Sulphuric acid early developments

The first nitration to be reported was that of beri2ene itself. Mitscher-lich in 1834 prepared nitrobenzene by treating benzene with fuming nitric acid. Not long afterwards the important method of effecting nitration with a mixture of nitric and sulphuric acids ( mixed acid ) was introduced, evidently in a patent by Mansfield the poor quality of early nitric acid was probably the reason why the method was developed. Since these beginnings, nitration has been the subject of continuous study. 

In the early 1980s, Nobel (a reagent manufacturing company) developed selective apatite collectors (Lilaflot series) based on modified fatty acids, which were capable of removing apatite without any loss of ilmenite. The pH in the ilmenite circuit was controlled with the use of sulphuric acid. In 1980, the tall oil used in the pyrite circuit was replaced with Lilaflot 100 (modified fatty acid). 

The main ingredients for the early alkyd resins, namely phthalic anhydride and glycerol, were already quite readily available at the time of their development. At that time, phthalic anhydride was made by catalytic oxidation of naphthalene with sulphuric acid. However, a considerable boost to the competitiveness of alkyds was the development from about 1917 of a much cheaper process for phthalic anhydride, based on catalytic vapour-phase oxidation of naphthalene. 

Aluminosilicates are the active components of amorphous silica—alumina catalysts and of crystalline, well-defined compounds, called zeolites. Amorphous silica—alumina catalysts and similar mixed oxide preparations have been developed for cracking (see Sect. 2.5) and quite early [36,37] their high acid strength, comparable with that of sulphuric acid, was connected with their catalytic activity. Methods for the determination of the distribution of the acid sites according to their strength have been found, e.g. by titration with f-butylamine in a non-aqueous medium using adsorbed Hammett indicators for the H0 scale [38],... 

Up to World War 1 most industrial countries experienced a rapid increase in the production of sulphuric acid. This was a basic input product for the manufacture of traditional industries (such as textiles, iron and steel), as well as the newer heavy chemicals (oil refining, artificial fertilisers, and explosives) and the emerging fine chemicals (such as synthetic dyes). The strongest reasons for the early rise of this industry in Spain are the abundance of raw materials (sea salt and pyrites) and the existence of a consumer industry (textiles). The development of the acid industry was, however, difficult and slow in the previous century. The story of the pioneer enterprise, Cros, founded by a native of southern France in the surroundings of Barcelona in the... 

Based on their early fundamental research of all-VRFBs, Skyllas-Kazacos et al. [25] also first developed some commercial products, for example, a 1 kW vanadium redox battery (VRB) cell stack. By employing 1.5-2 M vanadium sulphate, sulphuric acid in both half-cells, over 85% of theoretical capacity and 70-80% energy efficiency was obtained. Then in 1994, a 4 kW/12 kWh vanadium battery was evaluated in a demonstration solar house by Thai Gypsum Products Ltd. in Thailand under a license lirom the UNSW [26]. 

The current process for manufacturing Sulphamic Acid employed by most of the producers requires the disposal of a large quantity of dilute Sulphuric Acid. The process to manufacture Sulphamic Acid was developed by the autiior in early sixties and it has gone under certain modifications in order to improve the economics, but it is still hazardous and requires disposal of waste acid. This is described in detail to highlight need for innovation. Please refer Bibliography section. 

The initial attempts to develop a quantitative assay for sialic acids were colorimetric. The majority of these early methods were unsuitable because of their lack of specificity and/or sensitivity required for sialic acid analysis in biological materials or for enzymic assays. Some of these methods included diphenylamine (Ayala et al. 1951), tryptophane/perchloric acid (Seibert et al. 1948), sulphuric acid/acetic acid (Hess et al. 1957), hydrochloric acid (Folch et al. 1951) and the Ehrlich reagent, dimethyl-aminobenzaldehyde (Werner and Odin 1952). 

In 1949, the development of a catalyst based on a combination of platinum and an acidic component (e.g. A1203, A1C13) allowed the use of lower reaction temperatures than with the early catalysts.6 However, problems were still encountered with chlorine corrosion. In the 1960s, Universal Oil discovered that the addition of rhenium to a bifunctional Pt/Al203 catalyst resulted in slower deactivation by carbon deposition, and other dopants have since been found to modify the catalyst acidity and resistance to poisons, e.g. Cl, Sn, Ir. More recently, catalysts based on zeolites and noble metals have been shown to be more resistant to nitrogen and sulphur compounds, while giving a high activity and selectivity to branched alkanes. 

---