Claus Process Catalysts

Elemental sulfur also is recovered as a by-product in processing natural gas and petroleum. Refining operations of natural gas and petroleum crude produce hydrogen sulfide, which also may occur naturally. Hydrogen sulfide is separated from hydrocarbon gases by absorption in an aqueous solution of alkaline solvent such as monoethanol amine. Hydrogen sulfide is concentrated in this solvent and gas is stripped out and oxidized by air at high temperature in the presence of a catalyst (Claus process). 

A1203 (mostly y, in special cases a or q) support, catalyst Claus process, dehydration of alcohols to alkenes and ethers, support of hydrotreating catalysts, support for three-way catalyst... 

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

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). 

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%. 

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. 

In the second section, unconverted hydrogen sulfide reacts with the produced sulfur dioxide over a bauxite catalyst in the Claus reactor. Normally more than one reactor is available. In the Super-Claus process (Figure 4-3), three reactors are used. The last reactor contains a selective oxidation catalyst of high efficiency. The reaction is slightly exothermic ... 

Figure 4-3. The Super Claus process for producing sulfur (1) main burner, (2,4, 6,8) condensers, (3,5) Claus reactors, (7) reactor with selective oxidation catalyst.

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 ... 

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. 

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. 

Modop [Mobil Oil Direct Oxidation Process] A process for removing residual sulfur-containing gases from the tail gas from the Claus process. The catalyst is titanium dioxide pelletized with calcium sulfate. Developed in the 1980s by Rhone-Poulenc, Procatalyse, and Mobil Oil. Three plants were operating in Germany in 1995 and one in the United States. European Patents 60,742 78,690. 

MTE A process for recovering sulfur from acid gases, based on the Claus process, but using a circulating, powdered catalyst instead of the usual fixed catalyst bed. Developed in 1987 but not yet commercialized. 

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. 

Selectox Also called BSR/Selectox. A process for converting hydrogen sulfide in refinery gases to elemental sulfur. The gases are passed over a fixed bed of a proprietary catalyst (Selectox 33) at 160 to 370°C. Claimed to be better than the Claus process in several respects. Often used in conjunction with the Beavon process. Developed by the Union Oil Company of California and the Ralph M. Parsons Company, and first operated in 1978. Thirteen units were operating in 1996. 

Claus process for the desulfurization of gases, y-Ala03 catalyst deposited in the pores of the membrane. 

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