Membrane separation is known as an economic and environmental friendly mode of separation and is used in various types of separation processes. The major challenges regarding membrane separation are the internal and external fouling of the membrane which reduces the permeate flux of the membranes by inducing extra resistance to flow. Synthetic membranes are designed and implemented to separate solutes or particles in a feed stream by rejecting them and permitting the liquid to pass through the membrane pores; however, most of the feed streams, such as wastewaters, contain more than one type of solute. This yields a distribution of particle sizes in the feed. Many wastewaters contain supracolloidal particles (1-100µm). Most membrane separations aim to remove these particles from the feed solution. Wastewaters also contain colloidal particles (0.001-1µm). These particles are less concentrated than supracolloidal particles in the feed but they are more problematic since they are able to penetrate into the membrane pores and cause internal fouling which is the main source of irreversible flux decline. Fouling mechanisms are traditionally classified into four types. Among these mechanisms, standard pore blocking (pore constriction) refers to internal fouling while the other types model external fouling. On the effect of pore geometry, as a morphological factor, studies to date have been limited to external membrane fouling. However, it is believed that up to 80% of the permeate flux can be affected by pore constriction which is caused by particle penetration and deposition into membrane pores (internal fouling). The effect of pore geometry, as a factor, in flux decline due pore constriction of membranes was investigated in this work. Pore constriction by particles was approximated by maximum particle deposition onto the interior wall of the pores and simulated using MATLAB image processing toolbox (MIPT). Sixteen different basic geometries were considered for the simulation of pore constriction by particles. These include circular pores, 3 groups of rectangular, triangular and oval geometries at four different aspect ratios (3, 7, 15 and 30) and three combined geometries of star, cross and a rectangle with rounded ends. The simulation of maximum particle deposition onto pore walls was carried out for a range of particle diameters to pore hydraulic diameters (λ) of 0.1 to the complete rejection of the particle by the pore. As the result of the simulation, the ratio of the available pore cross-sectional area after pore constriction to initial pore cross-sectional area (α) and the ratio of pore channel hydraulic diameter after pore constriction to initial pore hydraulic diameter (β) were measured and recorded. It was observed that for λ<0.2 (small particles compared to pore size) some geometries showed the same values of α and β. However, for λ>0.2, other geometries showed different values of α and β. It was also observed that several geometries reject the particle at different λ ratios. Using the values of α and β, the fluxes of membranes having different pore geometries, after pore constriction by particles, were calculated and compared. These results show that for a very small particle size, compared to pore size, there is no preference for a specific geometry over another; however, for intermediate particle sizes, membranes having triangular and star pore shapes provide higher fluxes compared to other membranes. The effect of pore aspect ratio (PAR) on the flux of membranes after pore constriction was also examined. In order to compare the combined effect of pore geometry on particle rejection and pore constriction, fluxes of membranes having different pore shapes were compared in light of several pore size distributions (PSDs). For this part of the study, the pore geometries of circular, rectangular, triangular and oval were considered at four PARs. Different values for the hydraulic diameter of the largest rejecting pore (D_(H,LRP)) were observed for different geometries. Rectangular pores showed the largest values of D_(H,LRP), at a constant PAR, which affirms their superior rejection behavior. The overall flux of the membranes after pore constriction was determined by a combination of three effects: the position of D_(H,LRP) in the PSD, the pore constriction behavior of the pore geometry and the shape of the PSD. Generally, for the PSDs for which most of the pores in the membrane physically reject the particles, membranes having rectangular pores showed higher fluxes, due to the greater rejection of particles. However, for PSDs for which a major number of pores are constricted by the particles, membranes with triangular pores offered higher flux after membrane pore constriction. The results of this work indicate a new direction for the design of membranes having defined pore geometries.

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Reverse osmosis (RO) and nanofiltration (NF) membranes are pressure driven, diffusion controlled process. The influence of surface characteristics on membrane process performance is considered significant and is not well understood. Current mass transport models generally assume constant mass transfer coefficients (MTCs) based on a homogeneous surface. This work evaluated mass transfer processes by incorporating surface morphology into a diffusion-based model assuming MTCs are dependent on the thickness variation of the membrane’s active layer. To mathematically create such a surface layer, Gaussian random vectors embedded in a software system (MATLAB) were used to generate a three-dimensional ridge and valley active layer morphologies. A “SMOOTH” script was incorporated to reduce the influence of outlying data and make the hypothetical surfaces visually comparable to the AFM images. A nonhomogeneous solution diffusion model (NHDM) was then developed to account for surface variations in the active layer. Concentration polarization (CP) is also affected by this nonhomogeneous surface property; therefore, the NHDM was modified by incorporating the CP factor. In addition, recent studies have shown that the membrane surface morphology influences colloidal fouling behavior of RO and NF membranes. With consideration of the spatial variation of the cake thickness along the membranes, a fouling model was established by assuming cake growth is proportional to the localized permeate flow. Flux decline was assumed to be controlled by the resistance of cake growth and accumulated particle back diffusion at the membrane surface. A series of simulations were performed using operating parameters and water qualities data collected from a full-scale brackish water reverse osmosis membrane water treatment plant. The membrane channel was divided into a thousand uniform slices and the water qualities were iii determined locally through a finite difference approach. Prediction of the total dissolved solid (TDS) permeate concentration using the model was found to be accurate within 5% to 15% as an average percentage of difference (APD) using the NHDM developed in this research work. A comparison of the NHDM and the modified NHDM for concentration polarization (CP) with the commonly accepted homogeneous solution diffusion model (HSDM) using pilot-scale brackish water RO operating data indicated that the NHDM is more accurate when the solute concentration in the feed stream is low, while the NHDMCP appears to be more predictive of permeate concentration when considering high solute feed concentration. Simulation results indicated that surface morphology affects the water qualities in the permeate stream. Higher salt passage was expected to occur at the valley areas when diffusion mass transfer would be greater than at the peaks where the thin-film membrane is thicker. A rough surface tends to increase the TDS accumulation on the valley areas, causing an enhanced osmotic pressure at the valleys of membrane. To evaluate the impact of surface morphology on RO and NF performance, fouling experiments were conducted using flat-sheet membrane and three different nanoparticles, which included SiO2, TiO2 and CeO2. In this study, the rate and extent of fouling was markedly influenced by membrane surface morphology. The atomic force microscopy (AFM) analysis revealed that the higher fouling rate of RO membranes compared to that of NF membranes is due to the inherent ridge-and-valley morphology of the RO membranes. This unique morphology increases the surface roughness, leading to particle accumulation in the valleys, causing a higher flux decline than in smoother membranes. Extended fouling experiments were conducted using one of the RO membranes to compare the effect of different particles on actual water. It was determined that membrane flux decline was not affected by particle type when the feed water iv was laboratory grade water. On the other hand, membrane flux decline was affected by particle type when diluted seawater served as the feed water. It was found that CeO2 addition resulted in the least observable flux decline and fouling rate, followed by SiO2 and TiO2. Fouling simulation was conducted by fitting the monitored flux data into a cake growth rate model. The model was discretized by a finite difference method to incorporate the surface thickness variation. The ratio of cake growth term (�1) and particle back diffusion term (�2) was compared in between different RO and NF membranes. Results indicate that �2 was less significant for surfaces that exhibited a higher roughness. It was concluded that the valley areas of thin-film membrane surfaces have the ability to capture particles, limiting particle back diffusion.

The reduction of membrane productivity (i.e. membrane fouling) during operation occurs in virtually all membrane applications. Membrane fouling originates from the method by which membranes operate: contaminants are rejected by the membrane and retained on the feed side of the membrane while treated water passes through the membrane. The accumulation of these contaminants on the feed side of the membrane results in increased operating pressures, increased backwashing frequencies, increased chemical cleaning frequencies, and increased membrane replacement frequencies. The most significant practical implication of membrane fouling is increased operating and maintenance costs. As such, membrane fouling must be properly managed to ensure successful and efficient operation of membrane systems. This document presents four independent studies regarding the fouling of size exclusion and diffusion controlled membranes. A brief description of each study is presented below. The first study systematically investigated the fouling characteristics of various thin film composite polyamide reverse osmosis (RO) and nanofiltration (NF) membranes using a high organic surficial groundwater obtained from the City of Plantation, Florida. Prior to bench-scale fouling experiments, surface properties of the selected RO and NF membranes were carefully analysed in order to correlate the rate and extent of fouling to membrane surface characteristics, such as roughness, charge and hydrophobicity. More specifically, the surface roughness was characterized by atomic force microscopy, while the surface charge and hydrophobicity of the membranes were evaluated through zeta potential and contact angle measurements, respectively. The results indicated that membrane fouling became more severe with increasing surface roughness, as measured by the surface area difference, which accounts for both magnitude and frequency of surface peaks. Surface roughness was correlated to flux decline; however, surface charge was not. The limited range of hydrophobicity of the flat sheet studies prohibited conclusions regarding the correlation of flux decline and hydrophobicity. Mass loading and resistance models were developed in the second study to describe changes in solvent mass transfer (membrane productivity) over time of operation. Changes in the observed solvent mass transfer coefficient of four low pressure reverse osmosis membranes were correlated to feed water quality in a 2,000 hour pilot study. Independent variables utilized for model development included: temperature, initial solvent mass transfer coefficient, water loading, ultraviolet absorbance, turbidity, and monochloramine concentration. Models were generated by data collected throughout this study and were subsequently used to predict the solvent mass transfer coefficient. The sensitivity of each model with respect to monochloramine concentration was also analyzed. In the third study, mass loading and resistance models were generated to predict changes in solvent mass transfer (membrane productivity) with operating time for three reverse osmosis and nanofiltration membranes. Variations in the observed solvent mass transfer coefficient of these membranes treating filtered secondary effluent were correlated to the initial solvent mass transfer coefficient, temperature, and water loading in a 2,000 hour pilot study. Independent variables evaluated during model development included: temperature, initial solvent mass transfer coefficient, water loading, total dissolved solids, orthophosphorous, silica, total organic carbon, and turbidity. All models were generated by data collected throughout this study. Autopsies performed on membrane elements indicated membranes that received microfiltered water accumulated significantly more dissolved organic carbon and polysaccharides on their surface than membranes that received ultrafiltered water. Series of filtration experiments were systematically performed to investigate physical and chemical factors affecting the efficiency of backwashing during microfiltration of colloidal suspensions in the fourth study. Throughout this study, all experiments were conducted in dead-end filtration mode utilizing an outside-in, hollow-fiber module with a nominal pore size of 0.1 µm. Silica particles (mean diameter ~ 0.14 µm) were used as model colloids. Using a flux decline model based on the Happel's cell for the hydraulic resistance of the particle layer, the cake structure was determined from experimental fouling data and then correlated to backwash efficiency. Modeling of experimental data revealed no noticeable changes in cake layer structure when feed particle concentration and operating pressure increased. Specifically, the packing density of the cake layer (l-cake porosity) in the cake layer ranged from 0.66 to 0.67, which corresponds well to random packing density. However, the particle packing density increased drastically with ionic strength. The results of backwashing experiments demonstrated that the efficiency of backwashing decreased significantly with increasing solution ionic strength, while backwash efficiency did not vary when particle concentration and operating pressure increased. This finding suggests that backwash efficiency is closely related to the structure of the cake layer formed during particle filtration. More densely packed cake layers were formed under high ionic strength, and consequently less flux was recovered per given backwash volume during backwashing.

ABSTRACT Characterization Of Raw Milk Fouling On Plate-Type Heat Exchangers Using Different Alloys And Cow PhenotypeS Stephen Ernest Nelson Milk and other dairy products are widely used in many households today. Milk is a popular beverage that is seen as a healthy alternative to other synthetic beverages such as soda pop and other sugar based drinks. It became law that milk, and milk products are pasteurized before its release to the general public (FDA 2003). Pasteurization is a thermal process where the intent is to lower the concentration of microorganisms in the milk to render it safe to drink with heat (Bansal and Chen 2006). With all the thermal processing of the raw milk, this leads to thermal efficiency degradation of the heat exchangers used to pasteurize the milk (Bansal and Chen 2006) due to direct fouling of the heating surface. The buildup of organic and inorganic matter onto a metal surface from the constant heating of the milk on a stainless steel surface is called fouling. The exact mode on which the fouling layers nucleate and grow is unknown by the date of this writing. Milk fouling has been around as long as the pasteurization process. (Visser and Jeurnink 1997) Fouling rate is related to a function of variables. Fouling rate is a function of milk type, time, and temperature, age of the milk, seasonal variations, process equipment design and more. The main consensus of milk fouling initiation is that of the whey protein b-Lactoglobulin which constitutes about 0.32% in whole milk (de Jong 1997; Bansal and Chen 2005a; Bansal and Chen 2006). Table III shows the general compositions of the constituents in milk. In order to look for dependence between milk phenotypes and heated surface alloys, a design of experiment (DOE) was made. The experiment used three types of milk phenotypes to test for fouling differences. Also, four alloy compositions were also tested against the milk phenotypes. This produced a three by four matrix of variable combinations or 3x4 factorial design. It was hoped that these combinations will show a certain, but repeatable process condition which will produce lower fouling rate versus the control milk type. The milk phenotypes used in this experiment are phenotype AB-AB (control), AB-AA, and AB-BB. The phenotype of label before the hyphen was the k-casein phenotype, the label after the hyphen represented the b-Lacto globulin phenotype. The four metal types tested were stainless steel 304 (control), stainless steel 316, stainless steel 430, and titanium 6V 4Al. It was not feasible to change out the plates in the pilot scale milk pasteurizer at the pilot plant at the Dairy Products Technology Center (DPTC), or to make special replacement plates that exposed each metal to be tested on a single heat exchanger plate (AOAC-c 1995). The manufacturing of a complete laboratory scale milk pasteurizer for the study of milk fouling on metal plates proved to be very successful. The model flow cell heat exchanger produced high enough quality of milk foulant on the test coupons in comparison to the large scale fouling layers found in full scale dairy heat processing equipment. Although generally speaking, there was not a significant technology breakthrough of using different alloys as the material for the plates in milk pasteurizer heat exchangers, a method of creating the milk fouling layer on a smaller scale can be very useful in future works studying milk fouling. The titanium alloy showed a significantly lower fouling rate, this was probably mostly due to the highly passivated surface of the Titanium. It was also seen that the actual breed of cow could have played a significant role in fouling. The new FCHE model was produced to show the viability of creating a biofilm or milk fouling layer on any material provided that it is rigid enough. Microorganisms were also briefly studied on the foulant layer that was produced with the flow cell. This new approach should provide a basis for new and more advanced research of the mechanisms and nature of milk fouling in heat processing equipment.

Yes / Fouling on heat transfer surfaces due to scale formation is the most concerned item in thermal desalination industry. Here, a dynamic fouling model is developed and incorporated into the MSF dynamic process model to predict fouling at high temperature and high velocity. The proposed dynamic model considers the attachment and removal mechanisms in the fouling phenomena with more relaxation of the assumptions such as the density of the fouling layer and salinity of the recycle brine. While calcium sulphate might precipitate at very high temperature, only the crystallization of calcium carbonate and magnesium hydroxide are considered in this work. Though the model is applied in a 24 stages brine recycle MSF plant, only the heat recovery section (21 stages) is considered under this study. The effect of flow velocity and surface temperature are investigated. By including both diffusion and reaction mechanism in the fouling model, the results of the fouling prediction model are in good agreement with most recent studies in the literature. The deposition of magnesium hydroxide increases with the increase in surface temperature and flow velocity while calcium carbonate deposition increases with the increase in the surface temperature and decreases with the increase in the flow velocity.

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