In the past few years, the contamination by pesticides and heavy metals in surface water and groundwater has increased. Reverse osmosis is a unit process that has demonstrated capacity to remove dissolved pesticides and heavy metals from aqueous solution, and it is therefore worthwhile to consider this treatment process as a potential removal technique for hazardous constituents. The purpose of this investigation was to determine the effectiveness of a field scale reverse osmosis unit, with a spiral wound poly(ether/urea) membrane, in removing pesticides and heavy metals from a contaminated source. The removal efficiency for a single contaminant alone and a part of a mixture was examined. The performance of new and used membranes over time was also investigated. The average removal of pesticides was better than 99 percent. Reverse osmosis separation of pesticides was found to be dependent on the characteristics of the membrane and the physical/chemical properties of the pesticides. Pesticides in the mixed solution were found to behave independently. Sorption of the pesticides onto the reverse osmosis membrane was found to play a major role in the overall removal efficiency. Better than 99 percent average removal was achieved for all the metals except arsenic. The importance of the physical/chemical properties of the metal ions such as solubility, ionic radius, and electronegativity were determined. In tests to compare removal efficiency between new membrane and membrane which had been used, virtually no differences occurred. / Master of Science

The reverse osmosis performance of cellulose acetate membranes has been examined and analyzed for several aqueous systems where there is a strong attraction between the organic solute and the membrane material. The systems investigated included the aromatic hydrocarbons benzene, toluene, and cumene in single-solute aqueous solutions. Six cellulose acetate membranes, modified by annealing at different temperatures, were studied. Experiments were performed at four pressures (690, 1725, 3450, and 6900 kPa) and at several concentrations (in the range 5 to 260 ppm). The results were found to be markedly different than those observed in the absence of strong solute-membrane affinity. In particular, the solute-water separation decreased rather than increased with increasing pressure and the flux decreased with increasing concentration even though low concentrations, with low osmotic pressures, were studied. Qualitatively, the behavior was explained in terms of a porous membrane mechanism with both solute-membrane affinity and solute mobility varying as a function of solute position with respect to the membrane. The observed reduction in flux was expressed by an empirical equation as a function of concentration of solute in the boundary layer. The experimental results were analyzed quantitatively by several transport models. The irreversible thermodynamics phenomenological transport, solution-diffusion imperfection and extended solution-diffusion relationships generated parameters that were inconsistent with the original formulations of the models. The irreversible thermodynamics Kedem-Spiegler model, solution diffusion model, Kimura-Sourirajan analysis, and the three parameter finely-porous model were functionally unable to represent the data. Only the four parameter finely-porous model and the surface force-pore flow model were consistent with experimental results. From the finely-porous model the partition coefficient was found to be different on the high and low pressure sides of the membrane and this difference was a function of both pore size and solute. For the surface force-pore flow model, the agreement between the model and data was excellent. However, the surface force-pore flow model was considerably more difficult to use. / Ph. D.

Deposition of calcium carbonate (CaCO3) and calcium sulfate (CaSO4) causes serious processing problems and limits the productivity of seawater reverse osmosis (RO) desalination. The interactions between CaSO4 and CaCO3 in the dynamic seawater RO systems have been neglected previously because conventional studies mainly focused on individual compounds or mixed compounds in batch systems. The present work evaluates composite fouling behavior of CaSO4 and CaCO3 in a dynamic RO unit. The fouling experiments were performed at constant pressure and velocity by a partial recycling mode which permeate was withdrawn from the system during the recirculation of retentate to simulate the increasing of water recovery level. The fouling phenomena were monitored by the decline of flux. Scanning electron microscopy (SEM) with a combination of elemental dispersive x-ray microanalysis (EDS), and x-ray powder diffraction (XRD) was used to identify the morphological features, chemical compositions and crystalline phases of foulants. The interactions of CaSO4 and CaCO3 were investigated by the comparison between individual CaSO4 or CaCO3 fouling and composite fouling, and by varying SO42-/HCO3- molar ratio of the feed. A recently developed approach, Scaling Potential Index (SPI) incorporated with measured concentration polarization modulus (CP), for assessing the fouling tendency of inorganic salts on the membrane surface was validated in the dynamic tests. In addition, the effectiveness of two generic scale inhibitors, polyacrylic acid (molecular weight =2100, PA) and sodium hexametaphosphate (SHMP) were evaluated. Some of the highlights of the obtained results are as follows: ??????The precipitation kinetics, morphology and adhesive strength of composite scales were different from pure precipitates ??????CaSO4 precipitated as gypsum while CaCO3 precipitated as two crystalline phases: calcite and aragonite ??????The crystalline phases as well as precipitation kinetics were affected by SO42-/HCO3- ratio ??????Scaling Potential Index was able to predict the fouling tendency of CaSO4 and CaCO3 accurately ??????The dosage of PA and SHMP was effective to mitigate fouling Results of this work are significant, not only because they have made contribution to the fundamental understanding of composite inorganic fouling in RO membrane systems which was ignored previously, but also because they may play a key role in the development of scale control.

The optimization of a reverse osmosis (RO) system includes optimization of the design of the individual membrane modules, the system structure and the operating conditions of the system. Most previous studies considered either the optimal design of individual modules only or optimization of system structure and operating conditions for fixed module dimensions. This thesis developed a method to simultaneously optimize the module dimensions, system structure and operating conditions. The method comprised rules for generating a general superstructure for an RO system given the number of modules along with rules for generating technically and mathematically feasible sub-structures. The superstructure was based on maximum connectivity between unit operations. A connectivity matrix was used to represent the superstructure. The matrix was useful for checking sub-structure's feasibility and deriving a model for the sub-structure's optimization, comprising the minimum number of variables and constraints which minimized computational time and increased accuracy. For optimization, a nonlinear objective function of the annualized profit of the RO system was formulated, consisting of the revenue obtained from permeate sales, capital costs of the unit operations and operating costs for the system. It was found that RO system optimization is a nonconvex optimization problem. The most effective optimization procedure involved a combination of evolutionary computation, which was good for locating the global optimum, and a gradient-based method, which was superior in finding the exact optimum. Small population size, adaptive mutation rate and steady state replacement were the most efficient parameter settings for the evolutionary computation. Optimal design of two-stage RO systems with and without energy recovery, bypass and recycle streams was studied. Dimensions of predicted optimal modules approached those of current commercial modules but with much shorter feed channels. The mathematical optimum also had higher operating pressures. The optimum system structure was a series arrangement with different module dimensions in each stage. A sensitivity analysis showed that trends in the optimal design were similar when unit costs changed. An investigation of the scalability of the method for a three-stage RO system revealed several weaknesses. These are probably surmountable with the addition of more RO system specific knowledge.

Produced water handling has been an issue of concern for oil and gas producers as it is one of the major factors that cause abandonment of the producing well. The development of effective produced water management strategies poses a big challenge to the oil and gas industry today. The conversion of produced water into irrigation or fresh water provides a cost effective tool to handle excessive amounts of the produced water. In this research we proposed on-site produced water treatment units configured to achieve maximum processing throughput. We studied various advanced separation techniques to remove oil and dissolved solids from the produced water. We selected adsorption as the oil removing technique and Reverse Osmosis (RO) as the dissolved solids removing technique as being the best for our purpose. We performed experiments to evaluate operating parameters for both adsorption and RO units to accomplish maximum removal of oil and dissolved solids from the produced water. We compared the best models fitting the experimental data for both the processes, then analyzed and simulated the performance of integrated produced water treatment which involves adsorption columns and RO units. The experimental results show that the adsorption columns remove more than 90% of the oil and RO units remove more than 95% of total dissolved solids from the produced water. The simulation results show that the proper integration and configuration of adsorption and RO units can provide up to 80% efficiency for a processing throughput of 6-8 gallons per minute of produced water. From an oil and gas producer’s viewpoint output from the produced water treatment system is a revenue generating source. The system is flexible and can be modified for the applications such as rangeland restoration, reservoir recharge and agricultural use.

Electrodialysis (ED) experiments were conducted on reverse osmosis (RO)-concentrated solutions of NOM from six rivers. The ED processes successfully recovered 88 11% of TOC, and removed 83% 19% of SO42- and 67% 18% of H4SiO4. More importantly, the molar ratios of SO42- /TOC and H4SiO4 /TOC were reduced to a mean value of 0.0046 and 0.032, respectively, surpassing the goal for removal of SO42- (0.008) and almost achieving the goal for removal of H4SiO4 (0.021). The ED process can lower the SO42- /TOC ratio in samples whose initial SO42- /TOC ratios are already far below the limit of 0.008 used in this study. The coupled RO/ED process that has been described here offers a fast, simple, chemically mild (relative to other methods), and reproducible method of isolation of large quantities of relatively unfractionated, low-ash NOM from freshwaters. RO/ED was also successfully used for isolating and concentrating marine dissolved organic matter (DOM). The effort successfully recovered a median of 72% of the TOC from 200 L samples within six to nine hours of processing through a combination of ED and RO, greatly exceeding the current norm of 30%. The relatively high recovery of DOM implies that classes of DOM previously missing are included in these samples and should yield new insight into the chemistry of marine DOM. Freshwater samples processed by electrodialysis were analyzed for elemental composition and by capillary zone electrophoresis (CZE), 1H and 13C nuclear magnetic resonance spectroscopy (NMR), and electro-spray ionization mass spectrometry (ESI-MS). Bulk elemental composition, 1H- and 13C-NMR, and ESI-MS data provide evidence linking bioavailabilty to the bulk chemistry of NOM: the H/C and N/C molar ratios are positively and strongly correlated with bioavailability, as hypothesized. Using an independent dataset (STORET) of water quality parameters, calculated BOD/TOC ratios were found to be moderately correlated with measured bioavailabilities and can be used as a surrogate for bioavailability of geochemically diverse riverine DOM.

This thesis presents a study to enhance and improve a zero liquid discharge (ZLD) reverse osmosis process that uses seed crystals to promote crystallization of the dissolved salts in the residual brine while it is being treated by identifying those membrane materials that are most suitable for the process. In the study, a one plate SEPA Cell module by GE Osmonics was used to determine which membranes were most susceptible to fouling and/or membrane hydrolysis. A cellulose acetate (CA), polyamide (PA) low MWCO, and PA high MWCO membrane were tested under reverse osmosis conditions. The CA and thin film (TF) membranes were also tested for nanofiltration. The cell was operated under conditions that were determined to be optimum for each membrane by the manufacturer, GE Osmonics. A high pressure, low flow, positive displacement diaphragm pump circulated the saturated calcium sulfate solution with 2 % suspended solids through the cell while the reject and permeate were recycled back to the feed, thereby preserving a saturated solution to promote crystal growth and simulate the seeded reverse osmosis process. The temperature was maintained constant by adding an ice pack to the feed vessel when necessary. The transmembrane pressure differential was maintained constant by adjusting a back pressure valve on the concentrate outlet. The results illustrate that if potable drinking water is the intended use, then the nanofiltration cellulose acetate membrane should be used. If irrigation is the desired use, then the nanofiltration thin film membrane should be used. Overall, the reverse osmosis cellulose acetate membrane was observed to outperform all membranes when all performance parameters were normalized. However, this membrane was observed to be prone to degradation in a seeded slurry and therefore its lifetime should be analyzed further. The polyamide membrane initially had a high water transport coefficient, but fouling led to its rapid decline which was attributed to the membrane’s rough and protrusive surface. A lifetime test on the thin film and cellulose acetate revealed that when operated at their maximum pressure specified by GE Osmonics for a duration of 8 hours that no decrease in rejection occurred.

Produced water handling has been an issue of concern for oil and gas producers as it is one of the major factors that cause abandonment of the producing well. The development of effective produced water management strategies poses a big challenge to the oil and gas industry today. The conversion of produced water into irrigation or fresh water provides a cost effective tool to handle excessive amounts of the produced water. In this research we proposed on-site produced water treatment units configured to achieve maximum processing throughput. We studied various advanced separation techniques to remove oil and dissolved solids from the produced water. We selected adsorption as the oil removing technique and Reverse Osmosis (RO) as the dissolved solids removing technique as being the best for our purpose. We performed experiments to evaluate operating parameters for both adsorption and RO units to accomplish maximum removal of oil and dissolved solids from the produced water. We compared the best models fitting the experimental data for both the processes, then analyzed and simulated the performance of integrated produced water treatment which involves adsorption columns and RO units. The experimental results show that the adsorption columns remove more than 90% of the oil and RO units remove more than 95% of total dissolved solids from the produced water. The simulation results show that the proper integration and configuration of adsorption and RO units can provide up to 80% efficiency for a processing throughput of 6-8 gallons per minute of produced water. From an oil and gas producer’s viewpoint output from the produced water treatment system is a revenue generating source. The system is flexible and can be modified for the applications such as rangeland restoration, reservoir recharge and agricultural use.

Not available / text

As freshwater resources are limited and stressed, and as the cost of conventional drinking water treatment continues to increase, interest in the development of non-traditional water resources such as desalination and water reuse increases. Reverse osmosis (RO) is the predominant technology employed in inland brackish groundwater desalination in the United States, but the potential for membrane fouling and scaling generally limits the system recovery. The general hypothesis of this research is that electrodialysis (ED) technology can be employed to minimize the volume of concentrate waste from RO treatment of brackish water (BW) and thereby improve the environmental and economic feasibility of inland brackish water desalination. The objective of this research was to investigate the performance sensitivity and limitations of ED for treating BWRO concentrate waste through careful experimental and mathematical analysis of selected electrical, hydraulic, and chemical ED variables. Experimental evaluation was performed using a laboratory-scale batch-recycle ED system in which the effects of electrical, hydraulic, and chemical variations were observed. The ED stack voltage showed the greatest control over the rate of ionic separation, and the specific energy invested in the separation was approximately proportional to the applied voltage and equivalent concentration separated. An increase in the superficial velocity showed marginal improvements in the rate of separation by decreasing the thickness of the membrane diffusion boundary layers. A small decrease in the nominal recovery was observed because of water transport by osmosis and electroosmosis. Successive concentration of the concentrate by multiple ED stages demonstrated that the recovery of BWRO concentrate could significantly improve the overall recovery of inland BWRO systems. A mathematical model for the steady-state performance of an ED stack was developed to simulate the treatment of BWRO concentrates by accounting for variation of supersaturated multicomponent solution properties. A time-dependent model was developed that incorporated the steady-state ED model to simulate the batch-recycle experimentation. Comparison of the electrical losses revealed that the electrical resistance of the ion exchange membranes becomes more significant with increasing solution salinity. Also, a simple economic model demonstrated that ED could feasibly be employed, especially for zero-liquid discharge. / text