Sulfuric acid utilization

It is hard to overemphasize the importance of sulfuric acid in chemistry and in the economy. As far as chemicals are concerned, its impact on the economy is second to none. Without sulfuric acid utilization on a large scale, many of the products in general use would not exist, and our very way of life would be altered. The next section presents some of the essential chemistry of H2S04 to show why it so important. 

Figure 3.7 shows the changes in sulfuric acid utilization, 77H2SO45 ns a function of H2SO4 electrolyte concentration for the P- and N-series of batteries. 

Gimaev, R. N., Kondakov, D. I., Syunyaev, Z. I. (1973). Modem methods of sulfur acid utilization of oil refinery and petro chemistry residues. In Russian Neftekhim, M., 97p. 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

In all HF processes, the HF leaves the furnace as a gas, contaminated with small amounts of impurities such as water, sulfuric acid, SO2, or SiF. Various manufacturers utilize different gas handling operations, which generally include scmbbing and cooling. Cmde HF is condensed with refrigerant, and is further purified by distillation (qv). Plant vent gases are scmbbed with the incoming sulfuric acid stream to remove the bulk of the HF. The sulfuric acid is then fed to the furnace. Water or alkah scmbbers remove the remainder of the HF from the plant vent stream. 

Sulfation and Sulfonation. a-Olefin reactions involving the introduction of sulfur-containing functional groups have commercial importance. As with many derivatives of olefins, several of these products have appHcations in the area of surfactants (qv) and detergents. Typical sulfur reagents utilized in these processes include sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, and sodium bisulfite. 

The bottoms from the stripper (40—60 wt % acid) are sent to an acid reconcentration unit for upgrading to the proper acid strength and recycling to the reactor. Because of the associated high energy requirements, reconcentration of the diluted sulfuric acid is a cosdy operation. However, a propylene gas stripping process, which utilizes only a small amount of added water for hydrolysis, has been described (63). In this modification, the equiUbrium quantity of isopropyl alcohol is stripped so that acid is recycled without reconcentration. Kquilibrium is attained rapidly at 50°C and isopropyl alcohol is removed from the hydrolysis mixture. Similarly, the weak sulfuric acid process minimizes the reconcentration of the acid and its associated corrosion and pollution problems. 

Because sulfur suppHes, either as elemental sulfur or by-product sulfuric acid, have grown owiag to iacreased environmental awareness, demand for sulfur has decreased ia some consuming iadustries for the same reason. Industries such as titanium dioxide productions, which traditionally utilized sulfuric acid, have concerted to more environmentally friendly processes. In addition, many consumers who contiaue to use sulfuric acid are puttiag an emphasis on regenerating or recycling spent acid. 

Liquid SO is usually produced by distilling SO vapor from oleum and condensing it. This operation is normally carried out at a sulfuric acid plant where the stripped oleum can be readily refortified or reused. EHminating all traces of sulfuric acid from the SO vapor stream is important to minimize polymerization of the Hquid condensate. When this is done, it is frequently possible to utilize unstabilized Hquid SO if precautions are taken to prevent it from freezing before use. At some plants, gaseous 100% SO is utilized directly instead of producing Hquid. 

Extraction of Bertrandite. Bertrandite-containing tuff from the Spor Mountain deposits is wet milled to provide a thixotropic, pumpable slurry of below 840 p.m (—20 mesh) particles. This slurry is leached with sulfuric acid at temperatures near the boiling point. The resulting beryUium sulfate [13510-49-1] solution is separated from unreacted soflds by countercurrent decantation thickener operations. The solution contains 0.4—0.7 g/L Be, 4.7 g/L Al, 3—5 g/L Mg, and 1.5 g/L Fe, plus minor impurities including uranium [7440-61-1/, rare earths, zirconium [7440-67-7] titanium [7440-32-6] and zinc [7440-66-6]. Water conservation practices are essential in semiarid Utah, so the wash water introduced in the countercurrent decantation separation of beryUium solutions from soflds is utilized in the wet milling operation. 

Several related derivatives have also been utilized in this type of synthesis. Imino-chloromethanesulfenyl chlorides (184), prepared by the controlled addition of chlorine to isothiocyanates, react with amidines (161) to give 1,2,4-thiadiazolines (185) (71T4117). Chlorocarbonylsulfenyl chloride (186), prepared by the hydrolysis of trichloromethanesulfenyl chloride with sulfuric acid, reacted with ureas, thioureas and guanidines to give 1,2,4-thiadiazolidine derivatives (187) <70AG(E)54, 73CB3391). 

Ethoxy-2-cyclohexenone has been prepared by reaction of the silver salt of dihydroresorcinol with ethyl iodide and by the reaction of dihydroresorcinol with ethyl orthoformate, ethanol and sulfuric acid." The acid-catalyzed reaction of dihydroresorcinol with ethanol in benzene solution utilized in this preparation is patterned after the procedure of Frank and Hall. ... 

The Wenker aziridine synthesis entails the treatment of a P-amino alcohol 1 with sulfuric acid to give P-aminoethyl sulfate ester 2 which is subsequently treated with base to afford aziridine 3. Before the discovery of the Mitsunobu reaction, wbicb transforms an amino alcohol into an aziridine in one step under very mild conditions, the Wenker reaction was one of the most convenient methods for aziridine synthesis. However, due to the involvement of strong acid and then strong base, its utility has been limited to substrates without labile functionalities. 

Not surprising, the most prevalent synthetic utility is the assembly of the pyrrolidine ring. N-Chloroamine 27 was obtained by treatment of N-methyl-2-cyclopentylethylamine (26) with N-chlorosuccinimide. Under classic Hofmann-Loffler-Freytag reaction conditions, 27 was rearranged either thermally or by UV irradiation in sulfuric acid to bicyclic amine... 

In 1909, Robinson demonstrated the utility of acylamidoketones as intermediates to aryl-and benzyl-substituted 1,3-oxazoles through cyclization with sulfuric acid. Extension of sulfuric acid cyclization conditions to alkyl-substituted oxazoles can give low yields, for example 10-15% for 2,5-dimethyl-l,3-oxazole. Wiegand and Rathbum found that polyphosphoric acid can provide alkyl-substituted oxazoles 4 in yields equal to or greater than those obtained with sulfuric acid. Significantly better yields are seen in the preparation of aryl- and heteroaryl-substituted oxazoles. For example, reaction of ketoamides 5 with 98% phosphoric acid in acetic anhydride gives oxazoles 6 in 90-95% yield. ... 

Other examples of esterification with trialkyloxonium salts have been reported.7,8 The present procedure offers the advantages that the reactive carboxylate ion is generated in sitv and that a low-boiling, nonaqueous solvent is employed, whereby the experimental procedure is considerably simplified. A related method has been reported which utilizes a hindered amine wdth dimethyl sulfate [Sulfuric acid, dimethyl csterj as the alkylating agent.9 The present procedure is carried out under somewhat milder conditions and avoids the use of highly toxic reagents. 

One of the least expensive and popular techniques for the quant detn of bound N in energetic materials is that of titrimetry. There are currently three basic titrimetry systems used aq acid-base, redox and non-aqueous (involving both acid-base and redox systems in which there is association, not ionization of the re-actants). The simple aq acid-base titrimetry system has been shown, earlier in the article, being used in the Kjeldahl, De varda and Ter-Meulen procedures to detn liberated NH3. It is also utilized, for example, to detn nitrosyi-sulfuric acid in mixed acids, total acidity in nitric acid, NG in exp] oils, and the N content of... 

Using sulfur trioxide a nucleophilic aliphatic carbon and an aromatic nucleus may be connected by a sulfonyl bridge479 (equation 93). Instead of sulfur trioxide, sulfuric acid or chlorosulfonic acid is utilized mostly. The procedures differ mainly by the manner in which the water is eliminated480 e.g., a mixture of sulfuric acid and trifluoroacetic anhydride was used recently481. Similarly to equation 93,3-oxo-2,3-dihydrobenzothiophene 1,1-dioxide is available from acetophenone and chlorosulfonic acid482 (equation 94). 

To evaluate the heat exchange/productivity performances of the device and its environment, an acid-base neutralization involving sulfuric acid and soda has been performed. It is an instantaneous and exothermic reaction with AH = —92.4 kj moP (NaOH). Each experiment is characterized by the initial concentration of the reactants (from 10 to 30% in mass of soda and from 5 to 12% in mass of sulfuric acid). These concentrations are varied in order to evaluate the behavior of the reactor with respect to different amounts of heat generated (from 0.4 to 1.3 kW). Each run is performed with a variable utility flow rate (from 1 to 3 m h ). 

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