Recovery sulfur

Purification of refinery gases by elimination of hydrogen sulfide as well as Claus units for sulfur recovery began to make their appearance. 

The Eastman Chemicals from Coal faciUty is a series of nine complex interrelated plants. These plants include air separation, slurry preparation, gasification, acid gas removal, sulfur recovery, CO /H2 separation, methanol, methyl acetate, and acetic anhydride. A block flow diagram of the process is shown in Eigure 3. The faciUty covers an area of 2.2 x 10 (55 acres) at Eastman s main plant site in Kingsport, Teimessee. The air separation plant is... 

Gas purification processes fall into three categories the removal of gaseous impurities, the removal of particulate impurities, and ultrafine cleaning. The extra expense of the last process is only justified by the nature of the subsequent operations or the need to produce a pure gas stream. Because there are many variables in gas treating, several factors must be considered (/) the types and concentrations of contaminants in the gas (2) the degree of contaminant removal desired (J) the selectivity of acid gas removal required (4) the temperature, pressure, volume, and composition of the gas to be processed (5) the carbon dioxide-to-hydrogen sulfide ratio in the gas and (6) the desirabiUty of sulfur recovery on account of process economics or environmental issues. 

Control Room. The control room location can be critical to the efficient operation of a faciHty. One prime concern is to locate it the maximum distance from the most ha2ardous units. These units are usually the units where LPG or other flammables, eg, hydrocarbons that are heavier than air, can be released and accumulate at grade level. Deadly explosions can occur if a pump seal on a light-ends system fails and the heavier-than-air hydrocarbons coUect and are ignited by a flammable source. Also, the sulfur recovery unit area should be kept at a healthy distance away as an upset can cause deadly fumes to accumulate. 

The 1990 Amendments to the U.S. Clean Air Act require a 50% reduction of sulfur dioxide emissions by the year 2000. Electric power stations are beheved to be the source of 70% of all sulfur dioxide emissions (see Power generation). As of the mid-1990s, no utiUties were recovering commercial quantities of elemental sulfur ia the United States. Two projects had been aimounced Tampa Electric Company s plan to recover 75,000—90,000 metric tons of sulfuric acid (25,000—30,000 metric tons sulfur equivalent) aimuaHy at its power plant ia Polk County, Elorida, and a full-scale sulfur recovery system to be iastaHed at PSl Energy s Wabash River generating station ia Terre Haute, Indiana. Completed ia 1995, the Terre Haute plant should recover about 14,000 t/yr of elemental sulfur. 

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 absorption of sulfur dioxide in alkaline (even weakly alkaline) aqueous solutions affords sulfites, bisulfites, and metabisulfites. The chemistry of the interaction of sulfur dioxide with alkaline substances, either in solution, slurry, or soHd form, is also of great technological importance in connection with air pollution control and sulfur recovery (25,227,235—241). Even weak bases such as 2inc oxide absorb sulfur dioxide. A slurry of 2inc oxide in a smelter can be used to remove sulfur dioxide and the resultant product can be recycled to the roaster (242). 

Other factors which have a significant influence on process selection iaclude absolute quantity of sulfur present, concentration of various sulfur species, the quantity and concentration of other components ia the stream to be treated, quantity and conditions (temperature and pressure) of the stream to be treated, and, the location-specific environmental regulations governing overall sulfur recovery and allowable sulfur dioxide emissions (3). 

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 amount of combustion ait is tightly controlled to maximize sulfur recovery, ie, maintaining the appropriate reaction stoichiometry of 2 1 hydrogen sulfide to sulfur dioxide throughout downstream reactors. Typically, sulfur recoveries of up to 97% can be achieved (7). The recovery is heavily dependent on the concentration of hydrogen sulfide and contaminants, especially ammonia and heavy hydrocarbons, ia the feed to the Claus unit. 

A sulfur condenser follows the reactor. These processes, ie, Superclaus or Parson s Hi-Activity process, can boost the overall sulfur recovery to up to 99.2%. 

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%. 

In two processes under development as of 1997, the sulfur dioxide stream reacts with reduciag gas over a proprietary catalyst to form elemental sulfur. Both processes have achieved a sulfur recovery of 96% ia a single reactor. Multiple reactor systems are expected to achieve 99+% recovery of the feed sulfur. The direct sulfur recovery process (DSRP), under development at Research Triangle Institute, operates at high temperature and pressure. A similar process being developed at Lawrence Berkeley Laboratory is expected to operate near atmospheric pressure. 

The primary driver ia sulfur recovery appHcations is not economic potential, but rather environmental regulation. The capital investment required for sulfur recovery faciHties is significant. Increasing pressure to maximize recovery and throughput at minimum investment is constantiy being brought to bear on the chemical process iadustry. 

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