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John S. Eow
Department of Chemical Engineering, University of Leeds, Leeds, LS2 9JT, United Kingdom
i%e modified Clausprocess is the major technologyfor the f recovery of elemental sulfurfrom H S and SO2 A number o commercial technologiesfor the recovery o sulfurfrom acid f gases are also highlighted here. A Claus tail-gas clean-up treatment is essential to give high sulfur recovery efficiency from sour acid gases. Generally, the existing tail-gas clean-up technologies can be classified into two groups: those that attain 99%overall sulfur recovery efliciency, and those that achieve 99.9%efficiency, including the sulfur recovered in the Claus unit. Theseprocesses are the Amoco’s Cold Bed Adsolption (CBA), the SNPMLurgi Sulfreen, the IF8 the SCOT, the Beavon, and the Wellman-Lordprocesses. The SCOT process is generally the most reliable and flexible technology. Process comparisons are also summarized in terms of the sulfur recovey efficiency, hazards and disadvantages, reliability and advantages, plant capacity and ecological impacts. Several changes and new trends are also highlighted here, such as the introduction o non-permselectivecatalytic memf brane reactorsfor the Claus reaction, and the in situ adsoption o water inside the Clam catalytic reactor. ?be successful f utilization o H S by converting it to sulfur and H 2 attains f the triple objectives of waste minimization, resource utilization, and environmentalpollution reduction. Photochemical and plasmochemical methods are still in the development stage. Application of electrochemical technology to H2S requires further development. Research for an optimum porous catalyst structure is ongoingfor obtaining a relation o micropores and macropores which would provide effective f conversion of H S and SO2
Sulfur is often considered one of the four basic raw materials in the chemical industry. It can be produced from various sources using many different methods, such as conventional mining methods, o r it can be recovered as a byproduct from sulfur removal and recovery processes [ll. However, changes worldwide have affected sulfur sources and the amounts consumed in the last 30 years [ l l . Recovered sulfur production has become more significant as sour feedstocks are increasingly utiEnvironmental Progress (V01.21, No.3)
lized, and environmental laws on emissions and waste streams have continued to tighten worldwide [2, 31. For example, voluntary sulfur from the Frasch mining process supplied only 25% in 1995, compared to about 53% in 1980. Recovered sulfur increased from 5% of the total production in 1950, to 67% in 1996 111. Discovery and development of large sour natural gas fields in many countries have also been important factors in this rapid growth. Increased processing of sour crude oil and tighter pollution control has caused most refineries to recover the sulfur content of its crude oil. Historically, sulfur recovery processes focus on the removal and conversion of hydrogen sulfide (H2S) and sulfur dioxide (S02) to elemental sulfur [4, 51, as these species represent the largest source of potential sulfur emission [61. H2S occurs naturally in many natural gas wells, and is produced in large quantities in the desulfurization of petroleum stocks [7-91. It has been considered a liability, which only occasionally can be an asset, depending on the international sulfur price [51. It has a high heating value, but its use as a fuel is not possible because one of its combustion products is S o l , which is not environmentally acceptable. Therefore, one of the immediate alternative routes for the utilization of H2S is to break it down to its constituent elements of hydrogen and sulfur [lo, 111. Various processes for the removal of SO, in the combustion gases have been reviewed [121. The majority of the processes are based on a throw-away process, in which alkali or alkali earth metal reacts with SO, to form metal sulfate 113-171. However, this approach results in the disposal of large quantities of sulfate waste materials. Direct catalytic oxidation of SO2 to SOg, and subsequent absorption of SO3 in water to produce sulfuric acid, is an alternative method [17, 181. This approach applies to process or combustion gases containing moderate to high concentrations of SO2. Copper smelters are the primary example.
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Currently the modified Claus technology is widely used, compared to other processes, to produce elemental sulfur from H2S present in gases from oil refineries, natural gas, coal gasification an d other industries [9, 19-23. It was developed by C.F. Claus, in 1883 1241 and was significantly modified in the late 1930s by I.G. Farbenindustrie AG [251. Major improvements were not made in the technology itself or its application until such a process was required in the United States in 1950s. This technology h as n o w advanc e d t o a stage w h e r e overall recovery h a s increased from 9042% to the level of 98-99% of inlet sulfur [3, 23, 261.
STUDIES AND RESEARCH ON CIAUS PROCESS MECHANISMS AND TECHNOLOGY
3 + - S, + beat
Figure 1 shows a simplified process diagram of a Claus plant. Acid gas contains HzS, C 0 2 and H 2 0 as major components, an d N 2 a n d hydrocarbons a s minor components. Ammonia (NH3) is also present in sour water stripper gas [27, 281. The Claus furnace and the waste heat boiler are normally treated as a single unit [29, 301. Monnery, et al. [311 and Nasato, et al. [301 identified the reaction furnace as o n e of the most important, yet least understood, parts of the modified Claus process. The initial sulfur conversion occurs there, the SO2 required by downstream catalytic reactors is produced there, and contaminant destruction is supposed to take place there [22, 321. However, many side reactions also occur, reducing sulfur recovery and producing unwanted substances [201. According to Nasato, et al. [301, Kaloidas and Papayannakos [331 and Dowling, et al. , the disassociation and re-formation of H2S in the furnace is important as it provides a portion of the sulfur and a majority of the H2 for other reactions and consumes H2S that could be used in the Claus reactions. At temperatures below 1,000" C and residence times below 0.5 second, the H2.S cracking rate is insignificant [321. Below 950" C, the overall conversion of H2S is low even at a long residence time. Therefore, the main purpose of the reaction furnace is to provide optimum temperature and residence time so that the exiting ratio of H2S to SO2 is 2: 1, maximizing catalytic conversion downstream [221. The waste heat boiler, usually a shell and tube heat exchanger, cools the furnace exit gases from 1,188"C to 154" C in one or two tube passes, generating low-pressure steam [301. This is to condense the sulfur products (mostly Sg and S6, and a small amount of S2>[4, 21, 221. Moreover, at 154" C, the sulfur products are at their lowest viscosities [35, 361. Hence, the products would easily flow through the pipes into the sulfur pit. To prevent the pipes from becoming blocked, a low pressure jacketed steam generated in the waste heat boiler is introduced around the pipes. Two reactions are believed to occur in the waste heat boiler tubes:
where n is the average molecular species of the sulfur vapor product, with n = 2 to 8 and possibly more. In Reaction (3), about a third of the H2S is combusted in the reaction furnace to form a stoichiometric amount of S 0 2 , which is then reacted with the remaining H2S in Reaction 4 to yield elemental sulfur and water [23, 391. Reaction 3 is carried out in the furnace at 1,188"C, usually under partial oxidation [40, 411. Reaction 4 is an equilibrium reaction favored at low temperature in the presence of a catalyst [21, 37, 421. In order to increase conversion, Bonsu and Meisen 1431 proposed using fluidized bed reactors, rather than conventional fixed-bed reactors, so that the last reactor could be continuously operated below the sulfur dew point. According to Puchyr, et al. [211 and Bonsu and Meisen [431, if equilibrium conversion could be achieved in each reactor, the use of fluidized-bed reactors could result in an overall H2S conversion of 99.5 Yo. The most widely used Claus catalyst is non-promoted spherical activated alumina [23, 441. However, Paik and Chung  reported that Co-Mo/AlzOg, which is usually used for hydrodesulfurization of a petroleum feed stock, can convert SO2 with H2S selectively to elemental sulfur at lower temperature than that commonly used. However, the hydrogenation of SO2 to H2S occurring o n metal sulfide sites was found to be much slower than the Clam reaction on alumina 1181. T h e active sites for t h e SO2 hydrogenation was believed to be sulfur vacancies in metal sulfide, and the most effective catalyst had an ability to form and regenerate sulfur vacancies most easily. In the Claus process, other sulfur compounds will form, such as carbon disulfide (CS2) and carbon oxysulfide (COS), and these compounds can often contribute from 20 to 50% of the pollutants in the tail-gas [44, 451. COS and CS2 are usually hydrolyzed in the catalytic converter [21, 381, as shown below:
CS2 + 2H20 + 2H2S+ C02
The principal reaction of the Claus process are as
follows [4, 9, 22, 37, 381:
Studies carried out by Laperdrix, et al. [461 also reveal that the presence of 0 2 traces in the CSZ-H~O mixture caused a decrease in the activity of alumina and titania catalysts due to sulfate formation. IR studies show that sulfate species are reduced by H2S at 320° C on titania, in contrast to the sulfate species on alumina, implying that titania is much more effective than alumina when the CS2 i 2 0 feed also contains H H2S and 0 2 traces [461. The temperature of the first catalytic re a c to r is maintained at about 350" C to hydrolyze COS a n d CSz, while that of the subsequent r e a c t o r s is just above the sulfur vapor d e w point [421. Transition
metal oxides can be used to modify gamma-alumina Environmental Progress (V01.23, N0.3)
144 October 2002
No. 501 as a lower temperature should increase the exothermic reaction efficiency. 52-541. [31. mainly H2S. The catalyst exhibited a high and stable H2S conversion even at a sulfur loading of more than 60%. While in the feed without water. Water assists in the mechanical removal and transport of the sulfur formed by the particles of the active phase on the hydrophilic part of the support (i. has been recognized as being responsible for low activity in the COS hydrolysis [55. 52. Grancher 1581. [31. according to Ledoux. and a nickel-based active phase provide an active. October 2002 145 . the use of a new type of support. Alvarez. However.3) and H20. the produced sulfur would be deposited. Uncondensed gas. [261 and Steijns and Mars [571 also indicate that. [531 and Pineda and Palacios [541 showed that H2S conversions higher than 90% can be achieved using concentrations in the range of 1-5% with a relatively slow catalyst deactivation. because of sulfur deposition in the catalyst pores [37. 601. Sic). et al. unburned hydrocarbon and NH3. Opekar and Goar 1271. in the presence of Sn Environmental Progress (V01. Under these conditions. especially if the operation conditions and catalyst properties are optimized. S02. such as 5% water vapor.e. et al. these results cannot be obtained with current technology due to reaction kinetic limitations and. As a catalyst is being covered by sulfur..~~ ~ Recycle f o Tail-gas Unit rm I I feed TOTail-gas Unit ~ Preheater I Preheater I I I Steam t I G-l I I furnace boiler Boilkr feed water 1 0 0 w Condenser Condenser p. 54. Simplified two-stage Claus process flow diagram. N2. From thermodynamic calculations. CS. Conversion with low water content. a change in the process kinetics should be expected. apparently due to a competition with SO2 and H2S for adsorption sites.. was found to be 2 to 2. to form a catalyst that is effective at temperatures higher than the dew point of sulfur [47-491. COS. thermodynamics provide a strong incentive to operate the catalytic converters at low temperature [3.5 times higher than that obtained with 35% water content. thus deactivating the catalyst by fouling [3. Ledoux. The results by Laperdrix. especially at low temperatures. 511 and/or decreasing the specific surface area and pore volume [23.0 1 Reactor Reactor Sulphur Pit Figure 1. a rapid deactivation was observed. Unfortunately. leaving free access to the active particles even at high sulfur loading [31. 561 and a decrease in H2S conversion [571. H2S and SO2 can be produced. Thermodynamic calculations indicate the possibility of reaching efficiencies > 99% [501. The adverse effect of water on alumina catalyst. Anon [191. oxycarbide or oxide of Si) to the hydrophobic part (i. However. particularly. Laengrich and Cameron [21..21. et al. extremely selective and stable catalyst for the oxidation of H2S into elemental sulfur by 0 2 at relatively low temperature. and Pearson 1591 recommended three or four catalytic converters operating under steady state conditions at low temperature.e. are reacted in the lower temperature catalytic reactors [381. et al. such as Sic.
It may also be limited by the rate of external mass transfer if the linear velocity of the gases is too low. such as Sepiolite with a structural formula Si12Mg~030(OH)4(H20>4. 58. Therefore. and Dudzik and George [651 suggested that the sulfur radicals formed during the reaction also act as a catalyst. Table 1 shows a comparison among the major types of gas-treating processes. the outlet temperature of the first converter must exceed 350" C. [641. However. Moreover. et al. 62.1. depending on the temperature and the vicinity of the chains. closely related to its ability to preserve activity through fouling. [341. but requires an excess amount of O2 [721. and (5) the influence of reversible and irreversible catalyst aging [23. by contrast. 691. the types and concentrations of impurities present. cobalt molybdenum on alumina.with activity declining. air pollution laws and specifications to be met. (531. of the three process types. 711. The adsorption process is limited to a low volumetric Environmental Progress (V01. such as the Claus process. but are easily poisoned by water vapor. Consequently.21. for the reduction of SO2 with H2. Under the reaction conditions. Steijns. Paik and Chung [171 reported a new catalytic system.8H20 61. [621. Under this condition. Sulfur formed in each stage is condensed and recovered in the sulfur pit to achieve maximum conver146 October 2002 sion in the reactors. as well as the least number of hazards and disadvantages. the desirability of sulfur recovery. and the reaction decays. 671. in elemental or combined form (HzS. et a1. as well as capital and operating costs [2. Dry catalytic processes based on the selective catalytic oxidation of H2S to elemental sulfur have recently been developed 1721. Many factors affect the selection of the gas-treating process including the volume. et al. followed by the Claus reaction to produce elemental sulfur over acidic alumina support [171. yielding water and new sulfur radicals. 781. 21. In this process. the deactivation process under the same reaction conditions and temperature should be strictly related to the texture and macroporosity of the catalyst. and in order to maintain higher conversion of H2S [71. while iron-based catalysts are resistant against water. As the exposed surface decreases and sulfur radicals stabilize and condense. has the highest efficiency at 94% to 97%. et al. The second and third reactors operate at their lowest possible temperature. H2S and SO2 conversion at equilibrium are lower [371. 42. it is preferable to use catalyst of small particle size and large macroporosity. et al. et al. are critical because the reactants can diffuse less and less towards the solid active surface as sulfur deposits are produced in voids and throats of the porous system. [511Alvarez. the primary purpose of the reaction furnace and the waste heat boiler is to oxidize approximately 1/3 of the H2S feed to SO2 so that stoichiometric proportions of these two main reactants are present for the reactors [211.0. Examples of commercial catalysts developed for the processes are the titanium-based catalysts for the MODOP process [73. its problems can be easily solved by using the correct stoichiometric amount of air. are thus [51. (2) the influence of the mass and heat transfer inside the catalyst. Guijarro. Dowling. which is the temperature of the sulfur dew point. No. and wet oxidation have been used for removing H2S from gases [14. deactivating the catalysts [23. 541. many commercial processes based on adsorption. the activity of the catalyst was greatly enhanced. and CS2) is treated in the amine system [5. in which all of the air and the acid gas pass through the combustion zone. The Claus reaction rate is reduced in the second and third catalytic converters because of lower temperatures imposed by thermodynamics. about 80% yield of sulfur could be obtained. 59. 41. There are two principal process variations [6. with the remaining acid gas sent to the first catalytic reactor. micropores in catalysts are useless as they are normally lost with the first gram of sulfur produced [621. the reaction rate expression must be known. Reaction is limited by the rate of internal diffusion through the porous particle [231. Vanadium oxide catalysts have also been reported to be active with a stoichiometric amount of O2 [77. 681. (4) the effect of sulfur deposition as a function of the operating conditions. (3) the effect of catalyst granulometry. Factors possibly effecting the rate expression are: (1) the so-called kinetics of the Claus reactions and of the reverse reactions. Mesopores and small macropores. 60. There seems to be no diffusional limitation to the reactants in the macroporous system of the catalyst u p to the studied level of Guijarro. 741 and the iron-based catalysts for the Superclaus process [75. Titanium based catalysts require a stoichiometric amount of 0 2 . 671. When the feed ratio of H2 to SO2 is optimized to 3. The second is the split-flow process. which would result in greater activity and longer life of the catalyst [661. and acid feed gas [61. The first is the straight-through process. and conversion [681. the conversion process. absorption. The catalyst is active and selective for the production of sulfur at significantly lower temperatures (around 300" C). temperature. The open structure should allow a better reactant flow through the voids. so does the accessible reactive sulfur. in which all the air and at least 1/3 of the acid gas pass through the combustion zone. 761. The life and performance of a catalyst. COS. according to Alvarez. SO2 is first totally hydrogenated to H2S on the metal sulfide phase. fuel gas. the catalysts have not yet been widely used. From the investigation of the performance of treated alumina as catalyst at low temperature. [511 and Pineda and Palacios [52. it is clear that. and pressure of gas to be processed. Unrecovered sulfur. which can generally be categorized as adsorption. To reach the highest possible conversion of COS and CS2. So far not enough information is available on reaction kinetics in the presence of catalyst [23.[631.70. 661. Alvarez.3) . In designing the reactors. absorption. the selectivity required. ALTERNATIVE TECHNOLOGIES FOR SULFUR RECOVERY Beside the Claus technology. lower H2S and SO2 partial pressure. et al. The selective reduction of SO2 to elemental sulfur occurs in two reaction steps. due to uncertainty about water poisoning effect and long-term stability [721. From Table 1. 281. Pineda and Palacios [521 concluded that by applying either acidic or basic treatments to optimize the textural properties.
0 2 enrichment of i the combustion a r can be used t increase the o processing capacity of an existing unit and to extend operation to low concentrationH2S feed. corrosion and foaming.02% in incinerated SCOT Off-gas. - to convert H2S to sulphur. Comparison of the alternative processes for sulfur recovery.g.Amine absorption - processes can be applied when H2S Concentration is relatively low (e. . periodically. solution. components selectively.Water vapour a f f e c t adversely the equilibrium of the reaction of H2S and SO2 over the catalyst.2o in Claus off-gas to 0. MEA process require The sulphur removed via higher solvent circulation this process is usually not recovered. The Claus process has proven very reliable and is considered a mature technology. - - - - - - . 0 2 enrichment improves sulphur recovery. MEA lowest solvent cost The advancementof and lowest hydrocarbon cointegrated gasification absorption relative to other combined cycle (IGCC) mine process.85% in Claus off-gas to 4Oppm in incinerated SCOT Off-gS. October 2002 147 Environmental Progress (Vo1.Processing streams having lesser amounts of H2S may result in combustion flame instability. Fog formation during sulphur vapour condensation. having low concentration of H2S. So2 and removal of certain mercaptans. regenerated. Part one of two. The kinetics are incompletely understood. all of the iron - - - - - Other components in the oxide becomes sulphided feed gas may react with and degrade the amine and its adsorptive capacity becomes exhausted.The sorbent bed has a limited capacity.~~ ~~ ~~~~ Table 1. The zinc sulphide formed Solution must be purged cannot be oxidised back to and fiesh amine added zinc oxide. Limited to gas streams of Safety is most important as limited volumetric rate H2S is extremely toxic. The sulphur rates and higher and sorbent both undergo regeneration energy. Can achieved high purity in treated gas. . Many absorption processes operating range.Overtime. Molecular sieves Solvent can be regenerated developed to extend the for reuse. - . disposal. MEA removes both H2S Molecular sieves can be and COznonselectively. MEA process has shown a higher tendency towards Limited capacity of sorbent bed. Adsorption Process Absorption Process Conversion Process 94 % to 97 Y o .Limited volumetric rate having low concentration of H2S.3) . Operate at nearly atmospheric pressure. power plants developsthe fluidised bed adsorption bed processes which are able t withstand severe o operating condition. H2S concentration can be reduced fiom 0. SO2 concentration can be reduced fiom 0 4 Y .21. Safety is most important because H2S is extremely toxic and quickly paralyses the sense of smell. Molecular sieves can be also removed COzand to a controlled to target the lesser extent COS. <5-25 mol %). . No. increase contaminant destruction and more reliable operation.The most widely used - - - . Safety is most importaut as H2S is extremely toxic.
Suitable to employ various Claus tail-gas treatment processes. 1 catalyst bed and 1 sulphur condenser. and produce minimum ecological impact with a tail-gas treatment unit [40.Table 1. 1 condenser and a series of catalytic stages. . (2) based on familiar technology and easily adapt to existing Claus units. operating between 130" C and 150" C. 1 condenser . and containing conventional Claus catalyst. among the three. usually an indirect-fred unit with stainless steel tubes. one reactor is in service while the other is being regenerated. sometimes. (3) generate no secondary air/water pollution or waste. . ~ of feed gas with high ecological impact with a tail-gas treatment. developed by the Societe Nationale des Petroles d'Aquitaine (SNPA) and Lurgi Gesellschaft GmbH.3) 148 October 2002 .High operating costs due to sorbent materials disposal. Gas from the reactor is then incinerated. the tailgases were usually exhausted to atmosphere through a stack without any treatment. The former consists of processes which allow the Claus reactions to take place under more favorable conditions. Sometimes the gases were incinerated after leaving the last converter. The Institute Francais de Petrole (IFP) developed a treating process used for Claus plant tail-gas cleanup.Also affect workers' health. The gas is then cooled and the sulfur vapor condenses. At the same time that the capabilities of the conversion process have dramatically improved. In the adsorption process. uses a vapor-phase extended Claw reaction carried out below the sulfur dew point. the SNPMLurgi Sulfreen. The Claus process has also proven to be very reliable and mature [691. Claus technology has to be improved to obtain higher recovery rates. . depending on the process selected [51. Several processes have been studied for application as a Claus plant tail-gas cleanup service [2.The sulphur removed is . and (4) deliver a high degree of desulfurization over a wide range of operating conditions. The Sulfreen design uses a closed regeneration loop containing a sulfur condenser and a regeneration gas heater. heavy installation costs [91. While one reactor is on adsorption cycle. and the IFP processes . most Claus plants are unable to meet existing or proposed air pollution regulations in developed countries without additional methods of reducing or eliminating the sulfur content of the exhaust gas [5. Gas is returned to the Claus cycle just downstream of the first Claus sulfur condenser. 501. 1 cooler. feed rate containing low concentrations of H2S.2 adsorption towers. CLAUS TAIL-GAS TREATMENT TECHNOLOGIES In the early Claus sulfur recovery plants. Many commercial processes are based on low temperature Claus reactions or on the removal of H S from tailgases by absorption and adsorption 16 I. including sulfur recovered in the Claus main unit. The process operates in the same temperature range as the CBA method. costs . there are two broad classes of tail-gas cleanup treatment [21. and. As the need to reduce SO2 emissions receives greater emphasis. Hot gas from the first Claus reactor vaporizes the condensed sulfur and reactivates the catalyst.The disposal of sorbent material also affects the environment. . shifting the equilibrium towards higher conversion.Consists of 1 combustion furnace. as it is expensive in terms of investment and energy consumption. The Sulfreen process. 791. A Claus tail-gas desulfurization process should preferably be: (1) easy to operate and flexible. Environmental Progress (V01. 1 heat exchanger. . these processes require batch or periodic operation. These processes claim an overall sulfur-recovery efficiency of approximately 93%. Three processes under this group are Amoco's Cold Bed Adsorption (CBA). solvents leakage can affect the surrounding ecology. Comparison of the alternative processes for sulfur recovery. 8 Generally. . Part two of two. 661. At the present time. gas from the main Claus plant last condenser is fed to an adsorption reactor. 1 reboiler. No.Chemical and physical generally not recovered. Ecological Impact c . innovations and process optimization have reduced its capital and operating costs [ll. However.1 absorber. 1 waste heat boiler. 1 regenerator. with the produced sulfur being deposited on a alumina catalyst bed. regeneration for removing sulfur deposit from catalyst surface leads to a decrease in sulfur storage capacity and in initial desulfurization activity [31.High solvent costs. The low temperature favors equilibrium conversion. as illustrated in Figure 2. therefore it affects the environment. In the two-reactor case. However. can treat large amounts of feed gas with high H2S concentration. Only the Claus process.21. each employing 1 reheat. a second reactor is being regenerated. Adding a tail-gas cleanup process should be the last resort. Sulfur vapor condenses on the bed and is removed. and the SO2containing tail-gas was passed through a tall stack [581.
Bed B * (Regeneration) in which the tail-gas from the Claus unit is contacted by an IFP solvent. no fuel or steam is required except the condensate for make-up. No. The SOx is then sorbed onto a solid sorbent. The Mobil Oil SO. (1) Shell Claus O f G s f .rn Tail-gas Cleanup Treatment 99% sulfur (1) Amoco’s Cold Bed Adsorption (CBA) Process (2) SNPALurgi Sulfreen Process (3) IFP Process Figure 2. In normal operation. a high boiling point glycol.a Treating (SCOT) Process (2) Beavon Process (3) Wellman-Lord Process + recovery efficiency Stack Reducing gas steam L r i Sorbent Bed A (Sorption) sulfur - . liquid sulfur accumulates at the bottom of a packed contacter and is withdrawn. This entire process occurs above the sulfur melting point. which can then be recycled to the Claus plant for further processing. Treatment (MOST) process consists of combusting the Claus tail-gas with air. and the sulfur is reductively desorbed as a concentrated stream of mainly SO2 and HlS. As sulfur has low solubility in the IFP solvent. *. Major tail-gas cleanup treatment processes. converting all sulfur species to SOz/SOg [801. Both HZS and SO2 are thus absorbed.21. The Claus reaction then converts these compounds to sulfur.++ ) . Simplified MOST process flow diagram [391. Solvent is circulated back to the Environmental Progress (V01.3) top of the tower. Treated gas leaves the top of the tower and is incinerated.orbent Regeneration off-gas Figure 3. Catalyst screening for this October 2002 149 .
and the Wellman-Lord processes. stoichiometric HzS/SOZ . No. The concentration process is similar to the amine gas sweetening process commonly used in gas processing. 811. Bed A is loaded with sulfur. % H2S and 20 vol. and quickly paralyzes the . which contains 1 to 4% 0 2 . goes to sorbent Bed A.Requires good control of SOz over the catalyst. . while Bed B had its sulfur removed. The tail-gas contains some H2 and CO. In the reduction section. uptake. the valve positions are changed. Environmental Progress (V01. and 2 CBA processes for Claus plant.9%. A conventional stripper can be used to strip the acid gases from the solvent. The cooled gas. 3-Stage Claus with Tail-Gas Cleanup Unit indirect reheat Conversion efficiency (Overall recovery capacity) 95 % 97.The kinetics of the Claus . [391. A simplified process flow diagram of the MOST process is shown in Figure 3. 1 CBA. The SCOT process consists of a reduction stage. et al. At this moment. is then incinerated. - - application focuses on examining alumina and magnesium aluminates. causing the regeneration gas to flow through Bed A a n d the tail-gas to flow through Bed B. switching valves and the . The remaining tail-gas. and a vanadia/ceria-promoted. According to Stern. At the end of the cycle. all sulfur compounds and any free sulfur in the Claus tailgas are completely converted into H2S with H2 or a mixture of Ha and CO over a cobalt/molybdenum on alumina catalyst at a temperature of about 300" C [44. The hot gas is then cooled. and platinum. magnesium aluminate (V/Ce/Mg2A1205) spinel. is then countercurrently scrubbed by an alkanolamine solution in an absorption column [51. These gases are recycled to the Claus plant inlet. sulphur condenses on the . [391.8 % - 2-Stage Claus (96% recovery) with 1 CBA stage in tail gas cleanup unit Up to approximately 99 % 2-Stage Claus (96% recovery) with 2 CBA stages in tail gas cleanup unit Up to approximately 99. Reducing gas flows through Bed B to desorb the sulfur as a concentrated stream of H2S and S 0 2 . the MOST process. and water is condensed in a cooling tower. . the SO2 level in the effluent from the sorbent bed is below 1 ppmV [801. respectively. the Beavon. et al. vanadia.One major problem can multiple reactors. which can combust sulfur containing species and selectively capture SO2 produced. which is then diverted to the Claus unit. offers operational advantages over other wet scrubbing processes.3) October 2002 .5% Hzrs & aad Disadvantages . The tail-gas is then sent to the stack. Three commercial processes of this type are the Shell Claus Off-Gas Treating (SCOT). The process is described in detail by Stern.Fog formation can also ratio. A simplified flow diagram of the process is shown in Figure 4.Mechanical and maintenance problems associated wt the gasih switching valves and the regeneration gas blower and heater. where effective SO2 oxidation promoters are required.Requires good control of stoichiometric H 2 S / S 0 2 ratio. During most of the adsorption period. Comparison among three-stage Claus.HzS gas extremely toxic bed. with 54% and 46% SO. followed by a concentration stage that provides a H2S-rich stream to be recycled to the Claus plant. normally containing 200 to 300 ppmV HzS. The burner effluent. The process requires multiple reactor. This level corresponds to about 300 ppmV or less total sulfur in the exhaust gas. The materials with the highest SOx uptake are a commercial FCC SOx transfer additive. be a problem during Catalyst activity condensation of the gradually declines as sulphur vapour.Table 2. . The tail-gas is sent to a burner which oxidizes the remaining H2S to SO2 and SO3. where adsorption of the SOx takes place. . . 150 The second class includes processes capable of achieving overall sulfur recoveries in the range of 99.Water vapour affect regeneration gas blower adversely the equilibrium of the reaction of HIS and and heater.Catalyst activity gradually declines as sulphur condenses on the bed. The SCOT process has been designed for minimum pressure drop so that it can be easily added to an existing Claus unit. which normally contains up to 3 vol.The process requires sense of smell.21. Part one of two. with oxidation promoters such as ceria.Mechanical and maintenance problems process are incompletely associated with the gas understood. occur with the operation of the main burner (on reaction furnace). % C 0 2 .5% to 99.
1 CBA.Has proven very reliable . 1 condenser and 1 blower for addition. . ~ ~~ Reliability & Advantages Plant capacities Ecological impact costs a more stable flame. Comparison among three-stage Claus. . Problems have occurred with H2S spikes during the regeneration procedure which have resulted in occasional environment violations.Capital cost to convert is about % that of the Claus plant.Can reduce SO2content . highoperation.Can reduce SO2content . - .Use of modem. . - built a 1500 ltd sulphur plant with CBA near Calgary. mercaptons. not reduced. Poisoning by H2S. . . Much better contaminant destruction for compounds such as hydrocarbons.Has the lowest cost because no tail-gas treatment unit.Improved Claus thermal conversion. . .Example. - . efficient mixing equilibrium conversion.Low energy intensity. favours . Sulphur recovery units of 50 ltd or larger normally require a tail gas cleanup unit. Part two of two. Requires 2 reactors. A new sulphur recovery costs 1.More efficient at higher costs. . In most U.Table 2. etc.3) October 2002 151 . especially with leaner feeds. Nowadays. a sulphur recovery unit of 20 Itd or larger will require some form of tail gas cleanup. .Requires little plot space and only minor modification to an existing plant.Improvements are being made in better Claus catalysts and improved process control. constructionand materials proven in the Claus plant. .Uses the same to about 1500 ppmv.Safety is very important in plants handling and processing hydrogen sulphide gas. .Low energy .Levels of COS and CS2 are not reduced very much. - . states. and 2 CBA processes for Claus plant. NH3. and much wider turndown or turnup operations.260°F to 300°F for equilibrium conversion.S. Amoco .5 times more than a standard 3-stage Claus unit. main burners can result in . .Level of COS and CS2is .In Canada.21. 4 reactors. - construction and materials proven in the Claus plant. . operation. favours mature technology. No.Uses the same to less than 1000 ppmv. units without tail gas treatment cannot meet the regulations. 2 condensers. . .260°F to 300°F for and is considered as consumption. However it is the least efficient and unable t meet the o specifications. 2 blowers.Produce more but need more equipment and energy.Two new sulphur recovery units cost 3 times more than a standard 3-stage Claus unit. therefore affecting the surrounding air quality.Capital cost to convert is about that of the Claus Dlant. consumption.Reduced or nil oxygen breakthrough. Environmental Progress (V01.
In this process. and contacted by a sodium carbonate-bicarbonate solution at a pH > 7 to scrub o u t any SO2 that might have passed t h r o u g h t h e catalyst bed without being reduced.3) i 152 October 2002 . then cooled to about boo C and fed to an absorber. the Claus tail-gas is incinerated. developed by Ralph M.5%overall sulfur recovery. where the H2S in the feed gas is absorbed and oxidized to sulfur. as the Wellman-Lord process removes sulfur after the tail-gas is incinerated. Tankage can be added to allow operation for u p to three days while the regeneration cycle is down. Germany. the IFP. the solvent is also treated with sodium hydroxide. CS2 and CH SH for the reactor are low. at Wintershall AG. Simplified process flow diagram of the SCOT process. filtered. The Beavon/Stretford process can reduce sulfur emissions to several p p m . which is also used to maintain a temperature between 315" C and 370" C [821. and melted [821. The SO2 gas is recycled to the front end of the Claus unit. To complete the regeneration process. Comparison among the Sulfreen. The first industrial unit.Fuel Air t Fuel Emuent Recycle to front end Claus Unit e l Uni Furnace I ~~ Air Absorber Regenerator 9 Reactor Reactor Effluent Air SWS Stripper The Beavon process. aimed at 98. Sodium sulfide crystals precipitate here. a two-stage Claus with o n e CBA unit and a two-stage Claus with two CBA units. tail-gas from the Claus unit is first treated by a reducing gas over a cobaltmolybdenum catalyst to convert all sulfur-containing species to H2S. has been used in several Claus tail-gas cleanup units [821. and Environmental Progress (V01. which is used to dissolve the crystals. Residual concentrations of COS. Steam is used to drive off the SO2 and much of the aqueous solution in the evaporator/crystallizer (831. a n d has performed very satisfactorily. The recovered sulfur forms a I Figure 4.21. The solution reacts with SO2 to form bisulfide. The cooled gas then goes t o a Stretford absorber where it is contacted by a sodium carbonatesodium bicarbonate solution containing sodium vanadate. gas usually contains a significant portion of the required reducing agents. In the Wellman-Lord process. The reduced gases are t e n cooled in a condenser to about 150' C to 190" C. washed and dried. The Claus. where it is contacted by a sodium sulfide solution. Additional reducing gas is supplied by an auxiliary burner. Air is then used to oxidize the vanadium back to the pentavalent state. but is less effective than the SCOT process in removing CS2 or COS. or mitigating any CO which may pass through the Claus plant [391. Parsons Company and Union Oil of California. Additional holding time for this reaction is provided by a reaction tank. started in January 1978. The H2S/S02 ratio control is not critical. Table 2 provides a comparison among a three-stage Claus with indirect reheat unit. Gas from the evaporator/crystallizer is cooled to recover most of the vaporized water. forming a slurry.5 to 99. froth at the top of the oxidizer which is skimmed off. and an oxidation catalyst. No. Linden. reacting with any remaining bisulfide to form sodium sulfide and water.
4 % Clam plant (94% recovery) wt SCOT ih process tail gas cleanup unit 99. monitored by an analyser. Low operating ternperatwe at 125OC. . Comparison among Sulfreen. presenting a new set of operating problems. .Absorption column is aimed at achieving essentially complete removal of H2S while coabsorbing only a fraction of the C02 present.Flexibility and overall process reliability are . CS2 in the Claus tail gas for optimum performance. .High temperature needed - . Retrofit is not complicated as installation requires little plot space and does not recycle any gas to the Claus feed.Air control needed for correct H2S/S02ratio. Can be designed to operate from 20% of design fedrate up to full rate.~ ~~ Table 3. - - .1 %to 99.Controlled bum-off catalyst is not critical. .3) October 2002 153 . . . .Facility is compact. No fuel or steam is required other than condensate for makeup. . IFP.More complicated than CBA process. . . . . for catalyst at 575°F. .Require careful operation of the parent sulphur plant to achieve maximum recovery.Not very energy efficient.Some H2S is oxidised by injection of a small quantity of air.21. low H2S content.Operation of an IFF' installation is quite different fiom the parent Claw unit. and low volatility reducing solvent losses. .Catalyst life is good. operating temperature is quite low at 2609: to 300OF. N0.Presulphiding of the good. making SCOT process easier to operate.Recovered sulphur is high quality.Not a good selection for direct treating of the tail gas from Claus plant that processes a feed gas with a high C02. Part one of two Tail-Gas 2-Stage Claus (95. .The concentration - process is similar to the mine gas-sweetening processes. IFP solvent has good thermal and chemical stability. .Limited by equilibrium conversion and sulphur vapour pressure losses. . and SCOT processes for Claus plant.The reduction step converts essentially all sulphur-containiig compoundsto H2S.The simplicity of operation makes operator familiarisation more simple. .Changes in the feed have only a small effect on - Environmental Progress (V01. Proper operation of the Claus plant is required to miniiise COS.Mechanical and maintenance problems associated with the gasswitching valves and the regeneration gas blower and heater. in order to provide an optimal H2S/S02ratio at the Sulfieen reactor inlet.9 + % .5% ih Cleanup Unit recovery) wt Sulfieen process tail gas cleanup unit Conversion efficiency (Overall recovery capacity) Upt to approximately99% 2-Stage Claus (95% recovery) w t IFP ih process tail gas cleanup unit 98. followed by resulphidmg is said to restore catalyst to its original activity.Some difficulties present in the CBA and Sulhen processes.
For a new facility with keeping initial and of the Claus unit cost for operatingcosts down. COS and CS2 cos.Table 3. 1 solvent heater 40 Sulfreen units in virtually complete operation (in 1992)after for start up. 2 reactors using Capable of reducing the From 10 todstream day conventional Claus SO2content of the (sulphur intake) to 2100 catalyst beds. Comparison among Sulfreen. Utility requirements per 75-85% of the Claus unit. and SCOT processes for Claw plant. No. The IFP solvent is Capital costs equal to the Sulfreen investment relatively inexpensive. construction. Most widely used. Can be designed for minimum pressure drop to make it more suitable for add-on installation.D e not affect CS2and cause health problems. IFP. Produces no secondary waste streams. with capacity from 3 to 2100 tpd of fresh sulphur feed. overall sulphur recovery. can cause air pollution. 130 units (in 1992) are committed. 1 regeneration low as 1000 ppmV. - - - - - - - - - - - - - 154 October 2002 Environmental Progress (V01. . Operating costs are much lower than solvent-based Drocesses. 1 incineratedtail gas to as todstream day equivalent condenser. SCOT design optimised the conventionalversion for the best possible fit.With an excess of H2. Part two of two. CO in significant quantity can COS and CS2in the Claus in significant quantity.3) .Require only a contactor. . .e. amounts to 30% to 45% . costs of the Claus plant. residual and 5 presently under S02contents-= 10 ppm). . Proper operation of the Tail gas contains some The tail gas contains H2 and CO which is toxic Claus plant to minimise some H2 and CO.catalyst about 4 lb for conventional version and 5 Ib for the improved version. conversion of elemental Claus units &om about 50 Sulphur and SO2 into H2S to 2200 tpd of sulphur is obtained (i. ton of sulphur: electricity 300kW. and 40% to 55% for the the cost can be as low as improved version.21. Claus capacity. gas heater. Proven and familiar equipment is used in each step of this process. os tail gas.Reduces the sensitivity of the overall sulphur recovery facility to variations in the air supply rate. 1 pump.
. Claus plant wt Beavon process ih Tail-GS Cleanup Unit tail-gas cleanup unit Conversion effciency (Overall recovery capacity) Hazards& Disadvantages 99. .High capital cost because it requires . Total investment is approximately costs equal to that of the parent Claw plant. Comparison between Beavon and Wellman-Lord processes for a Claus plant.A bleed stream must be treated to take out sodium sulphate.HzS/SOzratio control is not critical to design tail gas treating.9 + Yo .No tail gas incinerator is required during nonnal operations.and Germany.Big space is needed. Selectox plants are in the U. .- Table 4.A reaction tank can provide additional holding time for reaction. . - .At high temperature around 600 to .S. . . 2 Beavon.To achieve SOt emission level at 200 ppmV or less.Absorber plugging.21.Some sections of the unit are coated process have limited its application. reduction of catalyst changeouts and any mechanical failure.The clean tail gas containing less 10 ppm HzS when using the newer solvents. . There are more than 15 Beavon MDEA plants in the U S and Japan. Ecological COS gases are treated by the Stretford impact process.Capital cost about 130-150%of the parent Claus unit for a 100 ltd unit. .Process chemistry and equipment are not familiar to many plant personnel. Environmental Progress (V01. - .After cooling in the reactor.4 Yo Claus plant w t Wellman Lord ih process tail-gas cleanup unit 99.Residual concentration of COSY CSz and CH3SHfiom the reactor are low.Plugging in the sulphur fioath lines. The exit gas is discharged with no further processing. . . thus compounding operating and training difficulties. To be able to achieve 100 ppmV or Plant capacities less total sulphur in tail gas. . exotic metallurgy. - .Suitable for add-on installations to any type of sulphur recovery plant if adequate plot space is needed. All pressures are near atmospheric. .The reducing catalyst life is only about 2 years.Concerns over vanadium used in the Reliability & Advantages every 6 months.CSZ. which are highly selective mine type solvents. HzS. High operating costs for sour gas disposal during absorber clean outs every 6 months. .Tankage can also be designed into the with plastic to avoid corrosion by deposited sulphur. This process is well-suited for high COz streams as it does not recycle C02with the SO2. - o facility t allow design operation for up to 3 days while the regeneration cycle is down.Absorber has to be clean-out about 700°F. N0. . .3) October 2002 155 . .
By considering the advantages and disadvantages of all the six methods in Tables 2 to 4 ... ... then the SCOT process is a good selection for direct treating of the tail-gas. This should help in a preliminary determination of the system for a particular requirement. The SCOT process can also be designed for minimum pressure drop. Vanadium/silica (V/SiO2) catalyst shows a decrease in the yield when excess water is introduced in the feed.sprbept. MODOP and Superclaus processes seem to be very attractive as they can convert H2S directly to elemental sulfur by selective catalytic oxidation and do not require periodic operation [91. . However. . One of the most important features of the SCOT process is that it can operate from 20% of design feed rate to full rate. Several companies are investing large amounts of money to improve the sulfur recovery process. Therefore. Superclaus uses ten times more 0 2 than the stoichiometric amount for converting H2S to sulfur.. Using excessive H2.. The sulfur formed can be separated from the almost completely converted gas emerging from the adsorptive reactor in a single stage of condensation. - Sulphur- the SCOT processes are given in Table 3... and (2) consider a Claus sulfur-recovery unit plus a tail-gas unit as a last resort.. The development unit at Courtaulds’ is part of BOC Gases’ program to develop the next generation of oxygen-based Claus processes and burners. with good catalysts. An alternative strategy that is much more thermodynamically efficient is the in situ adsorption of water inside the reactor using a packed bed with a mixture of catalyst and zeolite adsorbent [85l. . . Several new technologies are being studied or developed. Courtaulds already has a large Claus unit at its carbon disulfide plant. . its ability to cope with changes in the feed conditions minimizes any effect on overall sulfur recovery. % water vapor in the feed. Conventional technology for carrying out the Claus reaction involves a series of fixed bed catalytic reactors. The capital cost can be as low as 75% to 85% of the main Claus unit if the design is optimized [441. UK. as illustrated in Figure 5. .. Yo. it is clear that the SCOT process is generally the most suitable for a tail-gas treatment unit.. whereas the Superclaus catalyst is limited to H2S concentration of less than 5 vol. Part of the feed stream to this unit is diverted to the development unit. . current technology might not be able to cope with increasing capacity and concentration of H2S in the acid gas... Manchester. .. the amine system in the SCOT process is much easier to operate compared to other processes. Tables 1 to 4 summarize the recovery capability of several sulfur recovery systems.. the SCOT process can achieve a residual SO2 contents of less than 10 ppm. Therefore. thus making it more suitable for add-on installations. A Claus plant with a SCOT unit can achieve conversion of 99. Recently. .3) . and cannot be applied to treat H2S higher than 5%. .. Moreover. Moreover. Superclaus seems to be superior to MODOP since the catalyst for the former can tolerate the presence of water. . with interstage removal of sulfur by condensing the product vapor stream. The catalyst is known to show little decrease in the sulfur yield. If the feed gas to the Claus plant contain a low CO2 concentration and a high H2S content. The SCOT process... It is also quite environmentally-friendly since it produces no secondary waste streams. . is very reliable and flexible to disturbances. . POSSIBLE IMPROVEMENTS IN TAIL-GAS TREATMENT PROCESSES Claus sulfur recovery units at existing installations will need to process significantly more sour acid gas in the future. even in the presence of 30 vol.wat<r: . This allows high conversions in a single-stage Claus process. . ranging from the simple to the complex.(zpt)l&+) : b’..No... and other technologies are under further development. while Table 4 illustrates the comparison between the Beavon and the Wellman-Lord processes for a Claus plant. . the more stringent environmental regulations in the future might force some plants to shut down.3: .. .. and recovered sulfur plus the residual gas stream are both returned Environmental Progress (v01. .. . . . as shown in Figure 1.:c:ata&st. Several changes and new trends are currently being studied. . For example. BOC is investing in a development facility to improve the SURE oxygen-based Claus sulfur recovery process at Courtaulds Chemicals’ carbon disulfide production plant at Stretford. The sulfur-free gas can then be reheated and used for the regeneration of the second adsorptive reactor [851. it is claimed that Fe-Cr/Si02 catalyst can give sulfur yields of more than 90% at the Superclaus condition [841..9% or more. The use of a stoichiometric amount of 0 2 with V/SiO2 is possible to treat highly concentrated H2S I31. The following is a simplified guide for selecting a sulfur-recovery process configuration: (1) try a “best 156 October 2002 current technology” Claus sulfur unit first. The Claus system can be made more efficient by enriching o r replacing the combustion air with 0 2 .21.
The company plans to use a special ceramic membrane to separate the produced H2 from the elemental sulfur. thermal problems. No. protection of soldiers from chemical agents. efficient means to supply or remove heat from any large-scale membrane reactor will have to be developed. the relationship between micropores and macropores. Therefore. A non-permselective ceramic catalytic membrane reactor for the Claus reaction [861. 911. The active components of the catalyst can be easily incorporated within the membrane. By feeding the reactants on both sides of the membrane. as shown in Figure 6. This allows greater flexibility of the reactor to feed rates of H2S and S 0 2 . the combination of membranes and fluidized-bed reactors are advantageous because fluidized beds provide good temperature control. According to Adris and Grace [921 and Mlezko. which would provide effective conversion of H2S and SO2 during the entire period of adsorption until the reactor October 2002 157 . et al. Alberta). They have produced calcium oxide crystals coated with iron oxide. I901 suggest that the membrane reactor shown in Figure 6 can be used for kinetically fast exothermic heterogeneous reactions. The composition of the feed to the BOC development facility can be modified to represent virtually any commercial installation. et al. both of Kansas State University. However. Furthermore. accurate controlling of heat balances of the membrane reactor will be a major task for any large-scale industrial unit. are developing a sulfur content removal technique. In another development.e. The membrane functions as a physical barrier between the reactants which are fed to the Environmental Progress (V01. premixing of the reactants is avoided.650" C is being studied by the Alberta Sulfur Research Laboratory (ASRL). offering a greater surface area and a coating that helps increase the reactivity of calcium oxide with the acid gases. B61. et al. It is also often desired that all the products of a reaction be directed to one side of the membrane. such as the formation of explosive mixtures and the occurrence of thermal runaways. The H20 Figure 6. Kenneth Klabunde and Shawn Decker. and the removal of chlorinated compounds. a homogeneously active membrane can be produced by using sintered stainless steel as the membrane for the concept of separated feed of reactants [891. Any variation in the molar fluxes of the reactants will result in a shift of the reaction zone without affecting the reaction stoichiometry [861. This can be achieved by applying an overpressure at one side of the membrane to generate the combined effect of convective and diffusive flows [87-891. Therefore. including an alternative to incineration of industrial waste.370" C and 1. The 7 nm crystals are twice as efficient at removing SO2 as the current method.4SO2 + S + to the main Courtaulds plant. This reactor type has specific advantages for reactions requiring strict stoichiometric feed of reactants. Figure 6 also shows the arrangement of the ceramic membrane reactor for carrying out the Claus reaction 1861. Veldsink. 1931. Much attention is paid to the search for an optimum porous catalyst structure. will not take place "90. A new configuration of catalytic membrane reactor. the produced sulfur should be directed to the SO2 side [871. Calgary.21. research program will also develop computational fluid dynamics models for detailed kinetic studies of the Claus process. i. ASRL has built a semi-works unit and installed it at Petro-Canada's Wildcat Hills plant (near Cochrane. consists of two chambers separated by a non-permselective ceramic membrane. Klabunde also perceives many other possible applications for his research. RESEARCH ON NEW CONCEPTS FOR REMOVAL OF H2S FROM TAIL-GASES Thermal cracking of H2S at temperatures between 1. In this case. The laboratory is also working on a further development stage of the thermal cracker in which the ceramic material will also serve as a semipermeable membrane to allow the removal of H2 formed in the cracker..3) opposite sides of the membrane. introduced by Sloot.
Under modern 158 October 2002 1. Photochemical 194-971and plasmochemical [98-1031 technologies are still in the development stages and are not mature enough to be applied to large-scale chemical processing. Based on the considerations in this review.3) . membrane. while energy for cell metabolism is provided by incandescent light and H2S oxidation [201. while the electrochemical technology is established in certain areas. However. it is important to explore new ways of H2S and SO2 elimination which will lead to high conversions at minimum cost. As an alternative to the physico-chemical processes. Laengrich. Several changes and new trends in the conversion of H2S and SO2 to elemental sulfur have also been highlighted in this review paper. proper equipment materials. but its application to H2S requires further development. photosynthetic bacterium. The SCOT process is the most reliable and flexible to disturbances. Electrochemical technology [1041101 is established in certain areas. Two examples of the recent improvement in the Claus tail-gas treatment process are the introduction of the non-permselective catalytic membrane reactors and in situ water separation by zeolite f adsorbent.switches into the catalyst regeneration mode [661. the following two processes for the conversion of H2S and/or SO2 merit further analysis to act as the basis for a prospective commercial technology: (1) catalytic thermal decomposition at reduced pressure between 1. membrane technology.21. and environmental pollution reduction. the application has to wait until the technology matures to less demanding processes. the Sulfreen. Special appreciation is due to Professor Mojtaba Ghadiri for his various supports.R. a Claus tail-gas cleanup treatment is essential to achieve very high sulfur recovery efficiency. the local energy situation and/or the environmental regulations. the source. is essentially a technology for the future. 4th Edition. CONCLUSIONS environmental regulations in developed countries. The catalyst efficiency in tail-gas treatment processes is determined not only by the relation of micropore and macropore volume. A. New York. but also by the number of micropores that the reactant molecules must go through to get from one macropore to the next [661. making different processes desirable based on plant size. Photochemical and plasmochemical methods are still in the development stage. Established tailgas cleanup processes are Amoco's Cold Bed Adsorption. thermal diffusion. and the Wellman-Lord processes. "Tail-Gas Clean-up Addition May Solve Sulfur Plant Compliance Problem. Environmental Progress (V01. The autotrophic bacterium utilizes C 0 2 as carbon source. could convert H2S to elemental sulfur in a single step at atmospheric conditions." Oil and GasJournal.L. NY. March 20. Almost all the H2S could be converted in a residence time of a few minutes. not be a universal approach for the selection of a desulfurization process. the IFP. and knowledge of possible side reactions. Kirk-Othmer. The economics of a process may be influenced by diverse factors. resource utif lization. In addition. such as biochemical and biomedical separation processes. ACKNOWLEDGMENTS The author would like to acknowledge the assistance given by Mohd. John Lamb of University of Surrey for their helpful comments and suggestions. in fact. The larger the volume of micropores. 1978. Research for an optimum porous catalyst structure is ongoing in order to obtain a relation of micropores and macropores which would provide effective conversion of H2S and SO2 during the entire period of adsorption. resource utilization. temperature and concentration of H2S. Of the thermal methods. Cameron. but its application to H2S requires further development in the area of storage and disposal techniques. LITERATURE CITED The modified Claus process is the major technology currently used to recover elemental sulfur from H2S and SO2. and the smaller their size. Moreover. (2) the unavoidable production of H2S from gas plants. In fact. No. 1996. currently with the National Petroleum Company of Malaysia (Petronas). 1 1 came up with an alternative route 1 for the utilization of H2S by breaking it down to its constituents. and (2) two-step sulfide processes in the temperature range of 500" C to 650" C in fluidized bed reactors as reactorregenerator systems. Appreciation is also due to Yasser Hussain. the greater the amount of sulfur that can be extracted by the catalyst. Studies and research o n the Claus process mechanisms and technology have been described. The interest in utilization of H2S as a source of H2 and sulfur has intensified in recent years due to: (1) global prospect for hydrogen energy and waste minimization. it is unlikely that electrochemical processes can be competitive at today's electricity costs. refineries and metallurgical processes. pp 158-162. A suitable technology for the production of H2 and sulfur must meet the triple objectives of waste minimization.000" C and 1. the Beavon. John Wiley and Sons. there may. [201 demonstrated that the anaerobic. For chemicals as difficult as H2S. the SCOT. Chlorobium thiosulfatophilum. Basu. Raymont [LO. 2. A number of current commercial technologies for the recovery of sulfur from sour acid gas have also been described and compared. and the smaller the sulfur losses in the vapor phase. pp 432-445. et al. Therefore. which appears very attractive. and W.200" C in a fixed bed reactor.and environmental pollution reduction. and (3) the cost of a tail-gas clean-up process for Claus plants that can exceed the value of the recovered sulfur if the environmental regulations are made more stringent [81. Vol. Encyclopedia of Chemical Technol- ogy. Ron Towers and Dr. high concentrations of H2S or organics did not seem to affect the conversion efficiency. to increase sulfur recovery. Rusydan Abdul Naim and Ikhsan Masadi. and solar technologies have not yet developed very far [81. 23. The success in the utilization o H2S by breaking it down to elemental sulfur will signlfy the attainment o the three objectives of waste minimization.
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