Sulfur trioxide production

The original conception of the contact process is credited to a patent issued to P. Phillips in 1831 [46], but the practice of the principal components taught by this patent took nearly 50 years to bring to commercial success. The key step, the reaction of sulfur dioxide and air over a yellow-hot platinum surface to obtain sulfur trioxide, took extensive development work to obtain reasonable conversions. Coupling this initial catalytic oxidation to the hydration of the sulfur trioxide product was eventually achieved on the scale of 17,000 tonne/year by 1880, rising to 105,000 toime/year by 1890, by BASF (Badische... 

Sulfuric acid, the largest volume commodity chemical produced, is synthesized by the catalytic oxidation of sulfur dioxide, derived from combustion of sulfur or hydrogen sulfide, n The sulfur trioxide product is hydrated to form sulfuric acid. 

Stauffer Chemical Co. Westport, Connecticut 06881, USA. Sulfur trioxide product safety information leaflet. 

Product removal during reaction. Sometimes the equilibrium conversion can be increased by removing the product (or one of the products) continuously from the reactor as the reaction progresses, e.g., by allowing it to vaporize from a liquid-phase reactor. Another way is to carry out the reaction in stages with intermediate separation of the products. As an example of intermediate separation, consider the production of sulfuric acid as illustrated in Fig. 2.4. Sulfur dioxide is oxidized to sulfur trioxide ... 

In many cases, the a-haloketone does not appear to be an intermediate in this reaction, since reagents such as sulfur trioxide, sulfuric, or 60% nitric add lead to 2-aminothiazole but with lower yields (11 to 43%). Formamidine disulfide [-S-C(=NH)NH2]2, a product of the oxidation of thiourea, seems to be the intermediate in this reaction, since upon treatment with ketones, it gives 2-aminothiazole (604). However, the true mechanism of this reaction has not yet been completely elucidated. 

IS reversible but can be driven to completion by several techniques Removing the water formed m the reaction for example allows benzene sulfonic acid to be obtained m vir tually quantitative yield When a solution of sulfur trioxide m sulfuric acid is used as the sulfonatmg agent the rate of sulfonation is much faster and the equilibrium is dis placed entirely to the side of products according to the equation... 

On being heated with sulfur trioxide in sulfuric acid 124 5 tetramethylbenzene was converted to a product of molecular formula C10H14O3S m 94% yield Suggest a reasonable structure for this product... 

A typical up-draft sinter machine (Fig. 2) has an endless belt of malleable iron pallets with grate bottoms upon which the charge is evenly spread. Beneath the pallets, wind boxes produce an up-draft of air through the charge. At the feed end, an ignition box starts the roasting. The combustion products, mostly SO2 and SO, are collected, usually for sulfuric acid production (see Sulfuric acid and sulfur trioxide). 

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. 

In the United States, aluminum sulfate is usually produced by the reaction of bauxite or clay (qv) with sulfuric acid (see Sulfuric acid and sulfur trioxide). Bauxite is imported and more expensive than local clay, generally kaolin, which is more often used. Clay is first roasted to remove organics and break down the crystalline stmcture in order to make it more reactive. This is an energy intensive process. The purity of the starting clay or bauxite ore, especially the iron and potassium contents, are reflected in the assay of the final product. Thus the selection of the raw material is governed by the overall economics of producing a satisfying product. 

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. 

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. 

Inorganic Reactions. Thermal decomposition of Hquid sulfamic acid begins at 209°C. At 260°C, sulfur dioxide, sulfur trioxide, nitrogen, water, and traces of other products, chiefly nitrogen compounds, result. 

Sulfation is defined as any process of introducing an SO group into an organic compound to produce the characteristic C—OSO configuration. Typically, sulfation of alcohols utilizes chlorosulfuric acid or sulfur trioxide reagents. Unlike the sulfonates, which show remarkable stability even after prolonged heat, sulfated products are unstable toward acid hydrolysis. Hence, alcohol sulfuric esters are immediately neutralized after sulfation in order to preserve a high sulfation yield. 

By 1987, sulfur trioxide reagent use in the United States exceeded that of oleum for sulfonation. Sulfur trioxide source is divided between Hquid SO and in situ sulfur burning. The latter is integrated into sulfonation production faciUties. 

Sulfur trioxide reactivity can also be moderated through the use of SO adducts. The reactivity of such complexes is inversely proportional to their stabihty, and consequentiy they can be selected for a wide variety of conditions. Whereas moderating SO reactivity by adducting agents is generally beneficial, the agents add cost and may contribute to odor and possible toxicity problems in derived products. CeUulosic material has been sulfated with SO.—trimethyl amine adduct in aqueous media at 0 to 5°C (16). Sulfur trioxide—triethyl phosphate has been used to sulfonate alkenes to the corresponding alkene sulfonate (17). Sulfur trioxide—pyridine adduct sulfates oleyl alcohol with no attack of the double bond (18). 

Benzene. The reaction of sulfur trioxide and ben2ene in an inert solvent is very fast at low temperatures. Yields of 90% ben2enesulfonic acid can be expected. Increased yields of about 95% can be reali2ed when the solvent is sulfur dioxide. In contrast, the use of concentrated sulfuric acid causes the sulfonation reaction to reach reflux equiUbrium after almost 30 hours at only an 80% yield. The by-product is water, which dilutes the sulfuric acid estabhshing an equiUbrium. 

Sulfuric acid is the most important sulfur-containing intermediate product. More than 85% of the sulfur consumed in the world is either converted to sulfuric acid or produced direcdy as such (see Sulfuric acid and sulfur trioxide). Worldwide, well over half of the sulfuric acid is used in the manufacture of phosphatic fertilizers and ammonium sulfate for fertilizers. The sulfur source may be voluntary elemental, such as from the Frasch process recovered elemental from natural gas or petroleum or sulfur dioxide from smelter operations. 

Other Uses. Other uses include intermediate chemical products. Overall, these uses account for 15—20% of sulfur consumption, largely in the form of sulfuric acid but also some elemental sulfur that is used directly, as in mbber vulcanization. Sulfur is also converted to sulfur trioxide and thiosulfate for use in improving the efficiency of electrostatic precipitators and limestone/lime wet flue-gas desulfurization systems at power stations (68). These miscellaneous uses, especially those involving sulfuric acid, are intimately associated with practically all elements of the industrial and chemical complexes worldwide. 

Pan and cascade burners are generally more limited ia flexibiHty and are useful only where low sulfur dioxide concentrations are desired. Gases from sulfur burners also contain small amounts of sulfur trioxide, hence the moisture content of the air used can be important ia achieving a corrosion-free operation. Continuous operation at temperatures above the condensation poiat of the product gases is advisable where exposure to steel (qv) surfaces is iavolved. Pressure atomiziag-spray burners, which are particularly suitable when high capacities are needed, are offered by the designers of sulfuric acid plants. 

A basic research study on combustion of sulfur led to the postulation that sulfur trioxide may actually be the primary combustion product and that sulfur dioxide may then be produced by the further reaction of sulfur trioxide with sulfur vapor ki the oxygen-deficient region of the flame (261). 

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. 

Sulfur dioxide is usefiil as a solvent for sulfur trioxide in sulfonation reactions for example, in the large-scale production of alkylbenzenesulfonate surfactant (329). A newer use for sulfur dioxide is in cyanide detoxification in connection with cyanide leaching of precious metals from mine dumps. 

Gas leaving the economizer flows to a packed tower where SO is absorbed. Most plants do not produce oleum and need only one tower. Concentrated sulfuric acid circulates in the tower and cools the gas to about the acid inlet temperature. The typical acid inlet temperature for 98.5% sulfuric acid absorption towers is 70—80°C. The 98.5% sulfuric acid exits the absorption tower at 100—125°C, depending on acid circulation rate. Acid temperature rise within the tower comes from the heat of hydration of sulfur trioxide and sensible heat of the process gas. The hot product acid leaving the tower is cooled in heat exchangers before being recirculated or pumped into storage tanks. 

Sulfur (qv) is among the most widely used chemicals and often considered to be one of the four basic raw materials of the chemical iadustry. In 1993, worldwide production of sulfur reached 55 million metric tons (1). Production of sulfuric acid consumes the vast majority (- 90%) of sulfur (2) (see Sulfuric acid and sulfur trioxide). This acid is a steppiag stone ia the production of other sulfur-containing compounds, most notably ammonium sulfate fertilizer which accounts for 60% of the total worldwide sulfur consumption (2) (see Ammonium compounds Fertilizers). 

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