Sulfuric Acid from Sulfur Dioxide

In recent years the manufacture of sulfur dioxide and sulfuric acid has been increasing oriented to elemental sulfur as a starting material. Worldwide more than 60% of the fresh sulfuric acid is produced from elemental sulfur and 80% in the USA. 

Zinc blende, galena and copper pyrites are important raw material sources in the Federal Republic of Germany. These ores are utilized in the extraction of metals with sulfuric acid being produced as a byproduct, so-called metal acid. As a result of increased efforts in environmental protection, the proportion of recycled sulfuric acid e.g. from nitration reactions or oil refineries, has increased significantly in the last 20 years. 

Utilization of pyrites has, on the other hand, strongly decreased in importance in the Federal Republic of Germany for cost and environmental reasons. China, which produced 11.2 10 t of sulfuric acid from pyrites in 1993 

The worldwide production of pyrites, expressed as sulfur, was 7.46 10 t in 1993. The largest producer is China with ca. 4 10 t/a. Western Europe and the former 

Proportion of raw materials in the production of fresh sulfuric acid from. sulfur dioxide in the FRG in 1993 (%)  

---

Metal ion impurities in spent acid impose different recovery problems. For instance, iron residues in the spent acid from titanium dioxide manufacture may be removed by crystallization of first FeS04 7FI2O followed by crops of various iron(II) salts, or by electrodialysis [67]. Incidentally electrodialysis has also been used for sulfuric acid recovery from wastewater, either directly or after preconcentration on cation exchange resin [68]. 

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 ... 

Sulfur Dioxide Processing, Repriuts of 1972—1974 Chem. Eng. Prog, articles, AIChE, New York (1975). Contaius thirteen papers on flue gas desulfurization, two on SO2 control iu pulp and paper, one on sulfuric acid tail gas, one on SO2 from ore roasting, and two on NO from nitric acid. 

Magnesium sulfate heptahydrate may be prepared by neutralization of sulfuric acid with magnesium carbonate or oxide, or it can be obtained directly from natural sources. It occurs abundantly as a double salt and can also be obtained from the magnesium salts that occur in brines used for the extraction of bromine (qv). The brine is treated with calcium hydroxide to precipitate magnesium hydroxide. Sulfur dioxide and air are passed through the suspension to yield magnesium sulfate (see Chemicals frombrine). Magnesium sulfate is a saline cathartic. 

For environmental reasons, the entire process is handled by enclosed equipment. Lead recoveries of 96% can be obtained from the raw materials, and sulfur dioxide gas released in the process is used to produce sulfuric acid. Four plants are in operation as of 1994. Three are in Russia and one is in Italy. 

The aqueous sodium naphthenate phase is decanted from the hydrocarbon phase and treated with acid to regenerate the cmde naphthenic acids. Sulfuric acid is used almost exclusively, for economic reasons. The wet cmde naphthenic acid phase separates and is decanted from the sodium sulfate brine. The volume of sodium sulfate brine produced from dilute sodium naphthenate solutions is significant, on the order of 10 L per L of cmde naphthenic acid. The brine contains some phenolic compounds and must be treated or disposed of in an environmentally sound manner. Sodium phenolates can be selectively neutralized using carbon dioxide and recovered before the sodium naphthenate is finally acidified with mineral acid (29). Recovery of naphthenic acid from aqueous sodium naphthenate solutions using ion-exchange resins has also been reported (30). 

Nickel sulfate also is made by the reaction of black nickel oxide and hot dilute sulfuric acid, or of dilute sulfuric acid and nickel carbonate. The reaction of nickel oxide and sulfuric acid has been studied and a reaction induction temperature of 49°C deterrnined (39). High purity nickel sulfate is made from the reaction of nickel carbonyl, sulfur dioxide, and oxygen in the gas phase at 100°C (40). Another method for the continuous manufacture of nickel sulfate is the gas-phase reaction of nickel carbonyl and nitric acid, recovering the soHd product in sulfuric acid, and continuously removing the soHd nickel sulfate from the acid mixture (41). In this last method, nickel carbonyl and sulfuric acid are fed into a closed-loop reactor. Nickel sulfate and carbon monoxide are produced the CO is thus recycled to form nickel carbonyl. 

Research has shown that ascorbic acid can be produced from hulls of immature walnuts by extracting the hull with 0.2% sulfur dioxide solutions, and purifyiag the extract by adsorption on and elution from anion-exchange resias (see Ion exchange). Eluates from the anion-exchange step are concentrated, purified by organic solvent fractionations, decolorized, and crystallized (35). 

Benzene SuIfona.tion. In the benzene sulfonation process, benzene reacts with concentrated sulfuric acid to form benzenesulfonic acid at about 150°C. The benzenesulfonic acid is neutralized with sodium sulfate to produce sodium benzenesulfonate, which is then fused with caustic soda to yield sodium phenate. The sodium phenate is acidified with sulfur dioxide and a small amount of sulfuric acid to release the phenol from the sodium salt. The phenol yield by this process can be as high as 88 mol % to that of the theoretical value based on benzene. Plants employing this technology have been shut down for environmental and economic reasons. 

Phosphoms(V) sulfide is a mild skin irritant and may cause dermatitis in sensitive individuals. The primary health ha2ard results from the Hberation of hydrogen sulfide after contact with moisture. Contact with moisture also forms phosphoric acid. A secondary ha2ard is the formation of sulfur dioxide when phosphoms(V) sulfide bums. The oral LD q of in rats is 389 mg/kg the OSHA standard time-weighted average (TWA) is 1 mg /m (33). 

Phosphonic acid and hydrogen phosphonates are used as strong but slow-acting reducing agents. They cause precipitation of heavy metals from solutions of their salts and reduce sulfur dioxide to sulfur, and iodine to iodide in neutral or alkaline solution. 

It is apparent from these equations that significant quantities of sulfur dioxide are generated. For selenium, the reaction shown for oxidation of elemental selenium reverses itself at the lower temperatures employed for water scmbbing, thus regenerating sulfuric acid. The tellurium dioxide remains in the sulfated slimes. 

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). 

Occurrence. The metal sulfides, which are scattered throughout most of the world, have been an important source of elemental sulfur. The potential for recovery from metal sulfides exists, although these sources are less attractive economically and technologicaky than other sources of sulfur. Nevertheless sulfide ores are an important source of sulfur in other forms, such as sulfur dioxide and sulfuric acid. 

In addition to domestic production of Frasch and recovered elemental sulfur, U.S. requirements for sulfur are met with by-product sulfuric acid from copper, lead, molybdenum, and zinc smelting operations as well as imports from Canada and Mexico. By-product sulfur is also recovered as sulfur dioxide and hydrogen sulfide (see Sulfurremoval and recovery). 

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. 

---