Update 1 Oct 2011
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History of ion exchange


The table below shows the main development steps of ion exchange.
~1400 BC Moses experiments water debittering (Exodus 15, 22 - 25)
~330 BC Aristotle finds that sea water loses part of its salt contents when percolated through certain sand.
1850 Discovery of ion exchange by Thompson & Way (England).
1876 Zeolites recognised as carriers of base exchange in soils (Lemberg).
1901 Artificial zeolites used for removal of potassium from sugar juices.
1905 Commercial use of ion exchange with inorganic aluminosilicates (zeolites) developed by Gans (Germany).
1935 Industrial manufacture of sulphonated coals for water softening filters (Liebknecht and Smit).
1935 Synthetic ion exchange resins (phenol-formaldehyde polycondensates) invented by Adams & Holmes.
1940 First commercial phenol-formaldehyde ion exchange resins; both strongly acidic and weakly basic exchangers. Examples: Duolite C3 and Duolite A7.
1944 First patent for sulphonated polystyrene resin (D'Alelio, USA).
1946 McBurney invents strongly basic anion exchangers made by chloromethylation and amination of polystyrene.
1947 First commercial strongly acidic cation exchangers based upon cross-linked polystyrene.
1948 First commercial strongly basic anion exchangers based on McBurney's invention.
1948 Rohm and Haas introduces the first weakly acidic cation exchanger (methacrylic Amberlite IRC50).
1949 First commercial use of Mixed-bed resin technology.
1950 First use of weakly acid resins for recovery of antibiotics (streptomycin) from fermentation broth.
1950 First commercial synthesis of styrene-based weakly basic anion exchanger (Amberlite IRA45).
1950 Development of ion exchange resins in powdered form for sodium reduction therapy.
1951 First use of ion exchange resins for treatment of sugar.
1952 First commercial use of anion exchange resins for recovery of uranium from leach liquor.
1952 Invention and development of chelating polymers (Gregor).
1953 Rohm and Haas develops acrylic based weakly basic anion exchange resin (now Amberlite IRA67).
1957 Rohm and Haas introduces liquid anion exchange materials (Amberlite LA1, LA2).
1959 Discovery of phase extension polymerisation technique for production of macroporous ion exchange resins. Patents in Germany (Bayer), USA (Rohm and Haas) and UK (Permutit). Rohm and Haas used to call the products macroreticular.
1961 Rohm and Haas introduces macroreticular (macroporous) ion exchange resins for use as catalysts.
1963 Bayer files a patent for the "floating bed" (Schwebebett) packed bed ion exchange technology.
1965 New macroreticular polymeric adsorbents (Amberlite XAD2, XAD4, etc.) introduced.
1974 First commercial use of boron-specific resin (Amberlite IRA743, methyl-glucamine).
1988 Dow Chemical introduces uniform particle size Dowex Monosphere resins.

A few more details

As can be seen from the preceding table, the most active development period of ion exchange resins has been the middle of the 20th Century. Today, the technology is mature, and only small improvements are made in application process and column design, but little in the synthesis of resins, where chemistry has reached its limits.
Natural and synthetic sodium aluminosilicates (often called zeolites, have been used for water softening in the first part of the 20th Century. Capacity was low, and the silicates are somewhat soluble at high pH. One of the last products sold commercially in the 1970s was Decalso Y produced by Zerolit Ltd in the UK. Today, they are no longer used in ion exchange columns. However, aluminosilicates are still widely used as a component of washing powders for their water softening capability.

A natural zeolite called clinoptilolite is also still used in the nuclear industry for its high affinity for caesium. After the 2011 Fukushima disaster, bags of this zeolite have been dumped in the power station site in an attempt to eliminate radioactive 137Cs, or at least to prevent its propagation into the sea.

Sulphonated coal
In the 1930s through 1950s, this product has been a major cation exchanger. It can be used either in sodium or hydrogen cycle. However, its capacity is only about 1/4 of the capacity of a modern sulphonated polystyrene resin, so it has been totally superseded by synthetic products.
Synthetic resins
These are now the only significant products used in industrial ion exchange techology. About 95 % of the resins are based on styrenic polymers, 4 % on acrylates and only a very little fraction on other polymers. You can read more about resin structure and resin types in dedicated pages.

© François de Dardel