Sulfur dioxide reduction

Toxic or malodorous pollutants can be removed from industrial gas streams by reaction with hydrogen peroxide (174,175). Many Hquid-phase methods have been patented for the removal of NO gases (138,142,174,176—178), sulfur dioxide, reduced sulfur compounds, amines (154,171,172), and phenols (169). Other effluent treatments include the reduction of biological oxygen demand (BOD) and COD, color, odor (142,179,180), and chlorine concentration. 

Modem chrome-tanning methods are weU controUed and employ an extensive knowledge of the chemistry of the system. The most common chromium-tanning material used is basic chromium sulfate [12336-95-7] Cr(0H)S04, made by the reduction of sodium bichromate with sulfur dioxide or by sulfuric acid and a sugar. 

Impurities can be removed by formation of a gaseous compound, as in the fire-refining of copper (qv). Sulfur is removed from the molten metal by oxidation with air and evolution of sulfur dioxide. Oxygen is then removed by reduction with C, CO, in the form of natural gas, reformed... 

Gas Reduction. The use of a gaseous reduciag agent is attractive because the metal is produced as a powder that can easily be separated from the solution. Carbon dioxide, sulfur dioxide, and hydrogen can be used to precipitate copper, nickel, and cobalt, but only hydrogen reduction is appHed on an iadustrial scale. In the Sherritt-Gordon process, the excess ammonia is removed duting the purification to achieve a 2 1 ratio of NH iNi ia solution. Nickel powder is then precipitated by... 

Manufacture of 3-hydroxy-4-amino-l-naphthalenesulfonic acid involves the nitrosation of 2-naphthalenol, bisulfite addition, and reduction of the nitroso to the amino group by sulfur dioxide generated in situ (47). 3-Hydroxy-4-amino-l-naphthalenesulfonic acid is obtained in 80% yield. 

Air Pollution. Particulates and sulfur dioxide emissions from commercial oil shale operations would require proper control technology. Compliance monitoring carried out at the Unocal Parachute Creek Project for respirable particulates, oxides of nitrogen, and sulfur dioxide from 1986 to 1990 indicate a +99% reduction in sulfur emissions at the retort and shale oil upgrading faciUties. No violations for unauthorized air emissions were issued by the U.S. Environmental Protection Agency during this time (62). 

Rhenium oxides have been studied as catalyst materials in oxidation reactions of sulfur dioxide to sulfur trioxide, sulfite to sulfate, and nitrite to nitrate. There has been no commercial development in this area. These compounds have also been used as catalysts for reductions, but appear not to have exceptional properties. Rhenium sulfide catalysts have been used for hydrogenations of organic compounds, including benzene and styrene, and for dehydrogenation of alcohols to give aldehydes (qv) and ketones (qv). The significant property of these catalyst systems is that they are not poisoned by sulfur compounds. 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

A number of substances, such as the most commonly used sulfur dioxide, can reduce selenous acid solution to an elemental selenium precipitate. This precipitation separates the selenium from most elements and serves as a basis for gravimetry. In a solution containing both selenous and teUurous acids, the selenium may be quantitatively separated from the latter by performing the reduction in a solution which is 8 to 9.5 W with respect to hydrochloric acid. When selenic acid may also be present, the addition of hydroxylamine hydrochloride is recommended along with the sulfur dioxide. A simple method for the separation and deterrnination of selenium(IV) and molybdenum(VI) in mixtures, based on selective precipitation with potassium thiocarbonate, has been developed (69). 

The 1990 Amendments to the U.S. Clean Air Act require a 50% reduction of sulfur dioxide emissions by the year 2000. Electric power stations are beheved to be the source of 70% of all sulfur dioxide emissions (see Power generation). As of the mid-1990s, no utiUties were recovering commercial quantities of elemental sulfur ia the United States. Two projects had been aimounced Tampa Electric Company s plan to recover 75,000—90,000 metric tons of sulfuric acid (25,000—30,000 metric tons sulfur equivalent) aimuaHy at its power plant ia Polk County, Elorida, and a full-scale sulfur recovery system to be iastaHed at PSl Energy s Wabash River generating station ia Terre Haute, Indiana. Completed ia 1995, the Terre Haute plant should recover about 14,000 t/yr of elemental sulfur. 

Preparation. Thiophosgene forms from the reaction of carbon tetrachloride with hydrogen sulfide, sulfur, or various sulfides at elevated temperatures. Of more preparative value is the reduction of trichi oromethanesulfenyl chloride [594-42-3] by various reducing agents, eg, tin and hydrochloric acid, staimous chloride, iron and acetic acid, phosphoms, copper, sulfur dioxide with iodine catalyst, or hydrogen sulfide over charcoal or sihca gel catalyst (42,43). 

Reduction of sulfur dioxide to sulfur includes an industrially important group of reactions (227). Hydrogen sulfide reduces sulfur dioxide even at ambient temperature in the presence of water, but in the dry state and in the absence of a catalyst, a temperature of ca 300°C is required. 

Reduction of sulfur dioxide by methane is the basis of an Allied process for converting by-product sulfur dioxide to sulfur (232). The reaction is carried out in the gas phase over a catalyst. Reduction of sulfur dioxide to sulfur by carbon in the form of coal has been developed as the Resox process (233). The reduction, which is conducted at 550—800°C, appears to be promoted by the simultaneous reaction of the coal with steam. The reduction of sulfur dioxide by carbon monoxide tends to give carbonyl sulfide [463-58-1] rather than sulfur over cobalt molybdate, but special catalysts, eg, lanthanum titanate, have the abiUty to direct the reaction toward producing sulfur (234). 

Economic Aspects. Merchant sulfur dioxide is produced by eight North American manufacturers the total was about 410,000 metric tons in 1994 (310,000 in the United States, 90,000 in Canada). The largest producers in the United States are Rhc ne-Poulenc (from sulfur trioxide reduction by sulfur) and Hoechst Celanese. There is also a larger captive production. Growth of merchant sulfur dioxide is projected at 2—3%/yr. The mid-1995 price was 0.25/kg. 

Uses. The dominant use of sulfur dioxide is as a captive intermediate for production of sulfuric acid. There is also substantial captive production in the pulp and paper industry for sulfite pulping, and it is used as an intermediate for on-site production of bleaches, eg, chlorine dioxide or sodium hydrosulfite (see Bleaching agents). There is a substantial merchant market for sulfur dioxide in the paper and pulp industry. Sulfur dioxide is used for the production of chlorine dioxide at the paper (qv) mill site by reduction of sodium chlorate in sulfuric acid solution and also for production of sodium dithionite by the reaction of sodium borohydride with sulfur dioxide (315). This last appHcation was growing rapidly in North America as of the late 1990s. 

Chemical Properties. Anhydrous sodium sulfite is stable in dry air at ambient temperatures or at 100°C, but in moist air it undergoes rapid oxidation to sodium sulfate [7757-82-6]. On heating to 600°C, sodium sulfite disproportionates to sodium sulfate and sodium sulfide [1313-82-2]. Above 900°C, the decomposition products are sodium oxide and sulfur dioxide. At 600°C, it forms sodium sulfide upon reduction with carbon (332). 

In removing excess free chlorine from municipal or industrial water and from wastewater, sodium sulfite competes with bisulfite or sulfur dioxide. Other commercial appHcations of sodium sulfite in wastewater treatment include the reduction of hexavalent chromium to the less toxic Cr " salts as well as the precipitation of silver and mercury. 

Titanium Sulfates. Solutions of titanous sulfate [10343-61-0] ate readily made by reduction of titanium(IV) sulfate ia sulfuric acid solutioa by electrolytic or chemical means, eg, by reduction with ziac, ziac amalgam, or chromium (IT) chloride. The reaction is the basis of the most used titrimetric procedure for the determination of titanium. Titanous sulfate solutions are violet and, unless protected, can slowly oxidize ia coatact with the atmosphere. If all the titanium has been reduced to the trivalent form and the solution is then evaporated, crystals of an acid sulfate 3 Ti2(S0 2 [10343-61-0] ate produced. This purple salt, stable ia air at aormal temperatures, dissolves ia water to give a stable violet solutioa. Whea heated ia air, it decomposes to Ti02, water, sulfuric acid, and sulfur dioxide. 

Zinc does not react with nitrogen, even at elevated temperatures but zinc nitride, Zn N2, forms with ammonia at red heat. Zinc sulfide, the most common form of zinc in nature, is not reduced direcdy in commercial practice because of reactions of the zinc vapor during condensation. Rather, the sulfide is burned (roasted) to the oxide plus sulfur dioxide before reduction. However, zinc can be reduced to the metal at ca 1300°C with carbon or iron. 

A variety of models have been developed to study acid deposition. Sulfuric acid is formed relatively slowly in the atmosphere, so its concentrations are beUeved to be more uniform than o2one, especially in and around cities. Also, the impacts are viewed as more regional in nature. This allows an even coarser hori2ontal resolution, on the order of 80 to 100 km, to be used in acid deposition models. Atmospheric models of acid deposition have been used to determine where reductions in sulfur dioxide emissions would be most effective. Many of the ecosystems that are most sensitive to damage from acid deposition are located in the northeastern United States and southeastern Canada. Early acid deposition models helped to estabUsh that sulfuric acid and its precursors are transported over long distances, eg, from the Ohio River Valley to New England (86—88). Models have also been used to show that sulfuric acid deposition is nearly linear in response to changing levels of emissions of sulfur dioxide (89). 

Dithionites. Although the free-dithionous acid, H2S2O4, has never been isolated, the salts of the acid, in particular zinc [7779-86-4] and sodium dithionite [7775-14-6] have been prepared and are widely used as industrial reducing agents. The dithionite salts can be prepared by the reaction of sodium formate with sodium hydroxide and sulfur dioxide or by the reduction of sulfites, bisulfites, and sulfur dioxide with metallic substances such as zinc, iron, or zinc or sodium amalgams, or by electrolytic reduction (147). 

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. 

Various improvements in the sulfur dioxide reduction processes have been commercialized, including the Canadian International Paper Process (1946) and the Kesting, Persson, and Holst processes. A variation combining both chloride and sulfur dioxide reductant processes was developed and patented by KemaNord AB (47). 

Chlorine dioxide produced from the methanol reductant processes contains carbon dioxide and small amounts of formic acid. For this reason, sulfur dioxide and chloride-based chlorine dioxide processes are stih used for sodium chlorite production. This problem has been addressed by recycling a portion of the vapor from methanol-based generators so that formic acid further reacts to carbon dioxide ... 

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