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New simulation techniques can clearly define sulfur reactions and processes for TGTUs
M. Kilian* and G. Wozny** Due to global environmental rules, the sulfur content of fuels is steadily declining. The European Community is lowering the sulfur levels in gasoline and diesel to below 50 ppm beginning in 2005 under the Auto Oil II Programme. Similar programs are underway in North America and other developed regions. Refiners are endeavoring to separate more sulfur compounds from fuel products. Thus, final treatment units must manage even higher volumes of sulfur compounds-in particular, increasing volumes of hydrogen sulfide (H2S). Refineries will need to efficiently expand tail-gas-treating units. Selecting the proper sulfur removal process is not a straightforward decision, especially if the facility has an existing sulfur recovery unit (SRU). So what are the options? Using a process simulator can provide an opportunity for refiners to consider several treatment options. In the following case history, a process simulator is used to evaluate critical data and processing conditions to determine the best hydrodesulfurization and tail-gas treating options for this base case.1 Low-sulfur fuels. To produce and blend lower-sulfur content fuels, refiners have several processing options to consider. Separating sulfur components from feedstocks and refinery product streams will generate more H2S. Hydrodesulfinization processes use hydrogen at elevated temperatures to remove sulfur from fuel-product streams in the form of H2S. As a consequence of this heightened activity, sulfur recovery efficiencies must increase annually. In the near term, the refining industry will need to retrofit existing SRUs as well as install new facilities. Many options. Many tail-gas-treating processes are available. However, selecting the proper sulfur removal methodology is not straightforward decision. Conventional Claus plants are no longer capable of reaching the required sulfur recovery efficiencies (SREs) as shown in Table 1. Tail-gas treating units (TGTUs) using the sub-dewpoint, selective oxidation or SCOT principle and others are necessary The depth of the desulfinization depends on regional and predominant environmental regulations.
The calculated adiabatic temperature for the reaction furnace (RF) is 1. while ensuring a high onstream factor.0 98.9 (99.5 -type) (99. Plant and project engineers can evaluate different gas-treating and tail-gas cleanup processes. The reheaters were modeled as direct-fired fuel gas burners (100% methane). Existing New plant. % 97. can narrow the potential technology options to a smaller list to do more in-depth studies. % % 98. For the presented example. we will assume a typical acid-gas feed composition (mol%) of: • • • • 90% H2S 4% CO2 5% H20 1% C2H6.8 SCOT 97.513) Capacity <10 t/d 10-20 t/d 20-50 t/d 50 t/d New plant. and the bottom temperatures for the catalyst beds of 313 °C.0 99.0 95.0 97.0 97.0 99. Current (in planning) environmental regulations for several countries Sulfur recovery Germany Italy New plant. The kinetic reactions have also been calculated over the waste-heat boilers (WHB) where the gas is cooled rapidly. The amount of air to the inline burner is delivered so that no oxygen breakthrough occurs to the catalyst bed (95% stoichiometry). Many parameters and process characteristics impact which methodology will delivery the sulfur-removal efficiencies at the least cost.0 97.0 96. 204 °C and 189 °C respectively. Applying process simulation tools. The calculated outlet temperatures of the direct-fired burners are 245 °C.0 98.241 °C.0 97.5 Ranking TGTUs in terms of economy and recovery is not easy and requires a detailed review.0 96. operating companies must find a compromise between a high-sulfur recovery and minimized total costs (capital and operating).0 95. . 1 Base case-Three bed Claus plant.0 98.0 98.0 96. 227 °C and 194 °C. Yet.5 Canada New plant. % 90. especially for the SRU.Table 1. % plant.
Typical COS/CS2 hydrolysis after three years operation Temperature. The optimized outlet temperature of the first catalyst bed is an important factor. 164 °C and 125 °C. Table 3 shows the calculation results for the base case. the SRE reaches 98.5-in. no quench temperatures for the system are necessary.Due to the application of a complete kinetic model for the RF and WHB. the 99. .2 Conditional to the rich feed gas. it can determine the best total sulfur recovery. 1% for the second and third and due to a coalescer downstream of the last condenser and 0.33 s was obtained by modeling the WHB with 1. The COS/CS2 hydrolysis kinetics is favored by higher temperatures whereby the Claus reaction between H2S and SO2 is promoted by lower temperatures. a temperature dependent function (Table 2). % 300 90 310 94 320 95 330 96 340 97 The process gas temperatures at the sulfur condenser outlets are fixed at 190 °C. Assume all Claus beds operate at 100% of equilibrium conversions. A gas residence time of 0.5% SRE cannot be achieved via a three-bed standard Claus plant.30%. °C Hydrolysis. Other industrial tail-gas plant configurations should be considered.25% for the fourth. A typical furnace residence time of 1-second (1 s) is assumed. Contrary to often used fixed conversion rates for COS and CS2 in the first reactor. and 6-m length tubes. Table 2. Additionally. the calculated values are listed in this table. 180 °C. As mentioned earlier. Sulfur entrainment is 2% for the first. Bed three operates at 12 °C above the sulfur dewpoint.
50 33. then less H2S conversion may occur.44 100. 1.62 214.02 100. Results for three-reactor Claus plant (SRE 98.6 10.16 0.17 2.24 57.01 62.45 100.241 1.00 1. some undesired side reactions occur that will decrease the sulfur yield: H2S + 3/2 O2 → H2O + SO2 1/x (2) (3) (4) Sx + O2 → SO2 2H2S + SO2 ↔ 3/x Sx + 2H2O As shown in Fig.0 Temperature.0 320 1.57 0.6 0.07 303. In 1988.01 2.07 290.29 3.01 61.0 100.28 0.51 32.50 0.64 0.53 26.07 315. .0 125 1.0 1.18 0.3%) and two-reactor Claus and one SOP unit Air Acid RF WHB WHB Simulation 316 1.03 100.50 5.00 77. the inlet temperature to the selective-oxidation reactor has a significant effect.7 2.10 52.36 1.1 45 1.10 1.30 0.16 0.02 60.37 292.29 3.48 1.05 100.54 0.0 Tailgas TGTU simulation 125 1. The lower catalyst temperatures favor higher selectivities.40 2.5 3.00 0.30 0.30 3.00 24.00 0.Table 3.41 0. whereby higher temperatures cause higher H2S conversion.00 4.10 1.20 4.60 0.90 0.90 2.3 SOPs for H2S may replace the last Claus reactor with selective oxidation reactor and shift to the nonequilibrium reaction: H2S + ½ O2 → H2O + 1/x Sx (1) Unfortunately.0 90.15 0.41 316.1 0.08 27.88 1.07 0.34 294. If the temperature is too low.18 56.08 5. bar (a) Mole flow k Mole frac Sx H2S SO2 C2 COS N2 + Ar O2 H2O CO2 CO H2 CS2 Summary 93 1.0 Claus tailgas Enhanced Claus tailgas 125 1.00 100.01 100.21 0.03 0.03 0.83 6.14 0.72 2.01 0.25 3.10 20.26 3. a new SOP process increased Claus efficiency to approximately 99%.33 2.°C Pressure.23 0.67 33.6 0.39 0.0 Selective oxidation processes (SOPs) for H2S.24 100.
No contamination with chemicals is possible.01% can be achieved. and no other liquids are required. 1) is strongly exothermic. the SRE raises to 99. However. potential temperature excursions can occur. One main advantage of the SOP is avoiding the H2S to SO2 ratio of 2: 1. and the undesired reactions (Eqs. Remember: the Claus stages operate at off-ratio that reduces the total recovery efficiency. at a modified Claus Plant. the threshold value of 99. The disadvantage for SOPs is that an expensive catalyst is used. a 2% reduction on air to the thermal stage reduces the total SRE for the new SOP-enhanced unit by 0. Additionally. Since the selective oxidation reaction of H2S is extremely exothermic. a total SRE of 99.Conversely if the temperature is too high. However. reactor temperature will be rise approximately 500 °C. Fig. catalyst type. SOPs are fully catalytic and continuous processes with low investments and maintenance/ operational costs. 2-4) may lead to sulfur-recovery losses. catalyst activity and water/O2/SO2 content of the process gas.2 1 %. varying the total air amount to the thermal stage of the Claus unit.5% cannot be reached by using two Claus reactors followed by a selective oxidation reactor. such as amine solvents. Energy consumption is low. the same air reduction lowers the total SRE by approximately 1%. 1 %. For the conservative case with 97% H2S conversion and 88% selectivity. Methods that lower this component by direct conversion would be an . Only H2S is controlled. For example. no COS as well as CS2 will be converted or formed. SO2 is a resulting function of temperature. Table 3 compares the results for the SOP technologies using different simulation tools. Current commercial oxidation reactors can reach sulfur yields of 92%. Improved oxidation of H2S and hydrogenation for SO2-Claus tail-gas streams contain significant levels of SO2. The amount of air to the thermal Claus stage impacts the total SRE as shown in Fig. Because the first reaction (Eq.4 To find the ideal performance for the selective oxidation reactor with 97% conversion and a selectivity of 94%. 2 displays a sensitivity study for the best performance case. The optimum inlet temperature depends on several parameters: space velocity. then more SO2 forms due to the drop-off on the selectivity curve. 2.
The formed COS is not converted in subsequent process units. The process conditions are the same for the second Claus reactor because a small hydrogenation catalyst layer is wed in the bottom of the reactor. A conversion reactor can be used. Modeling of the selective catalytic SO2-reduction stage is not easy due to the numerous nonequilibrimn reactions. This condition limits applying both processes to treat acid gases with a lower hydrocarbon content in feed streams. . 7-9) are thermodynamically favorable with very large equilibrium constants. Similarly. A good mixing burner is required. another new methodology applies a novel selective-oxidation process. A new commercial process that hydrogenates SO2 is 5 6 available. The conversion percentages of the main species have been fixed so that plant data can be met. If the conservative case is assumed. Significant amounts of CO and H2 are produced from the thermal cracking of H2S and a reducing atmosphere in the Claus reaction furnace. Recovery improvement is possible by hydrogenating SO2 in the second reactor according to these reactions: SO2 + 3H2 → H2S + 2 H2O SO2 + 2 H2 → 1/x Sx + 2 H2O SO2 + 2CO → 1/x Sx + 2CO2 (7) (8) (9) Sulfur loss occur according to the well-known reverse Claus reaction and other side reactions: SO2 + 3CO ↔ COS + 2CO2 1/x (10) (11) (12) (13) (14) Sx + CO ↔ COS H2S+ CO ↔ COS + H2 1/x Sx + H2 → H2S 2COS + SO2 → 3/x Sx + 2CO2 Reactions (Eqs. The probable production of COS from high CO levels may be one disadvantage with this catalyst.opportunity to improve sulfur recovery.
The catalytic step can be easily modeled by using a Gibbs reactor. One advantage is that the H2S content in the second Claus converter will decrease. which is absorbed by an alkanolamine solution with only partial absorption Of C02. (Eqs. therefore.the SRE reaches 99. higher investment costs as well as pressure drop will make this option less attractive. This process converts nearly all sulfur components present in the Claus tail gas to H2S. The catalytic reactor contains a cobalt-nickel or cobalt-molybdenum catalyst and operates at temperatures of about 300 °C. The H2S will be stripped from the rich-mine solvent in the stripper and recycled to the Claus unit. Typical process reactions are the water-gas-shift reaction. The SCOT-type process. which is also too low to guarantee the threshold value of 99. The primary reactions affecting the kinetics that occur in the liquid phase are: MDEA + H2S ↔ MDEAH+ + HSMDEA + CO2 + H2O ↔ MDFAH+ + HCO3 - (very fast) (17) (slow) (18) . as well as the formation of Al2SO4. The purpose is a supply of reducing gas that is required for the subsequent catalytic step. the SRE achieves 99.5%. 7 and 13) and: COS + H2O → CO2 + HS CS2 + 2H2O → CO2 + 2H2S (15) (16) Undesired reactions in the catalytic step are (Eqs.3%. This lowers the SOP temperature and. yields more sulfur. 10-12) and the oxidation of SO2 to SO3. Increasing the number of catalytic stages will be a future opportunity However.46%. For the ideal performance.7 The Claus tail gas is first heated in an inline gas burner. which can be operated sub-stoichiometrically. Methyldiethanolamine (MDEA) has been recognized for its ability to selectively absorb H2S from the gas stream and used as an amine solvent (in this case 50-wt%). too.
a lower solvent temperature is associated with a significant higher heat duty. the kinetics of reaction (Eq. This ratio could be confirmed by a commercial-plant trial.3 (Fig. the lean solvent loading will decrease (Fig. This process coupling shows a significant minimum in energy consumption and visualizes the point where the plant should operate to meet the treating specifications. A case study for this mode of operation was done. Remember. Fig.9% can be achieved with two catalytic Claus stages and one SCOT-type unit.SO2 severely degrades the amine solvent and corrodes the quench tower. 4 illustrates the relationship of H2S in the offgas with dependence from the solvent loading (mol H2S/Mol MDEA) and flow. But at which Claus tailgas ratio can a carry-over of SO2 into the amine absorber be observed? The SO2 breakthrough should be avoided in all events. by increasing the solvent/gas ratio in the absorber. 18) is responsible that more CO2 reacts with the amine solution due to a higher contact time in the liquid phase and lower gas flowrate. However. A frequent operational problem with SCOT-type processes occurs if excessive SO2 is present in the Claus tail gas.With turndown flowrate. Fig. 4). The measured ratio achieved 0. A new relationship for the absorber/stripper is depicted in Fig. The “kinetic” selectivity for H2S removal will be reduced under turndown conditions. 18).6).8 The SO2 breakthrough can occur at an H2S/ SO2 ratio of 0. Also. In this special case a SRE of 99. 5. As stripping energy increases. The outcome from reduced H2S/SO2 ratio is a high temperature rise across the hydrogenation or SCOT-type reactor. Modeling ofabsorber/stripper units is quite complex due the numerous electrolyte reactions that occur (kinetics have an effect also. What is the minimal energy consumption at given gas quality for a SCOT-type plant? To get an answer. The cooler the column the slower the reaction rate of reaction (Eq. we must consider which effects are coupled. an approach to the lean solvent equilibrium for H2S and CO2 partial pressures occurs. 3 graphs the effect of the H2S content leaving the absorber as function of the solvent temperature. Increasing solvent flow decreases the liquid residence time on the tray.24 and the outlet temperature of the . Feed or pressure fluctuations in the Claus stage could be a probable cause.
A greater volume of sour water is formed and must be treated. These processes increase the Claus conversion because of the higher equilibrium conversion at sub-dewpoint temperatures. However. The direct oxidation of H2S . The excellent characteristics of the catalyst applied in the SCOT-type reactor ensure almost complete conversion of COS and CS2. For a three-reactor configuration. Sub-dewpoint processes (SDPs).5% is attainable. A cheaper catalyst in the first Claus reactor can be used. It is therefore not necessary to achieve high COS and CS2 conversion in the Claus unit. the heated Claus tail gas passes a hydrolysis bed (a titanium-activated catalyst). Additionally. Higher SRE can be achieved by applying a new three-step process: 11 In the first step. while the other is regenerated and cooled. two reactors are used. Traditionally. CO2 in the Claus tail gas is co-absorbed and recycled together with the H2S to the SRU and increases the total go flow to the Claus plant by 5-15 %.11 The tail gas from the upstream SRU is passed over a catalyst to convert nearly all of the COS and CS2 to H2S by hydrolysis. well proven and provide excellent sulfur recovery. SDPs extend the modified Claus process towards lower temperatures to form liquid sulfur. 11 The treated gas is fed to other stages and a SRE of 99. they incur higher investments as well as operating costs. Cyclic switching valves operate automatically by a logic sequencer. After the hydrolysis. then the reactors are switched.9 The catalyst operates at low temperatures so the sulfur is adsorbed onto the catalyst. One reactor is in adsorption. here. hydrogenation takes place with the adjustment of the H2S/SO2 ratio to 2. Minor recovery loss in the Claus stage can be negligible. As in every SDP. One solution raises tail gas ratio to four. sub-dewpoint step occurs. Extensions of SDPs are available. a maximum SRE of 99. The increased energy consumption also translates to higher CO2 emissions and will be more important at higher energy prices. The third step is the direct oxidation of H2S at a low bed temperature of 100 °C (below the freezing point of sulfur). continuous. SCOT-type processes are reliable. a second bed is required to regenerate the loaded bed.SCOT-type reactor raises from 313 °C during normal operation to 436 °C within two hours. SDP performance is limited by the presence of COS and CS2 in the Claus tail gas.34% can be calculated if the gas temperature leaving the cold reactor is 135 °C. Catalysts are regenerated by flowing hot gas through the reactor to heat the catalyst and desorb the sulfur. Additionally. almost 100% of the COS and CS2 is converted.
possible integration with existing facilities. SDPs can achieve high SREs and have low capital/operating costs (with some exceptions). Air is fed to the reactor and controlled via analysis of the H2S content at the outlet of the oxidation bed. Corrosion may result due to cyclic temperature swings (stress corrosion) and low/high temperatures in piping and equipment. The expected annual operating costs TGTUs are presented in Fig.85% 99. Technical summary.7. a deep cooler may be required to guarantee the 99. The threshold value of 99. A SRE of 99. In this simulation.3. Table 4 shows the simulated results for all cases investigated. one hydrolysis and two sub-dewpoint reactors with an included direct oxidation.90% Costs. High recoveries are only reached for H2S to SO2 ratios dose to 2:1. SDPs are not continuous operations.21% 99. High maintenance costs for the switching valves (eight on/off valves) are incurred.5% recovery level.01% 99. which is sometimes difficult to achieve. expense for utilities and feed composition. a typical refinery feedstock is used with a unit capacity of 100tpd sulfur. this method uses one Claus reactor. 11 Conversely. number of trains.46% 99.85% can be calculated.5% can be reached with SDP in combination of direct oxidation and with a SCOT-type process.30% 99. In all cases.30% 99. the assigned investment costs may vary due location. Assume: . 11 For the ideal performance.occurs after cooling gas from the second step. Summation of all predicted SREs 3 Claus beds 2 Claus beds + 1 bed selective oxidation (conservative) 2 Claus beds + 1 bed selective oxidation (ideal) 2 Claus beds + 1 bed selective oxidation + improved conversion of SO2 (conservative) 2 Claus beds + 1 bed selective oxidation + improved conversion of SO2 (ideal) 1 Claus bed + 2 cold beds (ideal) 1 Claus bed + 1 bed hydrolysis + 2 improved cold beds including direct oxidation 2 Claus beds + SCOT-type 98. However.5 Table 4. the TGTUs have a complete sulfur recovery facilities including the Claus plant. In this example. the go temperature leaving the cold reactor is 100 °C and the sulfur yield for the direct oxidation stage is 85%.34% 99. When using other TGT methodologies.
and V. A. Nov. 7-10. 12 Sala. G." 1999 International Suffier Conference.-Korea Joint Workshop on Energy and Environment." Sulfur Seminar. J. 2 Additional calculations were done with Sulsim for the WHB. 1 Acknowledgements The authors of the article would like to thank the Siemens AG.9-resuln and comparison with amine tail gas treatment. MCRC. Kwong." Stork Engineers & Contractors Sulfur Seminar 1999. Oil & Gas division and H. Oel-Gas-Chemie GmbH for their assistance in the research project. Turkey.• • The value of the exported steam is refunded Maintenance costs are 3% of the total investment costs and the capital charge is 20% per year. 9 Sulfreen. Huder of Lurgi. K. 2000. and G. van Nisselroy. S. 13-17.. K.. 1999. "Top treatment. Amsterdam. J. J. 21-25. pp~ 77 82. September 2002. operating companies should perform studies to determine the best solution for their case-specific application. "The Euroclaus Process. "Novel catalytic processes for acid gas treatment in the natural gas industry and coal-fired power plants. CBA. 3 Borsboom J. "Maximizing Claus plant efficiency. "Superclaus Process operating experience. 7 Lagol. Borsboom of Jacobs Netherlands as well as Dr. 13 Sulfreen. Industrial Solutions and Services Group.. and M.S." Hydrocarbon Engineering. Achema 2000. Maxisulf and Clinsulf. New. May 2001. 10 (Lurgi patent P 264 8 190)." Third U. 10 The Elf Aquitaines and Lurgi Hydrosulfreen Process. Istanbul. Oct. In any case. 1994. L. 8 CLAUSIM was used to do the evaluation." Hydrocarbon Engineering. 1999. A. 1999. The presented calculated results should only be used as a guideline. 11 Huder. and P. 19-23. 6 Chang. Calgary. Nomenclature SOP MDEA RF SDP SRE SRU TGTU WHB Selective oxidation Process Methyldiethanolamine Reaction furnace Sub-dewpoint process Sulfur recovery efficiency Sulfur recovery unit Tail-gas-treating unit Waste-heat boiler Literature cited Kilian. . Werzels. 4 Results based on the simulators Sulsim and CLAUSIM. L. "Doxosulfreen 99. "Recent developments in SCOT tail gas technology. May 22 27. Sept. Frankfurt. Wozny. 5 Borsboom.. M.
Germany. Fax: +49 9131-7-25074 E-Mail: rainer. Fig 1: Effect of inlet temperature on conversion and selectivity for sulfur Fig 2: Total sulfur recovery efficiency (SRE) Fig 3: The effect of H2S content leaving the absorber as a function of solvent temperature Fig 4: H2S content of offgas as a function of the lean solvent flow and loading Fig 5: Circulation flow vs. Gulf Publishing Company. he has worked at VTS GmbH an engineering and consulting company located at the premises of the PCK refinery.2800e" to: Siemens AG.*Michael Kilian obtained his chemical process engineer grade in 1999 from the Technical University Berlin. USA. Rainer Schulze. Since 1993 he became a Full Professor at the Technical University Berlin for Process Dynamic and Operation.1.. he was chief of the department Process and Plant Technology at the Henkel Co. Texas. thesis at Siemens AG. Germany.D. IT Plant Solutions 1 subdivision in Erlangen. stripping energy for treated gas quality Fig 6: SO2 breakthrough in a SCOT-type plant Fig 7: Comparision of annual operating costs in EUROS for a 100-tpd unit3. simulation. From 1999 to 2000.com .D. **Prof. Presently. he is preparing a Ph. No. Dr. department Industrial Solutions and Services Group. D-91050 Erlangen Tel.12 Published in „Hydrocarbon Processing“. Prof. thesis in the field of thermodynamics and Phase Equilibria in 1979 at the RWTH Aachen.: +49 9131-7-44544. control and optimization. Wozny obtained his chemical process engineer grade in 1976 from the RWTH Aachen. pp. Houston. Mr. From 1983 to 1993. 1983. Kilian develops optimization models Claus and tail-gas treating plants. He wrote his habilitation thesis in Process Simulation and Energy Optimization at the University Siegen. 45-49 Please address inquiries under keyword "I&S 0402. He finished his Ph. Dr. January 2003.schulze@siemens. G. in Duesseldorf. I&S GC P. Wozny authored more than 200 publications in the field of thermodynamics.
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