Sulfuric acid by-product

Until the 1970s, the main production countries of sulfamic acid were the United States, several European countries, and Japan. The large amounts of dilute sulfuric acid by-product generated led to the difficult situation of by-product acid disposal. Concomitandy, the start of chemical production in developing Asian countries caused successional sulfamic acid production withdrawal in the 1980s. As of the mid-1990s production countries are Japan, Taiwan, Indonesia, India, and China. The 1995 wodd production capacity was ca 96,000 metric tons. 

Both 25% and 65% oleum were introduced into chemical processing in search of stronger sulfonating agents. However, with the sulfonation process SO3 was used and the weak sulfuric acid by-product required disposal as a waste product. Enviromnental consideration led to large effluent treatment plants (ETPs) with consumption of lime in large quantities. As a result, heaps of waste gypsum were formed and posed solid waste disposal problem. 

Additional phosphonic acid is derived from by-product streams. In the manufacture of acid chlorides from carboxyUc acids and PCl, phosphonic acid or pyrophosphonic acid is produced, frequentiy with copious quantities of yellow polymeric LOOP. Such mixtures slowly evolve phosphine, particularly on heating, and formerly were a disposal problem. However, purification of this cmde mixture affords commercial phosphonic acid. By-product acid is also derived from the precipitate of calcium salts in the manufacture of phosphinic acid. As a consequence of the treatments of the salt with sulfuric acid, carbonate is Hberated as CO2 and phosphonic acid goes into solution. 

Sulfosahcyhc acid is prepared by heating 10 parts of sahcyhc acid with 50 parts of concentrated sulfuric acid, by chlorosulfonation of sahcyhc acid and subsequent hydrolysis of the acid chloride, or by sulfonation with hquid sulfur trioxide in tetrachloroethylene. It is used as an intermediate in the production of dyestuffs, grease additives, catalysts, and surfactants. It is also useful as a colorimetric reagent for ferric iron and as a reagent for albumin. Table 9 shows the physical properties of sahcyhc acid derivatives. 

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. 

Ethyl chloroacetate boiling at 142-145° was used. This ester can be prepared readily by refluxing for six hours a mixture of 200 g. of chloroacetic acid, 120 g. of absolute alcohol, and 25 g. of concentrated sulfuric acid. The product is purified in the conventional way, and the yield is 185 g. (70 per cent of the theoretical amount). 

Nitric acid, or aqua fortis as it was called in medieval times, has been known and used by mankind for centuries. At first, it was produced by heating a mixture of sodium nitrate (Chile saltpeter) and sulfuric acid. The product obtained was sodium hydrogen sulfate, and the nitric acid vapors escaping during this process were condensed ... 

Particulate emissions from zinc processing are collected in baghouses or ESPs. SO2 in high concentrations is passed directly to an acid plant for production of sulfuric acid by the contact process. Low-concentration SO2 streams are scrubbed with an aqueous ammonia solution. The resulting ammonium sulfate is processed to the crystalline form and marketed as fertilizer. 

By-product processing Hydrogen sulfide Conversion to elemental sulfur or sulfuric acid by liquid absorption, wet oxidation to elemental sulfur, combustion to SO2... 

N 21.95%, OB to CO 2 —7.52%, yel crysts from chlf, mp 190° (decompn). Was prepd by Blanksma (Ref 2), who nitrated 3,5-dinitro-phenol with an anhydr mixt of nitric-sulfuric acids. The product was pptd and recrystd from chlf. It is a powerful expl Refs 1) Beil 6,293 [284] 2) J. J. Blanksma,... 

Manufacture Mined phosphate rock is reacted with sulfuric acid. The product phosphoric acid is isolated as a 28-35% solution by filtering off the insoluble calcium sulfate co-product. CasfPOJj + SHzSO 2H3P04 + 3CaS04 phosphate sulfuric gypsum rock acid... 

By the autumn of 1939, Muller had tested 349 compounds. For his 350th compound, Muller combined the soporific chloral—the active ingredient in Mickey Finn knockout drops—with chlorobenzene and a catalyst, sulfuric acid. His product was dichlorodiphenyltrichloroethane, later known worldwide as DDT ... 

Mathieson (1) A process for making chlorine dioxide gas by passing sulfur dioxide, diluted with air, into aqueous sodium chlorate and sulfuric acid. The product is absorbed in water. Operated in the United States on a large scale for pulp-bleaching. 

Stratco A process for making a high-octane gasoline component by alkylation of C3 - C5 hydrocarbons with isobutane, catalyzed by sulfuric acid. The product is known as an alkylate. Operated in several oil refineries in the United States. 

Todd, F.A., "Sulfuric Acid Versus Elemental Sulfur as By-Products," C.F. Braun Co., FE-2240-54, January 1978. 

Sulfurous acid (H SOj) can be produced by burning sulfur to form sulfur dioxide (SOj) gas and by then dissolving the gas in water to form sulfurous acid. This is the acid produced by burning coal that has a high sulfur content the gaseous sulfur dioxide by-product of combustion then combines with atmospheric water to form acid rain. ... 

Some of its compounds, particularly the oxides, are used in chemical industries as catalysts to speed up organic chemical reactions. The yellow-brown vanadium pentoxide (V O ) is used as a catalyst to facilitate the production of sulfuric acid by the contact process. Vanadium pent-oxide is also used as a photographic developer, to dye textiles, and in the production of artificial rubber. When combined with glass, it acts as a filter against ultraviolet rays from sunlight. 

This step is essential in the manufacture of detergent active ingredients as it converts the sulfonic acids or sulfuric acid esters (products produced by processes I-M) into neutral surfactants. It is a potential source of some oil and grease, but occasional leaks and spills around the pump and valves are the only expected source of wastewater contamination. A process flow diagram is shown in Figure 14. 

One liter of water is added to the mixture then the precipitate is separated by suction filtration, pressed on the funnel, and washed with about 500 ml. of water. The product is transferred to a beaker, stirred well with about 500 ml. of cold water, then filtered and washed again on the funnel. This process is again repeated if necessary to remove the odor of acetic acid. After drying to constant weight in a vacuum desiccator over sulfuric acid, the product melts in the range between 55° and 60° (Note 8). The yield is 306-324 g. (85-90%) (Notes 9 and 10). 

The yellow solid product is separated by filtration, washed with ice water, and dried under reduced pressure over concentrated sulfuric acid. The product is recrystallized from a benzene-petroleum ether (b.p. range 95°-100°C) mixture yield 29 gm (92%), m.p. 107.5°-108.5°C. 

Ii5c k /—v raw 208.25 crysts (from MeOH), mp 112° forms aa oxime, mp 197—98°, Prepn N-tosylanthranilyl chloride with m-xylene AlCa gives 2,4-methyl-2 -(tosyIamino)benzo-phenone which is saponified by sulfuric acid the product is diazotized with,NaN02 (Ref 3)... 

Conjunct polymerization involves hydride abstraction from an olefin or oligomer by a carbocation. For example, during the oligomerization of isobutylene by dissolving it in 96% sulfuric acid, octene products may react with carbocation 1 [Eq. (13.4)] before they eliminate a proton to form trimethylpentenes 11... 

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