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History of Carbon

 

Historical Production and Use of Carbon Materials*

Date Significance
3750BC Earliest known use by the Egyptians and Sumerians. Wood chars (charcoal) used for the reduction of copper, zinc and tin ores in the manufacture of bronze. Charcoal also used as domestic smokeless fuel.
1500BC The first recorded application of charcoal for medicinal purposes was cited in Egyptian papyri. The principle use appears to have been the application of charcoal to adsorb odorous vapours from putrefying wounds and from within the intestinal tract.
400BC Hippocrates and Pliny record the use of charcoal to treat a wide range of complaints including epilepsy, chlorosis and anthrax.
450BC Recent studies of the wrecks of Phoenician trading ships suggest that drinking water was stored in charred wooden barrels. This practice was certainly still in use in the 18th Century for extending the use of potable water on long sea voyages. Hindu documents of the same period (450 BC) also refer to the use of sand and charcoal filters for the purification of drinking water.
157AD Claudius Galvanometer 500 medical treatises, many of them referring to the use of carbons of both vegetable and animal origin for the treatment of a wide range of diseases.
297AD Roman Emperor Diocletian ordered the total destruction of all scientific books within the Roman Empire, thereby setting back the progress of science within Europe by at least 1000 years.
 
18th Century
1773 The specific adsorptive powers of carbons (i.e. charcoal) were recognized by Scheele, who measured the volumes of various gases that could be adsorbed by carbons derived from different sources.
1777 It was reported that heat effects are associated with the adsorption of gases by charcoal. This is significant in that it led later to the "condensation theories of adsorption".
1785 Lowitz reviewed the known abilities of charcoals to adsorb odours emanating from medical conditions and published accounts of their ability to adsorb vapours from a range of organic chemicals. In addition, he studied the effectiveness of charcoal in decolorizing various aqueous solutions and, in particular, its commercial application to the production of tartaric acid. This appears to be the first systematic account of the adsorptive power of charcoal in the liquid phase. At this time, too, the developing sugar refining industry was looking for an effective means of decolorizing raw sugar syrups. However, the wood charcoals available at this time were not particularly effective in this role, presumably because their porosity had not been developed beyond the extent produced by carbonization.
1793 Kehl discussed the use of chars for the control of odours from gangrenous ulcers and discovered that carbon prepared from animal tissues could be used for removing colours from solution.
1794 An English sugar refinery successfully used wood charcoal for the decolorization of sugar syrups but kept the method of preparing the carbon a secret.
 
19th Century
1805 Gruillon introduced the first large-scale sugar refining facility in France using ground and washed wood charcoal for decolorizing syrups.
1805-1808 Delessert successfully demonstrated the use of charcoal for decolorizing sugar-beet liquor. He was directly responsible for the growth of the sugar beet industry in France. By 1808 all sugar refineries in Europe used charcoal as a decolorizer.
1811 Figuier discovered the greatly enhanced decolorizing capability of bone char compared with wood char. The sugar refining industry was quick to substitute bone char for wood char. Methods of regenerating the bone char by heating were discovered, and shortly afterwards a granulated bone char was developed which could be much more readily regenerated.
1815 By this date most of the sugar refining industry had switched to the use of granulated bone char as a decolorant.
1817 Joseph de Cavaillon patented a method of regenerating used bone chars. The method was not entirely successful.
1822 Bussy demonstrated that the decolorizing properties of carbons were inherent to the source material and also depended on the thermal processing and the particle size of the finished product. He demonstrated that carbonization at too high a temperature, or for too long, reduced the adsorptive properties and that porosity was important, although he had no means to measure this factor. He also heated blood with potash to produce a carbon with 20-50 times the decolorizing power of bone char. This is the first recorded example of producing an activated carbon by a combination of thermal and chemical processes.
1841 Schatten systematized the use of a hydrochloric acid wash prior to heating in the regeneration of bones chars. This effectively removed the minerals salts adsorbed on to the carbon. He also introduced in Germany the first continuous process vertical kiln for the manufacture and regeneration of bone chars.
1854 Stenhouse described the successful application of carbon filters for removing vapours and gases in the ventilation of London sewers.
1862 Lipscombe prepared a carbon to purify potable water.
1865 Hunter discovered the excellent gas adsorbent properties of carbons derived from coconut shells.
1868 Winser and Swindells heated paper mill waste with phosphates. Many of their disclosures are relevant to processes now in industrial use. They were not developed on a commercial scale because of engineering difficulties.
1881 Kayser first used the term 'adsorption' to describe the uptake of gases by carbons.
 
20th Century
1901 Von Ostrejko set the basis for the commercial development of activated carbons through processes involving (a) the incorporation of metallic chlorides with carbonaceous material before carbonization and (b) the mild oxidation of charred materials with carbon dioxide or steam at raised temperatures.
1911 Marketing of first industrially produced activated carbon, 'Eponit" (trade name), by the Fanto Works, Austria. They adopted von Ostrejko's gasification approach in the manufacture of Eponit from wood. It was marketed as a decolorizer for the sugar-refining industry. Until this time the principle user of active carbons was the sugar-refining industry and manufacturers produced active carbon by their own secret or patented process. All the principal types of reactor with the exception of the fluidized bed were by then in use.
1913 Wunsch heated a mixture of Eponit and zinc chloride and found that the decolorizing capacity of the reactivated material was greatly increased. Wunsch went on to prepare other active carbons with superior properties to those of Eponit by substituting wood and other carbon precursors for Eponit in his process. The zinc chloride process was used for many years, sometimes in combination with steam or carbon dioxide activation. It has now been largely superseded by the use of phosphoric acid as the chemical activant.
1914-1918 The introduction of poisonous gases into the battlefields of the First World War gave great impetus to the development of large-scale production methods for adsorbent carbons suitable for use in military respirators. Granulated carbons, with adequate adsorptive powers and providing low resistance to air flow through the respirator canister, were developed by activating wood chips with zinc chloride. These were first manufactured carbons with reliably controlled adsorptive and physical properties. A group studying under Chaney in the USA examined a wide range of precursors intended to produce adsorbents for gas-mask canisters. They determined that coconut shell yielded the best combination of required characteristics in the resulting carbon.
Post-1918 The wartime developments to mass-produce activated carbons with closely controlled characteristics lead to post-war expansion in the commercial production and application of carbons. In Europe considerable progress was made in the manufacture of active carbon from new raw materials. Coconut and almond shells with zinc chloride, yielded active carbons with high mechanical strengths and adsorptive capacities for gases and vapours.
1935-1940 In Czechoslovakia two varieties of pelletized carbons were produced from sawdust by zinc chloride activation, for the recovery of volatile solvents and for the removal of benzene from town gas. Mecklenburg, working on the dynamics of adsorption, and Kubelka, who interpreted sorption phenomena on active carbon by the mechanism of capillary condensation, developed a method for calculating the distribution of pore diameters in active carbon. The published a theoretical interpretation for the service time of a filter charged with active carbon. This theory and its mathematical development are now obsolete, but at the time represented a significant contribution in the field.
*Portions of the following text were taken from "Porosity in Carbons: Characterization and Applications" - edited by John W. Patrick; published and copyrighted (1995) by Edward Arnold, London - chapter 8, "Activated Carbons-Production and Application" by Frank Derbyshire, Marit Jagtoyen and Michael Thwaites. Permission to use excepts granted in November 2002.