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Thesis. 1976. Ph.D.--Massachusetts Institute of Technology. Dept. of Chemical Engineering. / Microfiche copy available in Archives and Science. / Vita. / Includes bibliographical references. / Ph.D.

Produced water is a major waste produced from oil and natural gas wells in the state of Texas. This water could be a possible source of new fresh water to meet the growing demands of the state after treatment and purification. This thesis describes a research project that evaluated the treatment of brine generated in oil fields (produced water) with ultrafiltration membranes. The characteristics of various ultrafiltration membranes for oil and suspended solids removal from produced water were studied to test whether they could be used in a pretreatment method. The research measured the effect of pressure and flow rate on performance of three commercially available membranes for treatment of oily produced water. Oil and suspended solids removal were measured by using turbidity and oil in water measurements taken periodically. The study also analyzed the flux through the membrane and any effect it had on membrane performance. The research showed that an ultrafiltration membrane provided turbidity removal of over 99% and oil removal of 78% for the produced water samples. The results indicated that the ultrafiltration membranes would be useful as one of the first steps in purifying the water. Membrane cleaning of produced water-fouled membranes by micellar solutions was investigated. A neutral pH and ambient temperature micelle solution for effective cleaning of oily water-fouled membranes was developed and studied. The performance of cleaning solutions on ultrafiltration membranes was investigated on laboratory size membrane testing equipment. Different micro emulsion solutions were studied to evaluate the effect of solution properties on cleaning performance. Three types of multiple membranes were studied, each having the same polyvinylidene fluoride (PVDF) material but with different nominal separation or flux characteristics. The data showed that the use of a micelle solution to clean the produced water-fouled membranes was a feasible and effective method. The study showed with further adjustment of the micelle solution the cleaning effectiveness could be optimized to provide double the effectiveness of current industry methods for membranes fouled by produced water.

Produced water is a major waste produced from oil and natural gas wells in the state of Texas. This water could be a possible source of new fresh water to meet the growing demands of the state after treatment and purification. This thesis describes a research project that evaluated the treatment of brine generated in oil fields (produced water) with ultrafiltration membranes. The characteristics of various ultrafiltration membranes for oil and suspended solids removal from produced water were studied to test whether they could be used in a pretreatment method. The research measured the effect of pressure and flow rate on performance of three commercially available membranes for treatment of oily produced water. Oil and suspended solids removal were measured by using turbidity and oil in water measurements taken periodically. The study also analyzed the flux through the membrane and any effect it had on membrane performance. The research showed that an ultrafiltration membrane provided turbidity removal of over 99% and oil removal of 78% for the produced water samples. The results indicated that the ultrafiltration membranes would be useful as one of the first steps in purifying the water. Membrane cleaning of produced water-fouled membranes by micellar solutions was investigated. A neutral pH and ambient temperature micelle solution for effective cleaning of oily water-fouled membranes was developed and studied. The performance of cleaning solutions on ultrafiltration membranes was investigated on laboratory size membrane testing equipment. Different micro emulsion solutions were studied to evaluate the effect of solution properties on cleaning performance. Three types of multiple membranes were studied, each having the same polyvinylidene fluoride (PVDF) material but with different nominal separation or flux characteristics. The data showed that the use of a micelle solution to clean the produced water-fouled membranes was a feasible and effective method. The study showed with further adjustment of the micelle solution the cleaning effectiveness could be optimized to provide double the effectiveness of current industry methods for membranes fouled by produced water.

Reproduction de : Thèse de doctorat : Chimie industrielle : Reims : 2005. / Titre provenant de l'écran titre. Bibliogr. f. 222-232.

Fouling is a major obstacle to the implementation of membranes in water purification applications. Hydrophilization of the membrane surface tends to mitigate fouling because hydrophobic interactions between foulants and the membrane are reduced. Polydopamine was deposited onto membranes to render their surfaces hydrophilic. The chemical structure of polydopamine, which was previously ambiguous, was investigated by many spectroscopic techniques. While previously thought to consist of covalently-linked monomers, polydopamine was found to be an aggregate of partly-oxidized dopamine units linked by strong, non-covalent secondary interactions. Polydopamine was also used as a platform for the molecular conjugation of other anti-fouling materials, such as poly(ethylene glycol), to the membrane surface. Membrane fouling was assessed by constant permeate flux crossflow filtration with an oil/water emulsion feed. The threshold flux--the flux at which the rate of fouling significantly increases--was determined by a well-established flux stepping technique. Membrane resistance evolution during fouling was compared for constant flux and constant transmembrane pressure operation using unmodified membranes. Below the threshold flux (slow fouling), good agreement in resistance evolution was found between the two operational modes; above the threshold flux, significant deviation was observed. The effect of polydopamine and polydopamine-g-poly(ethylene glycol) surface modifications was studied under constant flux crossflow fouling conditions. The surface modifications were found to increase the membrane resistance, resulting in higher transmembrane pressures in the modified membranes than in the unmodified membranes at fluxes below the threshold flux. Modified membranes were also compared to unmodified membranes with the same pure water permeance (same initial resistance). In this case, the modified membranes had lower transmembrane pressures during fouling than the unmodified membranes, suggesting that a preferred method of membrane surface modification is to begin with a membrane of higher permeance than required, and then surface-modify it to achieve the desired permeance. The efficacy of polydopamine and polydopamine-g-poly(ethylene glycol) surface modifications in reducing biofouling was also evaluated. Modified membranes showed reduced protein and bacterial adhesion in short-term tests, which are commonly used to assess biofouling propensity. However, long-term operation under hydrodynamic conditions mimicking those of an industrial module showed no benefit of the hydrophilic coatings in limiting biofouling. / text

The long term degradation of polyethersulfone (PES) based ultrafiltration membranes used in the dairy industry has been investigated. The main aim of the study was to identify characterisation techniques which could give an indication of the condition and performance of ultrafiltration membranes after long term exposure to sodium hypochlorite solution. Membranes were degraded using sodium hypochlorite solution at pH 9, 10, 11 and 12, and with 5000 ppm-days to 25,000 ppm-days of exposure at 55°C. The degraded membranes were studied using the following characterisation techniques: dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), tensile testing, field emission scanning electron microscopy with energy dispersive x-ray spectroscopy (FESEM-EDS), Fourier transform infrared-attenuated total reflectance spectroscopy (FTIR-ATR), contact angle, drop absorption, zeta potential, liquid-liquid displacement porosimetery (LLDP), protein separation, and colour measurement. The protein separation test included membrane throughput measurements (using casein-whey as feed), with size exclusion chromatography and gel electrophoresis to analyse the feed, permeate and retentate. Also a membrane disinfection experiment was performed to study the effect of sodium hypochlorite pH on disinfection of mixed dairy culture.

A bench-scale study was performed to optimize backwash frequency and air sparging conditions during ultrafiltration (UF) of natural surface waters in order to maximize water production and minimize irreversible fouling as well as operating and maintenance costs. Surface shear stress representing different air sparging conditions (continuous coarse bubble, discontinuous coarse bubble, and large pulse bubble sparging) was applied in combination with various backwash frequencies (0.5, 2 and 6 h) and fouling was assessed. Results indicated that air sparging with discontinuous coarse bubbles or large pulse bubbles significantly reduced the irreversible fouling rate while providing cost savings when compared to the baseline condition, which assumed a 0.5 h-backwash frequency and no air sparging during filtration. Cost savings were more pronounced at lower backwash frequencies, due to value associated with extra water produced over longer filtration times and longer membrane life resulted from fewer recovery chemical cleans because of lower irreversible fouling.

A bench-scale study was performed to optimize backwash frequency and air sparging conditions during ultrafiltration (UF) of natural surface waters in order to maximize water production and minimize irreversible fouling as well as operating and maintenance costs. Surface shear stress representing different air sparging conditions (continuous coarse bubble, discontinuous coarse bubble, and large pulse bubble sparging) was applied in combination with various backwash frequencies (0.5, 2 and 6 h) and fouling was assessed. Results indicated that air sparging with discontinuous coarse bubbles or large pulse bubbles significantly reduced the irreversible fouling rate while providing cost savings when compared to the baseline condition, which assumed a 0.5 h-backwash frequency and no air sparging during filtration. Cost savings were more pronounced at lower backwash frequencies, due to value associated with extra water produced over longer filtration times and longer membrane life resulted from fewer recovery chemical cleans because of lower irreversible fouling.

Boron is an element distributed widely in environment mainly in the form of boric acid or borate salts. Boron is an element of demand because of its use in many high technology materials. Moreover boron is an essential element for growth of plants, but may also result in toxicity when present in excessive amounts. As the range between a deficient and toxic amount of boron is very narrow, imbalances in boron nutrition are well-known. For the removal of boron from aqueous solutions, various methods exist which are chemical coagulation, adsorption, solvent extraction and ion exchange processes. In this study, an alternative, energy efficient and easily scalable membrane based method, polymer enhanced ultrafiltration (PEUF) was developed for removal of boron from aqueous boron solutions. PEUF process consists of two steps: complexing boron with a water soluble polymer then removing the complex by ultrafiltration. Previously, boron removal from aqueous solutions was studied in a continuous process with a commercial ligand, polyvinyl alcohol (PVA). In our study, three newly developed polymers, which are derivatives of N-methyl-D-glucamine (P1) and iminodipropylene glycol(P2 and P2G) were used as the boron complexing ligand. P1 and P2 are linear polymers, while P2G is cross linked version of P2. The pilot scale system utilized for the PEUF process accommodates a spiral wound cellulose cartridge with 10000 Da molecular weight cutoffs (MWCO). The effects of operating parameters on performance of PEUF were investigated. The experimental parameters studied are metal/polymer ratio (loading) (0.01-1), pH (7-10). Boron analyses of the samples were made by using ICP-AES. Maximum removal (retention) was 90.1 %. The permeate flux remained constant at around 20 L/m2.hr and was not affected by the operating parameters. Decrease in loading caused the retention of boron to increase. Also at high pH values, retentions were relatively higher. Results showed that PEUF could be a successful alternative method for removal of boron.