Proceedings of the 1st Annual Gas Processing Symposium H. Alfadala, G.V. Rex Reklaitis and M.M.

El-Halwagi (Editors) © 2009 Elsevier B.V. All rights reserved.

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Simulation of an Acid Gas Removal Process Using Methyldiethanolamine; an Equilibrium Approach
Hassan E. Alfadala, and Essa Al-Musleh
Department of Chemical Engineering,Qatar University, P.O. Box. 2713 Doha-Qatar

Abstract
Adopting a rigorous equilibrium stage model for simulating an amine-based Acid Gas Removal (AGR) process is not straightforward technique. It may also be a frustrating exercise in simulation. The complexity of the system is mainly attributed to the necessity of considering both chemical and phase equilibrium issues to characterize such an electrolytic system. This paper discusses an effective approach for simulating a Methyldiethanolamine (MDEA) system using Aspen Plus RadFrac equilibrium stage model. For thermodynamic modeling, the approach uses the electrolyte-NRTL model, Redlich-Kwong-Soave equation of state, and Henry’s law. Component Vaporization efficiencies were incorporated in the simulation to account for the departure from equilibrium. To test its validity, the latter approach was tested against real design data obtained from a plant located in the State of Qatar. Furthermore, another process simulator namely ProMax and developed by Bryan Research and Engineering, Inc. was used for the purpose of comparison. Challenges faced during this practice (e.g., unit operation convergence, recycle convergence, etc.) and troubleshooting are also considered. Keywords: MDEA, Aspen Plus, Simulation, equilibrium, reactive distillation.

1. Introduction
The removal of acid gases, H2S and CO2, from gas streams (sweetening) is essential for environmental, operational and health reasons. In general, acid gas pipeline specifications is 4.0 ppm H2S and 1.0% CO2. Processes utilizing aqueous alkanolamines as an absorption agent have become well established in this area. Compared to the most common alkanolamines, the tertiary MDEA (methyldiethanolamine) amine is known for its lower regeneration cost, its thermal and chemical degradation resistance, and lower corrosion rate. In addition, it has capability for selective H2S removal in the presence of CO2 and removal of both H2S and CO2. The objective of this work is to use Aspen Plus equilibrium approach model RadFrac for simulating an actual MDEA process located in the state of Qatar. Generally, such processes can be simulated using two methods; equilibrium stage method and rate based method. The letter method is known for its capability of handling actual trays and height of packing without the use of stage efficiencies. On the other hand, stage efficiencies are essential for the equilibrium stage method. Using an equilibrium stage model could be non practical to model the system into consideration. This is due to the

In addition. The rich amine in acid gases (leaving the bottom of the absorber) is then fed to a low pressure flash drum to flash the hydrocarbons coabsorbed in the amine solvent. Therefore. . The regenerator column performs better at high temperature and low pressure. the use of the phase equilibrium relation (eq. incorporating another term. Fig. the amine is cooled to a temperature that is 5 °C higher than the sour gas. Geometry. and j are vapor and liquid phase's composition.) and physical properties (ex. x .2 Alfadala and Al-Musleh difficulties that might be associated with finding suitable efficiencies. Lower temperatures could increase the rate of hydrocarbon coabsorption. This work uses the vaporization efficiency concept.1 Stage efficiency In most cases. 1 shows a typical process flow sheet for such process. The system mainly consists of a reactive absorption and desorption (regenerator) columns. volatility. this work is pointing on an effective way to predict such efficiencies adequately. These numbers convert vapor phase compositions from equilibrium compositions to non equilibrium compositions. 2). Therefore. namely efficiency. i. The rich amine is then regenerated in the desorber by mean of stripping steam supplied by the column reboiler. 2.). thermodynamic K-value. yij = ηij K ij xij (2) where ηij is vaporization efficiency of component i in stage j. hydraulic. Viscosity. On the other hand. Vapour phase composition should not be assumed to be at phase equilibrium. K . rich amine is heat exchanged with the amine leaving the column reboiler. Identifying adequate efficiency values are discussed in the subsequent section. etc. to the relation is essential. component index and stage index. Such hydrocarbons may be used as fuel. Model theory 2. This temperature reduction is achieved by using the amine rich/lean heat exchanger and air coolers. before entering the column. etc. Prior to recycling the lean amine back to the absorber. Therefore. vaporization efficiency represents positive multiple numbers introduced to the equilibrium relations (eq. Many efficiency relations are function of plate behavior (ex. Acid gases are removed in the absorber via the direct contact of the gas stream with the amine in which H2S and CO2 react exothermally. the desorber is equipped with a reflux system to improve the purification of the amine. yij = K ij xij (1) where y . 1) in modelling such electrolytic system is not practical.

kinetic controlled reactions and equilibrium controlled reactions (Bolhar-Nordenkampf et al.Simulation of an Acid Gas Removal Process Using Methyldiethanolamine. may be classified into two groups. identifying the reactions Figure 1: Typical AGR process using alkanolamine involved in the system is extremely important.. Those reactions are: Table 1:Typical reactions in AGR process Reaction 2H2O ↔ H3O + OH + + + + - Type ionization of water (equilibrium) dissociation of hydrogen sulfide (equilibrium) dissociation of bisulfide (equilibrium) 2+ 2- H2O + H2S ↔ H3O + HS H2O + HS ↔ H3O + S + H2O + HCO3 ↔ H3O + CO3 + dissociation of bicarbonate (equilibrium) dissociation of protonated alkanolamine (equilibrium) dissociation of carbon dioxide (kinetic) bicarbonate formation (kinetic) H2O + MDEA ↔ MDEA + H3O CO2 + H2O ↔ H3O + HCO-3 CO2 + OH. 2003). Consequently. Reactions occurring in MDEA-water liquid phase.↔ HCO-3 .2 Solution reactions K-values and enthalpies calculations need to take into accounts all the ionic and nonionic species existing in the liquid phase. an Equilibrium Approach 3 2.

Aspen will predict dried . The number of stages. therefore. Since the system into consideration contains dilute gases (ex. since the unit into consideration is an absorber. column pressure profile. 1989). Moving to the MDEA regenerator. Due to the highly non-ideal behaviour of the system. although. The approach shown in Fig. 3. 1983. Aspen Plus built in power law expression was used for simulating the bicarbonate reaction. Liquid holdups were identified using the relation developed by Bennett et al. 3 . S-2.3 Phase equilibrium Phase equilibrium is concerned with the distribution of each species between the liquid and vapour phases. The operating conditions and characteristic of the process are summarized in Table 2.. the flow rate of the components constituting the distillate stream ( H2S. supplying the absorber with a temperature profile as an estimate for a new run was found to be adequate. the distillate rate for the regenerator column is known (Table 2). the amount of acid gases absorbed are higher than those in reality. Consequently. were imported from the stripper (regenerator) feed stream and exported to be the stripper distillate via the use of a calculator block. CO2. The electrolyte NRTL and Redlich-Kwong-Soave equation of state are used in this work. It should be noted that in this work. CO2). reactive stages and their correspondence liquid holdup were specified to the absorber model. and C2H6) and supercritical species (ex. Thus the calculator block is identifying a suitable distillate specification. and modelling approach (equilibrium or rate) need all to be specified for the simulator. Fig. However. CH4. CO3-2 and some water). Henry's law is also considered with ACM model. 3. The kinetic parameters in the law were all retrieved from Aspen data base. the original rate was defined to Aspen. and 4 demonstrate the approach used for simulating the entire AGR process. the user needs to remove the reboiler and condenser specifications..4 Alfadala and Al-Musleh The dissociation of carbon dioxide is very slow (Austgen and Rochelle. those coefficients were obtained from Mokraoui al et. it may be neglected for such system. Aspen data base does not have Henry's binary coefficients for n-pentane and nhexane in water. HS-.1 Simulation approach Fig. sour gas and lean MDEA conditions. HCO3-2. H2S. binary parameters for the above models were all retrieved from Aspen data base. In addition. 2 was followed in simulating the absorber section of the process. therefore. In this work all the stages were assumed to be reactive. 2007 and defined to the simulator. 3. such distribution should be characterized by an activity coefficient approach (ACM). 2. In this work the absorber did not converged. the distillate rate in Table 2 should not be reasonable. Finally. The main reason behind this calculator block is as follow: so far the work is under equilibrium criteria. In this work. Therefore. 2. In case. the profile from the unconverged case was used. Simulating an actual MDEA process The simulation of Qatar's MDEA plant was based on the design data of the plant.

number of stages.00 35 0.92 2.A conditions Figure 2: Simulation approach for the MDEA abosrber .000.00 40 45 72 25 -4 Stripper 103.68 10.000. and missing Henry's low parameters Number of stages Reactions & liquid holdup Model: equilibrium Insert auxiliary equipments (ex.6 514 1.% Solution flow rate (kmol/h) Solution temperature (°C) MDEA composition (wt%) Acid gas flow (kmol/h) Reflux ratio Pressure (barg) Number of stages *Flash drum pressure is 10. Absorber 20.00 barg. In other words. In this work. pumps.Simulation of an Acid Gas Removal Process Using Methyldiethanolamine. reactions. an Equilibrium Approach 5 stages (liquid or vapour flow approaches zero). calculation mode. To complete the column specifications. feed stage.6 2.% CO2 mol.35 24 Define thermodynamic model.% COS mol. column pressure profile. etc) Temperature profile Run No Converged Yes Regenerator RadFrac (absorber) Column pressure Profile S. Table 2: Qatar's MDEA plant operating conditions and process characterstcs Parameter Sour gas flow rate (kmol/h) Sour gas temperature (°C) Sour gas molar composition H2 S mol.C’s mol. reflux ratio.39 5. coolers. the regenerator has converged directly without any problems.15×10 96. components. the column will not converge. and type of condenser were all defined to Aspen.% N2+H.G & L.

Fig 4 shows the block diagram for the simulated process. 5 shows how this material balance (for the absorber) behaves against different efficiency values. P. MDEA flash drum. water in LMDEA < water in LMDEA*). Applying this strategy had resulted in converging the flow sheet in three iterations in which the tolerance was 0. lean MDEA (LMDEA) needs to be recycled back to the absorber. 3.e. 4) to identify a makeup water amount (i. The convergence bottleneck was the water lost from the MDEA stream as it is processed from the absorber to the regenerator. and pumps downstream the regenerator. MDEA storage. the LMDEA tear stream will face convergence problems in terms of water content (i. Consequently. Each complete cycle (from the absorber to the convergence criteria block) is one iteration. Both H2S and CO2 efficiencies were varied against the flow rates of H2S and CO2 in the sweet and acid gas streams. . As number of iteration increases.0001. Absorber Insert calculator for stripper distillate rate Number of stages Reboler &. The calculation starts with the absorber in which the tear stream LMDEA* conditions were defined from Table 2. Model: equilibrium Run RadFrac (Regenerator) Reflux ratio Feed stage Column pressure profile Recycling the lean MDEA Figure 3: MDEA regenerator simulation approach Aspen will be iterating and updating the tear stream LMDEA* from the previous LMDEA (from step 7) till LMDEA meets tear stream convergence tolerance (i. Fig. partial cond. This recycling requirement was found to be accompanied with convergence problems. flow rates – LMDEA*T. This amount is then exported to the storage tank.2 Columns vaporization efficiencies Aspen plus built in sensitivity analysis tool was utilized to identify values for the absorber and regenerator efficiencies. flow rates | ≤ Tolerance ).e | LMDEAT. P.e WMkUp= WSweet Gas+WFlush Gas+WAcid GasWSour Gas). water lose from the solvent in each unit operations was exported to a calculator block (Fig. To overcome this. the more the water looses from the absorber. and regenerator.6 Alfadala and Al-Musleh After inserting the heat exchangers.

4.08 CO2 in Sweet Gas (kmol/h) 0.1 2.075 0.4 2.2 2.7 1.065 1.1 2.3 2.Simulation of an Acid Gas Removal Process Using Methyldiethanolamine.3 2.09 170 0.2 120 2 2. predicted rich and lean MDEA temperatures were deviating from the plant data by approximately 8.6 2.8 1.1 2. Results and discussion 4.8 H2S Efficiency Figure 5: Acid gas content in the sweet gas vs H2S efficiency at different CO2 efficiencies .055 0.1 2.6 1. the more the H2S content in the sweet gas.2 2.05 2 2. sweet gas CO2 content is not sensible to the H2S efficiencies.7 2.085 H2S in Sweet Gas (kmol/h) 0.8 165 160 155 150 145 140 135 130 125 1.2 0.5 2.5 1.7 2. 0.06 0.W Sour Gas ater W ater Acid Gas W ater Step [2] Step [3] Am lean/reach ine exchanger Figure 4: Block diagram for the simulated process One may see that as the H2S efficiency increases (at different CO2 efficiencies). an Equilibrium Approach 7 StopCalculation Step Criteria m et [8] Convergence criteria LM *-LM DEA DEA< З Start calculation Design LM DEA Criteria w not met as LM DEA* Sour Gas W ater Sw Gas eet RadFrac Absrober RM DEA W ater Sour Gas Flash 2 M DEA Flash Drum RM DEA W ater W ater W ater Step [1] Step [5] RadFrac Stripper Rich M DEA Distillate rate Acid Gas Calculator for stipper Distillate rate Step [4] LM DEA Step [7] W make up ater Storage Tank Step [6] Calculator for H2OM ukeup Total water .8 H2S efficiency 1.6 2. However.6 and 12.0 °C.07 0.1 Material and energy balance Main simulation outputs (Table 3 and 4) for the MDEA absorber and regenerator do match very closely the plant data.5 1.9 2 2.4 2. It is only influenced by those for the CO2.7 1. On the other hand.5 2.9 2 2. respectively.6 1.

7 H2S in sweet gas (ppm) 0. 2005). rich MDEA and acid gas streams were found to contain hydrocarbons less than those reported in the design data. Due to the lack of actual data the literature and a process simulator namely ProMax (which is the most popular process simulator for amine sweetening. the temperature starts to drop down as a result of the heat absorbed by the cooled gas entering the contactor. A temperature bulge was identified by both simulators. Therefore. For the absorber. Moreover.9 CO2 in sweet gas (mol.89 48 42. Table 3: Simulation results for the MDEA absorber MDEA Absorber Parameter Plant 3.8 H. the rate of reaction of H2S with the MDEA solution is fast. 6 and 7 for both columns. Kohl and Nielsen. H2S bulk removal in the first five stages of the . Near the middle of the tower (where the temperature is maximum)..C's in Acid gas (mol.8 0.C's co-absorbed (mol. Regarding the composition profiles in the absorber.%) 57 Acid gas Temperature (°C) 53 Lean MDEA Temperature (°C) 132. both ProMax and Aspen temperature profiles have similar behaviour. %) 0.064 Table 4: Simultion results for the MDEA regeneragtor MDEA Regenerator Parameter Plant H2S in Acid gas (mol.2 Columns profiles Temperature and composition profiles are presented in Fig.0 °C higher than that in Aspen.2 0.8 Alfadala and Al-Musleh It should be noticed here that a temperature of 144.15 Aspen 3.89 Aspen 35 57.1 H.24 4. it reacts exothermically with H2S and CO2 resulting in raising the temperature of both the vapour and liquid phases. %) 0.0 °C in the regenerator reboiler can result in amine degradation (Pandey. The behaviour of the temperature in the absorber may be explained as follow: as the MDEA solution flow down the absorber. Such behaviour was shown by Shiveler et al. Nevertheless. 2006 in which they have performed a thermal scanning on an industrial MDEA absorber.8 CO2 in sweet gas (mol.2 59 144 0. each simulated stage in ProMax is 10. %) 34.%) Sweet gas Temperature (°C) 47 Rich MDEA Temperature (°C) 50. 1997) were used for the purpose of comparison.

008 0.5 0. For CO2.0 1 5 9 40. Aspen's .0 0 5 10 Stage 15 20 25 30 0 0.03 Stage No.).004 0. Fine cleaning of the gas stream from H2S is mainly being achieved in the rest of the stages. However.02 30. all RadFrac stages were found to be necessarily to achieve CO2 pipe line specifications (about 1.  ProMax Aspen plus 13 17 21 25 ProMax (H2S) Aspen Plus (H2S) ProMax (CO2) Aspen (ProMax) Figure 6: Absorber temperature and composition profiles Such behaviour was obtained in Aspen and ProMax.4 0.0 80.003 0.015 0.1 0.01 12 10 15 15 Stages Aspen ProMax 15 Stage 14 16 Aspen ProMax 18 20 20 20 25 20 Aspen (H2S) Aspen (CO2) ProMax (CO2) ProMax (H2S) Aspen (H2S) Aspen (CO2) ProMax (CO2) ProMax (H2S) 22 25 30 25 24 26 28 30 30 Figure 7: Regenerator temperatue and composition profiles Moving to the regenerator.006 0.005 0.002 0.6 0.025 0.0 90.3 0.7 5 Temp.2 Mole Fraction (Vapor) 0.0 Mole Fraction‐vapor 0. C 100 110 120 130 140 150 0 0 0.007 0.005 0.Simulation of an Acid Gas Removal Process Using Methyldiethanolamine. C 60.0 70.0% mol. C 5 Mole Fraction 145 150 10 Stages 130 5 135 140 10 Stage 0 10 0. 50 0 60 70 80 90 Temp. This trend does mach those in ProMax and Bolhar-Nordenkampf. Furthermore. Bolhar-Nordenkampf work does confirm such attitude. an Equilibrium Approach 9 absorber was expected.0 50.009 0. both ProMax and Aspen plus predicted profiles having similar overall trends for both the composition and temperature.01 0.001 0. Temperature.

Houston. both profile shows that the change of temperatures from stage 6 down to the bottom are small. Eng. 2007. 1997. Eng. M. Chem. 2. Asia-Pac. 434-442.. To account for the non-ideality behaviour of the system. . D. Friedl. Shiveler. and T. Bennett. Gonzalez. Eng. & Cook. References A. 1060-1073. Koss. Pandey. 5. Fig. Rochelle.. Austgen and G. Kohl and R. The material and energy balances predicted by Aspen were found to be close to the design data. 2003. vaporization efficiencies for H2S and CO2 were defined for the MDEA absorber and regenerator.10 Alfadala and Al-Musleh temperature profile is shifted by around 10. Conclusion The use of Aspen plus RadFrac model for simulating Qatar's MDEA process was found to be able to predict good results. Retrofit of a H2S selective amine absorber using MellapakPlus structured packing. 701-715. 2006. Therefore composition change in these stages was also found to be small. The electrolyte-NRTL model. R. Redlich-Kwong-Soave equation of state. In addition. Bolhar-Nordenkampf.. 7 shows that bulk removal of H2S and CO2 are achieved in the first ten stages and purification of the traces is carried out in the rest. 2005. D. J. Chem. International Petroleum Technology Conference. 29. Model of vapour-liquid equilibria for aqueous acid gasalkanolamine systems using electrolyte-NRTL equation. Texas. Proc. M. New pressure drop correlation for sieve tray distillation columns. 1983. 2004.43. G. U. L. Nielsen. Gas Purification. 28. Gulf Publishing Company. A. Ind. Solis. Bueno. Regarding the temperature and compositions profiles. Tork. G.. L. American Institute of Chemical Engineers Journal. they were identified to have similar behaviour as those predicted by ProMax and those reported in the literature. Process Obtimization in Gas Sweetening Unit-A Case Study. J. 1989. P. Chem. Agrawal. Modelling selective H2S absorption and desorption in an aqueous MDEA-solution using a rate-based non-equilibrium approach..0 °C to the right of ProMax's profile. 232-244. and M. and Henry’s law were used for the thermodynamic framework.

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