The Claus Process

The Claus process to recover and recycle sulfur in the Le Blanc process, based on the procedure suggested by C. F. Claus in 1883, was introduced in 1887 by A. M. Chance. Alkali waste containing calcium sulfide was suspended in water, and hydrogen sulfide was generated by pumping carbon dioxide through the sluny  

Sulfur could then be recovered by passing the hydrogen sulfide, in a stream of air, through a kiln containing an iron catalyst. 

The modem two-step process converts hydrogen sulfide mixed with a stoichiometric volume of air to sulfur. In theory, one-third of the hydrogen sulfide is oxidized to sulfur dioxide in a carefully designed furnace, while the remaining hydrogen sulfide reacts with the sulfur dioxide to produce sulfur in two or more reactors containing a suitable catalyst. 

The study of adsorptive reactors for the Claus process represents a departure from most previous studies in that the equilibrium position is already well on the product side, with a conversion of 93 % being achievable for isothermal operation of gas with 10 mol% H2S without additional measures [30]. The need to attain conversions in excess of 99.5 % to ensure that the residual sulfur emissions meet environmental specifications [31] nevertheless makes the reaction system an interesting candidate for adsorptive equilibrium displacement. 

A simple tandem reverse-flow reactor scheme has been proposed for this purpose [11] (Fig. 7.5). By condensing the sulfur formed in the reactor outlet and reheating the residual anhydrous inert gas stream, one obtains a thermally efficient integration of the elutive adsorbent regeneration into the reactor operation. The arrangement depicted represents an adsorptive equivalent to the reverse-flow reactor with removal of a hot side-stream [6]. 

This process includes two main sections the burner section with a reaction chamber that does not have a catalyst, and a Claus reactor section. In the burner section, part of the feed containing hydrogen sulfide and some hydrocarbons is burned with a limited amount of air. The two main reactions that occur in this section are the complete oxidation of part of the hydrogen sulfide (feed) to sulfur dioxide and water and the partial oxidation of another part of the hydrogen sulfide to sulfur. The two reactions are exothermic  

After each reaction stage, sulfur is removed by condensation so that it does not collect on the catalyst. The temperature in the catalytic converter should be kept over the dew point of sulfur to prevent condensation on the catalyst surface, which reduces activity. 

Due to the presence of hydrocarbons in the gas feed to the burner section, some undesirable reactions occur, such as the formation of carbon disulfide (CS2) and carbonyl sulfide (COS). A good catalyst has a high activity toward H2S conversion to sulfur and a reconversion of COS and CS2 to sulfur and carbon oxides. Mercaptans in the acid gas feed results in an increase in the air demand. For example, approximately 5-13% increase in the air required is anticipated if about 2 mol% mercaptans are present. The increase in the air requirement is essentially a function of the type of mercaptans present. The oxidation of mercaptans could be represented as  

C2H5SH + %02 SO2 + 2CO2 + 3H2O Sulfur dioxide is then reduced in the Claus reactor to elemental sulfur. 

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The Claus process converts the H2S to sulfur by controlled combustion of the acid gas and Claus reaction on a catalyst. 

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). 

Certain of the above reactions are of practical importance. The oxidation of hydrogen sulfide in a flame is one means for producing the sulfur dioxide required for a sulfuric acid plant. Oxidation of hydrogen sulfide by sulfur dioxide is the basis of the Claus process for sulfur recovery. The Claus reaction can also take place under mil der conditions in the presence of water, which catalyzes the reaction. However, the oxidation of hydrogen sulfide by sulfur dioxide in water is a complex process leading to the formation of sulfur and polythionic acids, the mixture known as Wackenroeder s Hquid (105). 

The practical importance of the higher sulfanes relates to their formation in sour-gas wells from sulfur and hydrogen sulfide under pressure and their subsequent decomposition which causes well plugging (134). The formation of high sulfanes in the recovery of sulfur by the Claus process also may lead to persistance of traces of hydrogen sulfide in the sulfur thus produced (100). Quantitative deteanination of H2S and H2S in Claus process sulfur requires the use of a catalyst, eg, PbS, to accelerate the breakdown of H2S (135). 

The Claus process, which involves the reaction of sulfur dioxide with hydrogen sulfide to produce sulfur in a furnace, is important in the production of sulfur from sour natural gas or by-product sulfur-containing gases (see Sulfurremoval and recovery). 

When the Claus reaction is carried out in aqueous solution, the chemistry is complex and involves polythionic acid intermediates (105,211). A modification of the Claus process (by Shell) uses hydrogen or a mixture of hydrogen and carbon monoxide to reduce sulfur dioxide, carbonyl sulfide, carbon disulfide, and sulfur mixtures that occur in Claus process off-gases to hydrogen sulfide over a cobalt molybdate catalyst at ca 300°C (230). 

The Claus process is the most widely used to convert hydrogen sulfide to sulfur. The process, developed by C. F. Claus in 1883, was significantly modified in the late 1930s by I. G. Farbenindustrie AG, but did not become widely used until the 1950s. Figure 5 illustrates the basic process scheme. A Claus sulfur recovery unit consists of a combustion furnace, waste heat boiler, sulfur condenser, and a series of catalytic stages each of which employs reheat, catalyst bed, and sulfur condenser. Typically, two or three catalytic stages are employed. 

The Claus process converts hydrogen sulfide to elemental sulfur via a two-step reaction. The first step involves controUed combustion of the feed gas to convert approximately one-third of the hydrogen sulfide to sulfur dioxide (eq. 9) and noncatalytic reaction of unbumed hydrogen sulfide with sulfur dioxide (eq. 10). In the second step, the Claus reaction, the hydrogen sulfide and sulfur dioxide react over a catalyst to produce sulfur and water (eq. 10). The principal reactions are as foUow ... 

A derivative of the Claus process is the Recycle Selectox process, developed by Parsons and Unocal and Hcensed through UOP. Once-Thm Selectox is suitable for very lean acid gas streams (1—5 mol % hydrogen sulfide), which cannot be effectively processed in a Claus unit. As shown in Figure 9, the process is similar to a standard Claus plant, except that the thermal combustor and waste heat boiler have been replaced with a catalytic reactor. The Selectox catalyst promotes the selective oxidation of hydrogen sulfide to sulfur dioxide, ie, hydrocarbons in the feed are not oxidized. These plants typically employ two Claus catalytic stages downstream of the Selectox reactor, to achieve an overall sulfur recovery of 90—95%. 

Liade AG offers the Clintox process for sulfur dioxide removal. This process uses a physical solvent to absorb the sulfur dioxide. A concentrated sulfur dioxide stream is produced by regeneration. The Clintox process can be iategrated with the Claus process by recovering sulfur dioxide from the iaciaerated tail gases and recycling the sulfur dioxide to the front of the Claus unit. 

Sulfur Dioxide, Spray Towers Flue gases and offgases from sulfuric acid plants contain less than 0.5 percent SO9 smelter gases like those from ore processing plants may contain 8 percent. The high-concentration streams are suitable for the manufacture of sulfuric acid. The low concentrations usually are regarded as contaminants to be destroyed or recovered as elemental siilfur by, for example, the Claus process. 

An electrostatic precipitator is used to remove more tar from coke oven gas. The tar is then sent to storage. Ammonia liquor is also separated from the tar decanter and sent to wastewater treatment after ammonia recovery. Coke oven gas is further cooled in a final cooler. Naphthalene is removed in a separator on the final cooler. Light oil is then removed from the coke oven gas and is fractionated to recover benzene, toluene, and xylene. Some facilities may include an onsite tar distillation unit. The Claus process is normally used to recover sulfur from coke oven gas. During the coke quenching, handling, and screening operation, coke breeze is produced. The breeze is either reused on site (e.g., in the sinter plant) or sold offsite as a by-product. 

Current methods for removing sulfur from the hydrogen sulfide gas streams are typically a combination of two processes the Claus Process followed by the Beaven Process, SCOT Process, or the Wellman-Land Process. 

The Claus process consists of partial combustion of the hydrogen sulfide-rich gas stream (with one-third the stoichiometric quantity of air) and then reacting the resulting sulfur dioxide and unbumed hydrogen sulfide in the presence of a bauxite catalyst to produce elemental sulfur. Refer to the process flow diagram in Figure 7. 

Since the Claus process by itself removes only about 90% of the hydrogen sulfide in the gas stream, the Beaven, SCOT, or Wellman-Lord processes are often used to further recover sulfur. In the Beaven process, the hydrogen sulfide in the relatively low concentration gas stream from the Claus process can be almost completely removed by absorption in a quinone solution. 

The Beaven process is also effective in removing small amounts of sulfur dioxide, carbonyl sulfide, and carbon disulfide that are not affected by the Claus process. These compounds are first converted to hydrogen sulfide at elevated... 

Figure 7-7 shows a simplified process flow diagram of the Claus process. The first stage of the process converts H2S to sulfur dioxide and... 

Ultimately, pollution can only be avoided by complete removal of SO2 from the effluent gases, but this council of perfection is both technologically and economically unattainable. Many processes are available to reduce the SO2 concentration to very low figures, but the vast scale of power generation and domestic heating by coal and oil still results in substantial emission. SO2 can be removed by scrubbing with a slurry of milk of lime , CafOH) . Alternatively, partial reduction to H2S using natural gas (CH4), naphtlia or coal, followed by catalytic conversion to elemental sulfur by the Claus process can be used ... 

Currently, sulfur is mainly produced by the partial oxidation of hydrogen sulfide through the Claus process. The major sources of hydrogen sulfide are natural gas and petroleum refinery streams treatment operations. It has been estimated that 90-95% of the world s recovered sulfur is produced through the Claus process. Typical sulfur recovery ranges from 90% for a lean acid gas feed to 97% for a rich acid gas feed. ... 

Self-Test K.3A In the Claus process for the recovery of sulfur from natural gas and petroleum, hydrogen sulfide reacts with sulfur dioxide to form elemental sulfur and water 2 H2S(g) + S02(g) — 3 S(s) + 2 H20(1). Identify the oxidizing agent and the reducing agent. 

Sulfur is widely distributed as sulfide ores, which include galena, PbS cinnabar, HgS iron pyrite, FeS, and sphalerite, ZnS (Fig. 15.11). Because these ores are so common, sulfur is a by-product of the extraction of a number of metals, especially copper. Sulfur is also found as deposits of the native element (called brimstone), which are formed by bacterial action on H,S. The low melting point of sulfur (115°C) is utilized in the Frasch process, in which superheated water is used to melt solid sulfur underground and compressed air pushes the resulting slurry to the surface. Sulfur is also commonly found in petroleum, and extracting it chemically has been made inexpensive and safe by the use of heterogeneous catalysts, particularly zeolites (see Section 13.14). One method used to remove sulfur in the form of H2S from petroleum and natural gas is the Claus process, in which some of the H2S is first oxidized to sulfur dioxide ... 

The origin of the small Sy content of all commercial sulfur samples is the following. Elemental sulfur is produced either by the Frasch process (mining of sulfur deposits) or by the Claus process (partial oxidation of HyS) [62]. In each case liquid sulfur is produced (at ca. 140 °C) which at this temperature consists of 95% Ss and ca. 5% other sulfur homocycles of which Sy is the main component. On slow cooling and crystalhzation most of the non-Ss species convert to the more stable Ss and to polymeric sulfur but traces of Sy are built into the crystal lattice of Ss as sohd state defects. In some commercial samples traces of Ss or Sg were detected in addition. The Sy defects survive for years if not forever at 20 °C. The composition of the commercial samples depends mainly on the coohng rate and on other experimental conditions. Only recrystalhzation from organic solvents removes Sy and, of course, the insoluble polymeric sulfur and produces pure a-Ss [59]. 

In the Introduction it has already been mentioned that sulfanes are likely to occur in underground sulfur-rich deposits of sour natural gas. This gas is freed from H2S by washing with an alkaline solvent from which the hydrogen sulfide is later expelled by heating. The Claus process is then applied to convert H2S into elemental sulfur ... 

Owing to its excellent thermal and mechanical stability and its rich chemistry, alumina is the most widely used support in catalysis. Although aluminium oxide exists in various structures, only three phases are of interest, namely the nonporous, crys-tallographically ordered a-Al203, and the porous amorphous t]- and y-Al203. The latter is also used as a catalyst by itself, for example in the production of elemental sulfur from H2S (the Claus process), the alkylation of phenol or the dehydration of formic acid. 

Aquaclaus A modification of the Claus process in which hydrogen sulfide is removed from water by reaction with sulfur dioxide. Developed by Stauffer Chemical Company and operated by the Heflin Oil Company, in Queen City, TX. 

ASR Sulfoxide [Alberta Sulfur Research] A process for removing residual sulfur dioxide and hydrogen sulfide from the tail gases from the Claus process by wet scrubbing with a solution containing an organic sulfoxide. Elemental sulfur is produced. It had not been piloted in 1983. 

Beavon [Beavon Sulfur Removal] Also called BSR. A process for removing residual sulfur compounds from the effluent gases from the Claus process. Catalytic hydrogenation over a cobalt/molybdena catalyst converts carbonyl sulfide, carbon disulfide, and other... 

CBA [Cold bed adsorption] A variation of the Claus process in which the sulfur product is desorbed from the catalyst by a side stream of hot gas from the main process. Developed by AMOCO Canada Petroleum Company and operated in Alberta. 

Clauspol [Claus polyethylene glycol] A variation on the Claus process for removing hydrogen sulfide from gas streams, in which the tail gases are scrubbed with polyethylene glycol to remove residual sulfur dioxide. Clauspol 150 is a modification of this. Developed by the Institut Frangais du Petrole. 

CLINSULF [Carl von Linde sulfur] A variation of the Claus process in which the heat from the process is used to heat a second catalytic reactor. The process is designed for gases rich in hydrogen sulfide. First commercialized in 1992 and offered by Linde, Munich. 

Comprimo A version of the Claus process offered by Comprimo Engineers Contractors, The Netherlands. In 1983, plants using this process were being installed in Italy, Kuwait, France, and Japan. See also Superclaus. 

Concat A process for removing residual sulfur-containing gases from the off-gases from the Claus process, by oxidation to sulfur trioxide and hot condensation to sulfuric acid. Developed by Lurgi and first operated at Port Sulfur, LA, in 1974. 

CONOSOX A complex flue-gas desulfurization process using potassium carbonate solution as the wet scrubbing medium. The product potassium bisulfite is converted to potassium thiosulfate and then reduced with carbon monoxide to potassium carbonate for re-use. The sulfur is recovered as hydrogen sulfide, which is converted to elemental sulfur by the Claus process. Developed by the Conoco Coal Development Company and piloted in 1986. 

COPE [Claus Oxygen-based Process Expansion] A modification of the Claus process, which improves the recovery of the sulfur. The combustion stage uses oxygen instead of air. Introduced in 1985 and now licensed by Air Products Chemicals and Goar, Allison Associates. In 1990, six units were operating in the United States. 

Hydrosulfreen A process for removing sulfur compounds from the tail gas from the Claus process. It combines the Sulfreen process with an upstream hydrolysis/oxidation stage, which improves efficiency and optimizes the emission control. Developed jointly by Lurgi and Societe National Elf Aquitaine, and installed in 1990 in the Mazovian Refining and Petrochemical Works, near Warsaw, Poland. See also Oxysulfreen. 

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