Claus Sulfur Recovery Process

FIGURE 5—8 Typical temperature and pressure profile for a gas-field sulfur-recovery train processing acid gas with 85% of H2S through a three-stage Claus plant... 

A major source of sulfur is refinery and natural gas streams. This is done by the Claus process which was discovered more than 100 years ago and has been used by the natural gas and refinery industries for 50 years. In the Claus process, hydrogen sulfide from the gas stream is converted to elemental sulfur. Air is introduced into a furnace to oxidize about one-third of the hydrogen sulfide to sulfur dioxide. In the next stage, the reaction furnace, unconverted hydrogen sulfide reacts with the sulfur dioxide to form elemental sulfur. The Claus process generally produces an overall recovery of sulfur of 95-97%, but several modifications have been invented and sulfur recoveries of 99.9% are now achievable [6]. The chemistry is represented hy the following reactions the equilibrium to form elemental sulfur is favored at lower temperatures. 

The hydrogenation step is an extension of the technology of the Beavon Sulfur Recovery (BSR) process used for Claus plant tail gas cleanup (see Chapter 8). However, because of the more dilute sulfur dioxide concentration in boiler plant flue gas and the presence of oxygen... 

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). 

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. 

These redox processes are usually appHcable for small sulfur capacities. The sulfur is typically produced as a slurry, and can be upgraded to cake or molten sulfur. At low pressures, the redox processes can replace the amine Claus and tail gas cleanup processes with a single step, yet obtain sulfur recoveries of 99%. At higher pressures, the redox processes experience sulfur plugging and foaming problems. 

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%. 

This is a desirable side reaction in the first catalytic reactor of the Claus sulfur recovery process. 

A disadvantage of the hydrocarbon—sulfur process is the formation of one mole of hydrogen sulfide by-product for every two atoms of hydrogen in the hydrocarbon. Technology for efficient recovery of sulfur values in hydrogen sulfide became commercially available at about the same time that the methane—sulfur process was developed. With an efficient Claus sulfur recovery unit, the hydrocarbon—sulfur process is economically attractive. 

Raw material usages per ton of carbon disulfide are approximately 310 m of methane, or equivalent volume of other hydrocarbon gas, and 0.86—0.92 ton of sulfur (87,88), which includes typical Claus sulfur recovery efficiency. Fuel usage, as natural gas, is about 180 m /ton carbon disulfide excluding the fuel gas assist for the incinerator or flare. The process is a net generator of steam the amount depends on process design considerations. 

A bleed from the scmbbing system is sent to a sour slurry stripper. The water is then clarified and can be recycled to minimize the volume of effluent to be biotreated and discharged or evaporated. The acid gas from the acid gas removal system and from the sour slurry stripper is fed to a Claus plant, where salable elemental sulfur (qv) is produced. For maximum sulfur recovery and minimal sulfur emissions, the Shell Claus off-gas treating process (SCOT) is used. 

The Stretford Process sweetens and also produces sulfur. It is good for low feed gas concentrations of H2S. Economically, the Stretford Process is comparable to an amine plant plus a Claus sulfur recovery plant. Usually, the amine/Claus combination is favored over Stretford for large plants. Stretford can selectively remove H2S in the presence of high CO2 concentrations. This is the process used in the coal gasification example in the Introduction. 

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. 

There are many processes used in tail-gas treating. The Sulfreen and the Cold Bed Absorption (CBA) processes use two psirallel reactors in a cycle, where one reactor operates below the sulfur dew point to absorb the sulfur while the second is regenerated with heat to recover molten sulfur, tiven though sulfur recoveries with the additional reactors are normally 99-99.5% of the inlet stream to the Claus unit, incineration of the outlet gas may still be required. 

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. 

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. 

MCRC A variation on the CBA sulfur recovery process using multiple Claus converters. Developed by the Delta Engineering Corporation in 1983 and used in Canada, China, and Mexico. 

RSRP [Richards sulphur recovery process] A proposed modification of the Claus process in which liquid sulfur is used to cool the catalyst bed. Developed jointly by the Alberta Energy Company and the Hudson s Bay Oil Gas Company, but not reported to have been commercialized. 

SuRe [Sulphur recovery] A version of the Claus process in which the capacity of the plant is increased by using air enriched in oxygen in the production of the sulfur dioxide. There are two versions SURE SSB [Side Stream Burner], and SURE DC [Double Combustion], In the first, a small portion of the feed stream containing hydrogen sulfide is burnt sub-stoichiometrically in a second burner in the second, the hydrogen sulfide is oxidized in two stages, with cooling and sulfur separation between them. Both of these... 

Pujare NU, Tsai KJ, and Sammells AF. An electrochemical claus process for sulfur recovery. J Electrochem Soc 1989 136 3662-3678. 

Modified carbon fibers, 13 383-385 Modified cellulosic membranes, in hemodialysis, 26 825, 826-828t Modified chemical vapor deposition (MCVD), in fiber optic fabrication, 11 136-137, 138, 139 Modified-Claus sulfur recovery process, 23 601, 602... 

Process Alternatives. Process alternatives for sulfur recovery are shown schematically in Figure 2. The choice of either elemental sulfur or sulfuric acid will depend on economics and markets related to each plant location. Elemental sulfur may be produced by gas-phase oxidation (the Claus process) or liquid-phase oxidation (e.g., the Stretford process). Stretford units were described in Section 1 and are well discussed in the literature (1, 2> 5) Claus sulfur recovery efficiency is usually less than required by current air emission standards. Therefore, some form of tail-gas treating is required. Sulfuric acid may be produced by the well-known contact process (6). This process is licensed by a number of firms, each of which has its own... 

Tail Gas Cleanup Process Efficiency - Required process efficiency depends on applicable emission regulations. Low-efficiency processes result in up to 99.0-99.5% overall sulfur recovery when combined with the Claus plant and include the Sulfreen, SNPA/Haldor-Topsoe, CBA, IFP, and Beavon Mark II processes. High-efficiency tail-gas treating processes can achieve overall sulfur recoveries of 99.8% and above under ideal conditions. These include the Beavon Mark I, SCOT, Trencor, and Wellman-Lord processes. 

The generation of the required reducing gas is very expensive because natural gas or low sulfur oil are used. Both of these fuels are in short supply and do not offer long-term solutions to the problem. However, in certain industrial processes, like petroleum refineries, a reducing gas could be readily available. Also, if a Claus sulfur recovery plant existed on-site, the concentrated SO2 stream could be sent to the Claus plant where it would mix with the H2S containing gas streams. Final adjustment of the H2S S02 ratio would be necessary. If the overall sulfur balance were favorable, the need for a reducing gas could be avoided. Either of these options could make the use of a recovery process economically attractive for industrial applications. 

Claus Sulfur Recovery Process The Claus process is a controlled combustion process commonly used for the recovery of sulfur from H2S. Temperatures >2,000°F (1,093.3°C) are achieved during combustion and yields of about 95% are typical. The basic reaction involves the following ... 

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