Claus plant

One of the principal aspects of refinery gas cleanup is the removal of acid gas constituents, ie, carbon dioxide, CO2, and hydrogen sulfide, H2S. Treatment of natural gas to remove the acid gas constituents is most often accompHshed by contacting the natural gas with an alkaline solution. The most commonly used treating solutions are aqueous solutions of the ethanolamines or alkah carbonates. There are several hydrogen sulfide removal processes (29), most of which are followed by a Claus plant that produces elemental sulfur from the hydrogen sulfide. 

Fig. 6. Claus plant combustion schemes (a) straight-thm and (b) spHt-flow processes.

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 H2S comes out with the reactor products, goes through the product-recovery system of the FCCU, and eventually goes to a Claus plant for sulfur recovery. The metal oxide adsorbent recirculates with the spent cracking catalyst back to the regenerator for the next SO adsorption cycle. 

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 SCOTT process uses an amine to remove the HjS. The acid gas off the amine still is recycled back to the Claus plant. Other types oi processes oxidize the sulfur compounds to SO2 and then convert ihc SO to a secondary product such as ammonium thiosulfate, a fertilizer. These plants can remove more than 99.5% of the sulfur in the inlet stream to the Claus plant and may eliminate the need for incineration. Costs of achieving this removal are high. 

Before the syngas from WGS reactor is separated into its primary components, the sulphur compounds, mainly in COS and H2S form, are removed to avoid its emission to the atmosphere. Sulphur is then recovered in either as solid in a Claus plant or as sulphuric acid. 

Subsequently, H2S is removed from the syngas by a chemical or physical solvent. Upon regeneration of the solvent, the H2S is fed to a Claus plant to produce elemental sulfur. CO2 can be removed by the same solvent or in a separate absorber. 

Evaporation of solution releases Su2 which is recycled to Claus plant. 

Tail gas cleanup is required because a well-designed Claus plant with three catalytic stages and fresh catalyst will recover only 95-97% of its feed sulfur (8), which is not generally sufficient to meet current emission standards. In addition, feed impurities and catalyst aging will reduce overall recovery in some plants to about 92% just before catalyst changeout. Therefore, tail-gas cleanup is required. Tail-gas treating processes are generally classified as follows ... 

Recycle processes convert the sulfur species in the tail gas to a single compound which is captured, concentrated, and returned to the Claus plant. Examples are the SCOT (10), Trencor (11), and Wellman-Lord (8,12) processes. The first two recover and recycle H2S while the Wellman-Lord process recovers and recycles SO2. 

Independent conversion processes may not employ the Claus reaction for sulfur production and do not recycle the captured sulfur compounds to the Claus plant. Examples are the Beavon Mark I Process (Hydrogenation + Stretford) (13), the Beavon Mark II Process (Hydrogenation + Claus) (13), and the SNPA/Haldor-Topsoe Process (Catalytic Oxidation to SOi.) (9,10). 

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. 

In the SCOT process, the sulfur compounds in the Claus tail gas are converted to hydrogen sulfide by heating and passing it through a cobalt-molybdenum catalyst with the addition of a reducing gas. The gas is then cooled and contacted with a solution of diisopropanolamine (DIPA) that removes all but trace amounts of hydrogen sulfide. The sulfide-rich diisopropanolamine is sent to a stripper, where hydrogen sulfide gas is removed and sent to the Claus plant. The diisopropanolamine is returned to the absorption column. 

Installation of sulfur de-entrainment devices in the Claus Plant sulfur condensers to allow them to be recycled in the Stretford process ... 

These sub-dew point processes can increase the overall Claus plant sulfur recovery to up to 99%, as limited by equilibrium conversion and sulfur vapor pressure losses. Elf Aquitaine s Sulfreen process, Amoco s cold bed adsorption (CBA) process, and the Mineral and Chemical Resource Company (MCRC) process licensed by Delta Hudson are all variations on the cold bed sub-dew point process. 

Beavon, D.K., Hass, R.H. and Muke, B., "High Recovery, Lower Emission Promised for Claus-Plant Tail Gas", Oil Gas Journal, (1979) March 12. 

The sour natural gas sulfur recovery industry covers virtually the entire gamut of chemistry. From the sour gas reservoir to the Claus plant end product problems are encountered in thermodynamics, kinetics, corrosion, catalysis, redox, rheology and the environment - plus all the rest In reviewing recent developments in such a wide ranging field it is only possible to select examples. It is hoped, however, that these highlights will serve to illustrate the dynamism of the industry in recent years and the progress it has made in developing a new source of one of the world s most basic and essential elements in an environmentally acceptable manner. 

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