Sulfuric acid production commercial processes

Substrate Characterization. Test coupons and panels of 7075-T6 aluminum, an alloy used extensively for aircraft structures, were degreased In a commercial alkaline cleaning solution and rinsed In distilled, deionized water. The samples were then subjected to either a standard Forest Products Laboratories (FPL) treatment ( 0 or to a sulfuric acid anodization (SAA) process (10% H2SO4, v/v 15V 20 min), two methods used for surface preparation of aircraft structural components. The metal surfaces were examined by scanning transmission electron microscopy (STEM) In the SEM mode and by X-ray photoelectron spectroscopy (XPS). 

For commercial production the Griesheim Chem. Fabrik is reported to have used a process in which 1 part of TNT is heated at 150-200° with a mixture of 5 parts of fuming nitric acid and 10 parts of concentrated sulfuric acid. In a process devised by J. Meyer,7 picryl chloride (2,4,6-trinitrochlorobenzene) is reduced by means of copper powder in hot aqueous alcohol. The reported details are 25 kilos of picryl chloride, 8 kilos of copper 8 Ber., 9, 402 (1876) Ann., 215, 345 (1882). 

Three commercial processes, namely the oxidation of volatile organic compounds (VOC) for purification of industrial exhaust gases, SO2 oxidation for sulfuric acid production, and NO reduction by ammonia, have employed the periodic flow reversal concept. 

Polyterpene resins are related to the oldest reported polymerization, as they were first observed in 1789 by Bishop Watson by treatment of turpentine with sulfuric acid [92]. Commercial polyterpene resins are synthesized by cationic polymerization of /3- and a-pinenes extracted from turpentine, of rf,/-limonene (dipentene) derived from kraft-paper manufacture, and of d-limonene extracted from citrus peels as a by-product of juice industry [1,80,82,93]. The batch or continuous processes are similar for the three monomers. The solution polymerization is generally performed in mixed xylenes or high boiling aromatic solvent, at 30-55° C, with AlCl3-adventi-tious water initiation. The purified feedstream (72-95% purity, depending on monomer) is mixed in the reactor with solvent and powdered A1C13 (2—4 wt% with respect to monomer), and then stirred for 30-60 min. After completion of the reaction, the catalyst is deactivated by hydrolysis, and evolved HC1 is eliminated by alkaline aqueous washes. The organic solution is then dried, and the solvent is separated from the resin by distillation. 

Elemental sulfur, also called brimstone," is the preferred raw material for sulfuric acid production whenever it is available at a reasonable cost. Elemental sulfur may be mined by the well-known Frasch process or recovered from volcanic ores, sour" natural gas, or oil. It is also possible and sometimes commercially feasible to produce elemental sulfur from pyrites, other sulfide ores, and coal. 

Israel Mining Industries developed a process in which hydrochloric acid, instead of sulfuric acid, was used as the acidulant (37). The acidulate contained dissolved calcium chloride which then was separated from the phosphoric acid by use of solvent extraction using a recyclable organic solvent. The process was operated commercially for a limited time, but the generation of HCl fumes was destmctive to production equipment. 

Triple (Concentrated) Superphosphate. The first important use of phosphoric acid in fertilizer processing was in the production of triple superphosphate (TSP), sometimes called concentrated superphosphate. Basically, the production process for this material is the same as that for normal superphosphate, except that the reactants are phosphate rock and phosphoric acid instead of phosphate rock and sulfuric acid. The phosphoric acid, like sulfuric acid, solubilizes the rock and, in addition, contributes its own content of soluble phosphoms. The result is triple superphosphate of 45—47% P2 s content as compared to 16—20% P2 5 normal superphosphate. Although triple superphosphate has been known almost as long as normal superphosphate, it did not reach commercial importance until the late 1940s, when commercial supply of acid became available. 

The electrolytic processes for commercial production of hydrogen peroxide are based on (/) the oxidation of sulfuric acid or sulfates to peroxydisulfuric acid [13445-49-3] (peroxydisulfates) with the formation of hydrogen and (2) the double hydrolysis of the peroxydisulfuric acid (peroxydisulfates) to Caro s acid and then hydrogen peroxide. To avoid electrolysis of water, smooth platinum electrodes are used because of the high oxygen overvoltage. The overall reaction is... 

Specifications and Standards, Shipping. Commercial iodine has a minimum purity of 99.8%. The Committee of Analytical reagents of the American Chemical Society (67) and the U.S. Pharmacopoeia XXII (68) specify an iodine content not less than 99.8%, a maximum nonvolatile residue of 0.01%, and chlorine—bromine (expressed as chlorine) of 0.005% (ACS) and 0.028% (USP), respectively. In the past these requirements were attained basicaHy only by sublimation, but with processing changes these specifications can be met by direct production of iodine. Previously the impurities of the Chilean product were chiefly water, sulfuric acid, and insoluble materials. Improvements in the production process, and especiaHy in the refining step, aHow the direct obtainment of ACS-type iodine. Also, because of its origin and production process, the Chilean iodine has a chlorine—bromine impurity level of no more than 0.002%. 

Naphthalenesulfonic Acid. The sulfonation of naphthalene with excess 96 wt % sulfuric acid at < 80°C gives > 85 wt % 1-naphthalenesulfonic acid (a-acid) the balance is mainly the 2-isomer (P-acid). An older German commercial process is based on the reaction of naphthalene with 96 wt % sulfuric acid at 20—50°C (13). The product can be used unpurifted to make dyestuff intermediates by nitration or can be sulfonated further. The sodium salt of 1-naphthalenesulfonic acid is required, for example, for the conversion of 1-naphthalenol (1-naphthol) by caustic fusion. In this case, the excess sulfuric acid first is separated by the addition of lime and is filtered to remove the insoluble calcium sulfate the filtrate is treated with sodium carbonate to precipitate calcium carbonate and leave the sodium l-naphthalenesulfonate/7J(9-/4-J7 in solution. The dry salt then is recovered, typically, by spray-drying the solution. 

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. 

Esterification. Extensive commercial use is made of primary amyl acetate, a mixture of 1-pentyl acetate [28-63-7] and 2-metliylbutyl acetate [53496-15-4]. Esterifications with acetic acid are generally conducted in the Hquid phase in the presence of a strong acid catalyst such as sulfuric acid (34). Increased reaction rates are reported when esterifications are carried out in the presence of heteropoly acids supported on macroreticular cation-exchange resins (35) and 2eohte (36) catalysts in a heterogeneous process. Judging from the many patents issued in recent years, there appears to be considerable effort underway to find an appropriate soHd catalyst for a reactive distillation esterification process to avoid the product removal difficulties of the conventional process. 

Sulfamic acid [5329-14-6] (amidosulfuric acid), HSO2NH2, molecular weight 97.09, is a monobasic, inorganic, dry acid and the monoamide of sulfuric acid. Sulfamic acid is produced and sold in the form of water-soluble crystals. This acid was known and prepared in laboratories for nearly a hundred years before it became a commercially available product. The first preparation of this acid occurred around 1836 (1). Later work resulted in identification and preparation of sulfamic acid in its pure form (2). In 1936, a practical process which became the basis for commercial preparation was developed (3,4). This process, involving the reaction of urea with sulfur trioxide and sulfuric acid, continues to be the main method for production of sulfamic acid. 

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