Mathieson

A process based on a nickel catalyst, either supported or Raney type, is described ia Olin Mathieson patents (26,27). The reduction is carried out ia a continuous stirred tank reactor with a concentric filter element built iato the reactor so that the catalyst remains ia the reaction 2one. Methanol is used as a solvent. Reaction conditions are 2.4—3.5 MPa (350—500 psi), 120—140°C. Keeping the catalyst iaside the reactor iacreases catalyst lifetime by maintaining a hydrogen atmosphere on its surface at all times and minimises handling losses. Periodic cleaning of the filter element is required. 

Calcium Hypochlorite. High assay calcium hypochlorite [7778-54-3] was first commercialized in the United States in 1928 by Mathieson Alkali Works, Inc. (now Olin Corp.) under the trade name HTH. It is now produced by two additional manufacturers in North America (Table 5). Historically, it usually contained about 1% water and 70—74% av CI2, so-called anhydrous product, but in 1970, a hydrated product was introduced (234). It is similar in composition to anhydrous Ca(OCl)2 except for its higher water content of about 6—12% and a slightly lower available chlorine content. This product has improved resistance to accidental initiation of self-sustained decomposition by a Ht match, a Ht cigarette, or a small amount of organic contamination. U.S. production in the 1990s consists primarily of partially hydrated Ca(OCl)2, which is sold as a 65% av CI2 product mainly for swimming pool use. Calcium hypochlorite is also sold as a 50% av CI2 product as a sanitizer used by dairy and food industries and in the home, and as a 32% product for mildew control. 

Sulfur Dioxide Reductant. The Mathieson process uses sulfur dioxide, sodium chlorate, and sulfuric acid to produce chlorine dioxide gas with a much lower chlorine content. The sulfur dioxide gas reductant is oxidized to make sulfuric acid, reducing the overall acid requirement of the process. Air is used to dilute the chlorine dioxide produced by this process. The exit gases flow through a scmbber to which chlorate is added in order to remove any unreacted sulfur dioxide. Spent Hquor, containing some unreacted chlorate, sulfuric acid, and sodium sulfate, continuously overflows from this process. 

Small amounts of chlorine, amounting from 1 to 5% of the chlorine dioxide, ate present in the chlorine dioxide gas product from the Mathieson process. The purity of the chlorine dioxide gas can be increased at the expense of higher chlorate content in the spent Hquor if NaCl is not used in the reactor and a small amount of sulfur dioxide gas is present in the generator chlorine dioxide product gas stream. 

Chlorites and Chlorine Dioxide" under "Chlorine Compounds, Inorganic" in ECT 1st ed., VoL 3, pp. 696—707, byj. F. White, Mathieson Chemical Corp. "Chlorous Acid, Chlorites, and Chlorine Dioxide" under "Chlorine Oxygen Acids and Salts" in ECT 2nd ed., Vol. 5, pp. 27—50, by H. L. Robson, Olin Mathieson Chemical Corp. "Chlorine Dioxide, Chlorous Acid, and Chlorites," in ECT 3rd ed., VoL 5, pp. 612—632, by M. G. Noack and R. L. Doerr, Olin Corp. 

The hypochlorite solution also may be prepared conveniently from the calcium hypochlorite sold by the Mathieson Alkali Works under the trade name HTH and specified to contain not less than 65 per cent of available calcium hypochlorite. 

The thiosemicarbazide must be of good quality or the yield and quality of l-formyl-3-thiosemicarbazide will suffer. The thiosemicarbazide supplied by Olin Mathieson Chemical Corporation, obtained as a colorless free-flowing powder, can be used without purification. 

Brewis, D.M. and Mathieson, Flame treatment of polymers to improve adhesion. In Mittal, K.L. and Pizzi, A. (Eds.), Adhesion Promotion Techniques — Technological Applications. Dekker, New York, 1999, pp. 175-190. 

Chlorine dioxide, discovered in 1811 by Davy, was prepared from the reaction of potassium chlorate with hydrochloric acid. Early experimentation showed that chlorine dioxide exhibited strong oxidizing and bleaching properties. In the 1930s, the Mathieson Alkali Works developed the first commercial process for preparing chlorine dioxide from sodium chlorate. By 1939, sodium chlorite was established as a commercial product for the generation of chlorine dioxide. 

Neidleman, S. L. U.S. Patent 3,154,476 October 27, 1964 assigned to Olin Mathieson Chemical Corporation... 

Dihydrostreptomycin sulfate may be prepared from streptomycin sulfate by catalytic hydrogenation (Merck, Pfizer, Cyanamid), electrolytic reduction (Schenley, Olin Mathieson), or by sodium boro hydride reduction (Bristol), or by isolation from a fermentation process (Takeda). 

Dolliver, M.A. and Semenoff, S. U.S, Patent 2,717,236 September 6, 1955 assigned to Olin Mathieson Chemical Corp,... 

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