GAS PROCESSING DEVELOPMENTS

SPECIALREPORT

Designing a selective MDEA tail-gas treating unit

Following these protocols will enhance sulfur recovery efficiency
S. NAGPAL, Fluor, Gurgaon, India

elective amine-based Claus sulfur recovery units (SRUs) tail-gas treating units (TGTUs) have become the preferred option for enhancing sulfur recovery efficiency to above 99.8% while minimizing sulfur emissions. The most commonly used selective amine is a generic methyl diethanol amine (MDEA). The most commonly known process is the SCOT process. Over 400 such plants have been built and many others are under construction that are using the SCOT process. The TGTU process represents an extreme operating scenario for an amine gas-sweetening unit. While the TGTU process configuration is similar to a typical amine absorption-regeneration system, both the absorber and regenerator operate at extreme conditions. H2S and CO2 absorption occurs at low pressure just above atmospheric (typically 1 bara to 1.2 bara). Amine regeneration to very low lean amine H2S-loadings is required, leading to operation with a high steam requirement.* TGTUs preferably employ a selective amine solvent to minimize CO2 co-absorption and recycle it to the SRU. The SRU converts acid-gas feed into elemental sulfur and produces a tail-gas containing unconverted sulfur species. This gas is hydrogenated to reduce all unconverted sulfur species to H2S in a fixed-bed catalytic reactor, quench cooled with water and fed to the TGTU absorber. The product from the TGTU is off-gas that is sent to the incinerator while an acid-gas from the TGTU regenerator is recycled to the Claus SRU furnace. Fig. 1 shows a schematic of the SRU-TGTU process. This article discusses some key issues that engineers need to address when designing these units. There are several published articles that present qualiSulfur recovery unit tative effects of TGTU operating parameters. This article gives a more quantitative description Acid that can be used as a preliminary gas Converters, design guideline, using several Claus reheaters and Air furnace commercial process simulators. condensers Variation among different simulators will be highlighted. Sulfur
Selective H 2 S removal.

does not react directly with CO2 to form carbamate. The trimolecular reaction of MDEA with CO2 (Eq. 1), is slow, while the MDEA-H2S reaction (Eq. 2) is a fast proton transfer reaction that can be considered to be almost instantaneous.
R'R 2 N + CO2 + H 2 O R'R 2 N + H 2 S R'R 2 NH+ + HCO3 (1) (2) R'R 2 N+ + HS

This results in the kinetic selectivity shown by MDEA toward H2S absorption over CO2 absorption. However, maximum equilibrium loadings achievable for both H2S and CO2 are ~1 mole per mole of MDEA, provided that an adequate pressure-driving force is available in the gas phase and adequate contacting time is provided. Thus, selective H2S removal results are entirely due to the choice of gas-liquid contacting time being long enough for H2S removal but too short for equivalent CO2 capture. Optimum design for an amine contactor is required to allow necessary H2S removal but minimal CO2 co-absorption. Equipment over-sizing is not advisable as it leads to excessive CO2 absorption and recycle to the Claus SRU. Accurate computer models that consider inter-phase mass-transfer with simultaneous chemical reactions are required to simulate the adsorption/stripping process for optimal design and retrofitting of selective gas sweetening units. Use of equilibrium stage models with user-experience-based H2S and CO2 stage efficiencies, is a common approach for designing gas-sweetening units. However, this approach is not suitable for selective removal applications where tray performance is highly variable and can be sensitive to factors such as tray type/design, Tail-gas treating unit solvent loading, column temperaOff-gas ture profile, etc. Also, tray effi(to incineration) ciency estimation is difficult.
Tail gas Hydrogenation and quench TGTU absorber Lean amine

Process simulation. The

Rich amine

MDEA is a tertiary amine that

* Loading is dened as mole H2S or CO2 per mole amine in aqueous phase. FIG. 1

Acid gas (recycle to SRU furnace)

TGTU regenerator

Schematic of a sulfur recovery unit with a tail-gas treating unit.

performance of selective amine sweetening process simulators depends on two key model components: Vapor-liquid equilibrium (VLE) and rate models. Both H2S and CO2 absorption in the amine solution are reversible reactions. As mentioned above, the H 2S-amine

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each tray/packing section. With rate models, stage equations are the traditional equations of mass and energy balances for each stage, the vapor and liquid phases are now characterized by a bulk composition and an interfacial composition. These models typically assume that the bulk vapor and liquid phases are wellmixed and the resistances to mass-transfer are located in the two films at the vapor-liquid interface. Linear concentration profiles are assumed in the two films. Mass-transfer correlations are used to incorporate effects of system hydrodynamics. The vapor and liquid mass-transfer coefficients are estimated using appropriate correlations for the type of tray being simulated. Diffusivities in the multi-component vapor and liquid mixturesalong with other transport properties, such as density, viscosity, thermal conductivityare required to calculate the mass-transfer coefficients. Heat-transfer coefficients are commonly estimated using the Chilton-Colburn analogy. Rate model use requires the user to provide details of tray type, column diameter, weir height, down-comer width, number of passes, etc. These models report calculated tray efficiency for H2S and CO2. The rate model accuracy determines how well H2S selectivity or CO2 slip is estimated.***
Selective absorption at low pressure. There are several

reaction is extremely fast, and the process operates close to vaporliquid equilibrium with respect to H2S absorption/regeneration. On the other hand, the CO2-amine reactions for tertiary amines, such as MDEA, are slow in the absence of the much faster carbamate formation reaction that occurs for primary and secondary amines.** Thus, accurate rate models are required to determine the extent of CO2 removal while meeting H2S specification in the off-gas for incineration.
VLE model. VLE models, comprising a gas phase equation-ofstate (EOS) model and a liquid phase activity coefficient model are used to correlate experimental VLE data for the H2O-amineH2S-CO2 system over a range of amine concentrations, H2S and CO2 loadings, and temperatures. Fig. 2 compares VLE calculated with several simulators, with the VLE data for 50 wt% MDEA at 40C and 120C.1 Simulators 1, 2 and 3 are seen to fit the data quite well.1 Recent VLE data for this system reports significantly higher H2S partial pressures as a function of amine loading.2,3 Fig. 2 illustrates that Simulator 4 based VLE calculations for 50 wt% MDEA at 40C matches the later data. At 120C (regenerator condition), Simulators 1, 2 and 3 fit the data fairly well.1 At 120C, the lowest loading data reported was at 0.0095m/m.1 Extrapolation of the VLE data to lower H2S loadings down to 0.0010.005m/m is required, as TGTU regenerators are required to produce lean amine of this quality. Extrapolation of VLE models into this low loading region with scanty data adds to model prediction uncertainty. The above VLE model comparison indicates that the process simulator choice will have a significant impact on the design calculations as the simulators use different VLE models and even use different VLE databases for the VLE model parameter tuning. Rate model. The rate model (also called the non-equilibrium

challenges in the design of low-pressure tail-gas treating (TGT) absorbers. A typical case is used to illustrate these issues. The feed gas and lean amine to the absorber for this case are specified in Table 1.
1. Attainment of H2S specification in treated gas.

stage model) is used to calculate the approach to equilibrium on

10,000 1,000 100 H2S pressure, kPa 10 1 0.1 0.01 0.001 0.001 Jou data 120C Simulator 1 Simulator 2 Simulator 3 Jou data 40C Simulator 1 Simulator 2 Simulator 3 Simulator 4 Rogers data 40C

The overall sulfur recovery of the SRU-TGTU process is dependent on the TGT absorber off-gas H2S concentration. Attainment of sulfur recoveries in excess of 99.9% requires the off-gas H 2S spec to be 150 ppmv or less. (Note that a generic amine will be able to achieve a 250 ppmv H2S spec, a selective amine ~150 ppmv and a formulated amine ~10 ppmv.) Attaining this H2S spec in absorbers operating close to ambient pressure (1 to 1.2 bara) requires lean amine with very low H2S loading. Fig. 3 shows the off-gas H2S concentration variation with H2S lean amine loading at a column top temperature of 40C, estimated with various process simulators. Fig. 3 also illustrates the equilibrium H2S concentrations based on VLE data for 50 wt% MDEA at 40C.1,2 Note that the VLE data-based equilibrium H2S concentrations represent the lower limit of off-gas H2S concentration achievable. Off-gas H2S concentrations in the range 60150 ppmv are obtained for a lean amine with 0.005 H2S loading. Simulators 1, TABLE 1. Case study50 wt% MDEA absorber
Feed gas Flow, kmol/h Temperature, C Pressure, bara CO2, mol% 1,062 43.3 1.09 5.2 1.7 Treated-gas spec 2.1 14 H2S, ppmv 100 Lean amine Flow, kmol/h Temperature, C H2S loading, m/m CO2 loading, m/m 2,819 (88 TPH) 40 0.005 0.0001

0.01 H2S loading, m/m

0.1

H2S, mol% Column Diameter, m No. of Trays (Valve)

FIG. 2

Simulator estimation of H2S VLE in 50 wt% MDEA.

** Carbamate formation for secondary amine: R2NH + CO2 = R2NCOO + H+

44

*** CO2 slip (%) = 100 x moles of CO2 in off-gas/moles of CO2 in absorber feed.

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2. Maximizing CO2 slip. The low presCO2 slip, % Simulator 4 141 141 141 141 Simulator Simulator 1 2 84.4 79.1 71.3 65.1 84.8 79.5 72.1 66.7

TABLE 2. Impact of number of trays

H2S out, ppmv No. of trays 10 14 20 25 Simulator Simulator 1 2 307 135 93 85 244 100 70 66 Simulator 3 61 61 61 61

TABLE 3. Case study- regenerator column

Rich amine feed Temperature, C Flow, kmol/h MDEA concentration H2S loading, m/m CO2 loading, m/m 104 7544 50wt% 0.077 0.027 Column Condensor pressure Reboiler pressure Condensor temperature Diameter, m Trays (total) Trays (below feed location) Weir Height, cm 2.35 bara 2.6 bara 40C 3.3 27 24 5

sure TGT absorber is usually designed with just enough trays/packing height to ensure Simulator Simulator that the gas leaving the column top is close 3 4 to equilibrium with the lean amine entering 96.3 98.5 the column with respect to H2S. Avoid over design to minimize CO2 absorption. 96 98.0 Table 2 illustrates the impact of number 92.8 97.2 of trays on column performance. Increasing 91.1 96.8 the number of trays allows some reduction in off-gas H2S concentration, but this comes at the cost of increased CO2 co-absorption and it will eventual recycle to the Claus SRU. Typical CO2 slip observed in trayed MDEA TGTU absorbers ranges from 6085%, but this can vary considerably based on column design. Yet, Simulators 3 and 4 simulate an unrealistically high CO2 slip, and show no impact on the number of trays for treated gas H2S concentration. This suggests that 10 trays are adequate to reach H 2S equilibrium composition w.r.t feed lean amine. It should be noted that commercial-grade MDEA commonly has some DEA impurity, which can reduce CO2 slip, and result in increased off-gas H2S concentrations. Use of high-purity MDEA can enhance TGTU performance.
3. Optimal amine concentration. The maximum H2S

2 and 3, although all based on VLE data,1 reported significantly different results, essentially from different rate models. Simulator 4, which is based on the VLE data2 reported, gives higher off-gas H2S concentrations than all the other simulators at H2S lean loadings above 0.0040.005. Comparing Simulator 4 results with the equilibrium limit of H2S concentrations suggests that it is essentially an equilibrium based model with super imposed CO2 kinetic effects (to estimate CO2 selectivity). Operating experience has shown that absorber off-gas will typically approach 34 times the equilibrium H2S partial pressure on the absorber top tray.6 These simulator results indicate that attaining an off-gas spec of 100 ppmv will require a lean amine H2S loading of 0.005 m/m or lower. Use of a typical refinery gas-sweetening unit lean amine H2S loading of 0.010.015 m/m would allow the reduction of H2S to 250500 ppmv, which may not suffice to meet the required overall sulfur recovery target.
500 450 400 Off-gas H2S, ppmv 350 300 250 200 150 100 50 0 0.000 0.005 0.010 Lean amine H2S loading, m/m 0.015 Simulator 1 Simulator 2 Simulator 3 Simulator 4 Equilibrium limit @ 40C1 Equilibrium limit @ 40C2

loading achievable in the rich amine leaving the absorber bottom is controlled by the feed gas H2S partial pressure and amine concentration used. MDEA use became popular for refinery amine systems as it could be used at higher concentrations and with higher acid-gas loadings than the earlier generation primary and secondary amines, viz. MEA and DEA. MDEA also allows reduced CO2 pick-up in the absorbers. These factors resulted in operation with significantly reduced amine circulation rates. However, for the low-pressure TGTU absorber, operation with high amine concentration at high H2S loading is not feasible due to column bottom pinch. This leads to the question, Is there any benefit to operating TGTU absorbers at high amine concentrations? This is examined in Fig. 4, which illustrates the variation in off-gas H2S and CO2 concentrations with amine circulation
1,000 900 800 H2S in treated gas, ppmv 700 600 500 400 300 200 100 0 40 60 80 100 Amine circulation rate, TPH 4.0 120 4.1 4.2 H2S (50 wt% MDEA) H2S (20 wt% MDEA) CO2 (50 wt% MDEA) CO2 (20 wt% MDEA) 4.5 4.4 4.3 CO2 in treated gas, %mol

FIG. 4 FIG. 3 Off-gas H2S concentration dependence on H2S lean amine loading for the TGT absorber defined in Table 1. Absorber top pressure considered is 105 kPa.

Effect of amine concentration and amine circulation rate on off-gas H2S and CO2 concentration estimated with Simulator 2. Lean amine H2S and CO2 loadings considered were 0.005 m/m and 0.0001 m/m, respectively.

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3.00 Reboiler steam consumption (SSC), lb steam/gal rich amine 2.50 2.00 1.50 1.00 0.50 0.00 0.000 FIG. 5 SSC, lb steam/gal rich amine Simulator 1 Simulator 2 Simulator 3 Simulator 4 2.00 1.75 1.50 1.25 1.00

SPECIALREPORT

(a)

20

25

30

35 40 Number of trays

45 135

50

0.002

0.004

SSC, lb steam/gal rich amine

0.006 0.008 0.010 Lean H2S loading, m/m

0.012

0.014

2.00

(b)
Temperature

Reboiler specific steam consumption for producing lean amine of varying quality estimated with various simulators for the regenerator defined in Table 3.

1.90

130

3.5 3.0 SSC, lb steam/gal rich amine 2.5 2.0 1.5 1.0 0.5 0.0 Simulator 1 Simulator 2 Simulator 3 Simulator 4

1.80

SSC

125

1.70 195 FIG. 7

215 235 Reboiler pressure, kPa

255

120

Impact of number of trays and column pressure on reboiler specific steam consumption (SSC) for the case described in Table 3. Lean amine H2S loading considered was 0.005 m/m. Estimations were done with Simulator 2.

200

400 600 Off-gas H2S, ppmv

800

1,000

FIG. 6

Reboiler specific steam consumption required for associated tail-gas absorber off-gas H2S concentration estimated with various simulators.

rate for two amine concentrations, 20 wt% MDEA and 50 wt% MDEA. For the 50 wt% MDEA case, a sharp increase in off-gas H2S concentration is calculated at amine circulation rates below 50 TPH, which is indicative of a column bottom pinch. However, for the 20 wt% MDEA case, onset of pinch conditions occurs at a higher amine circulation rate of ~90 TPH. Thus, higher MDEA concentration use is estimated to allow operation with a lower amine circulation rate and a higher CO2 slip. (Typical MDEA application range is between 35 wt% and 50 wt%).
Amine regeneration. A typical rich amine feed to a TGTU regeneration column is considered to illustrate some design issues; this data is listed in Table 3. 1. Steam requirement. As previously discussed, a very low lean amine H2S loading of 0.005 m/m or lower is estimated to achieve off-gas H2S concentration below 100 ppmv. Attaining such low

lean amine loading requires high steam input to the amine regenerator column (ARC) reboilers. For the ARC case in Table 3, Fig. 5 shows a specific steam consumption (SSC) variation with H2S lean amine loading estimated with various simulators. All the simulators estimate a sharp increase in steam consumption as H2S lean loading decreases below 0.01 m/m. However, there is considerable variability in the calculated magnitude of specific steam consumption. Medium- and high-pressure refinery/gas plant absorbers required to reduce treated gas H2S to 440 ppmv can operate with H2S lean loading of 0.01-0.015m/m with a corresponding SSC of ~1 lb-steam/gal-amine. However, for the low-pressure TGTU that requires an H2S lean loading of ~0.005, ARC operates at significantly higher SSC of 1.5 lb-steam/gal-amine and is estimated with Simulators 2 and 3. However, Simulator 4 allows very low lean amine H2S loadings down to 0.003 m/m to be achieved with an SSC of 1 lb-steam/gal-rich amine. From an overall unit design perspective, it is useful to look at ARC steam requirements for attaining a target absorber off-gas H2S concentration. This is illustrated in Fig. 6. For off-gas H2S concentration >400 ppmv, the discrepancy between the simulators is fairly small, with SSC of 0.60.8 lb-steam/gal-rich amine for all simulators. However, for off-gas H2S concentrations below 200 ppmv, the simulator results deviate significantly. For instance, for 100ppmv H2S in off-gas, Simulator 2 estimates SSC two times that obtained from Simulator 4. This suggests that different simulator use can lead to significantly different design when targeting off-gas H2S that is below 200 ppmv. Reliability of these estimations is subject to the VLE data accuracy, especially at low H2S loading. Published VLE data
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at the ARC bottom conditions (H2S loading below 0.01 m/m, Considerable variability was found among commercial simulaand temperature above 120C) are scanty and of relatively lower tors with respect to SSC required for attaining off-gas H2S level accuracy. Thus, the estimations from the simulators should be below 200ppmv. Scanty VLE data at low H2S loadings results in validated using reliable operating data. uncertainty in the simulator estimation of steam requirements, ARC lean amine CO2 loading is calculated to be significantly and off-gas H2S concentrations at low loadings. Reliable operating lower than the H2S loading. This is due to the higher volatility/K data from existing units are thus required to validate the simulavalue of CO2 compared to H2S. The bulk of the CO2 in the tor results, and to optimize the steam consumption required to rich amine strips out rapidly in the trays attain low off-gas H2S concentration below the rich amine feed, while H2S and high overall sulfur recovery for stripping continues all the way down the SRU-TGT plant. A literature scan The gas industry would to the bottom of the column. At high found just a few relevant reports on specific steam consumptions, increase benefit from a common database operating data with TGT amine units. in CO2 loading in the rich amine feed The gas industry would benefit from a common database of reliable plant does not result in an increase in the spe- of reliable plant operating operating data that can be used in all cific steam consumption (SSC can even commercial simulators. decrease at increased feed rich-amine data that can be used in all Options that have been explored to CO2 loading). To a certain extent, the reduce steam consumption for TGT presence of CO2 acts as a strippping gas commercial simulators. units include acid-addition and splitfor H2S. This is in contrast to convenflow processes. 5 Acid addition can tional regenerators designed to produce lean amine with acid-gas loadings of 0.015 m/m (or higher) in allow production of lean amines with very low H2S loading which the specific steam consumption increases in proportion to (~0.001 m/m) with lower steam consumption. Split-flow ARC the feed rich amine acid-gas loading. are sometimes used for refinery units that have critical users, e.g. TGTU and fuel gas absorbers where any H2S slip ultimately results in more SO2 emissions and less-critical users (e.g., absorb2. Number of trays. Using a higher number of trays in the stripping section of the ARC can be employed to reduce steam ers for recycle gas in hydro-processing units) where bulk removal requirement for attaining a low lean amine H2S loading. Fig. 7a is sufficient. HP shows the effect of increasing the total tray number in the ARC on LITERATURE CITED steam required (SSC) to obtain a lean amine H2S loading of 0.005. 1 Jou, F., A. E. Mather and F. D. Otto,Solubility of H S and CO in Aqueous 2 2 The rate of reduction in SSC decreases as the number of trays Methyldiethanolamine Solutions, Industrial & Engineering Chemistry Process increases. Typically, 2025 trays are used in the TGTU ARC. Design Development, Vol. 21, pp. 539544, 1982.
2

3. Column pressure. ARC operation at higher pressure leads

to higher column temperatures and better regeneration. ARC operating pressures are limited on the lower side by back-pressure requirement from the downstream SRU and on the higher side by temperature limit for keeping amine degradation rates down at acceptable levels. Fig. 7b shows the effect of column pressure variation on steam consumption (SSC) and reboiler temperature, using Simulator 2. Simulators 1 and 3 give a lower sensitivity of SSC to column pressure. A low sensitivity due to counter balancing effects of higher acid-gas vapor pressure at higher temperature and higher column pressure has been previously reported.6 Reduction in SSC at higher pressures/temperatures comes at a cost of increased amine degradation rates. For generic MDEA solutions, recommended reboiler process-side temperatures are 125C or less (with steam temperature below 150C) to keep degradation rates in check.4
Conclusions. Accurate rate-based process simulators are

4 5

Rogers, W., J. A. Bullin and R. R. Davison, FTIR measurements of acidgas-methyldiethanolamine systems, AIChE Journal, Vol. 44 Issue 11, pp. 24232430, November 1998. Huttenhuis, P. J. G., N. J. Agrawal, J. A. Hogendoorn, and G. F. Versteeg, Gas Solubility of H2S and CO2 in aqueous solutions of n-methyldiethanolamine, Journal of Petroleum Science and Engineering, Volume 55, pp. 122134, 2007. Dupart, M. S., T. S. Bacon and D. J. Edwards, Understanding corrosion in alkanolamine gas treating plants, Hydrocarbon Processing, April 1993. Wong, V. W., J. Y. Mak and T. K. Chow, The DAP and STREP Processes for Acid Gas Removal, Acid Gas Enrichment, and Claus Tail-Gas Treating, Brimstone Sulfur Recovery Symposium, 2007. Huffmaster, M. A., Stripping requirements for selective treating with sulfinol and amine systems, Laurance Reid Gas Conditioning Conference, p. 262, 1997.

ACKNOWLEDGMENT The author thanks Ashwin Nagarajan and Michiel Baerends of Fluor for their assistance in preparing and reviewing the article.

required for optimal design of SRUsTGTUs. The TGTU absorber and regenerator columns operate at extreme conditions with respect to H2S lean amine loadings and steam consumption. Lean amine with H2S loading below 0.01 m/m is estimated to achieve TGT off-gas H2S spec below 200 ppmv. This, in turn, entails ARC operation with high steam consumption, with steam consumption increasing exponentially with decreasing lean amine H2S loading. Unlike conventional ARC where SSC is controlled by the feed rich amine acid gas loading, the TGT ARC SSC is controlled by the required off-gas H2S concentration and lean amine H2S loading.
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Soumitro Nagpal is a process specialist with Fluor India. He

has over 20 years experience in process design and development. Dr. Nagpals primary areas of work have been gas processing, gastreating, sulfur recovery, CO2 and SO2 capture, petcoke gasification and alumina refining. He developed rate-based models for selective gas-treating applications and used these models for process design and the revamp of gas-treating units in India. In the past, Dr. Nagpal has worked at Engineers India Limited and Imperial College, London. He received a BE in chemical engineering from Birla Institute of Technology & Science, Pilani and a PhD in chemical engineering from the University of Utah.

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