Sodium hydroxide is industrially produced as a 50% solution by variations of the electrolytic chloralkali process. Chlorine gas is also produced in this process. Solid sodium hydroxide is obtained from this solution by the evaporation of water. Solid sodium hydroxide is most commonly sold as flakes, prills, and cast blocks.
In 2004, world production was estimated at 60 million dry tonnes of sodium hydroxide, and demand was estimated at 51 million tonnes. In 1998, total world production was around 45 million tonnes. North America and Asia each contributed around 14 million tonnes, while Europe produced around 10 million tonnes. In the United States, the major producer of sodium hydroxide is Olin, which has annual production around 5.7 million tonnes from sites at Freeport, Texas; Plaquemine, Louisiana; St. Gabriel, Louisiana; McIntosh, Alabama; Charleston, Tennessee; Niagara Falls, New York; and Bécancour, Canada. Other major US producers include Oxychem, Westlake, Shintek, and Formosa. All of these companies use the chloralkali process.
Historically, sodium hydroxide was produced by treating sodium carbonate with calcium hydroxide in a metathesis reaction which takes advantage of the fact that sodium hydroxide is soluble, while calcium carbonate is not. This process was called causticizing.
This process was superseded by the Solvay process in the late 19th century, which was in turn supplanted by the Leblanc process and then chloralkali process which is in use today.
Sodium hydroxide is also produced by combining pure sodium metal with water. The byproducts are hydrogen gas and heat, often resulting in a flame.
This reaction is commonly used for demonstrating the reactivity of alkali metals in academic environments; however, it is not commercially viable, as the isolation of sodium metal is typically performed by reduction or electrolysis of sodium compounds including sodium hydroxide.