Synthesis of an Alkyl Polyoxyethylene Ether Sulfonate Surfactant and Its Application in Surfactant Flooding

Surfactant flooding as a potential enhanced oil‐recovery technology in a high‐temperature and high‐salinity oil reservoir after water flooding has attracted extensive attention. In this study, the synthesis of an alkyl alcohol polyoxyethylene ether sulfonate surfactant (C₁₂EO₇S) with dodecyl alcohol polyoxyethylene ether and sodium 2‐chloroethanesulfonate monohydrate, and its adaptability in surfactant flooding were investigated. The fundamental parameters of C₁₂EO₇S were obtained via surface tension measurement. And the ability to reduce oil–water interfacial tension (IFT), wettability alteration, emulsification, and adsorption was determined. The results illustrated that IFT could be reduced to 10^?3 mN m^?1 at high temperature and high salinity without additional additives, and C₁₂EO₇S exhibited benign wettability alternate ability, and emulsifying ability. Furthermore, the oil‐displacement experiments showed that C₁₂EO₇S solution could remarkably enhance oil recovery by 16.19% without adding any additives.     

Micellar and Interfacial Behavior of Cationic Benzalkonium Chloride and Nonionic Polyoxyethylene Alkyl Ether Based Mixed Surfactant Systems

Micellar and interfacial properties of mixed surfactant systems comprising benzalkonium chloride, a cationic surfactant and nonionic polyoxyethylene alkyl ether surfactants (POE: C₁₀E₇, C₁₀E₈, C₁₀E₉, C₁₀E₁₀) have been investigated by surface tension, fluorescence and dynamic light scattering techniques. Critical micelle concentration (CMC) for different mixing mole fractions has been investigated by surface tension and fluorescence measurements. Ideal CMC, mixed micellar composition (X ₁ ^m , X ₁ ^σ ), interaction parameters for mixed micelles (β ^m) and adsorption monolayer (β ^σ ), surface excess concentration (Г_max), minimum area per molecule (A _min) and related thermodynamic properties have also been determined. Lowering of the CMC and negative interaction parameter values indicate synergism in the mixed micelle and monolayer formed, whereas, thermodynamic parameters evaluated for the proposed mixed systems indicate stability of the resulting micelles and monolayer. Micellar aggregation number (N _agg) and hydrodynamic diameter (D _h) computed from fluorescence and dynamic light scattering measurements respectively illustrate micellar growth in the mixed state. Results obtained for the proposed mixed systems can be helpful in designing smart materials for industrial surfactant based formulations.     

Evaluating Dissolved Ozone in a Bubble Column Using a Discrete-Bubble Model

Ozonation has been widely applied in water treatment plants, so it is essential to figure out mass transfer and reaction kinetics in ozone contact tanks. In this study, a discrete-bubble model was established to calculate the dissolved ozone concentration in a countercurrent flow system. Results from batch experiments showed that an exponential relationship was well fitted between ozone reaction rate coefficient and ozone consumption amount, and the relationship was not affected by the ozone dosage. Therefore, it was applied in a discrete-bubble model, which was validated by experiments in a countercurrent bubble column with error less than 15%.     

Mass Balance Analysis of Ozone in a Conventional Bubble Column

Ozone transfer into potable water was studied in a conventional bubble column, and ozone mass balances have been calculated to determine ozone utilization efficiencies. Liquid and gas flow rates, as well as inlet ozone concentrations in the gas phase were varied. Using these data, it was possible to determine the ozone mass transfer coefficient, ozone transfer efficiency, and ozone consumption. A model of ozone transfer was established, and procedures for calculating the optimum design parameters and operating conditions are proposed.     

Radial Profiles of Gas Bubble Behavior in a Gas‐Liquid Bubble Column Reactor under Elevated Pressures

The effects of operating conditions on radial variation of gas holdups, bubble swarm rising velocity, and Sauter mean diameter were investigated in a bubble column reactor under elevated pressures using a conductivity probe method. Air served as gas phase and tap water as liquid phase with varying gas velocity and pressure. All three parameters increased constantly with higher superficial gas velocity. Maximum holdup, velocity, and Sauter mean diameter were found at the center of the cross section. Two different cases for Sauter mean diameter distribution were observed. The gas holdups increase continuously with higher system pressure, but decrease for bubble swarm rising velocity and Sauter mean diameter. According to experimental results, an empirical correlation of the gas holdup profiles is presented.     

Impact of Surfactant Addition on Oxygen Mass Transfer in a Bubble Column

The impact of sparger design and surfactant addition on the oxygen transfer rate in a bubble column was examined. Additionally, measurements were also made of the holdup and bubble size distribution, allowing both the interfacial area for mass transfer and the liquid film mass transfer coefficient to be determined for a range of industrially relevant superficial velocities. It was found that for the velocity range examined changes in the superficial velocity had a minimal impact on the observed value of liquid film mass transfer coefficient. In contrast, addition of both hydrophilic and hydrophobic surface‐active compounds led to an approximately threefold reduction in liquid film mass transfer coefficient.     

Design of a Pipe/Ring Type of Sparger for a Bubble Column Reactor

The sparger is an important accessory of bubble column reactors which governs the performance of the reactor. Specifically the sparger design becomes more important when the aspect ratio of the bubble column is low. The maldistribution and design of the sparger are of major concern and both these aspects are described in detail in the present work. Various methods for reducing maldistribution have been discussed and a simple method for its reduction is presented experimentally. Further a step‐wise design procedure for a pipe/ring type of sparger for bubble columns is presented together with a work example.     

Binary Mixed Micelles of Polyoxyethylene (10) Stearyl Ether with Polysorbate 20 and Polysorbate 60: Thermodynamic Description

Comprehension of the nature of the micellisation process is of great importance for the characterisation of micelles and the assessment of their applications. In this research, the influences of temperature and the length of the hydrophobic chain on the micellisation process of polyoxyethylene (10) stearyl ether (PE10) with polysorbate 20 and polysorbate 60 were studied. Values of critical micelle concentrations (CMC) of the individual surfactants and of their binary mixtures were acquired by spectrofluorimetric measurements, in the temperature range 273.15–313.15 K, using pyrene as a probe molecule. Obtained CMC values served for the calculation of interaction parameters and excess Gibbs energies of the mixed micelles. It was found that in PE10—polysorbate 20 mixed micelles (due to a shorter hydrophobic segment of polysorbate 20 molecule) PE10 alkyl chains were more likely to assume globular conformations in the interior of micelles, in comparison to PE10—polysorbate 60 mixed micelles (in which hydrophobic segments had the same lengths). For each analysed binary system, interaction parameter decreased with the rise of temperature. It could be assumed that on higher temperatures the hydrophobic chains of studied surfactants were more likely to take globular conformations, having higher values of conformational freedom. This observation implied that the process of micellisation was followed by an increase in entropy. Accordingly, the excess Gibbs energy of micellisation was determined not only by entropic contributions, but also by enthalpic input.     

Dynamic Matrix Control of a Bubble‐Column Reactor for Microbial Synthesis Gas Fermentation

A spatiotemporal metabolic model of a representative syngas bubble‐column reactor was applied to design and evaluate dynamic matrix control (DMC) schemes for regulation of the desired by‐product ethanol and the undesired by‐product acetate. This model was used to develop linear step response models for controller design and also served as the process in closed‐loop simulations. A 2 × 2 DMC scheme with manipulation of the liquid and gas feed flows to the column provided a superior performance to proportional integral (PI) control due to slow process dynamics combining the multivariable and constrained nature of the control problem. Ethanol concentration control for large disturbances was further improved by adding the flow of a pure hydrogen stream as a third manipulated variable. The advantages of DMC for syngas bubble‐column reactor control are demonstrated and a design strategy for future industrial applications is provided.     

CFD Simulations of a Bubble Column Operating in the Homogeneous and Heterogeneous Flow Regimes

Bubble columns are operated either in the homogeneous or heterogeneous flow regime. In the homogeneous flow regime, the bubbles are nearly uniform in size and shape. In the heterogeneous flow regime, a distribution of bubble sizes exists. In this paper, a CFD model is developed to describe the hydrodynamics of bubble columns operating in either of the two flow regimes. The heterogeneous flow regime is assumed to consist of two bubble classes: “small” and “large” bubbles. For the air‐water system, appropriate drag relations are suggested for these two bubble classes. Interactions between both bubble populations and the liquid are taken into account in terms of momentum exchange, or drag‐, coefficients, which differ for the “small” and “large” bubbles. Direct interactions between the large and small bubble phases are ignored. The turbulence in the liquid phase is described using the k‐ϵ model. For a 0.1 m diameter column operating with the air‐water system, CFD simulations have been carried out for superficial gas velocities, U, in the range 0.006–0.08 m/s, spanning both regimes. These simulations reveal some of the characteristic features of homogeneous and heterogeneous flow regimes, and of regime transition.     

Operating Characteristics and Performance of a Monolithic Downflow Bubble Column Reactor in Selective Hydrogenation of Butyne‐1,4‐diol

The effects of flow condition, bubble dispersion level, and liquid flow rate on the behavior of a novel monolithic downflow bubble column (M‐DBC) were investigated using a reaction model, the palladium‐catalyzed hydrogenation of butyne‐1,4‐diol. The stable and closely packed homogeneous bubble dispersion present in the bulk region of the M‐DBC allowed effective introduction of the gas‐liquid phase for formation of Taylor flow inside the monolith channels. The condition defined as the minimum level dispersion was required in order to obtain high selectivity towards the intermediate product, cis‐2‐butene‐1,4‐diol. Enhanced reaction rates were obtained at increasing the dispersion level and lowering the liquid flow rate. Comparison with the DBC employing 5 % Pd/C powder catalyst and 1 % Pd‐on‐Raschig‐ring revealed a better performance of the M‐DBC (1 % Pd loading) with the advantage of smaller reaction volume and intensified reaction rate. As an alternative to conventional three‐phase reactors, the M‐DBC was so simple due to its inherent characteristic operation and no specially designed device is required.     

浆态床合成气制二甲醚反应器数学模拟

建立了包括液相返混和催化剂颗粒沉降的合成气一步法制二甲醚浆态床反应器的数学模型,模拟计算了空速、原料气组成、反应温度、反应压力等反应条件对反应的影响。计算结果表明,CO转化率和二甲醚的选择性随温度增加、压力增大而提高,在一定温度、压力条件下,CO转化率随空速增大而减小,合成气含有一定量的CO2有利于CO转化率增加。     

Computer-Assisted Determination of Reaction Parameters for the Simulation of Micropollutant Abatement in Wastewater Ozonation

For the purpose of the simulation of the kinetics of the reaction of ozone with wastewater in a bubble column, the kinetics can be adequately described by two components and their respective rate constants. Ozone uptake and ozone steady states along a bubble column have been determined. A modeling procedure has been developed that allows us to describe this behavior and to simulate the degradation of micropollutants. For fast (diclofenac) and moderately fast (bezafibrate) reacting micropollutants this model describes their measured elimination well.     

Sodium Alkyl Ether Sulfonates (SAES): Dual Anionic‐Nonionic Behavior in Synthetic Brine Having High Salinity and Hardness

Due to the presence of non‐sulfonated residual alkyl ether (AE), sodium alkyl ether sulfonate (SAES) may exhibit clear point‐cloud point solubilization behavior in brine. Accordingly, the effect of temperature on the compatibility of iC17EOxS (x = 7 and 10), nC₁₇EO10S, along with their analogous nonionic surfactants iC₁₇EOxH (x = 7 and 10) and nC17EO10, in addition to iC9EO14 in brine has been investigated. Depending on their molecular structures, these surfactants exhibited concentration‐dependent clear point and cloud point solubilization behavior. The cloud point was associated with the AE component whereas the clear point was attributed to the sulfonated one. Interestingly, an increase in the cloud point of the nonionic component with respect to the corresponding nonionic AE (100 % active) was observed. Adding iC9EO14 (100 % active) to iC17EO7S (x_an = 0.0–0.362) resulted in a significant decrease in the clear point of iC17EO7S from above 100 °C to below 22 °C with a concomitant increase in iC17EO7/iC9EO14 mixture cloud point from 68 °C. (x_an = 0) to 72 °C (x_an = 0.325). This relatively modest increase by 4 °C was attributed to the interrelationship of different competitive mechanisms, namely an increase in mixed micelle charge with increasing x_an, the dehydration of OE groups via ion (SO₃^?)‐dipole (O → CH₂) interactions, and possible shielding of SO₃^? groups by iC9EO14 nearby extended EO groups. To the best of our knowledge, this is the first instance where dual anionic‐nonionic solubilization behavior of SAES in brine characterized by high salinity and hardness is being reported.     

Fast Production of Diacylglycerol in a Solvent Free System via Lipase Catalyzed Esterification Using a Bubble Column Reactor

In this study, diacylglycerols (DAG) were synthesized rapidly (~30 min) in a solvent‐free system via esterification of glycerol with fatty acids (FA, the mixture of 60 wt% palm oil deodorizer distillate and 40 wt% oleic acid) catalyzed by Lipozyme 435 (Novozymes A/S, Copenhagen, Denmark) using a bubble column reactor. The content of DAG, monoacylglycerols (MAG), triacylglycerols (TAG) and free fatty acids (FFA) in the crude product were 57.94 ± 1.60 wt%, 24.68 ± 2.08 wt%, 2.67 ± 1.72 wt% and 14.69 ± 1.22 wt%, respectively under the selected conditions, which were enzyme load of 5.0 wt%, glycerol/FA mole ratio of 7.5, initial water content of 2.5 wt%, reaction temperature of 60 °C, reaction time of 30 min and N₂ gas flow of 10.6 cm min^?1. The final product containing 91.30 ± 1.10 wt% of DAG was obtained by one‐step molecular distillation at 200 °C. The reusability of Lipozyme 435 was investigated by evaluating the esterification degree (ED) and the DAG content in the crude products in 30 successive runs. The enzyme retained 95.10 % of its original activity during 30 successive runs according to comparison of the ED. The new process showed a very high efficiency in production of DAG with a high purity. The ratio of positional isomers 1,3‐DAG to 1,2 ‐DAG was 2:1 in the final product. The certain plasticity (melting point of 44 °C) and content of unsaturated fatty acids made the product a valuable food ingredient.     

Ozonation Kinetics of Acid Red 27 Azo Dye: A Novel Methodology Based on Artificial Neural Networks for the Determination of Dynamic Kinetic Constants in Bubble Column Reactors

A procedure for the determination of initial parameter values for quadratically convergent optimization methods is proposed using artificial neural networks coupled with a non-stationary gas-liquid reaction model. The evaluation of the regression and the mean squared error coefficients of the neural network during its training process allow the parameter sensitivity analysis of the gas-liquid model. This analysis examines how many and which parameters of the model will be available depending on the observable information of the mathematical model. Numerical simulations show the relevance of the initial values and the non-linearity of the objective function. The methodology has been applied to the study of the reaction of the azo-dye Acid Red 27 with ozone in acid media. The rate constant is in the order of (1.6 ± 0.1) 10³ M^?1 s^?1 under the experimental conditions.     

Abatement of 4-Chlorophenol in Aqueous Phase by Ozonation Coupled with a Sequencing Batch Biofilm Reactor (SBBR)

The aim of this work was to assess the mineralization of 100 and 200 mg L^?1 4-chlorophenol (4-CP) solutions by ozonation-biological treatment. The results show that starting from a 4-CP initial concentration from 100 to 500 mg L^?1 and using an ozone flow rate of 5.44 and 7.57 g h^?1, 4-CP was completely removed. A kinetic constant around 9·10^?2 min^?1 was calculated for the ozone direct attack. The biodegradability (BOD₅/COD) of the pre-ozonated solutions increased from 0 until a range between 0.2–0.37. The combination of the ozonation and aerobic biological treatment in an aerobic sequencing batch biofilm reactor (SBBR) gave an abatement of more than 90% of the initial TOC.     

Ozonation of Phenol-Containing Wastewater Using O3/Ca(OH)2 System in a Micro Bubble Gas-Liquid Reactor

The degradation of phenol in aqueous solution was investigated in an integrated process consisting of O₃/Ca(OH)₂ system and a newly developed micro bubble gas-liquid reactor. The effects of operating parameters such as Ca(OH)₂ dosage, reactor pressure, liquid phase temperature, initial phenol concentration and inlet ozone concentration on degradation and mineralization (TOC removal) were studied in order to know the ozonation performance of this new integrated process. It is demonstrated that the degradation and TOC removal efficiency increased with increasing inlet ozone concentration and increasing Ca(OH)₂ dosage before 2 g/L, as well as decreasing initial phenol concentration. The optimum Ca(OH)₂ dosage should exceed Ca(OH)₂ solubility in liquid phase. The reactor pressure and liquid phase temperature have little effects on the removal and TOC removal efficiency. When Ca(OH)₂ dosage exceeded 3 g/L, the degradation and TOC removal of phenol almost reached 100% at 30 and 55 min, respectively. The intensification mechanism of Ca(OH)₂ assisted ozonation was explored through analysis of the precipitated substances. The mechanism for Ca(OH)₂ intensified mineralization of phenol solution is the simultaneous removal of CO₃^2- ions, as hydroxyl radical scavengers, due to the presence of Ca²⁺ ions. Results indicated that the proposed new integrated process is a highly efficient ozonation process for persistent organic wastewater treatment.     

费-托合成鼓泡浆态反应器的湍流区双气泡模型

A model for a bubble column slurry reactor is developed based on the experiment of Rhenpreuszen-Koppers demonstration plant for slurry phase Fischer-Tropsch synthesis reported by Koelble et al. This model is applicable to the operation in the churn-turbulent regime and incorporates the information on the bubble size. The axial dispersion model is adopted to describe the flow characteristics of the Fischer-Tropsch slurry reactor. With the model developed, simulations are performed to identify the steady state behavior of a Fischer-Tropsch slurry reactor of commercial size. Predictions of the two-bubble class model is compared with that of the conventional single- bubble class model. The results show that under a variety of conditions, the two-bubble class model gives results different from those for the single-bubble class model.