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THEORETICAL AND EXPERIMENTAL STUDY OF THE ABSORPTION RATE OF H2S IN CuSO4 SOLUTIONS: THE EFFECT OF ENHANCEMENT OF MASS TRANSFER BY A PRECIPITATION REACTION
H. ter Maat1,3, M. Al-Tarazi2, J.A. Hogendoorn2, J.P.M. Niederer2, G.F. Versteeg2 1 Procede Group B.V. P.O. Box 328, 7500 AH, Enschede, The Netherlands 2 University of Twente, Department of Chemical Engineering P.O. Box 217, 7500 AE, Enschede, The Netherlands
In this paper the desulfurization of gas streams using aqueous copper sulfate (CuSO4) solutions as washing liquor is studied theoretically and experimentally. The desulfurization is accomplished by a precipitation reaction that occurs when sulde ions and metal ions are brought into contact with each other. The absorption experiments of H2S in aqueous CuSO4 solutions were carried out in a Mechanically Agitated Gas Liquid Reactor. The experiments were conducted at a temperature of 293 K and CuSO4 concentrations between 0.01 and 0.1 M. These experiments showed that the process efciently removes H2S. Furthermore the experiments indicate that the absorption of H2S in a CuSO4 solution may be considered a mass transfer limited process at, for this type of industrial process, relevant conditions. The extended model developed by Al-Tarazi et al. (2004) has been used to predict the rate of H2S absorption. This model describes the absorption and accompanying precipitation process in terms of among others elementary reaction steps, particle nucleation and growth. The results from this extended model were compared to results obtained with a much simpler model, regarding the absorption of H2S in CuSO4 containing aqueous solutions as absorption of a gas accompanied by an instantaneous irreversible reaction. From this comparison it appeared that the absorption rate of H2S in a CuSO4 solution can, under certain conditions, be considered as a mass transfer rate controlled process. Under a much wider range of conditions the error that is made by assuming that the absorption process is a mass transfer controlled process, is still within engineering accuracy. This simplication allows for a considerable reduction of the theoretical effort needed for the design of a G/L contacting device. Furthermore, the simulations also indicated that the absorbent composition can be further optimized by the addition of a buffering solution (i.e., if the pH of the absorbent is controlled). A comparison of the experimental results and the simulated results showed that the extended model gives an under prediction of the H2S absorption rate for the experimental conditions applied.

INTRODUCTION Gas-liquid processes are commonly employed in the chemical industry. In the case of removal of H2S from a gas stream, the scrubbing solution may contain dissolved basic reagents (alkanolamines or NaOH), oxidizing chemicals (Fe3 ligands) or solids forming components (mostly Me2 ions). For a more complete overview of the existing
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technologies we would like to refer to the textbook by Kohl and Nielsen (1997). When the absorbed gaseous component reacts in the liquid, it is possible that the rate of absorption of the gaseous component is enhanced by the chemical reaction. Understanding how the reaction rate inuences the gas absorption rate is therefore a vital prerequisite for the design of an efcient contactor. For simple irreversible reactions this effect can readily be estimated using analytical or approximate solutions of various mass transfer models (See e.g. Westerterp et al. (1984)). For other cases (e.g. complex or equilibrium reactions) the effect of the reaction rate on the gas absorption rate cannot be determined analytically, making a numerical approach necessary. For the case of H2S absorption in, and reaction with, a metal sulfate containing solution, the rate at which H2S absorbs in the solution is the result of a number of process steps involving absorption and reaction. The reaction rate at which H2S and metal ions react to form solid metal sulde is determined by two processes; rst, the formation of new metal sulde nuclei and second, the growth of existing precipitates. All process steps need to be taken into account to yield an accurate description of the H2S absorption rate. Unfortunately, the rate of formation of new precipitate particles is a highly non-linear function of the concentration of the reacting com hnel and Garside (1992)). Furthermore, the rate of growth of ponents (Nielsen (1964), So existing particles is the result of a number of process steps (like diffusion of reacting components to the precipitate surface and the rate at which the ions are incorporated in the crystal), all of which can be rate-limiting. Clearly an accurate model incorporating all absorption and reaction steps is required to describe the rate of absorption of H2S in a metal salt solution. Such a model has been developed by Al-Tarazi et al. (2004). This extensive model was originally developed as a tool for the design of contactors for the removal of heavy metal salts from a liquid stream using H2S, but can also be used as a tool for the design of contactors for the removal of H2S from a gas stream using metal salt solutions. However, experimental results (e.g. ter Maat (2005)) seem to indicate that, for many operating conditions, the absorption of H2S into a CuSO4 solution can be described with a very simple model that considers the absorption of H2S in a CuSO4 solution to be a process of mass transfer accompanied by an instantaneous irreversible reaction, or even as gas phase mass transfer limited absorption process. In this contribution the results of this simplied approach will be compared with the results of the rigorous model of Al-Tarazi et al. (2004), and the applicability of this simplied approach will be discussed. Furthermore, experimental results are also compared to the model prediction.

LITERATURE The use of H2S for the (selective) precipitation of valuable metal compounds from leaching solutions has been known to the ore rening industry for a long time (for a review see Kroschwitz and Howe-Grant, 1991). Thus far, only limited fundamental research on the phenomenon of absorption of H2S in a solution, accompanied by a precipitation reaction of a highly insoluble metal sulde, has been performed. The work of Mishra and Kapoor (1978) can be regarded as a pioneering attempt to couple the concept of absorption of a gas
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in a reactive liquid and the theory of precipitation dynamics. They investigated the precipitation of cadmium(II) sulde from a cadmium(II) chloride solution in a bubble column reactor. The absorption of H2S in a diluted cadmium chloride solution could, according to their own conclusions, be described by assuming that the absorption of H2S into the solution was accompanied by an instantaneous irreversible reaction between H2S and the metal ion. The mass transfer model used in their study was based on the Higbie penetration model (Higbie, 1935). It must be noted however that the cadmium chloride concentration applied was so low, that the inuence of the reaction of the absorption rate was rather small, and therefore that the accuracy of their ndings might be debatable. The absorption of H2S into a diluted copper sulfate solution was investigated by Oktaybas et al. (1994), who used an experimental setup identical to the one used by Mishra and Kapoor (1978). Oktaybas et al. also used the Higbie penetration model and the assumption of an irreversible instantaneous reaction between H2S and Cu2 to explain the results. However, their model description did not explain the observed dependency of the reaction rate on the pH, observed at pH values below 2. It is likely that a change in one of the parameters, which were assumed to be constant (e.g. changes in the diffusion coefcient of H2S or the bubble rising velocity), or the rate of precipitation, was, at least partially, responsible for the observed change in the absorption rate. Broekhuis et al. (1992) investigated the removal of dilute H2S from a gas stream using copper and zinc sulfate solutions in a stirred cell reactor. Here, the rate of absorption of H2S in a copper sulfate solution was found to be gas phase mass transfer limited, while the absorption rate of H2S into a zinc sulfate solution was found to be a function of the amount of unconverted zinc sulfate. They did not attempt to present a fundamental description of the simultaneous absorption and precipitation of H2S in metal sulfate solutions. Ter Maat et al. (2005) investigated the removal of dilute H2S from a gas stream using copper, zinc and iron sulfate solutions in a bubble column reactor. The CuSO4 solution was shown to be the most suitable solution for H2S removal. The laboratory experiments indicated that the absorption of H2S in a CuSO4 solution, at the experimental conditions tested, is a gas phase mass transfer limited process. In the same study the applicability of a CuSO4 solution for the removal of H2S from a biogas stream was demonstrated on a pilot plant scale. The use of metal salt solutions for desulfurization has further been mentioned in open literature (Manning, 1979, Brown, 1980), and in the patents of Spevack (1980) and Harvey (1980), but no fundamental model description of the absorption of H2S into a metal salt solution, accompanied by a precipitation reaction, was presented. Such a fundamental model, which will also be used in this study describing the absorption of H2S into a solution of (a mixture of) metal salts, accompanied by a precipitation reaction, was developed by Al-Tarazi et al. (2004).

THEORY REACTION SCHEME Upon the absorption of H2S into an aqueous bivalent metal sulfate solution a number of reactions will occur. After H2S is dissolved in water (equation 1) it dissociates in two steps according to equations 2 and 3. When sufcient thermodynamic driving force
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SYMPOSIUM SERIES NO. 152 Table 1. Equilibrium constants Reaction 2 3 4 6 7 Equilibrium constant HS H3 O Ka1,H2 S H2 S 2 S H3 O Ka2,H2 S HS KSP Me2 S2 Kw H3 O OH Ka2,H2 SO4 H3 O SO4 HSO4 2 2.0 Numerical value pK 6.97 12.9 23.7 for ZnS 39.2 for CuS 14

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Source Horvath, 1985 Horvath, 1985 Dean, 1992 Horvath, 1985 Horvath, 1985

(i.e. at a supersaturation ratio larger than 1) is present the subsequent precipitation reaction between the sulde ion formed during the second dissociation step, and the metal ions can occur (equation 4). The supersaturation ratio is dened as shown in equation 5. Other reactions that can occur are the water equilibrium (equation 6), and the dissociation of the bisulfate ion (equation 7). The equilibrium constants of equations 2 to 7 are presented in Table 1. H2 S(G) ! H2 S(L)
k1,1 k1,2 k2,1 k2,2 k3

(1) (2) (3) (4) (5) (6) (7)

H2 S H2 O HS H2 O

! HS H3 O

! S2 H3 O

! MeS # Me2 S2 S Me S =KSP H3 O OH HSO 4 H2 O

! 2 H2 O

! H3 O SO2 4

SIMPLE MODEL DESCRIPTION It is likely that for a process in which highly insoluble precipitates (as is the case for copper sulde) are formed, the precipitation (nucleation) may be considered to be fast or even hnel, 1992, Nielsen, 1964). In that case, instantaneous with respect to mass transfer (So
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it is possible to derive a simple set of equations that describe the rate of absorption. For gas absorption accompanied by an instantaneous irreversible reaction the rate of absorption is determined by the mass transfer on both sides of the gas-liquid interface. Two cases can be distinguished: 1) a gas and liquid phase mass transfer limited regime and 2) a gas phase mass transfer limited regime. Case 1: gas and liquid phase mass transfer limited regime In case of an instantaneous irreversible reaction, components A (H2S) and B (Cu2) cannot exist simultaneously at the same location in the solution. In this case the overall mass transfer (volumetric transfer rate) can be described by equation 8. For the lm model the enhancement factor of the instantaneous irreversible reaction (for the overall mass is then dened as given in equation 9 (denition of equation 9 according transfer) EH 2 S;1 to lm model). Basic equations simple model description. J H2 S a
EH 2 S,1 CH2 S,G EH 2S 1 1 mkL,H2 S a kG,H2 S a   DCu CCu,L 1 DH2 S mCH2 S,G

(8)

(9) (10)

JH2 S a kG,H2 S aCH2 S

Case 2: gas phase mass transfer limited regime If the mass transfer rate of Cu2-ions from the liquid bulk to the interface is high compared to the mass transfer rate of H2S from the gas bulk to the interface, the gas side mass transfer resistance entirely determines the rate of absorption. The gas side limited mass transfer of H2S is expressed by equation 10. In case the simplication is allowed the minimum of these two boundary cases 1 and 2 denes the overall mass transfer rate in the absorption process. In this study, it will be investigated to which degree, and under which conditions, this simplication is allowed. A comparison of the absorption rate as predicted with the model and the extended model of Al-Tarazi will be made (Al-Tarazi et al. 2004, a short description is given in the paragraph Comparison with extended model). Furthermore, H2S absorption experiments will be carried out to verify the validity of both the extended model described by Al-Tarazi and the simplied model that assumes an instantaneous irreversible reaction.

EXPERIMENTAL SETUP The experiments were performed in a Mechanically Agitated Gas-Liquid Reactor (MAGLR) (See Figure 1). The experimental setup consisted of a gas mixing section, in which the desired gas ow is composed, a reactor section, and a gas analysis section. The MAGLR was operated batch wise with respect to the liquid phase and continuously
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Figure 1. Schematic representation of the experimental set-up

with respect to the gas phase. The glass double walled reactor, D 8.25 cm, V 1065 cm3, was operated batchwise with respect to the liquid phase and continuously with respect to the gas phase. The liquid could be intensely stirred with a six bladed rushton turbine, D 45 mm, H 11 mm, located 42 mm from the bottom of the reactor. The gas phase was mixed with a 2-bladed stirrer. Both stirrers were mounted on a single axis with a diameter of 10 mm. The speed of the stirrer could be varied between 0 and 2000 rpm. The reactor was equipped with 4 bafes. Gas was sparged into the liquid with a diffusor. The diffusor had 5 holes in a rectangular pitch with a diameter of 1 mm. The temperature of and the pressure in the reactor were recorded. In the gas mixing section a feed gas mixture with the desired ow rate and composition was prepared from pure gases using Brooks 5150 thermal mass ow controllers. The gas leaving the reactor was led through a caustic scrubber, before discharge to the atmosphere. A Tescom series 1700 back pressure regulator was used to regulate the reactor operating pressure. For H2S absorption experiments the gas-liquid reactor was lled with the desired solution (metal sulfate or sodium hydroxide). To avoid interference from gasses which might have absorbed from
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the atmosphere (e.g. N2 or CO2), the reactor contents were subsequently degassed by evacuation. The temperature of the metal sulfate solution in the reactor was maintained at 293 K, after which, at t 0, a gas stream with the desired composition was fed into the reactor at a owrate of 5.0 Nml/s. The pressure in the reactor was kept at 120 kPa. A small gas sample stream from the reactor efuent was diluted with air, and the H2S in that stream was converted to SO2 at 350 8C over stainless steel wool as catalyst. The resulting SO2 concentration in the sample stream was determined using a MAIHAK MULTOR 610 multicomponent IR analyser, which simultaneously determined the CO2 concentration (For details see also Ter Maat, 2005). The volumetric mass transfer coefcient of the MAGLR was determined from CO2 absorption experiments in pure water or metal sulfate solutions. These experiments were performed either by adding CO2 to a stream of pure N2 (to determine the physical characteristics of the setup), or to a mixture of N2 and H2S (to determine the kOVa during an H2S absorption experiment). EXPERIMENTAL RESULTS AND DISCUSSION During introductory (batch) experiments using a stirred cell with an undisturbed, at G/L interface, the formed copper sulde particles oated on the liquid surface, probably due to their hydrophobic nature. This hampered the interpretation of the experimental results. Therefore, the mechanically agitated gas-liquid reactor (in which the G/L interface is less static) was chosen as a model reactor. An extra advantage of the MAGLR is that the G/L behavior of an industrial absorber more closely resembles a MAGLR than a at interface model reactor. A drawback of this reactor type appeared to be that the Residence Time Distribution (RTD) of the gas phase could not be described by plug ow nor by CISTR like behaviour. A review article by Joshi et al. (1981) concludes that the gas phase RTD in MAGLRs is equivalent to a single CISTR or two CISTRs in series or in between the two. Hanhart et al. (1963) found that the RTD of the gas phase can be described adequately by a single CISTR at stirring speeds above the critical stirring speed (900 rpm for the setup used). At lower stirring speeds, as mostly applied during this study, the RTD of the gas phase can be described by 2 CISTRs in series. Thus, the concentration of the gas leaving the reactor cannot be readily used for the interpretation of the experimental results. This is especially important when the H2S conversion is high, and H2S concentrations in the gas phase may vary considerably from bubble to bubble. ABSORPTION OF H2S IN NaOH SOLUTIONS To characterize the experimental setup an H2S absorption experiment using an aqueous 0.0198 molar NaOH solution was performed. This experiment was continued up to the point where the NaOH solution was fully depleted. The reaction between H2S and NaOH is known to be instantaneous with respect to mass transfer (Danckwerts, 1970). The H2S absorption in a NaOH solution is therefore usually gas phase mass transfer limited, provided the gas does not consist of pure H2S and the concentration of NaOH is sufciently high. Therefore this experiment can be used to determine the H2S
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1.20 1.00

20

15 CGout,H2S[mol m-3] 0.80 0.60 0.40 0.20 0.00 2000 0 2500 3000 3500 Time [s] 4000 4500 10 COH- [mol m-3]

H2S concentration (lh axis) physical H2S absorption (lh axis) OH- concentration (rh axis)

Figure 2. The concentration of H2S in the gas stream leaving the reactor and the concentration of NaOH as a function of time. N 200 rmp

concentration in the gas leaving the reactor in the case of gas phase limited mass transport. At the start of the experiment 600 ml of a NaOH solution was added to the reactor. After the desired reaction temperature was reached a gas stream containing 2 V% H2S was fed to the reactor. In steady state (up to t 2000 s) the concentration of H2S in the gas leaving the reactor varied around 30 ppmV. The result of this experiment is shown in Figure 2: The NaOH concentration in the reactor was estimated by integrating over the H2S mass balance in time. It appeared that the H2S concentration of the gas leaving the reactor was not a function of the NaOH concentration of the solution until the NaOH solution was nearly depleted. Thus, up to this point H2S absorption takes place in the gas phase mass transfer limited regime. When the solution is depleted the H2S concentration in the reactor efuent increases rapidly. As reference the increase in H2S concentration that would occur in the case of physical absorption only is also shown. The time at which the curve for physical H2S absorption starts was chosen arbitrarily.

ABSORPTION OF H2S IN CuSO4 SOLUTIONS With the physical characteristics of the reactor known, the absorption of H2S in a copper sulfate solution was studied using a 0.5 M CuSO4. For H2S concentrations of 4% or more foaming occurred (This effect is also mentioned in Ter Maat et al., 2005). Therefore,
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the H2S concentration in the feed gas was kept at 2%. It appeared that very high H2S conversions could be obtained for a H2S percentage in the feed gas of 2 V% or lower; concentrations of H2S in the reactor efuent varied between 20 and 40 ppmV, which was comparable to the H2S concentration when using a NaOH solution as absorbent. Next, an experiment was carried without an 0.1 M CuSO4 solution up to the point where the CuSO4 solution was fully depleted. In steady state (up to t 13000 s) the concentration of H2S in the gas leaving the reactor again varied around 30 ppmV. The CuSO4 concentration had no inuence on the H2S conversion until the CuSO4 concentration dropped below 410 mol m23 (The copper concentration in the liquid was estimated from the integration of the H2S mass balance. The accuracy of this mass balance was approximately 510%). Only then the H2S concentration in the reactor efuent started to increase. Taken together with the results from the NaOH experiments this demonstrates that the H2S absorption in a copper sulfate solution most probably takes place in the gas phase mass transfer limited regime if the copper concentration is sufciently high. When the solution is depleted the H2S concentration in the reactor efuent increases rapidly. The experimental result is shown in Figure 3. As reference the increase in H2S concentration that would occur in the case of physical absorption only is also shown. In a series of experiments the inuence of the stirrer speed on the H2S concentration in the reactor efuent was investigated using a 0.1 M CuSO4 solution as absorbent

1.0 0.9 0.8 CH2Sout [mol m-3] 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 12000
H2S concentration (lh axis) physical H2S absorption (lh axis) Cu2+ concentration (rh axis)

20

10

0 13000 14000 15000 Time [s] 16000 17000

Figure 3. The concentration of Cu2 in the liquid and the concentration of H2S in the gas stream as a function of time. N 200 rmp 489

CCu2+ [mol m-3]

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Table 2. The concentration of H2S in the gas stream leaving the reactor as a function of stirrer speed. T 293 K, P 120000 Pa, V 700 ml, H2S 2 V%, CuSO4 0.1 M N [rpm] 50 100 150 200 250 H2S [ppmV] 39.0 45.3 35.1 33.2 42.2

(See Table 2). The concentration of H2S in the reactor efuent hardly changed with increasing stirrer speeds, which can be explained since the relatively small increase in the overall mass transfer coefcient that occurs with increasing stirrer speed may be offset by the increasing fraction of gas bubbles with a relatively short residence time (the gas phase will show a more CISTR-like behavior with increasing stirrer speed).

COMPARISON WITH EXTENDED MODEL Al Tarazi et al. (2004) have developed a model that describes mass transfer accompanied by reaction for the case of the precipitation of metal suldes in an aqueous solution containing heavy metal ions (notably Cu2 and Zn2) that is continuously contacted with a H2S containing gas. This model is thought to be able to predict the effect of operation, process conditions and reactor layout on the rate of H2S absorption, precipitation and particle size distribution. The gas phase was modelled using the lm model, and at the G-L interface local equilibrium was assumed. The solubility of the gas in the liquid was estimated from literature data (Horvath, 1985). The mass transfer zone was modelled according to Higbies penetration model (Higbie, 1935), and mass balances for all species were set up incorporating equations 27. As a driving force not only the concentration gradient was used, but the electrostatic potential gradient was also taken into account. The concentration prole of the individual species in the liquid, near the gas liquid interface, can be calculated as a function of contact time using equation 11 (penetration model). With the exception of the rate of precipitation, all reaction rate equations are (the summation of) rst order reactions. A mass balance for CuS was treated separately since the rate of crystal growth and nucleation are separate functions of the supersaturation ratio and for these, population balances are used (for details see Al Tarazi et al. (2004)). The electrostatic potential can be calculated by the use of the Nernst-Einstein equation (Newman, 1973) assuming dynamic electroneutrality (equation 12). The precipitation kinetics are taken into account through equations 13 to 15. The linear growth rate of particles is given by equation 13, the molar growth rate of particles is given by equation 14, and the molar rate of birth of new particles B0 is given by equation 15.
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Basic equations simple model description. @Ci @2 Ci F @(fCi ) ri Di 2 zi Di RT @x @t @x PNC i RT i1 zi Di @@C f(x, t) PNC 2 x F i 1 z i D i C i p !g CCu2 CS2 p 1 G kg KSP G0
1 X i 1 2 {brn(z, L2 i )GLi (Li Li1 )}

(11) (12) (13) (14)

B0 aPL3 0 kn

p !n CCu2 CS2 p 1 KSP

(15)

The particle size distribution of the formed metal sulde particles was calculated using the population balance as proposed by Randolph (1988). Further details of the model description, the applied boundary conditions and relations used to describe the population balances can be found in Al-Tarazi et al. (2004). How the various chemical reactions are related is shown in Figure 4.

Figure 4. Overview of the model 491

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The precipitation growth parameters; kg, g and nucleation parameters; kn and n were tted using laminar jet experiments (Al Tarazi et al., 2004). The model can now be used for the prediction of H2S absorption rate under various process conditions. As already pointed out in the introduction, if the precipitation reaction is sufciently fast, the absorption of H2S in the Me2-ions containing solution may be regarded as absorption of a gaseous component into a solution, accompanied by a very fast irreversible reaction (the simple model). This can occur when the driving force for the precipitation is sufciently high (as is usually the case for the formation of highly insoluble metal suldes). In this case the absorption rate can be described with equation 8 or, in the case of gas phase mass transfer limitation equation 10 which can be regarded as limited cases of the extended model given by Al-Tarazi et al. (2005). This simplication allows for a considerable reduction of the computation time needed for the design of a G/L contacting device. Downside of this simplied approach is the loss of data regarding the particle size distribution. The ratio of the maximal possible absorption rate as obtained with the simplied model (equations 8 and 10) to the ux predicted by the extended model by Al-Tarazi (based on equations 11 to 15) is shown in Figures 5 through 7. Each plot shows the ratio at a different pH.

Figure 5. Absorption of H2S in a CuSO4 solution: ratio of simulated absorption rate (extended model) and maximum possible absorption rate (simplied model) at pH 5.5, kL 1.1 1025 m s21, kG 1.1 1024 m s21 492

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Figure 6. Absorption of H2S in a CuSO4 solution: ratio of simulated absorption rate and maximum possible absorption rate at pH 3.5, kL 1.1 1025 m s21, kG 1.1 1024 m s21

From these gures it can be seen that the differences between the maximum possible ux as predicted by the simplied model and the predicted ux according to the extended model are small (, 30%) for large areas of the investigated combinations of Cu2 and H2S concentrations. At high concentrations of H2S and low concentrations of Cu2 the differences are negligible. Under process conditions that could realistically occur in a biogas desulfurization unit (, 2% H2S, high copper concentration, pH 3.5 or higher), the simplication can also be applied; however loss of accuracy will occur. At the remaining combinations Cu2 and H2S concentrations the simplied model will give a signicantly different result than the extended model (the lighter areas in Figures 5 through 7). However experiments have shown that the applicability of the simplied approach is better than may be expected based on the model results. H2S absorption experiments were carried out using an H2S concentration of 2 V% and a copper concentration that varied between 0.01 and 0.1 mole dm23. The experimental results showed that the absorption of H2S under these conditions may be considered gas phase limited. It may thus be assumed that the extended model (more aimed at giving a correct prediction of the particle size distribution of the produced CuS, than
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Figure 7. Absorption of H2S in a CuSO4 solution: ratio of simulated absorption rate and maximum possible absorption rate at pH 2.0, kL 1.1 1025 m s21, kG 1.1 1024 m s21

at giving a correct H2S absorption rate) gives an under prediction of the H2S absorption rate. Hence it may be concluded that the area in which the absorption may be described by the simplied approach may be more extended than suggested in Figures 5 to 7.

CONCLUSIONS In this study the desulfurization of gas streams using aqueous copper sulfate (CuSO4) solutions as washing liquor has been studied theoretically and experimentally. Absorption experiments were carried out in a Mechanically Agitated Gas Liquid Reactor. This reactor was characterized using the absorption of CO2 in water and the absorption of H2S in NaOH solutions. H2S absorption experiments were conducted at a temperature of 293 K and CuSO4 concentrations between 0.01 and 0.1 M. These experiments showed that the copper sulfate solution efciently removes H2S even at very low copper concentrations. The experimental results indicate that for industrially relevant process conditions the absorption of H2S in a CuSO4 solution may be considered a gas phase mass transfer limited process. An extended model developed
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by Al-Tarazi et al. (2004) has been used to predict the rate of H2S absorption and was compared to a simplied mass transfer model, assuming an instantaneous irreversible reaction. This comparison showed that the absorption rate of H2S in a CuSO4 solution can be considered a completely mass transfer controlled process under certain conditions. Under a much wider range of conditions the error that is made by assuming that the absorption process is a mass transfer controlled process, is still within engineering accuracy. A comparison of the experimental results and the simulated results of the extended model showed that the extended model gives an under prediction of the H2S absorption rate for the experimental conditions applied. NOMENCLATURE SYMBOLS a Specic surface area [m21] g Exponent in growth rate expression [2 ] k Reaction constant [s21], [m3 mole21 s21] k Mass transfer coefcient [m s21] m Gas distribution coefcient [2 ] n Exponent in nucleation rate expression [2 ] r Reaction rate [mole m23 s21] t Time variable [s] x Place variable [m] z Ion valency [2 ] B Particle nucleation rate [mole m23 s21] C Concentration [mole m23] D Diffusion coefcient [m2 s21] E Chemical enhancement factor [2 ] F Faraday constant [C mole21] G Particle growh rate [m s21] or [mole m23 s21] J Gas absorption rate [mole m22 s21] K Equilibrium constant [mole m23] L Particle diameter [m] N Stirrer speed [rpm] R Universal gas constant [mole J21 K21] S Degree of supersaturation [2 ] T Temperature [K] GREEK a b f r D

Particle shape factor (vol) [2 ] Particle shape factor (surf) [2 ] Electrostatic potential gradient [V m21] Density [kg m23] Denoting a difference [2 ]
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SUB-SCRIPTS a g i n w G L SP 0 1

referring referring referring referring referring referring referring referring referring Innite

to to to to to to to to to

acidity particle growth component i particle nucleation water gas liquid the solubility product critical nucleus

REFERENCES
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