Syngas fermentation to biofuel: Evaluation of carbon monoxide mass transfer coefficient (kLa) in different reactor configurations

Lignocellulosic biomass such as agri‐residues, agri‐processing by‐products, and energy crops do not compete with food and feed, and is considered to be the ideal renewable feedstocks for biofuel production. Gasification of biomass produces synthesis gas (syngas), a mixture primarily consisting of CO and H₂. The produced syngas can be converted to ethanol by anaerobic microbial catalysts especially acetogenic bacteria such as various clostridia species.One of the major drawbacks associated with syngas fermentation is the mass transfer limitation of these sparingly soluble gases in the aqueous phase. One way of addressing this issue is the improvement in reactor design to achieve a higher volumetric mass transfer coefficient (k_La). In this study, different reactor configurations such as a column diffuser, a 20‐μm bulb diffuser, gas sparger, gas sparger with mechanical mixing, air‐lift reactor combined with a 20‐μm bulb diffuser, air‐lift reactor combined with a single gas entry point, and a submerged composite hollow fiber membrane (CHFM) module were employed to examine the k_La values. The k_La values reported in this study ranged from 0.4 to 91.08 h^?1. The highest k_La of 91.08 h^?1 was obtained in the air‐lift reactor combined with a 20‐μm bulb diffuser, whereas the reactor with the CHFM showed the lowest k_La of 0.4 h^?1. By considering both the k_La value and the statistical significance of each configuration, the air‐lift reactor combined with a 20‐μm bulb diffuser was found to be the ideal reactor configuration for carbon monoxide mass transfer in an aqueous phase. © 2010 American Institute of Chemical Engineers Biotechnol. Prog., 2011     

Interactions of cell morphology and transport processes in the lovastatin fermentation

The cholesterol lowering drug, Lovastatin (Mevacor), acts as an inhibitor of HMGCoA reductase, and is produced from an Aspergillus terreus fermentation.Pilot scale studies were carried out in 800 liter fermenters to determine the effects of cell morphology on the oxygen transport properties of this fermentation. Specifically, parallel fermentations giving (i) filamentous mycelial cells, and (ii) discrete mycelial pellets, were quantitatively characterized in terms of broth viscosity, availability of dissolved oxygen, oxygen uptake rates and the oxygen transfer coefficient under identical operating conditions.The growth phase of the fermentation, was operated using a cascade control strategy which automatically changed the agitation speed with the goal of maintaining dissolved oxygen at 50% saturation. Subsequently stepwise changes were made in agitation speed and aeration rate to evaluate the response of the mass transfer parameters (DO, OUR, and k _L a). The results of these experiments indicate considerable potential advantages to the pellet morphology from the standpoint of oxygen transport processes.List of Symbols DO % sat. Dissolved oxygen concentration - k _L a h^–1 Gas-liquid mass transfer coefficient - OUR mmol/dm³h Oxygen uptake rate - P/V KW/m³ Agitator power per unit volume - V _s m/s Superficial air velocity - _app cP Apparent viscosity     

Mass transfer characteristics of a fermentation broth in a reactor: co-current downflow contacting reactor

Gas holdups, dispersion height, volumetric mass transfer coefficients and k_La of water and a yeast fermentation broth were studied in a co-current downflow contacting reactor. k_La and gas holdup increased with increasing superficial gas velocity and there was a parallelism between k_La and gas holdup. The values of k_La gas holdup, and dispersion height measured in the air/fermentation broth system were all lower than those in air/water system.     

Comparison of oxygen mass transfer coefficient in simple and extractive fermentation systems

Aeration and agitation are important variables to ensure effective oxygen transfer rate during aerobic bioprocesses; therefore, the knowledge of the volumetric mass transfer coefficient (k_La) is required. In view of selecting the optimum oxygen requirements for extractive fermentation in aqueous two-phase system (ATPS), the k_La values in a typical ATPS medium were compared in this work with those in distilled water and in a simple fermentation medium, in the absence of biomass. Aeration and agitation were selected as the independent variables using a 2² full factorial design. Both variables showed statistically significant effects on k_La, and the highest values of this parameter in both media for simple fermentation (241 s⁻¹) and extractive fermentation with ATPS (70.3 s⁻¹) were observed at the highest levels of aeration (5 vvm) and agitation (1200 rpm). The k_La values were then used to establish mathematical correlations of this response as a function of the process variables. The exponents of the power number (N³D²) and superficial gas velocity (V_s) determined in distilled water (α = 0.39 and β = 0.47, respectively) were in reasonable agreement with the ones reported in the literature for several aqueous systems and close to those determined for a simple fermentation medium (α = 0.38 and β = 0.41). On the other hand, as expected by the increased viscosity in the presence of polyethylene glycol, their values were remarkably higher in a typical medium for extractive fermentation (α = 0.50 and β = 1.0). A reasonable agreement was found between the experimental data of k_La for the three selected systems and the values predicted by the theoretical models, under a wide range of operational conditions.     

Oxygen mass-transfer performance of low viscosity gas-liquid-solid system in a split-cylinder airlift bioreactor

The O₂ mass-transfer coefficient, k _L a, decreased by 20% when the viscosity of a simulated broth increased from 1.38 × 10^–3 to 3.43 × 10^–3 Pa s in a split-cylinder airlift bioreactor with a broth volume of 41 l. When the paper pulp concentration was below 10 g l^–1, k _L a hardly changed. While at 30 g l^–1, k _L a decreased by 56%. C₂O₄ ^2– and Na⁺ were found to have some effect on the k _L a value.     

Dynamic measurement of the volumetric oxygen transfer coefficient in fermentation systems

A rapid and internally consistent technique has been developed to measure the volumetric oxygen transfer coefficient, k_La, in fermentation systems. The method consists of tracing the dissolved O₂ concentration of the fermentation broth during a short interruption of the aeration. The O₂ concentration trace thus obtained can be analyzed to determine the values of k_La. Additional experiments on prolonged O₂ starvation, carried out to find the limitation of the technique, suggest that O₂ uptake rate will vary if a prolonged (2–10 min.) O₂ starvation occurs.     

Studies on cephalosporin-C production in an air lift reactor using different growth modes of Cephalosporium acremonium

This paper deals with the studies on Cephalosporin-C production in a lab-scale airlift reactor using Cephalosporium acremonium. Various growth modes, viz. pellets and Siran supported bioparticles were used to improve the process over conventional free mycelial fermentation. Cephalosporin-C production was significantly improved by using bioparticles over the free mycelial culture, probably due to the enhanced mass transfer in the fermentation broth. However, the biofilm of the bioparticles became unstable as the fermentation proceeded, and increase in the free cells in the broth occurs. The maximum specific growth rate of free cells, pellets and Siran carrier were observed to be 0·037, 0·033 and 0·045 h⁻¹, respectively. The oxygen transfer coefficient also improved for the immobilised modes (100 h⁻¹, 70 h⁻¹ for Siran carrier and pellets) and thereby enhanced specific antibiotic productivity, 18–28% were observed.     

Vergleich von Messungen des kLa-Wertes nach der stationären und der dynamischen Methode bei der Fermentation von L-Lysin und Turimycin

The calculation and scale-up of fermentation processes need k_La as one of the most important engineering data. There are two methods to determine k_La depending on power input, aeration rate and the properties of the fermentation broth: static with a balance between air supply and exit, dynamic gassing out with following the changes of dissolved oxygen concentration during periods of air off and a following air on. Within early intervals of fermentation time the data from both methods agree well, while for later time intervals the dynamic method always gives much lower values for k_La than static. The only explanations for this phenomenon are quick changes in the oxygen metabolism or an enzymatic storage of oxygen. For both gassing out and saturation period it is possible to calculate the same absolute amounts of this additional oxygen.     

Oxygen mass transfer and gas holdup in a bubble column bioreactor with biosynthesis liquids

The influence of the rheology of some antibiotic biosynthesis liquids produced by Streptomyces aureofaciens, Nocardia mediterranei and Penicillium chrysogenum on the volumetric liquid phase oxygen transfer coefficient, k_La, and gas holdup, ε_G, together with the influence of superficial gas velocity, were studied in a bubble column bioreactor, using samples of fermentation liquids taken from industrial stirred tank fermenters, at 30-hour intervals during fermentation batch. The results were compared to those of previous studies from literature on non-Newtonian homogeneous fluids, such as CMC-Na, xanthan and starch solutions, respectively. In the heterogeneous broths, ε_G and k_La decreased with increasing apparent viscosity of the broth and increased with increasing superficial velocity. The experimental data were correlated using non-linear regression with correlation coefficients above 0.85.     

Oxygen transfer characteristics of a centrifugal, packed-bed reactor during viscous xanthan fermentation

The oxygen transfer properties of a novel, centrifugal, packed-bed reactor (CPBR) during viscous xanthan fermentation were determined with respect to the effects of the arrangement of the centrifugal, packed bed (CPB) and the recirculation loop (RL). Characterized by the maximum volumetric transfer coefficient (k_La) in xanthan broth, the aeration efficiency of CPBR was compared to those in stirred-tank reactors (STR) equipped with disc turbines (DT) or marine propellers (MP), and to that in a water-in-oil emulsion (WIO). As expected, STR-WIO showed the highest k_La (0.038 s^-1 at 2%) among all systems studied due to reduced broth viscosity; however, practical difficulties exist in product recovery. It was found that, at 3.5% xanthan the k_La in CPBR (0.018 s^-1) was higher than that of STR (0.005 s^-1) and close to that of STR-WIO (0.020 s^-1), indicating improved oxygen transfer at such a xanthan concentration. The exterior baffles along the rotating fibrous matrix offer additional agitation in the viscous broth. A gas-continuous arrangement, in which the CPB was kept above the broth, was able to elevate k_La to 0.023 s^-1, higher than that of STR-WIO. The external RL operated by a peristaltic pump was found to play an important role in CPBR aeration by providing better gas-liquid contact. With the improved oxygen transfer efficiency in CPBR at high xanthan concentrations, the CPBR system is practically the preferred system for xanthan fermentation. The characteristic roles of CPB arrangement and the RL should be considered primarily during scale-up operation.     

Gas–liquid mass transfer in an up-flow cocurrent packed-bed biofilm reactor

Gas–liquid mass transfer was investigated in an up-flow cocurrent packed-bed biofilm reactor. In aerobic processes gas–liquid mass transfer can be considered as a key operational parameter as well as in reactor scale-up. The present paper investigates the influence of the liquid phase mixing in the determination of the volumetric gas–liquid mass transfer coefficient (k_La) coefficient. Residence time distribution (RTD) experiments were performed in the reactor to determine the flow pattern of the liquid phase and to model mathematically the liquid phase mixing. The mathematical model derived from RTD experiments was used to evaluate the influence of the liquid mixing on the experimental estimation of the (k_La) in this reactor type. The methods used to estimate the k_La coefficient were: (i) dynamic gassing-out, (ii) sulphite method, and (iii) in-process estimation through biological conversion obtained in the reactor. The use of standard chemical engineering correlations to determine the k_La in this type of bioreactors is assessed. Experimental and modelling results show how relevant can be to take into consideration the liquid phase mixing in the calculations of the most-used methods for the estimation of k_La coefficient. k_La coefficient was found to be strongly heterogeneous along the reactor vertical axis. The value of the k_La coefficient for the packed-bed section ranged 0.01–0.12 s⁻¹. A preliminary correlation was established for up-flow cocurrent packed-bed biofilm reactors as a function of gas superficial velocity.     

Effects of hydrocarbon additions on gas-liquid mass transfer coefficients in biphasic bioreactors

The effects of aliphatic hydrocarbons (n-hexadecane andn-dodecane) on the volumetric oxygen mass transfer coefficient (k _L a) were studied in flat alveolar airlift reactor and continuous stirred tank reactors (CSTRs). In the flat alveolar airlift reactor, high aeration rates (>2 vvm) were required in order to obtain efficient organic-aqueous phase dispersion and reliablek _L a measurements. Addition of 1% (v/v)n-hexadecane orn-dodecane increased thek _l a 1.55-and 1.33-fold, respectively, compared to the control (superficial velocity: 25.8×10⁻³ m/s, sparger orifice diameter: 0.5 mm). Analysis of the gas-liquid interfacial areaa and the liquid film mass transfer coefficientk _L suggests that the observedk _L a increase was a function of the media's liquid film mass transfer. Addition of 1% (v/v)n-hexadecane orn-dodecane to analogous setups using CSTRs led to ak _L a increase by a factor of 1.68 and 1.36, respectively (superficial velocity: 2.1×10⁻³ m/s, stirring rate: 250 rpm). These results propose that low-concentration addition of oxygen-vectors to aerobic microbial cultures has additional benefit relative to incubation in purely aqueous media.     

Evaluation of Spray Cycle Bioreactor Using L-Alanine Degradation by Candida maltosa

The oxygen-supply capability of a spray cycle reactor was evaluated by using it for oxidative degradation of L-alanine. The volumetric oxygen transfer coefficient, k_La, was evaluated as a parameter for the oxygen supply. The liquid circulation rate in the spray cycle reactor was represented in terms of the number of circulations. The k_La increased with the number of circulations, especially by stirring in the reservoir vessel, reaching 272/h at 4.4/min of circulation numbers. This value was 1.4 times higher than that without stirring. The L-alanine degradation rate increased as the cell growth was promoted, and as the circulation numbers increased. Finally, the spray cycle reactor was evaluated by the specific degradation rate. This rate increased in proportion to the k_La, and was 8.8 times higher than that in the jar fermentor, suggesting that the spray cycle reactor is superior for oxygen-demanding fermentation.     

The volumetric oxygen mass transfer coefficient in antibiotic biosynthesis liquids

This paper approaches the problem of oxygen mass transfer. This transfer is in antibiotic biosynthesis liquids produced by microorganisms belonging to the actinomycete and fungi classes, which exhibit a shear thinning non-Newtonian rheological behaviour. The volumetric oxygen mass transfer coefficients in these liquids (k_L a_b) change during biosynthesis processes. The change is mainly due to rheological parameter modifications, such as increasing the consistency index (K) and decreasing the flow behaviour index (n). The values of k_L a_b were 3.0–6.5 times lower than those recorded in water, and their decreasing depended on the k_L a values obtained without biological liquid and on the nature of fermentation broths, as well. Starting from experimental data, two correlations were established between k_L a_b and P/V,υ_SG and P/V,υ_SG, N, respectively. These correlations contain a dimensionless factor (η_am/η_g), which takes into account the rheological properties of the liquid phase and offers the possibility for a fast and sufficiently accurate estimation of k_L a_b. The empirical correlations developed in the paper correspond reasonably well with the relatively wide variety of experimental data, as in the model proposed by PEREZ and SANDALL , and allow for the comparison of the fermentation batches of the same or different microorganisms; also, they may be applied to the workings of design, scale-up, control and monitoring of bioreactors.     

Enhancement of mass transfer characteristics and phenanthrene degradation in a two-phase partitioning bioreactor equipped with internal static mixers

Oxygen and substrate supply have always been considered physical constraints for the performance and operation of two-phase partitioning bioreactors (TPPB), widely used for the degradation of hydrophobic substrates. In this regard, the potential advantages of static mixers in upgrading the oxygen transfer and liquid-liquid dispersions in TPPB have been highlighted. In the present paper, the concomitant influence of static mixers on the gas-liquid mass transfer coefficient k _L a and on substrate bioavailability was examined in TPPB. The static method based on conventional forms was developed to estimate the oxygen volumetric mass transfer coefficient. Over a broad range of liquid and air flow rates, the presence of static mixers was found to significantly enhance k _L a relative to a mixer-free mode of operation. For identical conditions, static mixers improved the k _L a threefold. In the presence of external aeration supply, the boost in the k _L a was associated with an increase of 16% in the phenanthrene biodegradation rate due to bubble break up accomplished by the static mixers. On the other hand, static mixers were efficient in enhancing substrate bioavailability by improving the liquid-liquid interfacial area. This effect was reflected by a threefold increase in the degradation rate in the bioreactors with no external supply of air when equipped with static mixers.     

Oxygen transfer in an airlift reactor with multiple net draft tubes

A pilot scale airlift reactor with multiple net draft tubes was developed to improve oxygen transfer in the reactor. The reactor was 0.29 m in diameter and 2 m height. A steadystate sulfite oxidation method was applied to determine an overall volumetric mass transfer coefficient. Oxygen transfer of the proposed airlift reactor can be 60–100% higher than that of bubble columns under the same operating conditions.List of Symbols C ^* mol·dm^–3 saturated concentration of dissolved oxygen - C _L mol·dm^–3 bulk concentration of dissolved oxygen - G mol/min nitrogen flow rate - k _L a hr^–1 the volumetric gas-liquid mass transfer coefficient - Mo ₂ g/mol molecular weight of oxygen - OTR g/min the oxygen transfer rate - U _g cm/s superficial air velocity - V _L dm³ volume of the liquid phase - _in oxygen mole ratio in the inlet gas - _out oxygen mole ratio in the outlet gas     

Oxygen transfer in Streptomyces fermentation broths

The oxygen transfer coefficient has been investigated in S. noursci and S. lavendulae fermentation broths obtained from fermentors of different operating volumes (61., 30001., 20,0001.). Fermentors had K_La_s values ranging from 1.0 to 17.0 min^?1, calculated from sulphite oxidation rates. The dynamic measurement of the volumetric oxygen transfer coefficient. (K_La) has been performed in the different fermenting systems. As the fermentation progressed, especially in the first stages, K_La values have decreased in both fermentations and in each system of fermentors. In order to characterise the whole fermenting system an average K_La_s was calculated from the obtained K_La values. The average K_La grew with increasing K_La_s values and ranged from 0.03 to 3.72 min^?l. Some factors possibly having an influence on the, change of K_La have been studied. The oxygen transfer coefficients of the broths have been measured in falling films and ranged from 0.05 to 0.4 cm min^?1. The flow conditions have been characterized by Reynolds numbers of broths varying between 1.0 and 60.0. The average thickness of the falling films have been measured and plotted against Reynolds number. The Re⁺ which is the breaking-point of the plot increased as the fermentation proceeded. In the region of Re⁺ the values of the oxygen transfer coefficient increased rapidly. An approximate correlation could be established between the Re⁺ and the physical properties of fermentation broth.     

Determination of oxygen-transfer coefficients in viscous streptomycete fermentations

Two types of steam-sterilizable dissolved-oxygen probs were evaluated for use in fermentations. A galvanic-cell probe was selected over a polarographic probe because of its demonstrated ruggedness and dependability. Various methods for determining k_La in fermentors were compared and the oxygen balance method selected for use in viscous streptomycete fermentations. Rheological data are presented to identify a range of mash viscosity where many k_La measurement methods are not applicable. Oxygen transfer data are presented for streptomycete fermentations pilot fermentors.     

A new dynamic model for highly efficient mass transfer in aerated bioreactors and consequences for kLa identification

Gas–liquid mass transfer is often rate‐limiting in laboratory and industrial cultures of aerobic or autotrophic organisms. The volumetric mass transfer coefficient k_La is a crucial characteristic for comparing, optimizing, and upscaling mass transfer efficiency of bioreactors. Reliable dynamic models and resulting methods for parameter identification are needed for quantitative modeling of microbial growth dynamics. We describe a laboratory‐scale stirred tank reactor (STR) with a highly efficient aeration system (k_La ≈ 570 h^?1). The reactor can sustain yeast culture with high cell density and high oxygen uptake rate, leading to a significant drop in gas concentration from inflow to outflow (by 21%). Standard models fail to predict the observed mass transfer dynamics and to identify k_La correctly. In order to capture the concentration gradient in the gas phase, we refine a standard ordinary differential equation (ODE) model and obtain a system of partial integro‐differential equations (PIDE), for which we derive an approximate analytical solution. Specific reactor configurations, in particular a relatively short bubble residence time, allow a quasi steady‐state approximation of the PIDE system by a simpler ODE model which still accounts for the concentration gradient. Moreover, we perform an appropriate scaling of all variables and parameters. In particular, we introduce the dimensionless overall efficiency κ, which is more informative than k_La since it combines the effects of gas inflow, exchange, and solution. Current standard models of mass transfer in laboratory‐scale aerated STRs neglect the gradient in the gas concentration, which arises from highly efficient bubbling systems and high cellular exchange rates. The resulting error in the identification of κ (and hence k_La) increases dramatically with increasing mass transfer efficiency. Notably, the error differs between cell‐free and culture‐based methods of parameter identification, potentially confounding the determination of the “biological enhancement” of mass transfer. Our new model provides an improved theoretical framework that can be readily applied to aerated bioreactors in research and biotechnology. Biotechnol. Bioeng. 2012; 109: 2997–3006. © 2012 Wiley Periodicals, Inc.