Macromolecular components, including protein and polysaccharides, are viewed as one type of major foulants in the complex feed membrane filtration systems such as membrane bioreactor (MBR). In this thesis, the mechanisms of macromolecular fouling including protein and polysaccharide in the complex feed solution are explored by using Bovine serum albumin (BSA) and alginate as model solution. During the filtration of BSA and washed yeast with 0.22 ????m PVDF membrane, it was found that the critical flux of mixture solution was controlled by washed yeast concentration while the existence of BSA significantly changed the cake reversibility of much larger particles. The fouling mechanisms of alginate, as a model polysaccharide solution, were investigated both in dead end and crossflow membrane filtration. In the dead end experiments, it was found that the cake model appears to fit the entire range of the ultrafiltration data while the consecutive standard pore blocking model and cake model are more applicable to microfiltration membranes. The alginate was featured with high specific cake resistance and low compressibility despite some variations between different membranes. The specific cake resistance ( c ) is similar to c of BSA and actual extracellular polymer substance (EPS) in MBR systems reported in the literature, and higher than that of many colloidal particles. In a system contained alginate-particles mixture, it was found that the existence of alginate dramatically increased the cake specific resistance and decreased the cake compressibility. The fouling mechanism of alginate was also studied using long term cross flow filtration under subcritical flux. A two-stage TMP profile similar to that typically observed in MBR was obtained, confirming the important role of EPS during membrane fouling in MBR. In addition to adsorption, trace deposition of alginate also contributed to the initial slow TMP increase during the subcritical filtration. TMP increase during the long-term filtration was found not only due to the increase of the amount of deposition, but also the increase of specific cake resistance. A combined standard pore blocking and cake filtration model, using a critical pore size for the transition time determination, was developed and fit the experimental results well.

<p>In order to reduce the discharge of the greenhouse gas CO2, the use of biomass is nowadays promoted as fuel in boilers. Compared to boilers fired with coal and oil the biomass-fired boilers have more complications related to both fouling and corrosion on the heat transfer surfaces. After the combustion, unburned inorganic matter in state of vapour, melts and solid particles are transported in the flue gas and may form deposits on heat transfer surfaces.</p><p>Deposits on the heat transfer surfaces may result in both increasing corrosion and decreasing boiler efficiency as the heat transfer rate to the superheaters and reheaters decrease by deposits.</p><p>In order to understand the process of deposit build-up, the whole combustion and transport process had to be analysed including aspects such as, boiler design, fuel properties and combustion environment, followed by particle transport phenomena and the probability for particles to get stuck on the heat transfer tubes.</p><p>In this thesis numerical simulation of particle trajectories has been conducted as well as measurements of deposits on a special designed deposit probe followed by investigation of on-site measurements of deposit depth on the super-heater tubes in a circulating fluidised bed in Västerås, Sweden.</p><p>Numerical simulations of particle trajectories in the vicinity of two super-heater tubes were conducted in an Eulerian-Lagrangian mode considering the flue gas and ash particles phase. Particle impingements on the tubes were investigated for different particle sizes. The results from the particle trajectory simulations show that particle larger than 10 µm will mainly impinge on the windward side of the first tube but, however also on the sides of the second tube in the flue gas flow direction. In theory as well as from observations and measurements two tubes can merge together by the deposit build-up. Smaller particles are usually more dispersed due to turbulence and thermophorectic forces, resulting in a more even impingement distribution on the whole surface of the tubes.</p><p>Probe measurements reveal that the deposit layer growth rate have a significant temperature and time dependence. After the initial deposit build-up a sintering process occurs and sintering is also proven to be dependent on temperature and exposure time.</p><p>Soot-blowing is the most common method to reduce the effect of deposits on the heat transfer tubes. In the present thesis the soot boiling efficiency is therefore also investigated. The soot-blowing show a strong positive effect on the heat transfer rate in a short time (hours) perspective after a soot-blowing cycle is completed. This positive effect is much weaker when considering a time period of three years. This is an effect of fact that soot-blowing mostly remove the loose part of the deposit material leaving the hard sintered part unaffected.</p><p>The subject of deposit build up on superheater tubes in large scale boilers involves multi-discipline knowledge and historically, the related research is mostly conducted as measurements and experiments on operating plants. Possibly in the future, theoretical simulations will have a bigger part of research on deposit build-up where the calculations are to be calibrated through measurements on real sites plants.</p>

<p>Current global water scarcity and the spectre of a future critical shortage are driving the need for novel and energy saving water technology approaches. Desalination of seawater and the reuse of treated wastewater effluent, which have historically been viewed as undesirable water sources, are increasingly being explored as sources for reducing water consumption. Although the dominant technologies for taking these water sources to potable quality, energy consumption still makes them unsustainable for widespread application. Membrane distillation (MD) is an innovative water purification method that has shown promise as a technology that can address several of these issues. MD is a membrane process that produces very high quality product water. However, similarly to other thermal desalting processes, MD utilizes heat as the dominant source of energy rather than pressure, and can potentially be used to produce water at higher recoveries (and therefore less waste) than is feasible with existing approaches. Another important advantage of MD is that the water separation occurs at modest temperatures (<90oC), opening the door for the utilization of currently usable waste heat sources. Despite these advantages, MD is primarily a lab scale technology, and key questions concerning process performance, including flux magnitude, energy efficiency, fouling propensity, membrane performance, and long-term system performance must be addressed to fully vet this technology. </p><p>This work is represents an attempt to provide insight into several of these issues. The overarching approach taken throughout this project is the parallel evaluation of ceramic membranes alongside commonly used polymeric (PTFE) membranes. The combined factors of MD being a relatively nascent technology and the fundamental separation mechanism point toward initial real-world applications of MD for the treatment of high concentration water that may necessitate membranes exposure to harsher thermal and chemical environments. The robust and inert nature of ceramics make them ideal candidates for such application, although their hydrophilic surface do allow for direct implementation in MD. The first phase of this work details the evaluation of several candidate surface treatments for modifying ceramic membranes and shows that aluminum oxide ceramic membranes can be successfully modified with perfluorodecyltriethoxysilane to possess the necessary hydrophobicity for MD application. The effectiveness of the surface treatment in modifying the membrane surface chemistry was assessed using a multitude of analytical approaches, which showed that the modified ceramic surface attained high hydrophobicity and thus are suitable for application of the membranes in direct contact membrane distillation (DCMD).</p><p>The next phase of research details the development and verification of a model for DCMD performance. The relative membrane performance was compared, with the polymeric membrane consistently outperforming the modified ceramics, which was attributed to a combination of superior thermal and physical membrane characteristics. Beyond attempting to evaluate the performance differences, this model allows the consideration of various operational scenarios, focusing on membrane flux and energy performance as various membrane and operational parameters change to determine conditions that maximize MD performance as well as provide insight critical to develop MD-specific membranes. </p><p>Finally, membrane performance was evaluated during the treatment water containing various organic foulants as well for the treatment of municipal wastewater. The results showed that the level of fouling was highly dependent on foulant type, with alginate identified as a component that produces severe fouling under all conditions evaluated, and wastewater fouling being relatively minimal. Membrane cleaning solutions were implemented to show that near-complete flux recovery was attainable, and plain deionized water was shown to be as effective as sodium hypochlorite.</p> / Dissertation

Magnesium oxide-based additives have been used in kraft recovery boilers to minimize deposit accumulation on superheater and generating bank tubes. Due to inconclusive results observed in boilers and claims made for additive effectiveness backed by little scientific evidence, only a few mills still use the additives for fouling control. A systematic study was performed to examine the effect of MgO-based additives on deposit accumulation and removal under controlled laboratory conditions, and to evaluate the additive effect in a kraft recovery boiler. The results show that while the additive coating has no effect on deposition, it could ease deposit removal if a coating greater than 5 µm can be applied on the tube surface effectively. Separate injection of additive and black liquor had insignificant effect on deposition and removal. Results of the field study show that the amount of additive collected on the tube is too small to have an impact.

Magnesium oxide-based additives have been used in kraft recovery boilers to minimize deposit accumulation on superheater and generating bank tubes. Due to inconclusive results observed in boilers and claims made for additive effectiveness backed by little scientific evidence, only a few mills still use the additives for fouling control. A systematic study was performed to examine the effect of MgO-based additives on deposit accumulation and removal under controlled laboratory conditions, and to evaluate the additive effect in a kraft recovery boiler. The results show that while the additive coating has no effect on deposition, it could ease deposit removal if a coating greater than 5 µm can be applied on the tube surface effectively. Separate injection of additive and black liquor had insignificant effect on deposition and removal. Results of the field study show that the amount of additive collected on the tube is too small to have an impact.

The application of membrane bioreactors (MBRs) to wastewater treatment is increasing due to their ability to operate at high biomass concentrations and to deliver effluents of high quality. The major challenges associated with the application of MBRs is fouling which can shorten the useful life of the membrane, increase in the amount of energy consumed, and the cost for membrane cleaning. The main reasons for fouling are the deposition of solids as a cake layer, pore plugging by colloidal particles, adsorption of soluble compounds and biofouling. Fouling is a particular problem for activated sludge membrane bioreactors (AS-MBRs) since this process deals with liquors having a high concentration of total solids as well as dissolved compounds such as extracellular polymeric substances (EPS). The combination of a moving bed biofilm reactor and a membrane reactor (MBBR-MR) has significant potential. It may be considered as a compact wastewater treatment process which can compensate for the drawbacks of AS-MBRs. Readily biodegradable COD is removed in the MBBR while particulate matter is separated by the membrane. To further reduce the membrane fouling the effects of adding an intermediate coagulation stage was investigated critically on membrane fouling. The present study includes an overall assessment of the performance of a combined MBBR-MR system, based on the chemical oxygen demand (COD) removal efficiency and membrane fouling mechanism. The required test runs were conducted using pilot-scale MBBR and ultra filtration membrane. The pilot MBBR had a working volume of 1.8 m3 with a 60% carrier fill fraction. The MBBR was operated with loading rate of 78 ± 21 g/m2/d (HRT of 4 h). The ultra-filtration was spiral wound and composed of polyethersulfone (PES) with a pore size of 0.03 microns. The MBBR feed was obtained from a final treated wastewater effluent in a food processing plant located in SW Ontario. In this research, ferric chloride was also employed as a coagulant and influences of different coagulant doses and permeate fluxes on membrane fouling were studied. Based on the experimental results, it was found that the combination of MBBR with membrane filtration can produce a constant high quality permeate that is appropriate for water reuse purposes. The composition analysis of permeate showed that the stream is free of suspended solids and the average COD turns to 75 ± 25 mg/l. In addition, the MBBR had a SCOD removal of 76% ± 7% which is considered as a reasonable efficiency for a single reactor. Operating the membrane without adding coagulant caused rapid fouling in a short time period and the Trans Membrane Pressure (TMP) reached the maximum allowable pressure of 10 psi. However, addition of coagulant was found to decrease the fouling of the membrane as well as increasing the filtration time. The extent of the pre-coagulation effect on membrane fouling was found to strongly depend on the dosage of the coagulant and the MBBR effluent characteristics. A coagulant dose of 400 mg/l with a permeate flux of 7.6 LMH performed the best at reducing membrane fouling. Colloidal fouling was found to be a significant fouling mechanism at low coagulant dose (e.g. 200 mg/l), while cake formation appeared to be mainly responsible for fouling at higher coagulant doses. Permeate flux was found to have a significant effect on the fouling of the membrane. The presence of colloidal matters at low fluxes and TSS at higher fluxes were responsible for fouling of the membrane by blocking the pores and formation of the cake layer on the membrane surface, respectively. Then later addition of Dissolved Air Flotation (DAF) inside the factory had a noticeable effect on wastewater characteristics and consequently on fouling of the membrane. A 22% and 31% improvement in TCOD and TSS in the wastewater was observed leading to reduction in the fouling.

The objective of drinking water treatment is to provide water which is free of pathogens, is chemically and biologically stable, and is of good aesthetic quality. Natural organic matter (NOM) is present in all natural waters and can make meeting these goals more challenging. Not only does it undergo adverse reactions with disinfectants such as chlorine, it also impacts the biological stability of water within the distribution system and contributes to undesirable aesthetic qualities such as taste and odour. NOM has also been implicated in membrane fouling, which continues to be a significant operational problem preventing wider implementation of this process. Due to its highly variable heterogeneous nature, NOM can be difficult to characterize in terms of its specific composition, however recent analytical advancements are allowing for a better understanding of its behaviour in water treatment. Two promising tools for NOM characterization include Liquid Chromatography Organic Carbon Detection (LC-OCD) and Fluorescence Excitation Emission Matrix (FEEM) analyses. In this research both techniques were applied to samples taken from five full scale facilities in Ontario, Canada over all four seasons. The source waters for these treatment locations consisted of both river (Grand River, Ottawa River) and Great Lake waters (Lake Huron, Lake Erie, Lake Ontario), and an additional raw source (Saugeen River) was also monitored. The plants all employed granular media filtration, but had differences including enhanced coagulation, ozonation, biofiltration and sand ballasted flocculation. Other relevant water quality parameters were also monitored (TOC, DOC, UV254, pH, conductivity etc.) as well as plant operating conditions (dosages, flows, filter run times etc.) to investigate their impact on removal of specific NOM fractions. Four of the waters (Grand River, Ottawa River, Lake Erie and Lake Ontario) were selected based on the initial survey due to their NOM composition, for bench scale ultrafiltration (UF) membrane fouling experiments. The experiments were run at constant flux for a period of five days, with an automated permeation cycle and backwash. The impact of biopolymers on hydraulically reversible and irreversible fouling was of specific interest. Important seasonal trends were identified for all waters, with biopolymer content increasing at higher temperatures. Useful comparisons could also be made between different treatment processes including conventional and enhanced coagulation. The enhanced process while significantly improving the removal of humic substances, was not beneficial in terms of biopolymer removal, suggesting a different removal mechanism for these two fractions. The removal of low molecular weight ozonation by-products during full scale biofiltration was well demonstrated, and other fractions (building blocks, biopolymers) had varying degrees of removal, which was more dependent on temperature. Principle component analysis (PCA), an advanced multivariate statistical method, was successfully applied to a FEEM data set containing five different waters at varying degrees of treatment. Three principle components related to humic-like, protein-like and particulate/colloidal material were identified, and served as useful complementary information to the LC-OCD results. The humic-like component was found to have relatively good correlation to the humic fraction from LC-OCD analysis, with some deviation in the post-ozonation samples (which underwent greater structural changes not captured by LC-OCD). The biopolymer fraction was shown to have good correlation to hydraulically reversible membrane fouling across all four waters. The same could not be said for hydraulically irreversible fouling for which a combined fouling layer (with particulate and colloidal material) is hypothesized. This research provides those working in the water treatment sector with greater insight into NOM behaviour during various levels of treatment. As biopolymers were demonstrated to impact hydraulically reversible fouling (relatively independent of water quality), their removal prior to membrane filtration could significantly extend operational cycles by extending time between backwashes, thereby reducing energy requirements. As biopolymers are also suspected in forming a combined fouling layer, their removal can potentially minimize chemical cleaning requirements (and extend the life cycle of the membranes). The removal of biopolymers through coagulation was well demonstrated. Biofiltration is also expected to perform well as a membrane pre-treatment due its ability to remove biopolymers and particulate/colloidal matter. The ability of biofiltration to control biological re-growth in the distribution system (by removing low molecular weight biodegradable products) was also shown using LC-OCD and FEEM analysis.

Anaerobic membrane bioreactors may provide a sustainable technological solution for digestion of waste activated sludge due to their capacity to achieve substantial volatile solids (VS) destruction and positive energy balances with reduced digester volumes. However, membrane integrated anaerobic systems may have limitations that are imposed by membrane fouling and a decrease in biomass activity due to possible exposure of biomass to high shear conditions. This study characterised bioprocess and membrane performance under varying conditions, identified foulant type and origin and mechanism of fouling, and developed fouling control strategies by using low cross flow velocity and pressure anaerobic membrane systems. The study employed a pilot scale anaerobic digester integrated with negative and neutral tubular membranes; pilot and bench scale control digesters supported with bench scale filtration unit parametric studies. The membranes were polyvinylidene difluoride based with an average pore size of 0.02 micron and were operated at a constant cross flow velocity of 1 ms-1 and constant trans-membrane pressure of 30 kPa. Four operating conditions consisting of different combinations of HRT and SRT were evaluated. By integrating membranes into the digesters it was possible to simultaneously enhance digestion and increase throughput of the digesters without affecting its performance. The anaerobic membrane digester showed 48-49% volatile solids destruction at 30 days SRT under conventional and higher loadings of 1.2±0.4 and 2.1±0.6 kg COD m-3day-1. This was a 100% increase in performance compared to a control digester subjected to higher loading. This result was supported by the associated specific methane generation. The control digesters operated at a relatively higher SRT showed comparable VS destruction and gas generation to the anaerobic membrane running at a similar SRT. However the extra gas generated didn’t compensate heat required to maintain larger volume of the digester. In case of anaerobic membrane digesters due to the high rate feeding, increase biogas production and co-thickening, the energy balance increased by 144 and 200% under conventional and higher loading conditions respectively. Characterization of membrane performance showed that the average sustainable flux was 23.2±0.4 and 14.8±0.4 LMH during HRT-SRTs of 15-30 and 7-15 days respectively. The critical fluxes were in the range of 30-40, 16-17 and 20-22 LM-2H-1 during HRT-SRTs of 15-30, 7-30 and 7-15 days respectively. The decline in membrane performance at a higher loading was associated with the formation of cake layers on the membrane surface that led to reversible fouling. The additional decline in performance at extended SRT was attributed to irreversible fouling. The colloidal fraction of the sludge showed an overall higher fouling propensity during the long term pilot studies and short term filtration tests. The suspended solids fraction of the sludge showed a positive impact at concentration below 15 g/L but resulted in a decrease of membrane performance at higher concentrations. Further studies of foulant origin through a series of microscopic, membrane cleaning and sludge characterization studies showed that the colloidal proteins, soluble carbohydrates and inorganic materials such as iron, calcium and sulfur and their interaction to have a significant impact on membrane fouling. To control anaerobic membrane fouling by the digested sludge, integration of membrane relaxation techniques in the filtration cycle were found effective. By incorporating a unique relaxation technique to tubular membranes, it was possible to increase the sustainable flux to 29.2±1.8 and 34.5±2.5 LM-2H-1 for neutral and negative membranes during 15-30 HRT-SRT process condition. Addition of cationic polymers and sequential mechanical-citric acid membrane cleaning, that targeted both reversible and irreversible fouling was also found effective.

Cattle biomass (CB) has been proposed as a renewable, supplementary fuel for co-firing and reburning. Reburning coal with CB has the potential to reduce NOx and Hg emissions from coal fired systems. The present research focuses on three areas of combustion: 1) Biomass reburning experiments are conducted to determine the optimum operating conditions for the NOx reduction using blends of coal and CB as reburn fuels. 2) Since CB contains higher ash contents compared to coals, the fouling behavior is also investigated under the transient and short-time operation. 3) Finally CB contains higher Cl compared to coals, which oxidizes Hg to HgCl2. To understand the Hg oxidation behavior, a fundamental study of Hg oxidation in coal combustion is conducted using a plug flow reactor (PFR). The main parameters investigated are types of the reburn fuel, reburn equivalence ratios (ERRBZ), O2 concentrations in the reburn gas, injection angles of the reburn fuel, cross-sectional geometries of the reburn nozzles, symmetric and asymmetric reburn injections, reburn heat inputs, baseline NOx concentrations, and presence and absence of the heat exchangers (HEX). The results of reburning show that CB is a very effective fuel in NOx reduction, and the extent of NOx reduction is strongly dependent to the ERRBZ. The optimum conditions of the boiler operation for biomass reburning are as follows: ERRBZ = 1.1, 45° upward circular reburn nozzles, 12.5% O2 in the reburn gas, symmetric injection, and presence of HEXs. To make an effective reburn process, the baseline NOx concentrations must be higher than 230 g/GJ (0.5 lb/mmBTU) and the reburn heat input higher than 20%. The results of ash fouling show the presence of ash in the hotter region of the furnace seems to promote heat radiation thus augmenting the heat transfer to the HEX. The growth of the layer of ash depositions over longer periods typically lowers overall heat transfer coefficients. The addition of HCl to Hg containing gases in the PFR significantly increases Hg oxidations. The addition of NO inhibited the overall reaction and shifted the reaction temperature higher while the addition of O2 promoted Hg oxidations and lowered the reaction temperature. For heterogeneous cases, the use of the VWT catalyst promotes the reduction of Hg0 and shifted the reaction temperatures lower than those for homogeneous cases.

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.