda ash (predominantly sodium carbonate (Na2CO3)) from brine (as a source of sodium chloride (NaCl)) and from limestone (as a source of calcium carbonate (CaCO3)). The overall process is:
- 2 NaCl + CaCO3 → Na2CO3 + CaCl2
The actual implementation of this global, overall reaction is intricate. A simplified description can be given using the four different, interacting chemical reactions illustrated in the figure. In the first step in the process, carbon dioxide (CO2) passes through a concentrated aqueous solution of sodium chloride (table salt, NaCl) and ammonia (NH3).
In industrial practice, the reaction is carried out by passing concentrated brine through two towers. In the first, ammonia bubbles up through the brine (salt water) and is absorbed by it. In the second, carbon dioxide bubbles up through the ammoniated brine, and sodium bicarbonate (baking soda) precipitates out of the solution. Note that, in a basic solution, NaHCO3 is less water-soluble than sodium chloride. The ammonia (NH3) buffers the solution at a basic pH; without the ammonia, a hydrochloric acid byproduct would render the solution acidic, and arrest the precipitation.
The necessary ammonia "catalyst" for reaction (I) is reclaimed in a later step, and relatively little ammonia is consumed. The carbon dioxide required for reaction (I) is produced by heating ("calcination") of the limestone at 950 - 1100 °C. The calcium carbonate (CaCO3) in the limestone is partially converted to quicklime (calcium oxide (CaO)) and carbon dioxide:
The sodium bicarbonate (NaHCO3) that precipitates out in reaction (I) is filtered out from the hot ammonium chloride (NH4Cl) solution, and the solution is then reacted with the quicklime (calcium oxide (CaO)) left over from heating the limestone in step (II).
CaO makes a strong basic solution. The ammonia from reaction (III) is recycled back to the initial brine solution of reaction (I).
The sodium bicarbonate (NaHCO3) precipitate from reaction (I) is then converted to the final product, sodium carbonate (washing soda: Na2CO3), by calcination (160 - 230 C), producing water and carbon dioxide as byproducts:
The carbon dioxide from step (IV) is recovered for re-use in step (I). When properly designed and operated, a Solvay plant can reclaim almost all its ammonia, and consumes only small amounts of additional ammonia to make up for losses. The only major inputs to the Solvay process are salt, limestone and thermal energy, and its only major byproduct is calcium chloride, which is sold as road salt.
In the modified Solvay process developed by Chinese chemist Hou Debang in 1930s, the first few steps are the same as the Solvay process. However, the CaCl2 is supplanted by ammonium chloride (NH4Cl). Instead of treating the remaining solution with lime, carbon dioxide and ammonia are pumped into the solution, then sodium chloride is added until the solution saturates at 40°C. Next, the solution is cooled to 10°C. Ammonium chloride precipitates and is removed by filtration, and the solution is recycled to produce more sodium carbonate. Hou's process eliminates the production of calcium chloride. The byproduct ammonium chloride can be refined, used as a fertilizer and may have greater commercial value than CaCl2, thus reducing the extent of waste beds.
Additional details of the industrial implementation of this process are available in the report prepared for the European Soda Ash Producer's Association.
Uses of soda ash
Soda ash is used in many industrial processes, and its production is sometimes used as an indicator of economic health. The principal current uses include:
- Glass making: More than half the worldwide production of soda ash is used to make glass. Bottle and window glass (Soda-lime glass) is made by melting a mixture of sodium carbonate, calcium carbonate and silica sand (silicon dioxide (SiO2)).
- Water treatment: Sodium carbonate is used to soften water (precipitates out Mg2+ and Ca2+ carbonates). This is used both industrially and domestically (in some washing powders).
- Making soaps and detergents: Often sodium carbonate is used as a cheaper alternative to lye (sodium hydroxide (NaOH)).
- Paper making: Sodium carbonate is used to make sodium bisulfite (NaHSO3) for the "sulfite" method of separating lignin from cellulose.
- As a common alkali in many chemical factories because it is cheaper than NaOH and far safer to handle.
- Making sodium bicarbonate: NaHCO3 is used in baking soda and fire extinguishers. Although NaHCO3 is produced in the Solvay process, heating it to remove the ammonia it is contaminated with decomposes some NaHCO3, so it is actually cheaper to react the finished Na2CO3 product with CO2.
- Removing sulfur dioxide (SO2) from flue gases in power stations. This is becoming more common, especially where stations have to meet stringent emission controls.
The name "soda ash" is based on the principal historical method of obtaining alkali, which was by using water to extract it from ashes. Wood fires yielded potash and the active ingredient potassium carbonate. The word "soda" (from the Middle Latin) originally referred to certain plants that grow in salt marshes; it was discovered that the ashes of these plants yielded the useful alkali "soda ash." The cultivation of such plants for production of soda ash reached a particularly high state of development in the 18th Century in Spain, where the plants are named barrilla; the English word is "barilla." The ashes of kelp also yield soda ash, and were the basis of an enormous 18th Century industry in Scotland. Alkali was also mined from dry lakebeds in Egypt.
By the late 18th century, however, these sources were insufficient to meet Europe's burgeoning demand for alkali for soap, textile, and glass industries. In 1791, the French physician Nicolas Leblanc developed a method to manufacture soda ash using salt, limestone, sulfuric acid, and coal. Although the Leblanc process came to dominate alkali production in the early 19th century, the expense of its inputs and its polluting byproducts (including hydrochloric acid gas) made it apparent that it was far from an ideal solution.
It has been reported that in 1811 French physicist Augustin Jean Fresnel discovered that sodium bicarbonate precipitates when carbon dioxide is bubbled through ammonia-containing brine— which is the chemical reaction central to the Solvay process. The discovery wasn't published. As has been noted by Desmond Reilly, "The story of the evolution of the ammonium-soda process is an interesting example of the way in which a discovery can be made and then laid aside and not applied for a considerable time afterwards." Serious consideration of this reaction as the basis of an industrial process dates from the British patent issued in 1834 to H. G. Dyan and J. Henning. There were several attempts to reduce this reaction to industrial practice, with varying success.
In 1861, the Belgian industrial chemist Ernest Solvay turned his attention to the problem; he was apparently largely unaware of the extensive earlier work. His solution, an 80-foot (24 m)-tall gas absorption tower in which carbon dioxide bubbled up through a descending flow of brine, together with efficient recovery and recycling of the ammonia, proved effective, and by 1864, Solvay and his brother Alfred had acquired good financial backing and constructed a plant in the Belgian town of Charleroi. The new process proved more economical and less polluting than the Leblanc method, and its use spread. In 1874, the Solvays expanded their facilities with a new, larger plant at Nancy, France.
In the same year, Ludwig Mond visited Solvay in Belgium and acquired rights to use the new technology. He and John Brunner formed the firm of Brunner, Mond & Co., and built a Solvay plant at Winnington, near Northwich, Cheshire, England. The facility started up in 1874. Mond was instrumental in making the Solvay process a commercial success; he made several refinements between 1873 and 1880 that removed byproducts that could slow or halt the mass production of sodium carbonate through use of the process.
In 1884, the Solvay brothers licensed Americans William B. Cogswell and Rowland Hazard to produce soda ash in the US, and formed a joint venture (Solvay Process Company) to build and operate a plant in Solvay, New York.
By the 1890s, Solvay process plants produced the majority of the world's soda ash.
In 1938, large natural deposits of the mineral Trona were discovered near the Green River in Wyoming. Sodium carbonate can be mined from this source less expensively than it can be produced by the Solvay process, and with the closing of the original Solvay, New York plant in 1986, there have been no Solvay-based plants operating in North America. Throughout the rest of the world, however, the Solvay process remains the major source of soda ash.
Byproducts and wastes
The principal byproduct of the Solvay process is calcium chloride (CaCl2) in aqueous solution. The process has other waste and byproducts as well. Not all of the limestone that is calcined is converted to quicklime and carbon dioxide (in reaction II); the residual calcium carbonate and other components of the limestone become wastes. In addition, the salt brine used by the process is usually purified to remove magnesium and calcium ions, typically to form carbonates; otherwise, these impurities would lead to scale in the various reaction vessels and towers. These carbonates are additional waste products.
In inland plants, such as that in Solvay, New York, the byproducts have been deposited in "waste beds"; the weight of material deposited in these waste beds exceeded that of the soda ash produced by about 50%. These waste beds have led to water pollution, principally by calcium and chloride. The waste beds in Solvay, New York substantially increased the salinity in nearby Onondaga Lake, which is among the most polluted lakes in the U.S. and is a superfund pollution site. As such waste beds age, they do begin to support plant communities which have been the subject of several scientific studies.
At seaside locations, such as those at Saurashtra, Gujarat, India, the CaCl2 solution may be discharged directly into the sea, apparently without substantial environmental harm. At Osborne, South Australia, a settling pond is now used to remove 99% of the CaCl2 as the former discharge was silting up the shipping channel.
Carbon sequestration and the Solvay process
Variations in the Solvay process have been proposed for carbon sequestration. One idea is to react carbon dioxide, produced perhaps by the combustion of coal, to form solid carbonates (such as sodium bicarbonate) that could be permanently stored, thus avoiding carbon dioxide emission into the atmosphere. Variations in the Solvay process have been proposed to convert carbon dioxide emissions into sodium carbonates, but carbon sequestration by calcium or magnesium carbonates appears more promising. However, the amount of carbon dioxide exhausted by mankind as compared to the amount which can be used for carbon sequestration with calcium or magnesium is very low. Moreover, variation on the Solvay process will most probably add an additional energy step, which will increase carbon dioxide emissions. This helped to industrialize during the 20th century
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