Modeling and Optimization of Direct Contact Membrane Desalination Water Purification Systems Using Computational Fluid Dynamic Analysis by Jeremiah Blair Jones An Engineering Project Submitted to the Graduate Faculty of Rensselaer Polytechnic Institute in Partial Fulfillment of the Requirements for the degree of MASTER OF ENGINEERING Major Subject: MECHANICAL ENGINEERING Approved: _________________________________________ Norberto Lemcoff, Project Adviser Rensselaer Polytechnic Institute Hartford, Connecticut May 2015 1 © Copyright 2015 by Jeremiah Blair Jones All Rights Reserved ii CONTENTS LIST OF TABLES ............................................................................................................ iv LIST OF FIGURES ........................................................................................................... v NOMENCLATURE ......................................................................................................... vi LIST OF KEYWORDS .................................................................................................. viii ACKNOWLEDGMENT .................................................................................................. ix ABSTRACT ...................................................................................................................... x 1. Introduction.................................................................................................................. 1 1.1 Background ........................................................................................................ 1 1.2 Problem Statement ............................................................................................. 5 2. Theory and Methodology ............................................................................................ 7 2.1 Theory ................................................................................................................ 7 2.1.1 2.2 Theoretical System ................................................................................. 7 Methodology ...................................................................................................... 9 2.2.1 Computational Fluid Dynamic Model ................................................... 9 2.2.2 Model Optimization ............................................................................. 17 3. Results and Discussion .............................................................................................. 19 3.1 Effect of System Flow Input Velocity ............................................................. 19 3.2 Effect of System Flow Inlet Temperatures ...................................................... 22 3.3 Effect of Flow Channel Length ........................................................................ 24 3.4 Effect of Membrane Porosity ........................................................................... 26 4. Conclusion ................................................................................................................. 29 5. References.................................................................................................................. 31 Appendix A. Seawater Fluid Property Equations ............................................................ 33 Appendix B. COMSOL Multiphysics 1D, 2D, 3D Plots ................................................. 34 Appendix C. Constant Water Vapor Diffusion Coefficient Error ................................... 46 iii LIST OF TABLES Table 1: Initial Boundary Conditions .............................................................................. 12 Table 2: Initial Material Properties .................................................................................. 13 Table 3: 2-D Model Meshing Boundary Edge Distributions........................................... 16 Table 4: Varying Inlet Velocity Only Results, Constant DF............................................ 19 Table 5: Varying Inlet Velocity Only Results, Varied DF ............................................... 21 Table 6: Varying Inlet Temperature ................................................................................ 23 Table 7: Varying Channel Length ................................................................................... 24 Table 8: Varying Membrane Porosity Only Results........................................................ 26 iv LIST OF FIGURES Figure 1: Osmotic and Reverse Osmotic Flow [4] ............................................................ 2 Figure 2: Residential Reverse Osmosis System [5] ........................................................... 4 Figure 3: Industrial Reverse Osmosis System [6] ............................................................. 4 Figure 4: Cylindrical, Spiral Wound Reverse Osmosis Membrane Pass [7] ..................... 7 Figure 5: Simplified Cross-Flow Desalination Membrane Pass [8] ................................. 8 Figure 6: Membrane Mass Flux Resulting from Vapor Pressure Difference .................... 9 Figure 7: Simplified 2-D Model Geometry .................................................................... 12 Figure 8: First Meshing Pattern Using Free Triangular ................................................... 15 Figure 9: Second Mesh using Distribution and Mapping ................................................ 17 Figure 10: Concentrate and Product Concentration as a Function of Inlet Velocity ....... 20 Figure 11: Comparison of Constant DF Results to Varying DF Results .......................... 22 Figure 12: Concentrate and Product Concentrations as a Function of Concentrate Inlet Temperature ..................................................................................................................... 23 Figure 13: Concentrate and Product Concentrations as a Function of Length ................ 25 Figure 14: Concentrate and Product Concentration as a Function of Porosity................ 27 v NOMENCLATURE Symbols cp Constant Pressure Heat Capacity [J/(kg*K)] ci Concentration of species i (mol/m3) Di F Diffusion Coefficient of species i (m2/s) F Outside Body Forces (N) h Flow Channel height (m) I Identity Factor ji Molecular mass flux of species I [kg/(m2*s)] k Thermal Conductivity [W/(m*K)] L Flow channel length (m) Mi Molar mass of species i (kg/mol) Ni Concentration Flux of species i [mol/(m2*s)] p Pressure (Pa) R Universal Gas Constant [J/(mol*K)] T Temperature (K) t Thickness (m) Q Heat flux (W) u Velocity field (m/s) vav Average Inlet Velocity (m/s) Greek Letters ρ Density (kg/m3) μ Dynamic viscosity (Pa*s) θ Membrane Porosity ω Mass fraction Σ Summation of vi Subscripts 0 Initial co Concentrate Stream p Porous membrane domain pr Product water Stream w Water species vii LIST OF KEYWORDS KEYWORD DEFINITION CFD Computational Fluid Dynamics Cocurrent Fluid flow condition which all flows travel in parallel to each other with the same flow direction. Convection Mechanism of heat transfer through liquids and gases Countercurrent Fluid flow condition which all flows travel in parallel to each other with opposite flow directions. Desalination Process of removing dissolved salts from water. Diffusion Process by which molecules are transported as a result of their kinetic energy of random motion. FE Finite Element Porosity Percentage of a solid which is open space Reverse Osmosis Process which utilizes a semi-permeable membrane and an applied pressure greater than the osmotic pressure to remove dissolved particles from a solution. Semi-permeable membrane Membrane which allows the transport of certain molecules/ions to pass through while preventing the flow of other molecules/ions. viii ACKNOWLEDGMENT In the arduous process that was completing this project, there were many influences that helped ensure success. The most notable of said influences would be my girlfriend Hannah Frank. Whether it was providing moral support, ensuring that I was adequately distracted on weekends, or unknowingly giving me something to compete against (e.g. getting a graduate school GPA of 4.0 in Biomedical Engineering) Hannah was unwaveringly always there. Another much needed thanks goes to my professor and academic advisor, Norberto Lemcoff. Without his continual advice, suggestions, and sometimes much needed constructive criticism on my unorthodox methodology for utilizing COMSOL Multiphysics, completion of this project would have with much more difficulty. I would also like to thank my family for their constant support and my friends and coworkers for the ongoing reminder that life outside of graduate school is a lot more enjoyable than life in graduate school. Finally I must thank General Dynamics Electric Boat (GD EB) for providing with the financial motivation to obtain my Masters of Engineering degree. Without the GD EB academic reimbursement program, returning to school would likely not have occurred. ix ABSTRACT Water is a very valuable resource both with respect to the continued survival of humans and to various industrial capabilities. Although water happens to be one of the most abundant resources, the amount of clean freshwater available for human consumption and industrial uses is limited. One process which was developed to remedy the limited supply of freshwater is desalination. This process removes salt and other elements from seawater thus producing freshwater. In order to keep up with the continually increasing demand for clean freshwater, the methods and processes available to convert the more abundant, but less useable, seawater to freshwater must be evaluated and optimized. This project used a finite element model and computational fluid dynamic analysis to evaluate a concurrent two-dimensional direct contact membrane desalination system to determine what system characteristics and operating conditions could be changed to optimize the system performance. The results of the evaluations performed indicated that by increasing channel length, increasing porosity, increasing the inlet temperature of the concentrate stream, or decreasing the inlet velocity condition the salt concentration in the product water leaving the system could be decreased. The results obtained along with the literature review conducted in support of the modeling and evaluations also showed that limitations exist with respect to desalination system optimization. Each change to the system parameters or characteristics has the potential to affect the influence of other system characteristics and could ultimately results in a worse system performance. With this in mind, it is necessary to ensure that the designs and design considerations used for desalination systems are robust and highly vetted. x 1. Introduction 1.1 Background Water is a very important resource and is used for a variety of applications, most notably sustaining human life. Other applications which utilize water are hydroelectric plants, nuclear power plants, heating and cooling systems. Even though water is very abundant, covering approximately 70% of earth’s surface [1], not all of it is able to be readily utilized. Water’s inability to be directly utilized is a result of the water containing undesirable ions and compounds. The most common compound found in the water is Sodium Chloride, or salt. Approximately 97% of the water on earth is considered seawater, i.e. having a large concentration of salt [2]. The large concentration of salt in seawater makes it unsafe for human consumption and no longer suitable for applications which require pure water (e.g. nuclear power plants). In order to combat the continuing need for purer water, various methods have been developed so that contaminants can be removed from the water. One of the first uses of such a method dates back to ancient Egyptian cultures, where a painting on a tomb wall depicts what appears to be siphoning of liquids using sedimentation [3]. Since then, significant improvements have been made in the water purification industry. In particular, much advancement has been made in the capability of removing salt, or salinity, from water. This process is referred to as desalination, and is often accomplished using one of the following three methods: distillation, direct contact membrane microfiltration (e.g. reverse osmosis), or electrodialysis. Osmosis is a naturally occurring process whenever two solutions with different concentrations of solute are separated by a semi-permeable membrane1. The difference in concentration causes the solvent to travel from the solution with the lower solute concentration, through the semi-permeable membrane, into the solution with higher concentration of solute. This process continues until the concentration of the two solutions has equalized. To counter osmotic flow, some pressure must be applied to the higher concentration solution in order to prevent pure solvent from going through the 1 A semi-permeable membrane is one which allows the flow of solvent but not the flow of solute. 1 semi-permeable membrane separating the two liquids; this is known as the osmotic pressure. If the pressure is increased above the osmotic pressure the solvent will pass from the solution with higher concentration, back through the membrane, and into the solution with lower concentration. This process is called reverse osmosis and can be utilized to purify a solution. Figure 1 depicts side by side the osmosis, osmotic equilibrium, and the reverse osmosis process. In both the osmosis and reverse osmosis frames the white arrows indicate the flow of solvent. The desalination process is primarily driven by the pressure applied to the system, as indicated by the metallic plunger in the “Reverse Osmosis” picture in Figure 1, and the difference in solution concentrations. Figure 1: Osmotic and Reverse Osmotic Flow [4] Another method of accomplishing direct contact membrane desalination is with two solutions of different temperature and concentration flowing in parallel, separated by a semi-permeable membrane. Solvent will diffuse from one solution, across the membrane, into the other solution. The solute is restricted from diffusing across the membrane. Similarly to reverse osmosis, differences in concentration and pressure are the driving force of this process. However, unlike reverse osmosis which uses mechanical means to apply a backpressure to drive the desalination, this process utilizes the difference in temperature which results in a vapor pressure gradient which ultimately drives solvent through the membrane. To accomplish these purifications, a continuous stream of a solution is passed through a module containing a semipermeable membrane. As the characteristic pressure of the 2 system is increased, the membrane allows solvent to pass through. Both the solvent and the now higher concentration solution are extracted from the module containing the membrane, thereby the process can continuously produce purer water. Most commonly this is used to remove impurities, such as fluorides or heavy metals, from drinking water and to reduce the salinity of seawater to produce potable water aboard naval vessels. This is a very useful application as it allows for naval vessels to utilize the vast amount of seawater surrounding them to produce water for drinking, showering, dishwashing, etc. Direct contact desalination systems can vary significantly in size and complexity. Systems used in residential applications tend to be fairly small and compact, due to the size constraints that exist in residential property. Figure 2 shows an example of a household desalination system which utilizes reverse osmosis. These systems generally use one membrane accompanied by multiple inline filters (to remove sediments and chlorine from incoming water which could damage the membrane) and a pressurized storage tank (to account for fluctuations in demand). Based on the smaller size, these systems generally are capable of removing up to 1,500 to 1,800 ppm of TDS (Total Dissolved Solids). Industrial applications are usually larger and more complex. Figure 3 shows an example of a membrane skid of a reverse osmosis system. Generally industrial applications also have a water pre-treatment skid to remove solutes or sediment that may be harmful to the membranes (e.g. activated charcoal filter). The pretreatment skid may also utilize heaters/chillers to manipulate the temperature of the incoming water. One important point that should be mentioned is that the industrial system utilizes many membranes to accomplish the purification. This is usually necessary as industrial applications have stricter product water requirements than those in household applications, or the incoming water contains more TDS than in household applications. As a result, the industrial desalination systems are costly to operate and maintain. Improvements in desalination membrane and/or system performance can help reduce these costs. 3 Figure 2: Residential Reverse Osmosis System [5] Figure 3: Industrial Reverse Osmosis System [6] 4 1.2 Problem Statement Although this is a very useful process, there are various factors which can affect the performance of a direct contact membrane desalination system. An increase in the pressure applied to the membranes or solution flow will result in an improved performance (product solution concentration will decrease, and rate at which product solution is created will increase). Depending on the solution being purified, fouling of the membranes can occur, which will negatively affect performance. In residential applications, where water is not as abundant as in naval vessel applications (surrounded by seawater), an issue can arise since significant amounts of reject water are required to produce useable amounts of product water. This can drain available resources and/or be very costly (e.g. running a well dry, significant electrical cost to have the desalination system constantly running). In order to prevent adverse effects, improvements can be made to the desalination system design. Although naval vessels have an abundant source of water, the high salt concentration of the ocean requires the water be processed through many membranes to produce acceptable product water. The introduction of more membranes results in an increase in both manufacturing and maintenance costs. If, however, each of the membranes/passes were designed to be more efficient there would no longer be a need for as many membranes/passes. Possible improvements in membrane/pass design are increasing the pressure of the system, choosing a better membrane material such as a composite, or changing the incoming or product water flow characteristics. Another problem that occurs with the use of desalination systems is the development of waste. The more efficient the process is, the more concentrated the solution being rejected by the membrane becomes. This can create problems with the disposal of said concentrated output. In the example of a residential reverse osmosis system being used to remove total dissolved solids from drinking water, if the water rejected by the membrane becomes too concentrated with TDS it may not be allowed, per government regulations, to be disposed of in sewer/septic lines. This project plans to focus on the performance of the direct contact desalination membranes. Also, a follow-up study 5 could analyze the waste created by more efficient systems, and how this waste can be handled/diluted in accordance with regulations. 6 2. Theory and Methodology This project will analyze the performance of a single membrane direct contact desalination system. Most commercially available direct contact desalination systems utilize a single membrane pass. Although larger systems use multiple membrane passes in series, investigating a single membrane could easily be extrapolated to determine the larger system performance results. Therefore the results of modeling a single pass can be utilized in the design and operation of a wide variety of direct contact membrane desalination systems. 2.1 Theory 2.1.1 Theoretical System One conventional desalination system is a reverse osmosis system utilizing spiral wound membrane configurations to filter salt out of water. Figure 4 depicts a partially extruded membrane pass. The salt water flows in through the feed channel into the membrane assembly. Backpressure applied to the system causes pure water to pass through the semi-permeable membrane into the permeate carrier (a spiral wound channel which is wrapped in between layers of the membrane). The permeate carrier allows the product water to travel from the outside into the center where a “punctured” product water tube collects and flows the product water out. Simultaneously, the salt that is rejected by the membrane causes an increase in concentration in the feed stream which is ultimately pushed through the feed channels and leaves the system as concentrate. Figure 4: Cylindrical, Spiral Wound Reverse Osmosis Membrane Pass [7] 7 Although the spiral wound membrane configuration is commonly used for a wide range of applications, to accommodate the time constraints of this project a simpler model ultimately had to be chosen. To accomplish this, a direct contact membrane desalination model was chosen (Figure 5). In this model, seawater (feed) is introduced on one side of the system and flows across the semi-permeable membrane. Concurrently, a second stream is introduced to flow in parallel to the feed stream across the other side of the membrane (product/permeate). The driving mechanism for mass transfer in this system is the difference in vapor pressure between the feed and permeate streams. Since the vapor pressure is a function of the stream temperature, the ultimate driving force of the mass transfer becomes the temperature difference between the feed and permeate stream. With a sufficient temperature difference, water is transferred across the membrane while salt is rejected. This process is depicted in Figure 6. As may be evident by comparing the system products, this simplified model has strong correlation to the spiral wound reverse osmosis filtration system. Figure 5: Simplified Cross-Flow Desalination Membrane Pass [8] 8 Mass Flux Hot/Concentrate Cold/Product Stream Stream Figure 6: Membrane Mass Flux Resulting from Vapor Pressure Difference 2.2 Methodology 2.2.1 Computational Fluid Dynamic Model Computational Fluid Dynamics (CFD) is a method of analysis which utilizes finite element models to solve problems relating to the flow of fluids. CFD can be used to verify analytical results in basic situations or tackle more complicated problems that cannot be solved analytically. The CFD program used to accomplish this project was COMSOL Multiphysics. In order to utilize CFD, first the physics and FE (Finite Element) models need to be created. Initially a two-dimensional model is created. 2.2.1.1 CFD Physics Models In order to develop an accurate representation of the desalination process, three existing physics models contained in COMSOL had to be used simultaneously. The three physics models were Laminar Single-Phase Fluid Flow, Heat Transfer in Fluids and Transport of Diluted Species. The Laminar Single-Phase Fluid Flow physics module is used to model the solution flows through the system. Since the mass transport mechanism is a result of the difference in water vapor pressures, fluid flow is assumed to 9 only occur in the two solution channels (i.e. no fluid flow through the membrane). As a result, the Laminar Flow physics module only applies to the solution channel domains. For the flow of the solutions, the module utilizes the continuity and Navier Stokes equations for incompressible flow, shown in Equations 1 and 2. 𝜌∇ ∗ 𝒖 = 0 (1) 𝜌 ∗ (𝒖 ∗ ∇)𝒖 = ∇ ∗ [−𝑝 ∗ 𝑰 + 𝜇 ∗ (∇𝒖 + (∇𝐮)𝑇 )] + 𝐹 (2) The Transport of Diluted Species physics module is used to model the mass transfer of diluted species through the membrane. Since water is being transferred from the “concentrate” stream to the “product” stream, water was chosen as the “diluted species”, and therefore all of the model concentrations refer to water. The mass transfer of the diluted species utilizes Equations 3 and 4: ∇ ∗ (−𝐷𝑖 ∇𝑐𝑖 ) + 𝒖 ∗ ∇𝑐𝑖 = 𝑅𝑖 (3) 𝑁𝑖 = (−𝐷𝑖 ∇𝑐𝑖 ) + 𝒖𝑐𝑖 (4) These equations model the flow of water in the fluid phase through the porous membrane as well as the dilution of water in the concentrate and product streams. As mentioned before, the primary transfer mechanism for water in direct contact membrane distillation is in the vapor phase. Therefore, a flux discontinuity had to be created at each side of the membrane domain to account for the transfer of water vapor from the concentrated stream to the product stream. The flux discontinuity is modeled using Equations 5, 6, and 7: 𝑁𝑖 = 𝐹 (𝐷𝑣𝑎𝑝𝑜𝑟,𝑖 ∗𝜃2 ) 𝑅∗𝑇𝑎𝑣𝑒 ∗ (𝑃𝑣𝑎𝑝𝑜𝑟,2 − 𝑃𝑣𝑎𝑝𝑜𝑟,1 ) (5) Where, 𝑃𝑣𝑎𝑝𝑜𝑟,𝑖 = 133.3 ∗ 𝑒 5132 20.386− 𝑇 [9] (6) 𝐹 𝐷𝑣𝑎𝑝𝑜𝑟,𝑖 = −2.775𝑒 −6 + 4.479𝑒 −8 ∗ 𝑇 + 1.656𝑒 −10 ∗ 𝑇 2 [10] (7) ℎ𝑚 10 Equation 5 is developed integrating Equation 8, which represents the flux through a porous solid according to Fick’s Law, over the length of the membrane, and using Equation 9 for the effective diffusivity of a porous membrane [11]. 𝑑𝑐 𝐷 𝑑𝑝 𝑁𝑖 = −𝐷𝑒 ∗ 𝑑𝑥 = − 𝑅∗𝑇𝑒 ∗ 𝑑𝑥 (8) 𝐷𝑒 = 𝐷𝐴,𝐵 ∗ 𝜃 2 (9) 𝑎𝑣𝑒 It is important to note the dependency of the mass transport on only the temperatures of the domains. Therefore, changes in inlet concentrations will not affect the amount of mass flux that occurs at the membrane boundaries. In order to account for the temperature effects on the mass transfer, the Heat Transfer in Fluids physics module was used to model the thermal behavior of the three domains throughout the process. The heat transfer module utilizes the conservation of energy for conductive and convective heat transfer, as shown in Equation 10. 𝜌 ∗ 𝑐𝑝 ∗ 𝒖 ∗ ∇𝑇 = ∇ ∗ (𝑘𝑒𝑞 ∗ ∇𝑇) + 𝑄 (10) After choosing the physics models in COMSOL, the geometry and initial conditions were defined. For this model, two 0.2 meter by 0.001 meter flow channels were stacked on top of each other, separated by a 0.0001 meter by 0.2 meter membrane, as shown in Figure 7. 11 10 9 7 8 5 6 4 1 3 2 Figure 7: Simplified 2-D Model Geometry These dimensions were chosen for the initial model to satisfy the condition that the length of the flow channels be significantly larger than the thickness of the membrane layer (in this model, the length of the flow channels is 2000 times larger than the membrane thickness). Once the geometry was determined and coupled appropriately, the boundary conditions and material properties were defined, as shown in Table 1 and Table 2. Table 1: Initial Boundary Conditions Boundary Label Parameter Name Parameter Value/Condition Normal Inflow Velocity = .1 m/s, 1 Concentrated Inlet Ti = 313 K, C0,w=55,000 mol/m3 2 Wall No-Slip 3 Concentrate Outlet 4 Wall No-Slip, Flux Discontinuity 5 Wall No-Slip 6 Wall No-Slip Pressure = 0 Pa, Outlet heat flux 12 Normal Inflow Velocity = .1 m/s, 7 Diluted Inlet Ti = 293 K, C0,w = 55,000 mol/m3 8 Wall 9 Diluted Outlet 10 Wall No-Slip, Flux Discontinuity Pressure = 0 Pa, Outlet heat flux No-Slip Table 2: Initial Material Properties Material Property Value Porous Medium Porosity 0.83 [12] Membrane Thickness, t 0.0001 m Molar Mass, Water 0.018 kg/mol Molar Mass, Salt 0.058 kg/mol Diffusion Coefficient, Concentrate, Water 2.68 10-5 m2/s Diffusion Coefficient, Product, Water 2.484 10-5 m2/s Diffusion Coefficient, Membrane, Water 10-12 m2/s Average Diffusion Coefficient, Water Vapor 2.6017 10-5 m2/s Average Temperature for Concentration Flux 303.5 K The inlet concentration value for both the concentrated and product streams was assumed to be that of the incoming seawater, which has a salinity of approximately 3.5% and contains numerous ions other than sodium and chloride [13]. Therefore, an inlet water species concentration of 55,000 mol/m3 was chosen. The inlet flow condition and concentrate outlet pressure condition were chosen to allow the flow to pass through the system without restriction, ultimately isolating the driving mechanism of the desalination process to the temperature gradient. The membrane porosity for the base case was chosen to coincide with previous research done for direct contact membrane distillation 13 processes [12]. This porosity value will be varied in this project to determine its effect on the system performance and efficiency. When calculating the concentration flux, a constant water vapor diffusion coefficient and average temperature were assumed. The water vapor diffusion coefficient was determined by calculating the average of the diffusion coefficient at the inlet temperatures of the hot and cold streams. The assumed average temperature is simply the average of the two inlet temperatures. These assumptions were made to simplify the equations that were simultaneously solved by COMSOL Multiphysics, therefore decreasing the run time of the program. The constant average temperature assumption was validated calculating the average temperature for the membrane domain after each run. The constant water vapor diffusion coefficient assumption was validated by carrying out one set of runs without a constant coefficient and comparing the results. The values for the density, dynamic viscosity, thermal conductivity, and specific heat capacity all depend on both temperature and salt concentration. The equations used to determine these values are shown in Appendix A and derived from Sharqawy et al. [14]. Since the Appendix A equations are dependent on salt concentration, the model output water concentration has to be converted to be used as an input. To do so, Equations 11, 12 and 13 below were used. 𝜌𝑤 = 838.466 + 1.40051 ∗ 𝑇 − 3.01121𝑒 −3 ∗ 𝑇 2 + 3.71821𝑒 −7 ∗ 𝑇 3 𝜌 𝑐𝑠𝑤 = (𝑀𝑤 − 𝑐) (11) (12) 𝑤 𝑀 𝑠𝑎𝑙𝑡 𝑆𝑠𝑤 = 𝑐𝑠𝑤 ∗ (1000∗𝜌 ) (13) 𝑠𝑤 Equation 11 calculates the density of pure water as a function of temperature. Equation 12 converts this calculated pure water density to a concentration by dividing by the molar mass of water, and then subtracting the concentration being solved for as part of the evaluation. c is the dependent variable of the Transport of Diluted Species physics module. Since the density of the seawater solution is being calculated simultaneously 14 with Equation 12, which is also dependent on the concentration, a density value of 1.025 kg/L was chosen to reduce computational complexity and model run time. 2.2.1.2 CFD Model Meshing Before the aforementioned calculations could be performed, a mesh had to be created for each of the three domains (two flow channels and one membrane layer). Since COMSOL Multiphysics allows for a variety of meshing patterns, two meshes were created and then compared to determine the more accurate FE model. The first mesh utilizes the free triangular meshing function with a sizing calibrated for general physics of normal sizing. This meshing pattern results in a total of 24,249 meshing elements. Figure 8 is a zoomed in picture of the first mesh. Figure 8: First Meshing Pattern Using Free Triangular The second mesh utilizes the distribution function of COMSOL Multiphysics. This function allows the user to input how many rows of meshing elements each boundary should be broken into. The user can then use the mapping feature of COMSOL 15 Multiphysics to extrude the mesh across the remainder of the domain. Table 3 shows the distribution used for each boundary edge of the model. The boundary edge numbers in the table correspond to Figure 7. Since the flow channels are of matching geometries, they can both utilize the same mesh. However, since the membrane layer is significantly thinner than the flow channels, a finer mesh had to be used. Table 3: 2-D Model Meshing Boundary Edge Distributions Boundary Edge Distribution Value 1 10 2 200 3 10 4 200 5 10 6 10 7 10 8 200 9 10 10 200 Figure 9 is a zoomed in picture of the 2-D model and meshing described above. These meshing patterns result in a meshing element total of 6,000, all of which are quadrilateral elements. 16 Figure 9: Second Mesh using Distribution and Mapping Although the second mesh with quadrilateral elements utilizes a mesh which is finer in the vertical direction for the membrane domain, the first mesh with triangular elements utilizes a mesh finer in the horizontal direction for all three domains near the membrane boundaries. Since the model uses flux discontinuities at the top and bottom membrane boundaries, the number of meshing elements within the membrane domain is not as significant as the number of meshing elements used for the flow channels near the membrane boundaries. Therefore, the meshing with triangular elements was chosen. 2.2.2 Model Optimization Once a baseline model was established, the model parameters were varied to optimize the system performance. The system performance was based on the outlet concentration for both the concentrate and product channels. The parameters chosen for this project to be varied in the optimization process were the overall channel length, channel average velocity inlet condition, membrane porosity and inlet temperature conditions. To accomplish the optimization, all of the aforementioned parameters were held constant except for one. This one parameter was varied and the resulting system performance 17 was tabulated. This process was then repeated for each of the optimization parameters. Since the species being transferred from the hot concentrate stream to the colder product stream was water, it is necessary to verify that the product stream concentration is maintained below that of pure water at the specified inlet temperature (i.e. 293 K results in a pure water concentration of 55,536.41 mol/m3). Any solutions with outlet product concentrations higher than this value were either discarded or included and prefaced appropriately for discussion purposes. Another model limitation was the inlet temperature of the hot stream. If the temperature is too high, the membrane performance and integrity can begin to diminish. In order to prevent this, most systems maintain a very tight control of both the upper and lower temperature limits. In this project, a maximum temperature of 54.85 °C and a minimum temperature of 19.85 °C were assumed. These assumptions are consistent with previous research of different desalination membrane systems [15]. 18 3. Results and Discussion The results from the optimization runs described above were compiled in tables and plots to better show trends and general system behavior as a result of each optimization trial. These tables and plots are included and discussed below. It should be pointed out that all the concentration values indicated below are of water. Therefore an increase in resultant product stream concentration refers to a decrease in the salt concentration. Appendix B contains the 1D, 2D, and simulated 3D plots created by COMSOL Multiphysics for the case with a channel length of 0.1 m, channel height of 0.001 m, a membrane thickness of 0.0001 m, an initial velocity of 0.25 m/s, and inlet temperatures of 293 K to 328 K. These plots depict the concentration, temperature, pressure and velocity profiles throughout the model. These plots are intended to be visual aids to the data included and discussed herein. 3.1 Effect of System Flow Input Velocity Table 4 shows the results when the inlet velocity condition is varied while maintaining constant the channel length, inlet temperatures, and membrane porosity for a channel height of 0.001 m. Figure 10 is a graphical representation of the data contained in Table 4. Table 4: Varying Inlet Velocity Only Results, Constant DF Inlet Velocity Effect (L = 0.2, h = 0.001, hp = 0.0001) vavg = vavg = vavg = vavg = 0.05 0.1 0.15 0.2 305.31 307.45 308.54 309.19 Outlet Temp (K) Concentrate Outlet Conc 54,579 54,788 54,858 54,893 (mol/m3) 300.67 298.45 297.33 296.66 Outlet Temp (K) Product Outlet Conc 55,421 55,212 55,142 55,107 (mol/m3) 19 vavg = 0.25 309.63 54,914 296.23 55,086 Case 1 - Varying Inlet Velocity 55500 Outlet Concentration (mol/m3) 55400 55300 55200 55100 55000 Concentrate 54900 Product 54800 54700 54600 54500 0 0.05 0.1 0.15 0.2 0.25 0.3 Velocity (m/s) Figure 10: Concentrate and Product Concentration as a Function of Inlet Velocity As is evident by analyzing the curves shown on Figure 10 and comparing sequential columns in Table 4, as the velocity is increased the system performance is decreased. As the velocity increases, the product stream outlet concentration decreases and that of the concentrate increases. Similarly, as the velocity increases, the outlet temperature for the product stream decreases and the outlet temperature for the concentrate stream decreases. This behavior is to be expected. As the velocity increases, the residence time decreases. Therefore, further increases in velocity will drive the system outlet characteristics to approach the inlet conditions, as the relative amount of fluid capable of being desalinated goes to zero. Figure 10 shows that, as velocity increases, both concentrate and product stream concentrations approach 55,000 mol/m3, the inlet concentration value. It is important to note that although decreasing velocity in this case resulted in improved system performance, there is a limit to how much the velocity can be lowered. This limit is dependent on other system characteristics such as channel length and inlet initial 20 temperatures. What should be avoided are the concentrate and product stream outlet temperatures reaching equilibrium. When this temperature equilibrium is reached, the system no longer has the ability to force more pure water from the concentrate stream (i.e. the system loses the vapor pressure differential driving force). This can occur with low velocities in long channels and systems with an initial small temperature difference between concentrate and product streams. As discussed above, the data shown in Table 4 and Figure 10 was calculated assuming the diffusion coefficient of water vapor was constant throughout the process. To confirm this assumption the same evaluation was performed using Equation 7 to calculate the diffusion coefficient based on temperature with each calculation. The data collected during this evaluation is summarized in Table 5. The concentrations from Table 5 as well as the constant diffusion coefficient concentrations from Table 4 are plotted concurrently in Figure 11. Table 5: Varying Inlet Velocity Only Results, Varied DF Inlet Velocity Effect (L = 0.2, h = 0.001, hp = 0.0001) vavg = vavg = vavg = vavg = 0.05 0.1 0.15 0.2 305.31 307.45 308.54 309.19 Outlet Temp (K) Concentrate Outlet Conc 54,578 54,788 54,858 54,893 (mol/m3) 300.67 298.45 297.33 296.66 Outlet Temp (K) Product Outlet Conc 55,419 55,210 55,141 55,106 (mol/m3) 21 vavg = 0.25 309.63 54,914 296.23 55,085 Case 1 - Varying Inlet Velocity 55,500 Outlet Concentration (mol/m3) 55,400 Concentrate Varied Df 55,300 55,200 55,100 Product - Varied Df 55,000 54,900 Concentrate Const. Df 54,800 54,700 Product - Const. Df 54,600 54,500 0 0.05 0.1 0.15 0.2 0.25 0.3 Velocity (m/s) Figure 11: Comparison of Constant DF Results to Varying DF Results The comparison of results shown in Figure 11 confirms the validity of assuming a constant water vapor diffusion coefficient calculated based on the two inlet conditions. The difference between results at each data point is very small. The largest error between Table 4 and Table 5 values is 0.00902%, which corresponds to the outlet concentration for the product stream at a velocity of 0.05 m/s. Appendix C contains the tabulated errors for each run shown in Table 4 and Table 5. 3.2 Effect of System Flow Inlet Temperatures Table 6 shows the results when the inlet temperature conditions are varied while maintaining constant the channel length, membrane porosity, and inlet velocity. Table 6 shows the results for a channel length of 0.2 m, membrane porosity of 0.45, and inlet velocity of 0.25 m/s. Figure 12 is a graphical representation of the data contained in Table 6. 22 Table 6: Varying Inlet Temperature Inlet Temperature Effect (L = 0.2, h = 0.001, hp = 0.0001, vavg = 0.25) Tco=313, Tco=318, Tco=323, Tco=328, Tpr=293 Tpr=293 Tpr=293 Tpr=275 Outlet Temp 309.63 313.74 317.84 321.96 (K) Concentrate Outlet Conc 54,914 54,876 54,828 54,770 (mol/m3) Outlet Temp 296.23 297.03 297.84 298.65 (K) Product Outlet Conc 55,086 55,124 55,172 55,229 (mol/m3) Case 2 - Varying Inlet Hot Temperature Outlet Concentration (mol/m3) 55,300 55,200 55,100 55,000 Concentrate Product 54,900 54,800 54,700 310 315 320 325 330 Inlet Hot Temperature (K) Figure 12: Concentrate and Product Concentrations as a Function of Concentrate Inlet Temperature As is evident by comparing all four columns in Table 6, an increase in the inlet temperature of the concentrate stream, while maintaining the product water stream inlet temperature constant, results in improved system performance. For each run, the increase in inlet temperature results in a decrease in concentrate stream outlet concentration as well as an increase in product water outlet concentration (lower 23 salinity). By increasing the concentrate inlet temperature, the pressure differential within the membrane is increased, therefore the driving force for the water vapor through the membrane is increased causing more of the water vapor to flow through. 3.3 Effect of Flow Channel Length Table 7 shows the results when the channel length is varied while maintaining constant the membrane porosity, inlet temperature condition and inlet velocity. Table 6 shows the results for membrane porosity of 0.45, inlet velocity of 0.25 m/s, and inlet temperature difference of 293 K to 328 K. Figure 13 is a graphical representation of the data contained in Table 7. Table 7: Varying Channel Length Channel Length Effect (h = 0.001, hp = 0.0001, vavg = 0.25) L= L = 0.1 L = 0.15 L = 0.2 0.225 323.84 323.53 321.96 321.73 Outlet Temp (K) Concentrate Outlet Conc 54,883 54,822 54,770 54,742 (mol/m3) 296.94 297.98 298.65 299.10 Outlet Temp (K) Product Outlet Conc 55,117 55,173 55,229 55,258 (mol/m3) 24 L = 0.25 321.2992 54,714 299.47 55,286 Case 3 - Varying Channel Length Outlet Concentration (mol/m3) 55,400 55,300 55,200 55,100 55,000 Concentrate 54,900 Product 54,800 54,700 54,600 0 0.05 0.1 0.15 0.2 0.25 0.3 Channel Length (m) Figure 13: Concentrate and Product Concentrations as a Function of Length The results in Table 7 show that as the length of the flow channel increases, the product water outlet concentration increases and the concentrate water concentration decreases. Intuitively these results make sense. By increasing the length of the channel, the length of the membrane and therefore the area of filtration increase. An increase in filtration area allows for more salt to be rejected, decreasing the concentrate water outlet concentration, and more product water to be produced, increasing the product water outlet concentration. Similar to the limitations when reducing the system inlet velocity, limitations exist in the effectiveness when increasing the channel/membrane length. As the channel length is increased further, the increases in performance will start to diminish until further increases result in no improvements at all. The physical meaning of this stabilization of product water outlet concentration is that for the given parameters the output of the membrane has been maximized. This maximization occurs when the concentrate stream and product stream temperatures reach equilibrium. When the temperature difference no longer exists, the system lacks a driving force for the water vapor to be transported 25 through the membrane. Therefore, if the membrane length was increased further the product water concentration will remain constant. 3.4 Effect of Membrane Porosity Table 8 shows the results when the membrane porosity is varied while maintaining constant the channel length, inlet temperature and inlet velocity. Table 8 shows the results for a channel length of 0.2 m, inlet velocity of 0.25 m/s and inlet temperatures of 293 K and 328 K. Figure 14 is a graphical representation of the data contained in Table 8. Table 8: Varying Membrane Porosity Only Results Membrane Porosity Effect (L = 0.2, h = 0.001, hp = 0.0001, vavg = 0.25) θ= θ= θ= θ= θ= 0.25 0.35 0.45 0.55 0.65 Outlet Temp 321.96 321.96 321.96 321.97 321.97 (K) Concentrate Outlet Conc 54,929 54,861 54,770 54,657 54,521 (mol/m3) Outlet Temp 298.64 298.64 298.65 298.66 298.67 (K) Product Outlet Conc 55,071 55,139 55,229 55,343 55,479 (mol/m3) 26 θ= 0.83 321.98 54,219 298.69 55,780 Outlet Concentration (mol/m3) Case 4 - Varying Membrane Porosity 56,000 55,800 55,600 55,400 55,200 55,000 54,800 54,600 54,400 54,200 54,000 Concentrate Product 0 0.2 0.4 0.6 0.8 1 Porosity Figure 14: Concentrate and Product Concentration as a Function of Porosity As stated in the initial conditions above, the first porosity that was modeled was θ = 0.83. However, the resulting product outlet concentration was 55,780 mol/m3, which is greater than the pure water concentration limit of 55,536 mol/m3, and therefore not a valid data point. For this reason, the data point associated with θ = 0.83 on Figure 14 and the line leading from the next valid run is shown as dotted. The remaining four runs for this case resulted in valid product outlet concentrations. These four runs indicate that as the membrane porosity is decreased, the system performance also decreases. The porosity of the membrane is the percent of the membrane which is open space. Therefore by decreasing the porosity of the membrane, the pores and open space within the membrane layer decrease which decreases the ability of the water vapor to pass through the membrane. As the porosity approaches zero, the amount of water vapor capable of passing across the membrane layer also goes to zero. Although the opposite is true, that increasing porosity will allow more water vapor to pass across the membrane layer, increasing porosity too much could also allow salt and seawater to flow across the membrane more readily. It is important to note though that the ability of salt and seawater to flow across the membrane is not only a function of porosity. Other membrane characteristics also have an effect on the overall mass transfer, e.g. the membrane pore size and membrane permeability. Based on the limited scope of this 27 project, the increase in capability for salt and seawater to flow across the membrane as porosity is increased was not modeled. 28 4. Conclusion The purpose of this project was to model a direct contact membrane desalination system and determine how said model could be optimized. This was accomplished by varying initial parameters or system characteristics such as channel length, inlet velocity, inlet initial temperatures, and membrane porosity. As discussed above, an improvement in the system performance can be realized with specific changes to each of the aforementioned parameters. The following changes resulted in increased performance (i.e. increase in the product water outlet concentration): - Increasing channel length - Increasing membrane porosity - Increasing the inlet concentrate temperature while maintaining the inlet product temperature constant - Decreasing inlet concentrate and product velocities Although initially it may seem possible to just increase or decrease one or more of the above parameters until the desired results are obtained, this is not always the case. Due to system performance limitations, which were not all capable of being captured by this project, some parameters are only capable of being optimized a certain amount before either no further increases in performance are noted or negative performance effects are realized. Also, it is important to note that changes to any of the four parameters noted above could have an impact, either positive or negative, on one of the other four. For example, significantly increasing the channel length could result in a necessary increase in inlet velocities to prevent reaching the equilibrium scenario briefly discussed in Case 1. This interdependency of all of the system parameters makes the system design a very involved process. As such, it is very important that all parameters, even those not discussed and evaluated herein, to be modeled and considered. It is also important to consider all of the system limitations during the design phase. Based on the timeframe in which this project had to be completed in and the resources available during the completion, the scope of this project had to be limited. Therefore, there are still beneficial evaluations which can be performed to improve the design and 29 performance of desalination systems. The following serves as a summary of such follow up evaluations which can be performed: - Evaluating cases where the concentrate and product inlet velocities were not equal to each other. - Evaluating counter-current flow cases. - Determining appropriate modeling conditions that would allow an increase of salt and seawater to permeate the membrane with an increase of membrane porosity. - Modeling a three-dimensional desalination system and compare to the twodimensional results obtained herein. The three-dimensional model could evaluate a rectangular channel and compare that to the results of a cylindrical model. 30 5. References [1] V. I. Grover, Water: Global Common and Global Problems, Enfield, NH: Science Publishers, 2006. [2] I. Shiklomanov, "World Fresh Water Resources," in Water in Crisis: A Guide to the World's Fresh Water Resources, P. H. Gleick, Ed., New York, Oxford University Press, 1993. [3] M. N. Baker, The Quest for Pure Water, New York: The American Water Works, Inc., 1948. [4] ESP Water Products, "Water Filtration and Purification Products; Reverse Osmosis Systems," 2009. [Online]. Available: http://espwaterproducts.com/reverse-osmosissystem.htm. [Accessed 18 February 2015]. [5] Water King, "Water King's Genesis Reverse Osmosis System," 2012. [Online]. Available: http://www.waterkingwater.com/el_paso_reverse_osmosis.htm. [Accessed 16 April 2015]. [6] Degrémont Technologies Ltd., "REVERSE OSMOSIS SKIDS," Suez Enviroment, 2015. [Online]. Available: http://www.degremont- technologies.com/dgtech.php?article458. [Accessed 16 April 2015]. [7] The Purchase Advantage, "Tory RO Membranes; TM-Series Element," 2015. [Online]. [Accessed 18 February 2015]. [8] General Electric, Cross Flow Filtration Method Handbook, Piscataway: General Electric Company, 2014. [9] M. Adaramola, Solar Energy: Applications, Economics, and Public Perception, Boca Raton: CRC Press, 2014. [10] R. E. Bolz and G. L. Tuve, Handbook of Tables for Applied Engineering Science, New York: CRC Press, 1976. [11] N. Wakao and J. M. Smith, "Diffusion in Catalyst Pellets," Chemical Engineering Science, vol. 17, pp. 825-834, 1962. [12] H. J. Hwang, K. He, S. Gray, J. Zhang and I. S. Moon, "Direct Contact Membrane 31 Distillation (DCMD): Experimental Study on the Commercial PTFE Membrane and Modeling," Journal of Membrane Science, vol. 371, no. 1-2, pp. 90-98, 2011. [13] P. Castro and M. Huber, Marine Biology, McGraw-Hill Companies, 2012. [14] M. H. Sharqawy, J. H. Lienhard V and S. M. Zubair, "Thermophysical Properties of Seawater: A Review of Existing Correlations and Data," Desalination and Water Treatment, no. 16, pp. 354-380, 2010. [15] A. Alkhdhiri, N. Darwish and N. Hilal, "Membrane Distillation: A Comprehensive Review," Desalination, vol. 287, pp. 2-18, 2012. [23] J. H. Nam and M. Kaviany, "Effective Diffusivity and Water-Saturation Distribution in Single- and Two-Layer PEMFC Diffusion Medium," International Journal of Heat and Mass Transfer, no. 46, pp. 4595-4611, 2003. [24] M. Flury and T. F. Gimmi, "Solute Diffusion," in Methods of Soil Analysis, Part 4, Physical Methods, J. H. Dane and C. Topp, Eds., Madison, Soil Science Society of America, 2002, pp. 1323-1351. [25] R. E. Zeebe, "On the Molecuar Diffusion Coefficients of Dissolved, CO2, HCO3-, and CO2- and Their Dependence on Isotopic Mass," Geochimica et Cosmochimica Acta, no. 75, pp. 2483-2498, 2011. [26] F. Franks, Water: A Matrix of Life, Cambridge: The Royal Society of Chemisty, 2000. [27] H. Yasuda, C. E. Lamaze and L. D. Ikenberry, "Permeability of Solutes through Hydrated Polymer Membranes," Die Makromolekulare Chemie, vol. 118, no. 2858, pp. 19-35, 1968. 32 Appendix A. Seawater Fluid Property Equations Seawater Density [kg/m3]: 𝜌𝑠𝑤 = (𝑎1 + 𝑎2 ∗ (𝑡 − 273.15) + 𝑎3 ∗ (𝑡 − 273.15)2 + 𝑎4 ∗ (𝑡 − 273.15)3 + 𝑎5 ∗ (𝑡 − 273.15)4 ) + (𝑏1 ∗ 𝑆 + 𝑏2 ∗ 𝑆 ∗ (𝑡 − 273.15) + 𝑏3 ∗ 𝑆 ∗ (𝑡 − 273.15)2 + 𝑏4 ∗ 𝑆 ∗ (𝑡 − 273.15)3 + 𝑏5 ∗ 𝑆 2 ∗ (𝑡 − 273.15)2 ) Where, 𝑎1 = 9.999𝑒 2 , 𝑎2 = 2.034𝑒 −2 , 𝑎3 = −6.162𝑒 −3 , 𝑎4 = 2.261𝑒 −5 , 𝑎5 = −4.657𝑒 −8 , 𝑏1 = 8.020𝑒 2 , 𝑏2 = −2.001, 𝑏3 = 1.677𝑒 −2 , 𝑏4 = −3.060𝑒 −5 , 𝑏5 = −1.613𝑒 −5 Seawater Dynamic Viscosity [kg/(m*s)]: 𝜇𝑠𝑤 = 𝜇𝑤 ∗ (1 + 𝐴 ∗ 𝑆 + 𝐵 ∗ 𝑆 2 ) Where, 𝐴 = 1.541 + 1.998𝑒 −2 ∗ (𝑡 − 273.15) − 9.52𝑒 −5 ∗ (𝑡 − 273.15)2 𝐵 = 7.974 − 7.561𝑒 −2 ∗ (𝑡 − 273.15) + 4.724𝑒 −5 ∗ (𝑡 − 273.15)2 𝜇𝑤 = 4.2844𝑒 −5 + (0.157 ∗ ((𝑡 − 273.15) + 64.993)2 − 91.296)−1 Seawater Specific Heat [kJ/(kg*K)]: 𝑐𝑠𝑤 = 𝐴 + 𝐵 ∗ 𝑡 + 𝐶 ∗ 𝑡 2 + 𝐷 ∗ 𝑡 3 Where, 𝐴 = 5.328 − 9.76𝑒 −2 ∗ 𝑆 + 4.04𝑒 −4 ∗ 𝑆 2 𝐵 = −6.913𝑒 −3 + 7.351𝑒 −4 ∗ 𝑆 − 3.15𝑒 −6 ∗ 𝑆 2 𝐶 = 9.6𝑒 −6 − 1.927𝑒 −6 ∗ 𝑆 + 8.23𝑒 −9 ∗ 𝑆 2 𝐷 = 2.5𝑒 −9 + 1.666𝑒 −9 ∗ 𝑆 − 7.125𝑒 −12 ∗ 𝑆 2 Seawater Thermal Conductivity [mW/(m*K)]: log10 (𝑘𝑠𝑤 ) = log10 (240 + 0.0002 ∗ 𝑆) + 0.333 343.5 + 0.037 ∗ 𝑆 𝑡 0.434 ∗ (2.3 − ) ∗ (1 − ) 𝑡 647 + 0.03 ∗ 𝑆 33 Appendix B. COMSOL Multiphysics 1D, 2D, 3D Plots 34 35 36 37 38 39 40 41 42 43 44 45 Appendix C. Constant Water Vapor Diffusion Coefficient Error Error Between Constant DF and Varied DF v = 0.05 v = 0.1 v = 0.15 v = 0.2 v = 0.25 2.247E- 1.283E- 6.409E- 3.203E- 3.203EOutlet Temp (K) 05 05 06 06 06 Concentrate Outlet Conc -7.329E- -3.651E- -3.646E- -1.822E- -1.821E(mol/m3) 03 03 03 03 03 -2.717E- -1.020E- 3.335E- -6.808E- -3.405EOutlet Temp (K) 05 05 04 06 06 Product Outlet Conc -9.023E- -7.245E- -5.441E- -3.629E- -3.631E(mol/m3) 03 03 03 03 03 *All values are percent error. 46