Simulation of ammonia removal from industrial wastewater streams by means of a hollow-fiber membrane contactor

The performance of a hollow-fiber membrane contactor in removing ammonia from aqueous solution was simulated. An unsteady state 2D mathematical model was developed to study the ammonia stripping in the hollow-fiber membrane contactor. Two sets of equations were considered for the membrane contactor and the feed tank. CFD technique was applied to solve the model equations in which concentration distribution was determined using continuity equation. Velocity field is also determined using Navier–Stokes equations for the contactor. The model was implemented in linked MATLAB–COMSOL Multiphysics. COMSOL software was applied to solve the model equations for the contactor while MATLAB software was employed to consider changes in the concentration of the feed tank. Predictions of the model were then validated against experimental data which were found to be in good agreement. The assumption of Knudsen diffusion for the transport of ammonia molecules through the membrane pores increased the accuracy of the model. The effect of different parameters including feed velocity, feed concentration and pH on the removal of ammonia was investigated. The results of simulation revealed that the developed model can be used to evaluate the effective parameters which involve in the ammonia removal by means of membrane contactors.     

Numerical modeling and optimization of wastewater treatment using porous polymeric membranes

A new modeling approach was developed for prediction of ammonia removal from water by means of porous membranes. The model was based on adaptive neuro‐fuzzy interface system (ANFIS) to simulate ammonia stripping from water by means of hollow‐fiber membrane contactors. The predictions aimed to obtain optimum conditions for ammonia stripping using the Taguchi method. The initial concentrations of ammonia, pH of the ammonia solution, velocity of the feed, and the presence of excess ions in the ammonia feed solution were considered as the input properties. On the other hand, mass transfer coefficient was considered as output. The prediction results revealed that the pH of the ammonia feed has a significant effect on the separation of ammonia from water. The results also showed that the prediction of ANFIS model and experimental data match well and that the model can be used for prediction of porous membranes. Furthermore, simulated annealing was also used to determine controllable conditions to find the highest mass transfer coefficient. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Simulation of Membrane Distillation for Purifying Water Containing 1,1,1‐Trichloroethane

Vacuum membrane distillation is modeled for the purification of water containing organic matter. The separation medium is a hollow‐fiber membrane contactor that is simplified to a two‐dimensional structure with a single porous membrane wall. The model considers the transport phenomena of a vacuum membrane distillation system in porous media, in which the aqueous volatile organic solution was considered as an incompressible and steady fluid. The numerical simulation of the two‐dimensional model of vacuum membrane distillation for an aqueous solution of 1,1,1‐trichloroethane was established under steady state. The effects of the bulk feed temperature and the feed flow rate on the percentage of 1,1,1‐trichloroethane removal from an aqueous solution are discussed.     

Hollow fiber membrane contactor as a gas-liquid model contactor

Microporous hollow fiber gas-liquid membrane contactors have a fixed and well-defined gas-liquid interfacial area. The liquid flow through the hollow fiber is laminar, thus the liquid side hydrodynamics are well known. This allows the accurate calculation of the fiber side physical mass transfer coefficient from first principles. Moreover, in the case of gas-liquid membrane contactor, the gas-liquid exposure time can be varied easily and independently without disturbing the gas-liquid interfacial area. These features of the hollow fiber membrane contactor make it very suitable as a gas-liquid model contactor and offer numerous advantages over the conventional model contactors. The applicability and the limitations of this novel model contactor for the determination of physico-chemical properties of non-reactive and reactive gas-liquid systems are investigated in the present work. Absorption of CO₂ into water and into aqueous NaOH solutions are chosen as model systems to determine the physico-chemical properties for non-reactive and reactive conditions, respectively. The experimental findings for these systems show that a hollow fiber membrane contactor can be used successfully as a model contactor for the determination of various gas-liquid physico-chemical properties. Moreover, since the membrane contactor facilitates indirect contact between the two phases, the application of hollow fiber model contactor can possibly be extended to liquid-liquid systems and/or heterogeneous catalyzed gas-liquid systems.     

Numerical simulation studies on heat and mass transfer using vacuum membrane distillation

A general 2D mathematical model was developed to simulate the purification of water from volatile organic compounds (VOCs) via vacuum membrane distillation (VMD) process in hollow fiber membrane contactors. The model was developed for hydrophobic membrane material conditions, taking into consideration axial and radial diffusion in the tube, membrane and compartments of the contactor and was simplified to the two‐dimensional structure with a single porous membrane wall. The simulation has studied the mass and heat transfer of VMD system in the porous media, in which aqueous volatile organic solution was considered as an incompressible and steady fluid. Effect of the downstream pressure on the removal of 1, 1, 1‐trichloroethane (TCA) was studied to validation of simulation results with experimental data that it was obtained from literature. The temperature, Reynolds number, and total mass flux (convective and diffusive) distribution of TCA are determined in the membrane module. POLYM. ENG. SCI., 54:2553–2559, 2014. © 2013 Society of Plastics Engineers     

Membrane Gas-Solvent Contactor Pilot Plant Trials of CO2 Absorption from Flue Gas

Membrane gas-solvent contactors have received much attention for CO₂ absorption, as the approach incorporates advantages from both solvent absorption and membrane gas separation. This study reports on pilot plant trials of three membrane contactors for the separation of CO₂ from flue gas. The contactors were porous polypropylene (PP), porous polytetrafluoroethylene (PTFE), and non-porous polydimethylsiloxane (PDMS), with the solvent PuraTreatTM F^TM. To enable performance comparison, laboratory measurements based on a gas mixture of 10% CO₂ in N₂ were also undertaken on the same contactor–solvent systems. It was found that the PP contactor experienced significant pore wetting in both laboratory and pilot plant studies. In contrast, the PTFE contactor experienced only minor pore wetting in the laboratory. However, in the pilot plant trial of the PTFE contactor extensive pore wetting was observed, and the overall mass transfer coefficient measured was comparable with the PP contactor. The non-porous PDMS contactor had an overall mass transfer coefficient two orders of magnitude less than the PP contactor, due to the greater mass transfer resistance of the polymeric film. However, the non-porous membrane does not experience pore wetting, which resulted in the overall mass transfer coefficient being similar for both laboratory and pilot plant measurements.     

Reduction of CO2 emissions by a membrane contacting process☆

A membrane-based gas–liquid contacting process was evaluated in this work for CO₂ removal from flue gases. The absorption of CO₂ from a CO₂–N₂ mixture was investigated using a commercial hollow fiber membrane contactor and water or diethanolamine as absorbing solvents. Significant CO₂ removal (up to 75%) was achieved even with the use of pure water as absorbent. By using aqueous amine solutions and chemical absorption, mass transfer improved, and CO₂ removal was nearly complete (∼99%). A mathematical model was developed to simulate the process and it was validated with experimental data. Results show that membrane contactors are significantly more efficient and compact than conventional absorption towers for acid gas removal.     

The Application of Membrane Contactors for the Removal of Ammonium from Anaerobic Digester Effluent

The present study investigated the removal of ammonia from anaerobic digester effluent using membrane contactors. For mass transfer, hollow fiber membrane contactors offer a multitude of advantages compared to stripping technologies. In conventional applications of membrane contactors, the ammonia rich solution circulates through the fibers. For this kind of application, the very high content of suspended solids in digester effluents requires an additional removal step in order to guarantee undisturbed operation conditions. In a new approach, the membrane fibers were simply submerged into the anaerobic digestate and the performance was investigated at moderate temperatures ranging from 20 to 40°C and pH values lying in the range of 8.6 to 10.0. It was demonstrated that the new approach can be applied efficiently for the treatment of particle rich solutions with high ammonia concentrations of 3.000–3.500 mg/L, obtaining removal rates from 80 up to 98.5%. The mass transfer coefficients lay in the range of 12.4–37.0 × 10^?3 m/h and were absolutely comparable to values reported by other authors.     

Modeling and simulation of mass transfer in near-critical extraction using a hollow fiber membrane contactor

In this study is presented a general methodology to predict the performance of a continuous near-critical fluid extraction process to remove compounds from aqueous solutions using a hollow fiber membrane contactor. The stabilization of the gas-liquid interface in the membrane porosity and a high surface area to contact both phases represent some of the advantages that hollow fiber contactors offer over conventional contactor devices for the extraction of compounds from liquid feeds.A mathematical model has been developed integrating a resistances-in-series mass transfer system that takes into account boundary layers, membrane porosity and thermodynamic considerations with mass balances of the membrane contactor. Simulation algorithms were easily implemented with low calculation requirements.The system studied in this work is a membrane based extractor of ethanol and acetone from aqueous solutions using near-critical CO₂. Predictions of extraction percentages obtained by simulations have been compared to the experimental values reported by Bothun et al. [2003a. Compressed solvents for the extraction of fermentation products within a hollow fiber membrane contactor. Journal of Supercritical Fluids 25, 119-134]. Simulations of extraction percentage of ethanol and acetone show an average difference of 36.3% and 6.75% with the experimental data, respectively. More accurate predictions of the extraction of acetone could be explained by a better estimation of the transport properties in the aqueous phase that controls the extraction of this solute.When the model was validated, the effect of the configuration and the operating parameters was studied and local mass transfer resistances were evaluated. The proposed approach allows the evaluation of the relevance of membrane hydrophobicity for extraction in solutions under different thermodynamic conditions. This original methodology based on well-known phenomenological equations represents a general approach which could be applied in other processes using membrane contactors with different configurations.     

可逆气态膜-多效膜蒸馏-精馏过程脱除水相氨氮副产氨水

可逆气态膜-多效膜蒸馏-精馏耦合工艺可用于脱除料液或废水中的氨氮并得到高纯浓氨水。考察了磷酸二氢铵为可逆吸收剂时气态膜法脱氨效果和多效膜蒸馏-精馏法吸收完成液再生效果。实验结果表明:可逆气态膜总传质系数K和单程氨氮脱除率η分别可达13.9 μm·s^-1和97.5%,废水氨氮值可降至5 mg·L^-1以下;吸收完成液经多效膜蒸馏预浓缩后再经精馏再生可同时得到浓度为5%～18%的氨水。该耦合过程电耗极小的同时蒸汽耗量为28~40 kg·m^-3废水,约为单纯精馏过程的1/5。此外气态膜脱氨和多效膜蒸馏预浓缩过程有效地阻止了废水中挥发性杂质进入浓氨水产品。该过程对气态膜和膜蒸馏用微孔疏水膜组件的稳定性要求苛刻,长期操作试验显示聚四氟乙烯膜能够满足此要求。     

New criteria for application of the well-mixed model to gas-liquid mass transfer studies

The well-mixed model presents several advantages for the evaluation of interphase mass transfer rates in gas-liquid contactors: it simplifies the mathematical analysis and eliminates the need for measuring numerous mixing parameters. Although the well-mixed model corresponds to a theoretical concept, it is shown in this paper that, under certain conditions, it can be safely applied to the liquid phase of contactors for the purpose of determining the overall volumetric mass transfer coefficient K_La_L. Based on a computer simulation of absorption and mixing processes, simple criteria were developed that specify the conditions for which the well-mixed model is applicable in practice, for either a semi-batch gas-liquid contactor or a continuous flow absorber at steady-state. The dimensionless group K_La_Lτ_c, where τ_c is the average circulation time in the liquid phase of the contactor, was found to be a key parameter in establishing the validity of the well-mixed model.     

New absorption liquids for the removal of CO2 from dilute gas streams using membrane contactors

A new absorption liquid based on amino acid salts has been studied for CO₂ removal in membrane gas-liquid contactors. Unlike conventional gas treating solvents like aqueous alkanolamines solutions, the new absorption liquid does not wet polyolefin microporous membranes. The wetting characteristics of aqueous alkanolamines and amino acid salt solutions for a hydrophobic membrane was studied by measuring the surface tension of the liquid and the breakthrough pressure of the liquid into the pores of the membrane. The dependence of the breakthrough pressure on surface tension follows the Laplace-Young equation. The performance of the new absorption liquid in the removal of CO₂ was studied in a single fiber membrane contactor over a wide range of partial pressures of CO₂ in the gas phase and amino acid salt concentrations in the liquid. A numerical model to describe the mass transfer accompanied by multiple chemical reactions occurring during the absorption of CO₂ in the liquid flowing through the hollow fiber was developed. The numerical model gives a good prediction of the CO₂ absorption flux across the membrane for the absorption of CO₂ in the aqueous amino acid salt solutions flowing through the hollow fiber.     

CO2 Capture Using Activated Amino Acid Salt Solutions in a Membrane Contactor

An activated solution based on amino acid salt was proposed as a CO₂ absorbent. Piperazine (PZ) was selected as an activating agent and added into the aqueous glycine salt to form the activated solution. A coupling process, which associated the activated solution with a PP hollow fiber membrane contactor, was set up. An experimental and theoretical analysis for CO₂ capture was performed. The performances of CO₂ capture by the coupling process were evaluated using the PZ activated solution and the non-activated glycine salt solution. A numerical model for the simulation of the hollow fiber membrane gas–liquid mass transfer was developed. Typical parameters such as outlet gas phase CO₂ concentration, capture efficiency, and mass transfer coefficient for the activated solution were determined experimentally. The effects of operation temperature and liquid CO₂-loading on mass transfer coefficient and capture efficiency were discussed in this work. Axial and radial concentration profiles of CO₂ in the fiber lumen and mass transfer flux were simulated by the model. Results show that the performances of the PZ activated glycine salt solution are evidently better than that of the non-activated glycine salt solution in the membrane contactor for CO₂ capture. Elevation of the operation temperatures can enhance the overall mass transfer coefficient. The activated solution can maintain higher capture efficiency especially in the case of high CO₂-loadings. The gas phase CO₂ concentration with the activated solution is lower than that with the non-activated solution whether along axial or radial distances in the fiber lumen. The model simulation is validated with experimental data.     

Enhancing CO2 absorption efficiency using a novel PTFE hollow fiber membrane contactor at elevated pressure

The internal structure design of membrane module is very important for gas removal performance using membrane contactor via physical absorption. In this study, a novel membrane contactor developed by weaving polytetrafluoroethylene (PTFE) hollow fibers was applied to remove CO₂ from 60% N₂ + 40% CO₂ mixture (with CO₂ concentration similar to that of biogas) at elevated pressure (0.8 MPa) using water as absorbent. Compared with the conventional module with randomly packed straight fibers, the module with woven PTFE fibers exhibited much better CO₂ absorption performance. The weaving configuration facilitated the meandering flow or Dean vortices and renewing speed of water around hollow fibers. Meanwhile, the undesired influences such as channeling and bypassing were also eliminated. Consequently, the mass transfer of liquid phase was greatly improved and the CO₂ removal efficiency was significantly enhanced. The effects of operation pressure, module arrangement, feed gas, and water flow rate on CO₂ removal were systematically investigated as well. The overall mass‐transfer coefficient (K_OV) varied from 1.96 × 10^?5 to 4.39 × 10^?5 m/s (the volumetric mass‐transfer coefficient K_La = 0.034–0.075 s^?1) under the experimental conditions. The CO₂ removal performance of novel woven fiber membrane contactor matched well with the simulation results. © 2017 American Institute of Chemical Engineers AIChE J, 64: 2135–2145, 2018     

SIMULATION AND PROCESS OPTIMIZATION OF A MEMBRANE-BASED DENSE GAS EXTRACTION USING HOLLOW FIBER CONTACTORS

Supercritical fluid and membrane technology coupling is a relatively new concept applicable to solvent separation and solute extraction. In these processes a hydrophobic or hydrophilic macroporous membrane is used as a two-different-nature solutions contactor. This methodology is an alternative to conventional liquid solution supercritical fluid extraction processes, which are associated with high investment costs. In the present work, a membrane-based supercritical fluid extraction module is modeled, simulated, and optimized as an independent industrial-scale operational unit. UniSim design suite R390 software from Honeywell was used as the platform for the simulation. Acetone and ethanol literature extraction results and methanol experimental extraction results (27.6% to 14.5% with a 10 wt.% aqueous solution; 7.1% to 5.9% with a 500 ppm aqueous solution) were used for validation of the model and definition of the semi-empirical equation parameters. The generated industrial-scale system optimization, which used a modular membrane arrangement, was strongly dependent on thermodynamic, economic, and energetic variables (higher mass transfer resistance in the carbon dioxide phase increased the number of membranes needed; process feasibility was affected by the number of membrane units, carbon dioxide flow rate, and product added value; compression energy requirements affected the optimization result). The modeled system proved to be an important aid in the design, scaling, and optimization of systems that use membranes as phase contactors in liquid solution supercritical carbon dioxide extraction.     

Transport of Au(CN)2 − by Mixtures of Amine Primene JMT and Phosphine Oxide Cyanex 923 Using the Pseudo-Emulsion Based Hollow-Fiber Strip Dispersion Technology

The transport of Au(CN)₂ ^? between alkaline aqueous solutions and organic phases consisting of a mixture of the amine Primene JMT and the phosphine oxide Cyanex 923 in xylene was studied using the pseudo-emulsion based hollow-fiber strip dispersion (PEHFSD) technology. The feed phase was passed through the lumen side, and the pseudo-emulsions of the extractant mixtures and NaOH were passed through the shell side in a countercurrent mode using a single hollow-fiber contactor for extraction and stripping. In this membrane technology, the strippant (NaOH solution) is dispersed in the organic (Primene JMT + Cyanex 923 in xylene) membrane solution in a tank with an impeller stirrer adequate to form strip dispersion. The pseudo-emulsion phase is circulated from the reservoir tank to the membrane contactor to provide a constant supply of the organic solution to the membrane fibers. Furthermore, this technology allows a direct contact between the organic and strip solutions, providing a greater area for stripping and facilitating the metal recovery from the strip solution once both phases are separated. Various hydrodynamic and chemical parameters, such as flow of feed phase, extractant mixtures and gold concentrations, organic diluents, variation in feed pH, and the selectivity of the system with respect to the transport of different metal-cyano complexes, were investigated. Aqueous and membrane mass transfer coefficients were estimated for the present system.     

Membrane contactor for CO2 absorption applying amino-acid salt solutions

A novel composite solution based on amino-acid salt as a CO₂ absorbent was proposed. Coupling process of membrane contactor and the composite solution was investigated. The performance of the coupling was experimentally compared between the single and composite solution. Overall mass transfer coefficients were determined. Effects of various factors such as flow rates and operation temperatures on mass transfer of membrane contactor were studied. Comparison of prediction for overall mass transfer coefficients using a resistance in series model with experimental values was performed. Results show that, performance of the composite solution is evidently better than that of the single solution. The overall mass transfer coefficient with the composite solution is much higher than that with the single solution. Higher operation temperature can enhance mass transfer of membrane contactor. Operation parameters such as flow rates can promote mass transfer, but the promotion is limited. Enhancement of mass transfer relies essentially on chemical reaction. Model values are in good agreement with experimental ones.     

Mass transfer correlations for membrane gas-solvent contactors undergoing carbon dioxide desorption

Membrane gas-solvent contactors are a hybrid technology combining solvent absorption with membrane gas separation, which demonstrates potential for CO₂ capture through the ability of the membrane to rigidly control the mass transfer area. Membrane contactors have been successfully demonstrated for CO₂ absorption, and there is strong research interest in using membrane contactors for the complimentary CO₂ desorption process to regenerate the solvent. However, understanding and modelling the various stages of mass transfer in the desorption process is less well-known, given the existing mass transfer correlations had been developed from absorption experiments. Hence, mass transfer correlations for membrane contactors are reviewed here, and their appropriateness for desorption analysed. This is achieved through simulating CO₂ desorption through a membrane contactor from loaded 30wt% monoethanolamine solvent to enable comparison of the correlations. It was found that the most cited correlations by Yang and Cussler were valid for shell side parallel flow, while that of Kreith and Black was viable for shell side cross flow. A limitation of all of these correlations is that they assume single phase flow on both sides of the membrane; however, the high temperature of CO₂ desorption can lead to partial solvent vaporisation and hence two phases present on one side of the membrane contactor during desorption. A mass transfer correlation is established here for two phase parallel flow on the shell side of a membrane contactor, based on experimental results for three composite and one asymmetric hollow fibre membrane contactors stripping CO₂ from loaded MEA at 105-108℃. This correlation is comparable to that reported in the literature for mass transfer in other two phase systems, but differs from the standard format for membrane contactors in terms of the exponent on the dimensionless Schmidt and Reynolds numbers.     

Carbon dioxide stripping in ceramic hollow fibre membrane contactors

Ceramic hollow fibre membrane contactors have been applied to carbon dioxide stripping from monoethanolamine (MEA) solution at high temperature where most polymeric membranes would fail to operate. The experimental results show that the membrane contactors are immune from hydrodynamic problems, such as flooding and loading, since the gas and liquid phases can totally be separated by the hollow fibre membranes. The height of transfer unit (HTU) of the contactor was determined to be as low as 15 cm and is dependent on the fluid velocities. The mass transfer coefficients were theoretically predicted and found to be within a reasonable deviation. The mass transfer resistance in the liquid phase was found to be the majority of the total resistance.     

Stripping of acetone from isopropanol solution with membrane and mesh gas-liquid contactors

Stripping of acetone from isopropanol utilizing nitrogen as a sweeping gas was conducted in gas/liquid contactors with slit type microchannels and containing flat sheet, metal and Teflon tortuous pore membranes or microfabricated metal meshes with straight pores. The contactor consisted of parallel metal plates, gaskets, and the membrane or the microstructured mesh so that passages for gas and liquid phases were formed. These slit type microchannels were 200 μm thick for both gas and liquid phases. All the membranes/meshes were wetted by the isopropanol solution. Breakthrough of one phase into the other was successfully described if contortion of the gas/liquid interface was considered at the pore ends. Various conditions during acetone stripping were investigated such as membrane type, gas and liquid flowrates and inlet acetone concentration. A contactor employing a Micro-Etch metal mesh with 76 μm openings and thickness of 50 μm offered the lowest mass transfer resistance and resulted to the best acetone stripping performance. The separation efficiency increased by increasing the gas/liquid flowrate ratio, but was not affected when increasing the inlet acetone concentration. Good agreement between the experiments and an one-dimensional model with no adjustable parameters was observed.