Chloralkali process

thumb|upright=1.75|Old drawing of a chloralkali process plant ([[Edgewood, Maryland)]]

The chloralkali process (also chlor-alkali and chlor alkali) is an industrial process for the electrolysis of sodium chloride (NaCl) solutions. It is the technology used to produce chlorine and sodium hydroxide (caustic soda), which are commodity chemicals required by industry. Thirty five million tons of chlorine were prepared by this process in 1987. In 2022, this had increased to about 97 million tonnes. The chlorine and sodium hydroxide produced in this process are widely used in the chemical industry.

Usually the process is conducted on a brine (an aqueous solution of concentrated NaCl), in which case sodium hydroxide (NaOH), hydrogen, and chlorine result. When using calcium chloride or potassium chloride, the products contain calcium or potassium instead of sodium. Related processes are known that use molten NaCl to give chlorine and sodium metal or condensed hydrogen chloride to give hydrogen and chlorine.

The process has a high energy consumption, for example around of electricity per tonne of sodium hydroxide produced. Because the process yields equivalent amounts of chlorine and sodium hydroxide (two moles of sodium hydroxide per mole of chlorine), it is necessary to find a use for these products in the same proportion. For every mole of chlorine produced, one mole of hydrogen is produced. Much of this hydrogen is used to produce hydrochloric acid, ammonia, hydrogen peroxide, or is burned for power and/or steam production.

History

The chloralkali process has been in use since the 19th century and is a primary industry in the United States, Western Europe, and Japan. It has become the principal source of chlorine during the 20th century. The diaphragm cell process and the mercury cell process have been used for over 100 years but are environmentally unfriendly through their use of asbestos and mercury, respectively. The membrane cell process, which was only developed in the past 60 years, is a superior method with its improved energy efficiency and lack of harmful chemicals. In 1833, Faraday formulated the laws that governed the electrolysis of aqueous solutions, and patents were issued to Cook and Watt in 1851 and to Stanley in 1853 for the electrolytic production of chlorine from brine.

:2 NaCl + 2 H2O → 2 NaOH + H2 + Cl2

Without a membrane, the OH− ions produced at the cathode are free to diffuse throughout the electrolyte. As the electrolyte becomes more basic due to the production of OH−, less Cl2 emerges from the solution as it begins to disproportionate to form chloride and hypochlorite ions at the anode:

:Cl2 + 2 NaOH → NaCl + NaClO + H2O

The more opportunity the Cl2 has to interact with NaOH in the solution, the less Cl2 emerges at the surface of the solution and the faster the production of hypochlorite progresses. This depends on factors such as solution temperature, the amount of time the Cl2 molecule is in contact with the solution, and concentration of NaOH.

Likewise, as hypochlorite increases in concentration, chlorates are produced from them:

: 3 NaClO → NaClO3 + 2 NaCl

This reaction is accelerated at temperatures above about 60 °C. Other reactions occur, such as the self-ionization of water and the decomposition of hypochlorite at the cathode, the rate of the latter depends on factors such as diffusion and the surface area of the cathode in contact with the electrolyte.

Electrodes

Due to the corrosive nature of chlorine production, the anode (where the chlorine is formed) must be non-reactive and has been made from materials such as platinum metal, graphite (called plumbago in Faraday's time), A mixed metal oxide clad titanium anode (also called a dimensionally stable anode) is the industrial standard today. Historically, platinum, magnetite, lead dioxide, manganese dioxide, and ferrosilicon (13–15% silicon) have also been used as anodes. Platinum alloyed with iridium is more resistant to corrosion from chlorine than pure platinum. Unclad titanium cannot be used as an anode because it anodizes, forming a non-conductive oxide and passivates. Graphite will slowly disintegrate due to internal electrolytic gas production from the porous nature of the material and carbon dioxide forming due to carbon oxidation, causing fine particles of graphite to be suspended in the electrolyte that can be removed by filtration. The cathode (where hydroxide forms) can be made from unalloyed titanium, graphite, or a more easily oxidized metal such as stainless steel or nickel.

Manufacturer associations

The interests of chloralkali product manufacturers are represented at regional, national and international levels by associations such as Euro Chlor and The World Chlorine Council.

References

External links

Animation showing the membrane cell process
Animation showing the diaphragm cell process