PII: S0043-1354(01)00031-8 Wat. Res. Vol. 35, No. 13, pp. 3041–3048, 2001 # 2001 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0043-1354/01/$ - see front matter EFFECTS OF IMPURITIES ON OXYGEN TRANSFER RATES IN DIFFUSED AERATION SYSTEMS JIA-MING CHERN*, SHUN-REN CHOU and CHOU-SHENG SHANG Department of Chemical Engineering, Tatung University, 40 Chungshan North Road, 3rd Sec., Taipei, 10451 Taiwan (First received 20 October 2000; accepted in revised form 22 December 2000) Abstract}A series of unsteady-state reaeration tests were performed in a 500-L tank at 0.81–4.58 m3/h diffused-air flow rate and 288–302 K water temperature. Three different types of impurities: soybean oil, surfactant, and diatomaceous earth were doped to simulate the impurities in wastewaters and the effects of the impurities on the oxygen transfer rate were investigated. The ASCE and the two-zone oxygen masstransfer models were used to analyze the unsteady-state reaeration data and the volumetric mass-transfer coefficients determined from the unsteady-state reaeration data were correlated as a function of the diffused-air flow rate, water temperature, and impurity concentration. The results showed that the alpha factors based on the ASCE model are less sensitive to the impurity concentration while the presence of the impurities significantly reduces the alpha factors in the gas bubble zone. The saturation DO concentration and volumetric oxygen mass-transfer rate can be predicted by the two-zone model along with the correlation obtained in this study. # 2001 Elsevier Science Ltd. All rights reserved Key words}mass transfer, bubble aeration, soybean oil, surfactant, suspended solids NOMENCLATURE a A A1 A2 b CGO2 Cimp CO2 C0 C1 CO 2 CO 2 ;S C1;o 2 g G ki KL a KLB aB KLS aS P P0 parameter defined in equation (15), atm cross-sectional area of the aeration tank, m2 parameter defined in equation (12), dimensionless parameter defined in equation (13), kmol/m3 parameter defined in equation (16), atm/m gas-phase oxygen concentration in the gas bubble, kmol/m3 impurity concentration, ppm dissolved oxygen concentration at time t, kmol/m3 initial dissolved oxygen concentration, kmol/m3 equilibrium dissolved oxygen concentration at 1 atm pressure, kmol/m3 equilibrium DO in the water at position Z, kmol/ m3 equilibrium DO in the water at atmospheric pressure, kmol/m3 saturated dissolved oxygen concentration, kmol/m3 gravity acceleration constant, m/s2 nitrogen molar flow rate, kmol/hr correlation parameters defined in equation (20), i ¼ 128 volumetric mass transfer coefficient in the ASCE model, 1/hr bubble-zone volumetric mass transfer coefficient, 1/hr surface reaeration-zone volumetric mass transfer coefficient, 1/hr gas pressure at the depth ZS Z, atm atmospheric pressure, atm *Author to whom all correspondence should be addressed. Tel.: +886-2-2592-5252 ext 3487; fax: +886-2-25861939; e-mail: [email protected] PW R Q t T y y0 VOTR Z ZS water vapor pressure, atm gas constant, atm-m3/kmol-K diffused air flow rate, m3/h aeration time, h water temperature, K mole ratio of oxygen in the gas bubble, kmol O2/ kmol N2 feed mole ratio of oxygen in the gas bubble, kmol O2/kmol N2 volumetric oxygen transfer rate, kmol O2/h-m3 position above the diffuser, m water depth, m Greek symbols a alpha factor defined in equation (4), dimensionless b beta factor defined in equation (5), dimensionless e the gas holdup dimensionless r water density, kg/m3 y theta factor defined in equation (6), dimensionless INTRODUCTION Oxygen transfer or aeration plays an important role in biological wastewater treatment processes. For example, effective operation of the activated sludge process requires an adequate supply of dissolved oxygen to support the microbial oxidation processes that occur in the aeration tanks. The oxygen transfer process is the primary use of electrical energy in the secondary treatment process and represents a significant capital cost as well. Therefore, significant 3041 3042 Jia-Ming Chern et al. attention has been paid to the design and operation of aeration systems with lower capital cost and higher aeration efficiency in the wastewater treatment processes. Many different types of aeration systems have been developed over the years to improve the energy efficiency of the oxygen transfer process. In order to evaluate the performance of different types of aeration systems, the American Society of Civil Engineers (ASCE) and US EPA jointly developed a standard for the measurement of oxygen transfer in clean or tap water (ASCE, 1984). The standard conditions recommended by ASCE is zero dissolved oxygen level, 208C water temperature, and 1 atm pressure. The oxygen transfer rate at non-standard conditions is adjusted by the so-called alpha, beta, and theta factors which depend on the types of aerators, mixing or turbulence intensity, and wastewater characteristics, etc. (Gilbert, 1979; Stenstrom and Gilbert, 1981; Doyle and Boyle, 1985; Eckenfelder, 1989; Asselin et al., 1998). The effects of impurities in wastewater on the oxygen transfer rate have been studied and contradictory results have been reported. Zieminski et al. (1967) studied the behavior of air bubbles in dilute aqueous solution and found that the volumetric mass-transfer coefficient increased in the presence of mono- and di-carboxylic acid and aliphatic alcohol. Zieminski and Lessard (1969) studied the effects of chemical additives on the performance of an air– water contactor and attributed the increase of the oxygen transfer rate to the increase of the surface area. Koide et al. (1976) studied the mass transfer from single bubbles in aqueous solutions containing surfactants and reported the volumetric mass-transfer coefficient decreased in the presence of surfactants. Kawase and Ulbrecht (1982) studied the effect of surfactant on the terminal velocity of gas bubbles and mass-transfer rate in a non-Newtonian fluid and found that the bubble terminal velocity and volumetric mass-transfer coefficient both decreased in the presence of surfactant. Gurol and Nekouinaini (1985) studied the effect of organic substances on the mass-transfer rate in bubble aeration and reported the volumetric mass-transfer coefficient was decreased by the surface-active compound, but increased by the alcohol and carboxylic acids. Wagner and Pöpel (1996) studied the effect of surface-active agents on oxygen transfer rate in a fine-bubble aeration system and found that the volumetric mass-transfer coefficient decreased in the presence of surfactant. Weng et al. (1997) studied the effect of soybean oil on the oxygen transfer in penicillin production and found that soybean oil acted as a good foam inhibitor but decreased the oxygen transfer rate. Leu et al. (1998) studied the effects of surfactants and suspended solids on oxygen transfer rate and found the volumetric mass-transfer coefficient decreased with increasing surfactant or suspended solid concentration to a minimum and then increased as the impurity concentration increased. All the studies in the literature used the ASCE oxygen mass transfer model to evaluate the effect of impurities on the volumetric mass-transfer coefficient. This paper presents the experimental results of unsteady-state reaeration tests at various water temperatures and diffused air flow rates in the presence of soybean oil, surfactant, and suspended solids that are commonly found in domestic wastewaters. The unsteady-state reaeration data will be analyzed by both the conventional ASCE model and a new two-zone model (Chern and Yu, 1995, 1997, 1999) recognizing that there exist two different mass-transfer zones in diffused aeration systems, the gas bubble zone and the surface reaeration zone. The volumetric mass-transfer coefficients in the two mass-transfer zones of the two-zone model can be calculated from the ASCE model parameters and the effects of the impurities on the volumetric mass-transfer coefficients in the gas bubble zone and surface reaeration zone will be discussed separately. ASCE MASS TRANSFER MODEL The ASCE standard is based on the unsteady-state reaeration technique where in the body of clean test water is first deoxygenated using cobalt chloride and sodium sulfite solution and then reaerated back to ‘‘saturation’’ or steady-state conditions with accurate experimental measurement of the dissolved oxygen level with time. The following simplified mass transfer model is used to analyze the reaeration data obtained: dCO2 ¼ KL aðC1;O CO2 Þ 2 dt ð1Þ where CO2 is the dissolved oxygen concentration the saturation dissolved oxygen at time t, C1;O 2 concentration, and KL a the volumetric mass-transfer coefficient for oxygen. Equation (1) can be readily integrated to yield the following expression for CO2 as a function of time CO2 ¼ C1;O ðC1;O C0 ÞexpðKL atÞ 2 2 ð2Þ where C0 is the initial dissolved oxygen concentration at t ¼ 0. A nonlinear regression analysis based on the Gauss–Newton method is recommended by ASCE to fit equation (2) to the experimental data using KL a, C1;O and C0 as three adjustable model 2 parameters. The volumetric oxygen transfer rate (VOTR) at zero DO concentration is calculated by the following equation: VOTR ¼ dCO2 ¼ KL aC1;O 2 dt ð3Þ The alpha factor, a, is the ratio of the volumetric mass-transfer coefficient in wastewater to that in clean or tap water and is expressed as (Stenstrom and Effects of impurities on oxygen transfer rates Gilbert, 1981) a¼ KL aðwastewaterÞ KL aðtap waterÞ ð4Þ The beta factor, b, is the ratio of the saturation DO concentration in wastewater to that in clean water and is expressed as (Stenstrom and Gilbert, 1981) b¼ C1;O ðwastewaterÞ 2 ðtap waterÞ C1;O 2 ð5Þ Assuming that the gas-phase oxygen concentration does not vary with time and using at Z ¼ 0; y ¼ y0 as the boundary condition to equation (7), and at t ¼ 0, CO2 ¼ C0 as the initial condition to equation (8), we developed an analytical solution for the dissolved oxygen concentration as a function of the aeration time (Chern and Yu, 1997) CO2 ¼ The theta factor, y, is used to adjust the volumetric mass-transfer coefficient at non-standard water temperature (Stenstrom and Gilbert, 1981) KL aT ¼ KL a298 yT298 ð6Þ A generally accepted value of the temperature correction factor, y is 1.024 (Stenstrom and Gilbert, 1981). 3043 KLB aB A2 þ KLS aS CO 2 ;S KLB aB A1 þ KLS aS KLB aB A2 þ KLS aS CO 2 ;S þ C0 KLB aB A1 þ KLS aS ð11Þ exp½ðKLB aB A1 þ KLS aS Þt where A1 ¼ h i 1 qffiffiffiffiffiffi p a 2 exp K1 b ZS 2b b K 1 2ZS n pffiffiffiffiffiffiffiffi h pffiffiffiffiffiffiffiffiio a a ZS K1 b erf 2b erf 2b K1 b ð12Þ TWO-ZONE MASS TRANSFER MODEL Consider a diffused aeration system in which the gas (air) is diffused into the liquid near the bottom of the aeration tank and flows upward through the liquid to the surface of the tank. The bubbling motion of the gas creates effective bulk motion and mixing of the liquid in the tank and a turbulent liquid surface. There exist two different mass-transfer zones and mechanisms for oxygen mass-transfer in diffused aeration systems: the gas bubble dispersion masstransfer zone exits below the turbulent liquid surface and the turbulent surface mass-transfer zone exists in the shallow region of the liquid surface. Each of these mass-transfer zones must be separately analyzed and properly accounted for in the overall mass-transfer model. The governing equations of the two-zone model are as follows: eA @CGO2 @y KLB aB ð1 eÞAðCO ¼ G CO2 Þ 2 @Z @t ð7Þ dCO2 AZS ð1 eÞ ¼ dt Z ZS 0 KLB aB ðCO CO2 Þ 2 ð1 eÞA dZ þ KLS aS ð1 eÞ ð8Þ ðCO CO2 ÞAZS 2 ;S ¼ C1 CO 2 yðP PW Þ y0 ð1 PW Þ C1 f1 exp½K1 ZS ða bZS Þ g K1 ZS ð1 PW Þ ð13Þ K1 ¼ KLB aB ð1 eÞAC1 y0 ð1 PW ÞG a ¼ P0 PW þ rgð1 eÞZS b¼ rgð1 eÞ 2 ð9Þ ð10Þ ð14Þ ð15Þ ð16Þ It is interesting to find that the two-zone model gives the same mathematical form of the dissolved oxygen concentration as the ASCE model. Therefore, the model parameters KLB aB and KLS aS can be determined from the ASCE model parameters by solving the following simultaneous algebriac equations: KL a ¼ KLB aB A1 þ KLS aS C1;O ¼ 2 KLB aB A2 þ KLS aS CO 2 ;S KLB aB A1 þ KLS aS ð17Þ ð18Þ Once the volumetric mass-transfer coefficients are calculated, the volumetric oxygen transfer rate at zero DO can be calculated by the following equation: VOTR ¼ KLB aB A2 þ KLS aS CO 2 ;S Equation (7) represents the oxygen mass balance in the gas phase, equation (8) the oxygen mass balance in the liquid phase, and equation (9) the equilibrium oxygen concentration in the tank. In equation (9), the gas pressure is a function of the liquid depth P ¼ P0 þ rgð1 eÞðZS ZÞ A2 ¼ ð19Þ According to equation (19), the oxygen transfer rate consists of two terms: one from the gas bubble zone and the other from the turbulently aerated surface. Depending on the water depth, and the type of diffusers used, one of these two terms can be the major contributor to the overall oxygen transfer. For example, the gas bubble zone represents the major portion of the overall oxygen transfer in a deep aeration tank with fine bubble diffusers in comparison with the surface reaeration zone. 3044 Jia-Ming Chern et al. Experiment All of the unsteady-state reaeration tests were conducted in a 500-L aeration tank. The experimental details follow the ASCE standard (ASCE, 1984) and were briefly described in the previous paper (Chern and Yu, 1997). Commercial soybean oil (President Co., Taiwan), commercial surfactant with primary ingredient of sodium dodecylbenzene sulfonate (Formosa Chemicals & Fibers, Taiwan), and diatomaceous earth (Grefco Minerals, USA) were added to the tap water to simulate commonly found impurities in wastewaters. At the beginning of each test run, the cobalt chloride and the impurity were simultaneously added to the tank and the tank liquid was aerated for at least 30 min to allow uniform distribution of the cobalt chloride and the impurity. Then pre-dissolved sodium sulfite solution was added and reaerated back to 99% of saturation. In addition to aeration tests in the 500-L tank, the saturation DO concentrations at atmospheric pressure in the presence of impurities were measured in a 2-L flask with a DO meter (WTW, OXI 96). The surface tension of the tap water in the presence of soybean oil and surfactant was measured by a surface-tension meter (Kruss Co., Model K-6). The experimental conditions for the unsteady-state reaeration tests are summarized in Table 1. RESULTS AND DISCUSSION A series of unsteady-state reaeration tests in clean water were conducted first to determine the volumetric mass-transfer coefficients at varying water temperatures and diffused-air flow rates. The Gauss– Table 1. Summary of the experimental conditions Atmospheric pressure Water temperature Diffused air flow rate Tank cross-sectional area Water depth Gas holdup Soybean oil concentration Surfactant concentration Silica concentration 758.3–762.1 mmHg 288–302 K 0.81–4.58 Nm3/h 0.541 m2 0.87–0.88 m 0.003 0–8.48 ppm 0–8.48 ppm 0–3180 ppm Newton method and equation (2) were used to determine the ASCE model parameters from which the two-zone model parameters were calculated by solving equations (17) and (18) simultaneously. The volumetric mass-transfer coefficients in both the ASCE and two-zone models can be correlated as a function of water temperature and diffused air flow rate: KL a ¼ k1 þ k2 Qk3 yT293:15 ð20Þ where KL a is the volumetric mass-transfer coefficient of unit h1, Q the diffused air flow rate of unit m3 h1. The correlation parameters in equation (20) are listed in Table 2 and the comparison between the experimental and predicted volumetric mass-transfer coefficients is shown in Fig. 1. As shown in Fig. 1, the predicted volumetric mass-transfer coefficients scatter around the diagonal line with a R2 value of 0.95. This indicates that equation (20) can be used to correlate the volumetric mass-transfer coefficients of clean water at varying water temperatures and diffused-air flow rates satisfactorily. As is shown in Table 2, k3 ¼ 0:69 for KLB aB and k3 ¼ 1:54 for KLS aS . This suggests that the diffused air flow rate has a stronger influence on the volumetric masstransfer coefficient in the surface reaeration zone than on that in the gas bubble zone. Table 2 also shows that the water temperature has a stronger influence on the volumetric mass-transfer coefficient in the gas bubble zone than on that in the surface reaeration zone (y ¼ 1:058 in the gas bubble zone and y ¼ 1:019 in the surface reaeration zone). Some previous test results showed that the saturation DO concentration C1;o2 was affected by the presence of impurities. In the ASCE model, the saturation DO concentration is treated as a model parameter to best fit the unsteady-state reaeration data. The saturation DO concentrations in the presence and absence of impurities are determined from the best fit of the reaeration data, and the beta factor is used to account for the impurity influence. In the two-zone model, the saturation DO concentration is not treated as a model parameter; it depends on the volumetric mass-transfer coefficients Table 2. Correlation parameters for the volumetric mass-transfer coefficients in the clean water and for the alpha factors in the presence of impurities Parameter k1 k2 k3 y Soybean oil k4 Soybean oil k5 Surfactant k4 Surfactant k5 Diatomaceous earth k4 Diatomaceous earth k5 ASCE-model KL a Gas bubble zone KLB aB Surface reaeration zone KLS aS 1.93E-9 0.85 0.73 1.036 0.380 0.630 0.619 0.797 0.780 2.94E-03 0 0.32 0.69 1.058 0.147 0.880 0.205 0.804 0.0594 3.77E-03 0.47 0.13 1.54 1.019 0.622 0.304 1.198 0.670 1.579 3.45E-03 Effects of impurities on oxygen transfer rates Fig. 1. Experimental and predicted volumetric mass-transfer coefficients in the clean water. Fig. 2. Equilibrium DO concentrations at atmospheric pressure in the presence of impurities. in the gas-bubble and surface reaeration zones as shown in equation (18). In order to calculate the two volumetric masstransfer coefficients from the ASCE model parameters using equations (17) and (18), we need to know the equilibrium DO concentrations at 1 atm ðC1 Þ and atmospheric pressure ðCO Þ. Theoretically 2 ;S the equilibrium DO concentration is a function of water temperature and composition from thermodynamic point of view. To investigate the effect of impurities on these equilibrium DO concentrations, tap water containing varying amounts of impurities was prepared and the results were shown in Fig. 2. It is clearly shown in Fig. 2, that the equilibrium DO 3045 Fig. 3. Experimental and predicted unsteady-state reaeration curves at different soybean oil concentrations. concentrations at 1 atm and atmospheric pressure are almost not affected by the impurities in the concentration range of concern. Therefore, for any test water temperature we can directly find the corresponding equilibrium DO concentration (Eckenfelder, 1989) or calculate the equilibrium DO with a suitable correlation equation to determine the volumetric mass-transfer coefficients in the two zones from the ASCE model parameters. After the mass-transfer coefficient correlations in the clean water were obtained and the effects of the impurities on the equilibrium DO at atmospheric pressure were clarified, another series of unsteadystate reaeration tests in the presence of impurities were conducted. Typical reaeration curves calculated by the two-zone model and the experimental reaeration data obtained in the presence of soybean oil at constant water temperature and diffused air flow rate are shown in Fig. 3. Following the same procedure, the oxygen volumetric mass-transfer coefficients (KL a of the ASCE model, KLB aB , and KLS aS in the twozone model) can be calculated from the unsteadystate reaeration data. For a given set of operating conditions (water temperature and diffused-air flow rate), the volumetric mass-transfer coefficients (KL a of the ASCE model, KLB aB , and KLS aS in the twozone model) in the absence of impurity were first calculated by equation (20), the alpha factors were then calculated by equation (4). Although the volumetric mass-transfer coefficients in the presence of impurities were found to vary with the water temperature, diffused air flow rate, and impurity concentrations, the alpha factors averaged from different diffused air flow rates and water temperatures were found to depend on the impurity concentrations only. The following empirical equation is proposed to correlate the alpha factor as a 3046 Jia-Ming Chern et al. Fig. 4. Experimental and predicted alpha factors at different soybean oil concentrations. function of the impurity concentration: a ¼ k4 þ ð1 k4 Þexp k5 Cimp Fig. 5. Experimental and predicted alpha factors at different surfactant concentrations. ð21Þ where Cimp is of unit ppm. The correlation parameters in equation (21), determined from nonlinear regression, are also listed in Table 2 and the comparisons between the predicted and experimental alpha factors in the presence of different impurities are shown in Figs 4–6. As shown in Fig. 4, all the alpha factors decrease exponentially with increasing soybean oil concentration and eventually reach constant values. For any given soybean oil concentration the ASCE-model alpha factor is less than the surface-zone alpha factor but greater than the bubble-zone alpha factor. Since the soybean oil molecules may orient themselves on the interfacial surface of the gas bubbles and create a barrier to diffusion of oxygen; the mass-transfer coefficient KLB will thus decrease significantly. However, the presence of soybean oil will decrease the surface tension and results in a decrease in the gas bubble size; the specific mass-transfer area a will thus increase. The combined effects, as shown in Fig. 4, show that KLB aB decreases with increasing soybean concentration. The alpha factor also decreases with increasing soybean oil concentration in the surface reaeration zone, but it is greater than that in the gas bubble zone. This suggests that the surface turbulence may restrict the formation of the oil film; as a result, the soybean oil has a weaker influence on reducing the mass-transfer rate in the surface reaeration zone. Fig. 6. Experimental and predicted alpha factors at different diatomaceous earth concentrations. Similar trends can also be found for the alpha factors in the presence of surfactant, as shown in Fig. 5. Eckenfelder (1989) pointed out that the retardation of mass-transfer rate is more significant in bubble aeration than in surface aeration where highly turbulent liquid surface restrict the formation of an adsorbed surfactant film. It is interesting to find that the alpha values in the surface reaeration zone are greater than unity. This suggests that the reduction of the surface tension may cause more air Effects of impurities on oxygen transfer rates Fig. 7. Experimental and calculated saturation DO concentrations in the presence of impurities. 3047 available gas–liquid mass-transfer area. In the surface reaeration zone, some suspended solids floating on the water surface adsorb a thin water film and provide more gas–liquid mass-transfer area. This may explain the increase of the alpha factor in the surface reaeration zone. For a given set of operating conditions, the volumetric mass-transfer coefficients in the gasbubble and surface reaeration zones can be calculated from equations (20) and (21); the system saturation DO concentration and the volumetric oxygen mass-transfer rate can thus be calculated by equations (18) and (19), respectively. Figures 7 and 8 show the experimental and predicted saturation DO concentration and the volumetric oxygen masstransfer rate, respectively. The experimental saturation DO concentration and the volumetric oxygen mass-transfer rate are actually those calculated from the ASCE-model. CONCLUSIONS * * * Fig. 8. Experimental and calculated volumetric oxygen transfer rates in the presence of impurities. entrainment and therefore enhance the oxygen transfer rate in the surface reaeration zone. Although many studies showed that suspended solids had little effect on the alpha factor, there is little or no consensus concerning the effect of suspended solids on the alpha factor (Gilbert, 1979). In this study, we also found that the ASCEmodel alpha factor was not significantly affected by the diatomaceous earth (a ffi 0:8), but remarkable effects of the diatomaceous earth on the alpha factors in the gas bubble and surface reaeration zones were identified, as shown in Fig. 6. Since no significant viscosity change due to the addition of diatomaceous earth was measured, we attributed the decrease of gas-bubble zone alpha to the change of hydrodynamic behavior of gas bubbles and the decrease of * A series of unsteady-state reaeration tests in the presence of soybean oil, surfactant, and diatomaceous earth were performed and the reaeration data were successfully analyzed by the ASCE and the two-zone oxygen mass-transfer models to obtain the volumetric mass-transfer coefficients. Empirical equations were successfully used to correlate the volumetric mass-transfer coefficient and alpha factor. With the correlation equations, the effect of the impurity on the alpha factor, saturation DO concentration, and volumetric oxygen transfer rate can be predicted by the two-zone model satisfactorily. For a given impurity concentration and diffused air flowrate, the alpha factor calculated by the ASCE-model is greater than that in the gas bubble zone but less than that in the surface reaeration zone. The addition of the impurities reduce the oxygen transfer rate in the gas bubble zone (alpha factor 51), but surfactant and diatomaceous earth can enhance the oxygen transfer rate in surface reaeration zone (alpha factor >1). Acknowledgements}The financial support from the National Science Council of Taiwan, Republic of China is greatly appreciated. REFERENCES ASCE (1984) ASCE Standard Measurement of Oxygen Transfer in Clean Water. American Society of Civil Engineers. 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