Sulfur production processes

Product removal during reaction. Separation of the product before completion of the reaction can force a higher conversion, as discussed in Chap. 2. Figure 2.4 showed how this is done in sulfuric acid processes. Sometimes the product (or one of the products) can be removed continuously from the reactor as the reaction progresses, e.g., by allowing it to vaporize from a liquid phase reactor. 

The concentrated hydrogen sulfide gas is then sent to the sulfur production unit (Claus process). 

Sulfur also occurs in natural gas and petroleum crudes and must be removed from these products. Formerly this was done chemically, which wasted the sulfur new processes now permit recovery. Large amounts of sulfur are being recovered from Alberta gas fields. 

Citric Acid Separation. Citric acid [77-92-9] and other organic acids can be recovered from fermentation broths usiag the UOP Sorbex technology (90—92). The conventional means of recovering citric acid is by a lime and sulfuric acid process ia which the citric acid is first precipitated as a calcium salt and then reacidulated with sulfuric acid. However, this process generates significant by-products and thus can become iaefficient. 

A modification of the NSP production process involves use of a mixture of sulfuric and phosphoric acids. The resultant product is referred to as enriched superphosphate and can contain up to 40% P2O5. The usual P2O5 content of enriched superphosphate is about 27%. 

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. 

Nonetheless, production and use of nitric phosphates ia Europe are continuing to grow. In general, nitric phosphate processes are somewhat more compHcated than sulfur-based processes and requite higher investment. In the past, several attempts have been made to estabHsh commercial acceptance of this type process ia the United States, but plant operations have been relatively short Hved because of low sulfur prices and resultant competition from sulfur-based processes. 

Processes for Triacetate. There are both batch and continuous process for triacetate. Many of the considerations and support faciUties for producing acetate apply to triacetate however, no acetyl hydrolysis is required. In the batch triacetate sulfuric acid process, however, a sulfate hydrolysis step (or desulfonation) is necessary. This is carried out by slow addition of a dilute aqueous acetic acid solution containing sodium or magnesium acetate (44,45) or triethanolamine (46) to neutrali2e the Hberated sulfuric acid. The cellulose triacetate product has a combined acetic acid content of 61.5%. 

The process options reflect the broad range of compositions and gas volumes that must be processed. Both batch processes and continuous processes are used. Batch processes are used when the daily production of sulfur is small and of the order of 10 kg. When the daily sulfur production is higher, of the order of 45 kg, continuous processes are usually more economical. Using batch processes, regeneration of the absorbant or adsorbant is carried out in the primary reactor. Using continuous processes, absorption of the acid gases occurs in one vessel and acid gas recovery and solvent regeneration occur in a separate reactor. 

In 1991, there were approximately 418 sulfur production plants associated with oil and gas production in operation throughout the world. Approximately 86% of these plants were based on the Claus process, and there were 118 Claus units operating in natural gas processing faciHties (11). 

First Alternative. Figure 1 illustrates the first of the two alternative production processes. Here the mother Hquor from the sodium nitrate crystallization plant, normally containing about 1.5 g/L iodine as iodate, is decanted for clarification and concentration homogenization. From there the solution is spHt into two fractions. The larger fraction is fed into an absorption tower where it is contacted with SO2 obtained by sulfur combustion. In the absorption tower iodate is reduced to iodide according to the following reaction ... 

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%. 

Because of restrictions in equipment si2e, magnesium nitrate processes were initially limited to small plants. Improvements in the materials of constmction have led to increased capacities and a lower capital cost. Sulfuric acid processes are usually preferred when reconcentration of the sulfuric acid is not requited, ie, when the dilute sulfuric can be used to make another product. 

Sources of sulfur are called voluntary if sulfur is considered to be the principal, and often the only, product. Sulfur has also been recovered as a by-product from various process operations. Such sulfur is termed involuntary sulfur and accounts for the largest portion of world sulfur production (see Sulfur REMOVAL AND RECOVERY). 

Pyrite is the most abundant of the metal sulfides. Eor many years, until the Erasch process was developed, pyrite was the main source of sulfur and, for much of the first half of the twentieth century, comprised over 50% of world sulfur production. Pyrite reserves are distributed throughout the world and known deposits have been mined in about 30 countries. Possibly the largest pyrite reserves in the world are located in southern Spain, Portugal, and the CIS. Large deposits are also in Canada, Cypms, Einland, Italy, Japan, Norway, South Africa, Sweden, Turkey, the United States, and Yugoslavia. However, the three main regional producers of pyrites continue to be Western Europe Eastern Europe, including the CIS and China. 

The reduction ia tetraethyl lead for gasoline production is expected to iacrease the demand for petroleum alkylate both ia the U.S. and abroad. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used. However, concerns over the safety or potential regulation of hydrofluoric acid seem likely to convince more refiners to use the sulfuric acid process for future alkylate capacity. 

Sulfur can be produced direcdy via Frasch mining or conventional mining methods, or it can be recovered as a by-product from sulfur removal and recovery processes. Production of recovered sulfur has become more significant as increasingly sour feedstocks are utilized and environmental regulations concerning emissions and waste streams have continued to tighten worldwide. Whereas recovered sulfur represented only 5% of the total sulfur production ia 1950, as of 1996 recovered sulfur represented approximately two-thirds of total sulfur production (1). Recovered sulfur could completely replace native sulfur production ia the twenty-first century (2). 

In a modem carbon disulfide plant, all operations are continuous and under automatic control. On-stream times in excess of 90% are obtainable. The process is in three steps melting and purification of sulfur production and purification of carbon disulfide and recovery of sulfur from by-product hydrogen sulfide. A typical process appears in the flow diagram of Figure 1 (50). 

Isopropyl Ether. Isopropyl ether is manufactured by the dehydration of isopropyl alcohol with sulfuric acid. It is obtained in large quantities as a by-product in the manufacture of isopropyl alcohol from propylene by the sulfuric acid process, very similar to the production of ethyl ether from ethylene. Isopropyl ether is of moderate importance as an industrial solvent, since its boiling point Hes between that of ethyl ether and acetone. Isopropyl ether very readily forms hazardous peroxides and hydroperoxides, much more so than other ethers. However, this tendency can be controlled with commercial antioxidant additives. Therefore, it is also being promoted as another possible ether to be used in gasoline (33). 

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

A modem petroleum refinery is a complex system of chemical and physical operations. The cmde oil is first separated by distillahon into fractions such as gasoline, kerosene, and fuel oil. Some of the distillate fractions are converted to more valuable products by cracking, polymerization, or reforming. The products are treated to remove undesirable components, such as sulfur, and then blended to meet the final product specifications. A detailed analysis of the entire petroleum production process, including emissions and controls, is obviously well beyond the scope of this text. 

Gas treating is defined here as removal of H2S and CO2. Other sulfur compounds are discussed where applicable. Dehydration and sulfur production are not included, except for discussing sulfur production in the Stretford Process and for selective H2S removal. H2S must be removed from natural gas and process streams for health reasons and prevention of corrosion. Natural gas pipeline specifications require no more than % grain/100 SCF. This is equivalent to 4ppmv or 7ppmw (for a 0.65 specific gravity gas). By comparison, the human nose can detect... 

Implementation of cleaner production processes and pollution prevention measures can yield both economic and environmental benefits. The following production-related targets can be achieved by measures such as those described above. The numbers relate to the production processes before the addition of pollution control measures. In sulfuric acid plants that use the double-contact, double absorption process, emissions levels of 2 to 4 kilograms of sulfur dioxide... 

Pollution prevention is always preferred to the use of end-of-pipe pollution control facilities. Therefore, every attempt should be made to incorporate cleaner production processes and facilities to limit, at source, the quantity of pollutants generated. The choice of flash smelting over older technologies is the most significant means of reducing pollution at source. Sulfur dioxide emissions can be controlled by ... 

Virgin naphtha hydrofining processing conditions have been standardized at 550°F, 4 V/hr/V, 300-400 psig and 400-500 SCF/B of 70% H treat gas. Such conditions will make a 4 ppm sulfur product of most stocks of interest. 

Sulfa-Check process uses sodium nitrite (NaN02) in aqueous solution to oxidize H2S to sulfur. This process was developed and patented by NL Treating Chemicals and is now a product of Exxon Energy Chem-... 

Another improvement (less by-products) has been made over the fuming sulfuric acid process operated commercially for the hydrolysis of 2-perfluoroal-kylethyl iodides. It entails the use of sulfur trioxide in liquid sulfur dioxide [52, 5J (equation 52). 

Multiple reactors achieve 95-96% conversion and recovery, and stringent air pollution legislation has now pushed this to 99%. A similar sequence of reactions is used for sulfur production from crude oil except that the organosulfur compounds must first be removed from the refinery feed and converted to H2S by a hydrogenation process before the sulfur can be recovered. 

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