Rozprawy doktorskie na temat „Removal of Sulfer compound”

Adsorption combined with aqueous phase electrochemical regeneration has been shown by researchers at The University of Manchester (UoM) to offer an alternative approach to the removal of organics from waters and wastewater's. The process, based on a regenerable graphite intercalation compound (GIC) adsorbent, produces no secondary waste, is energy efficient and chemical free. A company, Arvia Technology Ltd., was set up in 2007 to commercialise the technology. As part of a growth and development strategy Arvia investigated other possible applications of the technology and found that odour removal from gas streams might be a good fit with technology features. This Engineering Doctorate (EngD) was a direct investigation into both this technology fit and into the market opportunity for technologies treating odours and volatile organic compounds (VOCs) in gas streams. The research conducted demonstrated that the technology in its different applied forms had certain process drawbacks. Where mass transfer, adsorption and regeneration were combined in a single unit, enhanced transfer as a result of higher pollutant Henry's coefficient was offset by lower adsorbate affinity which varied with hydrophobicity. This relation between affinity and hydrophobicity was different for oxygen functionalised aromatic molecules than for the aliphatic molecules studied. Where adsorption occurred in the gaseous phase and regeneration in the aqueous phase, disadvantages such as short adsorbent packed bed lifetimes and lower current efficiencies of oxidation as a result of adsorbate desorption were shown to be an issue. When the above process challenges were set against the challenging market environment and relatively small market opportunity (approx. £52 million in Europe, 2012) it was difficult to recommend further broad research into the technology. However it was concluded that the concept might still be usefully applied to odour and VOC abatement and that further work should focus on a two phase system with a gas phase adsorbent regeneration technique. The relation observed between adsorbate affinity, hydrophobicity and structure allowed the demonstration of the preferential removal of phenol from solutions containing significantly higher concentrations of aliphatic molecules. This finding is considered the most important project output as it highlights an opportunity to develop Arvia's water treatment technology into a targeted water treatment system for the removal of specific, industrially important, organic contaminants.

Helium tracer experiments were conducted to characterize conservative tracer behavior in a wedge-shaped lysimeter containing alternating layers of unsaturated silty sand, and clay loam. Experiments were conducted with trichloroethylene and 1,1,1-trichloroethane to determine if air stripping in unsaturated soil could be characterized by mass transfer from the sorbed to the liquid to the vapor phase. Batch experiments were conducted to measure liquid--vapor mass transfer. Solid-liquid-vapor mass transfer was characterized by measuring the vapor phase re-equilibration after the air stripping experiment. The Discrete State Compartment model was used to simulate a conservative gas tracer. The results were compared to the helium tracer. Liquid-vapor, and solid-liquid-vapor mass transfer were modeled by fitting simulated data to experimental data. The conservative tracer, and mass transfer models were combined to simulate air stripping in unsaturated soil.

To date, most studies on the fate and removal of endocrine disrupting compounds (EDCs) and pharmaceutical and personal care products (PPCPs) in wastewater focus on their fate in municipal wastewater treatment plants, and mostly under aerobic condition. There are limited studies related to anaerobic condition and (to our knowledge) no study on the removal of EDCs in landfill leachate by AnMBR. Moreover, for most studies under anaerobic condition, the removal of EDCs was only reported in the liquid phase; solid phase extraction was not reported, thereby preventing mass balance in the studies. This research was conducted to investigate the potential of AnMBR for reduction of organic strength and removal of EDCs in landfill leachate. A novel lab-scale upflow anaerobic sludge blanket (UASB) reactor equipped with dual-flat sheet ultrafiltration and microfiltration membrane modules was designed and constructed to test the potential to remove EDCs and traditional landfill leachate constituents (COD, turbidity). The target EDC was 17β-estradiol (E2), a prevalent female hormone used for contraceptives and hormone replacement therapy. Due to the nature of packaging and widespread use in households, the entry of E2 into landfills is highly likely, and has been reported. The quantification of E2 from liquid phase in this project is performed by the use of solid-phase microextraction (SPME) with GC/MS. Batch assays were conducted to determine the anaerobic biodegradability of E2 as well as to measure the respective distribution coefficients of E2 to PAC, colloids and anaerobic sludge biomass. In the adsorption batch assays, it was found that the PAC has stronger adsorption potential than anaerobic sludge. The adsorption potential of E2, E1 and EE2 on sludge follows the order E2>EE2>E1 which correlates to the Kow values (4.01, 3.67, 3.1, respectively). However, all three compounds showed the same adsorption potential to the Norit 20B PAC. The biodegradability of E2 was investigated in both liquid and solid phase and under several conditions such as methanogenesis, methanogenesis with aid from PAC, and methanogenesis with additional alternative electron acceptors added (sulfate and nitrate). E2 was found to transform to E1 under all tested conditions. The compounds are present in both liquid and solid phase. E2 and E1 were not detected (< 4ng/L and <10ng/L, respectively) in the liquid phase after 25 days in most cases except the case of adding additional sulfate. The AnMBR was designed, fabricated and operated for 2 years. During the stable condition period of the AnMBR, the high removal efficiencies of COD and E2 achieved were around 92% and 98%, respectively. However, E2 was still detected in the effluent at average concentrations of 30-40 µg/L range. To expand hormone retention and removal by the AnMBR, as well as to control membrane fouling, powder activated carbon (PAC) was added to the reactor. After the PAC was added, the concentration of E2 was reduced to less than the detection limit (4ng/L) in both MF and UF effluents. The log removal of E2 in the AnMBR system increased immediately from 1.7 without PAC to 5.2 after PAC was added. This study demonstrated that the AnMBR has high potential for removal of E2, and with aid from PAC, the AnMBR can remove E2 from landfill leachate to levels below detection limit.

In-based III-V compound semiconductors have higher electron mobilities than either Si or Ge and direct band gaps. These properties could enable the fabrication of low power, high-speed n-channel metal oxide semiconductor field effect transistors (MOSFETs) and optoelectronics combining MOS technology with photonics. Since thermal and native oxides formed on III-V surfaces exhibit large current leakage and high densities of trap states, a key to incorporating these materials into advanced devices is the development of processing steps that form stable interfaces with dielectric layers. In this thesis, a processing flow consisting of native oxide removal using HF chemistries and deposition of high dielectric permittivity films using atomic layer deposition was investigated. Understanding the reaction mechanisms of these processes could provide the means of controlling composition and structure, yielding a desired electronic behavior. Quantitative X-ray photoelectron spectroscopy analysis of surfaces was coupled with electrical measurements on MOS capacitors of the interface quality in order to understand the nature of high-k/III-V interface defects and their repair. Ex situ liquid phase HF etching removed InSb, InAs, and InGaAs(100) native oxides and produced an Sb- or As-enriched surface, which oxidized when exposed to air. A 5 to 22 °A thick As- and Sb-rich residual oxide was left on the surface after etching and < 5 min of air exposure. The results showed that group V enrichment originated from the reduction of group V oxides by protons in the solution and the preferential reaction of HF with the group III atom of the substrate. A sub-atmospheric in situ gas phase HF/H2O process removed native oxide from InSb, InAs, and InGaAs(100) surfaces, producing an In or Ga fluoride-rich sacrificial layer. A 50 to 90% oxide removal was achieved and a 10 to 25 °A-thick overlayer consisting of mainly In and Ga fluorides was produced. The composition and morphology of the sacrificial layer were controlled by the partial pressure of H2O as well as the ratio of HF to H2O used. Water played a critical role in the process by directly participating in the etching reaction and promoting the desorption of fluoride etching products. Accumulation of thick fluoride layer at high HF to water partial pressure ratios prevented adsorption and diffusion of etchant to the buried residual oxide. When oxide was removed, HF preferentially reacted with In or Ga atoms from the substrate, enriching the surface with group III fluorides and producing approximately one monolayer of elemental group V atoms at the interface. Interface reactions occurred during atomic layer deposition of Al2O3, in which trimethylaluminum (TMA) removed surface oxides and fluorides. Chemically sharp InSb/Al2O3 and InGaAs/Al2O3 interfaces were achieved for gas phase HF-etched InSb and liquid phase HF-etched InGaAs. A ligand transfer mechanism promotes nucleation of Al2O3 and removal of III-V atoms from the sacrificial oxide and fluoride layers as volatile trimethyl indium, gallium, arsenic, and antimony. These reactions have been explained by the relative bond strength of surface and precursor metal atoms with O and F. Interaction of a InSb(100) surface with TiCl4 as a model for metal halide ALD precursors showed that similar ligand transfer reactions occured. Adsorbed chlorine from the dissociative adsorption of TiCl4 on the InSb surface at elevated temperature, however, preferentially etched In atoms from the substrate and produced a roughened surface. The quality of InGaAs/Al2O3 interfaces prepared by solvent cleaning and liquid phase HF were assesed electrically using capacitance-voltage and conductance measurements. Surface recombination velocity (SRV) values were extracted from the measurements to represent the net effect of interface defects, which includes defect density and capture cross section. The InGaAs/Al2O3 interface prepared by solvent cleaning consisted of interfacial native oxides while that etched in liquid phase HF consisted of submonolayer arsenic oxide. The two chemically contrasting interfaces, however, gave similar SRV values of 34.4±3.7 and 28.9±13.4 cm/s for native oxide and liquid phase HF prepared samples, respectively. This suggests that the presence or absence of oxides was not the only determining factor. Post Al2O3 deposition annealing in forming gas and NH3 ambient significantly improved the electrical quality for both surfaces, as shown by SRV values between 1 to 4 cm/s which is comparable to that of an ideal H-terminated Si surface. XPS analysis showed that the contribution from elemental As and Ga2O3 at the interface of both surfaces increased after annealing in forming gas and NH3, likely due to thermal or hydrogen-induced reaction between interfacial As oxide and Ga atoms in the substrate. There was no correlation between the atomic coverages of interfacial elemental As and oxides to the SRV values. High activity defects at III-V/Al2O3 interfaces are associated with interfacial dangling bonds which were passivated thermally and chemically by annealing in forming gas and NH3.

Biomass gasification could potentially mitigate the actual dependency on fossil fuels. The practical application of this technology still faces many challenges to be considered a sustainable and profitable energy production source. One of the drawbacks of this technology is the production of undesirable by-products such as high molecular weight hydrocarbons collectively known as “tar” and sulfur compounds. These unwanted compounds must be removed before syngas end-use applications as they can foul pipes and reduced the performance of equipment downstream the gasifier as well as poison the catalyst used for upgrading the syngas. Catalytic steam reforming stands as an appealing tar removal technology in the small and medium sized gasification plants where heat management is crucial and recovery of the energy content within the tar compounds is desirable avoiding wastewater effluents and disposal of adsorbents. Nickel based catalysts have been the preferred choice in industrial applications for the reforming reactor. However, deactivation by carbon deposition is at present an unresolved problem which must be addressed before commercial application of biomass gasification technology. Moreover, the presence of sulfur compounds even at the low concentration found in most biomass feedstocks is deleterious for the steam reforming activity of the catalyst. This thesis comprises four experimental studies, each of them deal with a specific arguments of the hot gas cleanup technology of biomass syngas. The main focus was on the steam reforming activity of nickel-based catalyst and the effect of sulfur and the potassium-sulfur interactions on the steam reforming performance of the catalyst. The main contributions from these studies are; 1) the development of a less time and energy consuming synthesis procedure for the production of a mayenite-supported nickel catalyst using low-cost precursors. This new method involves the addition of the nickel precursor during the mayenite synthesis procedure. Compared to the “wet impregnation” technique the developed method showed slightly lower toluene steam reforming activity but greater stability, which was ascribed to a higher carbon deposition tolerance. 2) Better understanding on the sulfur poisoning of catalysts under steam reforming conditions at laboratory scale. The results evidenced that for a deeper knowledge of the sulfur poisoning, the calculation of the sulfur coverage should be more accurate and new methods for its measurement are required. 3) Comprehension of the mechanism of interaction between potassium and sulfur on a sulfur passivated commercial nickel catalyst under reforming conditions using real biomass syngas. The preferential adsorption site for sulfur and potassium was determined for the applied experimental conditions and catalyst and a mechanism involving the interaction of potassium with the sulfur chemisorbed on the active sites was proposed

The reduction of sulphur in transportation fuel has gained significant importance as the regulatory agencies worldwide react to air quality concerns and the impact of sulphur oxides on the environment. The overall objective of this research was to identify, develop and characterize, based on underlying scientific principles, sorbents that are effective in removal of refractory sulphur compounds from fuel through the process of selective adsorption. It was determined that impregnation of powdered activated carbon with a transition metal (TM) significantly boosted the adsorption performance of the activated carbon. It is hypothesized that the impregnation resulted in the formation of new adsorptive sites that strongly interacted with the lone pairs of electrons on sulphur and nitrogen while having minor impact on the existing oxygen functional groups on the surface of the activated carbon. The percent loading of the TM was determined through wet adsorption study. The best performing sorbent was shown to have maximum adsorption capacities of approximately 1.77 and 0.76 mmol-S/g-sorbent for DBT and 4,6 DMDBT, respectively, with approximately 100% regenerability through solvent wash and thermal treatment. On average, the PTM impregnation showed approximately 137% increase in adsorption capacity of the activated carbon. The sorbent also has good adsorption capacities for organo-nitrogen compounds (i.e., quinoline and carbazole) and a low selectivity towards aromatics, which is desired in adsorptive desulphurization. The surface morphology of the activated carbon, the oxygen functional groups on the surface of the activated carbon, as well as strong (chemisorption) interaction between the TM???s partly vacant and far reaching ???d??? orbital and lone pair electrons on sulphur and nitrogen are considered to be the main contributing factors to the observed enhancement. It was established in this study that the adsorption isotherms of the impregnated activated carbons best fit Sips isotherm equation, which is a combination of the Langmuir and Freundlich equations. This finding fits well with our initial hypothesis regarding the introduction of new adsorptive sites as a result of TM impregnation and that the sites did not fit well with Langmuir???s monolayer and uniform adsorption mechanism. A kinetic study of the sulphur adsorption using a flow reactor showed a good fit with pseudo second order kinetic model, indicative of an adsorption that is highly dependent on the concentration of available sites on the surface of the sorbent. On average, as expected, the TM impregnated ACC exhibited a higher initial rate of adsorption. The adsorption onto TM sites tends to be more exothermic than adsorption (mainly physisorption) on activated carbon. Therefore, more thermodynamically favoured chemisorption is expected to occur more rapidly than physisorption. It was determined that on average, the initial adsorption rate does not change significantly with temperature while the sulphur adsorption capacity decreases with increase in temperature. It is postulated that the increase in temperature increases surface diffusivity but impedes diffusion flux. The impediment of the diffusion flux will result in reduction in adsorbed quantity. It was also shown that the intra-particle diffusion exists in the adsorption of DBT on TM impregnated activated carbon, however, it is not likely that the overall adsorption is controlled or noticeable impacted by it. As the temperature of the reactor increases the Weber-Morris intra-particle diffusion plot moves away from the origin, and thus intra-particle diffusion becomes less of a controlling mechanism. This further confirms the fact that the boundary layer (i.e., surface diffusion) and potentially adsorptive interactions at the surface are the dominating mechanisms in the sulphur adsorption onto TM impregnated activated carbon. It was determined that the distribution of TM species on the surface of the activated carbon is relatively inhomogeneous, with some areas showing well dispersed TM species while other areas showing large clusters. Different impregnation method that can improve dispersion on the surface may significantly enhance adsorption performance of the sorbent. Furthermore, in this study impregnation of activated carbon using several other transition metals were examined. It was determined that other less expensive transition metals can also improve the adsorption performance of the activated carbon. Further study on less expensive options for impregnating the activated carbon may be beneficial.

碩士
中原大學
環境工程學系
105
The objective of this study is to develop an adsorbent that can simultaneously adsorb dichromate and chromium ion. Various concentrations of organic compounds, such as ethyl xanthate, L-cysteine and dodecyl sulfate, containing sulfur atom were used to intercalate Mg-Al layered double hydroxides (Mg-Al LDHs) through a co-precipitation method. The produced adsorbents were used to adsorb dichromate and chromium ion under pH 4 and 5. The adsorbents were characterized by XPS, SEM, FTIR and XRD. The adsorption capacity of target contaminants was calculated by adsorption equilibrium and the possible adsorption mechanism was discussed. The results indicated the Mg-Al LDHs intercalated with ethyl xanthate, L-cysteine and dodecyl sulfate can effectively adsorb dichromate and chromium (III) ion. The adsorption mechanism for chromium ion was regarded as complexation reaction. Because carbonate was found in the interlayer, the adsorption mechanism for dichromate was assumed as anion exchange. The demonstrated the synthesized adsorbents can remove cationic and anionic heavy metal ions. The adsorbents produced by the modification are in addition to the poor adsorption effect obtained after the dodecyl sulfonate intercalation, and the other two anionic organisms can produce high adsorption capacity for the contaminants. For the heavy metal solution at two pH values, the LDHs intercalated by dodecyl sulfonate adsorbs cationic heavy metal contaminants at pH= 5, and the LDHs intercalated by ethyl xanthate removed cationic and anionic heavy metals at pH4 and pH5. The LDHs intercalated by L-cysteine can generate a better effect for the cationic and anionic heavy metal ions at pH5. The overall efficiency of the adsorbent is decrease as the following order: ethyl xanthate-LDHs> cysteine-LDHs> dodecylsulfonate-LDHs.

碩士
明新科技大學
化學工程研究所
96
The main purpose of this study is to remove the toxic compound, Aristolochic Acid, existing in Aristolochia liukiuensis. The scientific and safe biomaterial Carbopol is utilized to remove Aristolochic Acid from natural product to nontoxic or less toxic status. Hence the first step for this research is to develope the methodology for analyzing the amount of Aristolochic Acid existing in Aristolochia liukiuensis. A suitable High Performance Liquid Chromatography (HPLC) method with stationary phase of RP-18 (10 μm) and mobile phase of 66% methanol：34% DI water was developed for Aristolochic Acid identification and quantification. Carbopol, which possesses high molecular weight, is cross-linked water-soluble polyacrylic acids polymer. It was used for the purpose of removing toxic compound, since they both are having polar functional groups. The carboxylic acid functional group of Carbopol was identified by Fourier Transform Infrared Spectrometer (FT-IR). Carbopol, which is available in different viscosity grades, has no effect on the biological activity of the drug while has excellent thickening and suspension effects. Therefore Carbopol polymer is also used in this research for making the control-release formulation. Carbopol and the detoxified natural medicine are blended to prepare gelatinic product. Both stability kinetics and the release pattern were tested for the prepared product. The release rate by disintegration is near 100% after five hours but the dissolution rate is only 10% after three hours. The prepared product is stable under room temperature for five days.

Pharmaceutically active compounds (PhACs) have been found in wastewater effluents and receiving waters around the world. As yet there are no jurisdictions that regulate their release, or their impact on receiving water ecosystem health. The issue is complex due to the number of PhACs that exist, the variability in their structure and function, the variability in removal during different wastewater treatment processes, the potential for formation of metabolites and transformation products, and a lack of information on the impacts due to their presence on receiving waters. Gemfibrozil is a lipid regulating drug that is commonly found in wastewater effluents and receiving waters. It has been shown to partially degrade during biological wastewater treatment processes and has also been shown to produce reaction products through reactions with free chlorine. This thesis investigated the removal and transformation of gemfibrozil through several different wastewater treatment processes, namely biological removal and chlorination. Reactions between gemfibrozil and free chlorine led to the identification of four reaction products. The structures of three of the four reaction products were elucidated. The kinetics of formation of these reaction products were then investigated at a range of pH values, and in two wastewater matrices. One reaction product, 4’-ClGem was shown to form under conditions relevant to wastewater treatment. The impacts of gemfibrozil and 4’-ClGem presence on the abundance of suspended and biofilm bacteria in a simulated receiving water experiment were evaluated. It was shown that changes in the water matrix had more of an impact on bacterial abundance than presence of gemfibrozil or 4’-ClGem. A bacterial dose-response experiment showed a negative response at 10 mg/L exposure to 4’-ClGem, which is orders of magnitude higher then what would be found in receiving waters. In order to prevent the formation of chlorinated reaction products, it is necessary to remove gemfibrozil prior to disinfection. Recirculating biofilters (RBS), a biological technology for onsite or small-scale wastewater treatment, were explored as a potential treatment process for gemfibrozil removal. Results indicate that RBFs show promise as a robust technology to remove greater than 50% of influent gemfibrozil.

碩士
明志科技大學
環境與資源工程研究所
100
Arsenic is a strong toxic element and drinking arsenic contaminated water for a long period of time will cause blackfoot disease and cancers. There are studies showing the groundwater contains arsenic and its concentration in ranges from 10μg/L up to 1800μg/L in the south western and north eastern coastlines of Taiwan. In this study, manganese oxidant was used to adsorb/oxidize arsenic and treat water contaminated with organic matters. The main substance added to the contaminated water is commercialized standard organic matter that contains different functional groups and extracted organic matter from natural water. By alternating initial pH values with different adding orders and discuss the reaction mechanisms and the influences of natural organic matters to the arsenic removal with manganese oxidants. The results have shown that manganese oxidants and organic matters reacted with As(III)/As(V) reaches equilibrium in two hours. In acidic condition (pH2), small molecules of organic matters are undissociated and may compete with arsenic for adsorption sites on the surface of manganese oxidants. Hence arsenic removal was not improved and restrained. In both neutral condition (pH7) and alkaline condition (pH11), organic matters were dissociated and may have complexes reactions with arsenic follow with adsorption and removal by manganese oxidants, as a result, arsenic is removed. With the purpose of increasing arsenic removal rate in the mixture of manganese oxidants, organic matter and arsenic, addition of lactic acid will increase oxidation rate and arsenic removal rate. However, addition of resorcinol in acidic condition will decrease arsenic removal rate due adsorption site competition. Therefore, orders of arsenic removal rate in different combinations of manganese oxidants, organic matters, and arsenic are: As + org Mn > Mn + As org > Mn + org As. Furthermore, changes in total organic carbon concentration has similar trend with arsenic removal rate. The quantity content trend of functional groups of different sizes of organic matter is <10KD > 10~50KD > 50~100KD. Both As(III) and As(V) removal rates decreased by different molecular sizes of organic matter, and As(III) removal rate increases only under acidic condition.

The study examined the removal mechanism of non-acclimated and acclimated aerobic activated sludge for 29 target organic micropollutants (OMPs) at low concentration. The selection of the target OMPs represents a wide range of physical-chemical properties such as hydrophobicity, charge state as well as a diverse range of classes, including pharmaceuticals, personal care products and household chemicals. The removal mechanisms of OMPs include adsorption, biodegradation, hydrolysis, and vaporization. Adsorption and biodegradation were found to be the main routes for OMPs removal for all target OMPs. Target OMPs responded to the two dominant removal routes in different ways: (1) complete adsorption, (2) strong biodegradation and weak adsorption, (3) medium biodegradation and adsorption, and (4) weak sorption and weak biodegradatio. Kinetic study showed that adsorption of atenolol, mathylparaben and propylparaben well followed first-order model (R2: 0.939 to 0.999) with the rate constants ranging from 0.519-7.092 h-1. For biodegradation kinetics, it was found that benzafibrate, bisphenol A, diclofenac, gemfibrozil, ibuprofen, caffeine and DEET followed zero-order model (K0:1.15E-4 to 0.0142 μg/Lh-1, R2: 0.991 to 0.999), while TCEP, naproxen, dipehydramine, oxybenzone and sulfamethoxazole followed first-order model (K1:1.96E-4 to 0.101 h-1, R2: 0.912 to 0.996). 4 Inhibition by sodium azide (NaN3)and high temperature sterilization was compared, and it was found that high temperature sterilization will damage cells and change the sludge charge state. For the OMPs adaptation removal study, it was found that some of OMPs effluent concentration decreased, which may be due to the slow adaptation of the sludge or the increase of certain bacteria culture; some increased due to chromic toxicity of the chemicals; most of the OMPs had stable effluent concentration trend, it was explained that some of the OMPs were too difficutl to remove while other showed strong quick adaptation. A new module combined of sequencing batch reactor (SBR) and nanofiltration membrane filtration (NF-MBR) was developed to further study the OMPs removal and to exam the concept of compounds (CRT). The NF-MBR was proved to be a promising bioreactor, as OMPs were rejected by NF membrane which leaded to a low OMPs concentration in permeate water, the apparent removal rate was over 80% for most of the OMPs.

碩士
國立中正大學
化學工程研究所
90
The main purpose of the research is to develop adsorbent for removal VOC from waste gas. The main factors for consideration are: mechanical strength, regeneration temperature, and auxiliary-fuel. Adsorbent are fabricated to certain shape by screwed-extruding forming machine. Performance of the adsorbent was tested with a continuous fixed-bed reactor and the concentration of VOC was analyzed by HP-GC6890 gas chromatograph. Before the performance test, preliminary experiment indicated that the adsorbed water would reduce adsorption capacity. Therefore, prior to the tests, the adsorbent was purged with dry air at 300 C. Two kinds of binder, nature-clay and pseudo-boehmite (V-5) are used in this study. The experimental results indicated that both clay and pseudo-boehmite can make adsorbent with qualified mechanical strength, but pseudo-boehmite has much higher adsorption capacity.Moreover, with pseudo-boehmite as binder, USY-Zeolite presents the best performance and for the preparation recipe the optimal calcinations temperature is 450 C. Too low temperature (200 C), the adsorbent will be dissolved in water, whereas too high temperature, zeolite crystal in the adsorbent will be destructed, as evidence by SEM and XRD characterization, resulting in a decrease of adsorption capacity.

Water is an important resource. It is used for domestic, industrial, agricultural and recreational purposes. The quality of water is, however, significantly deteriorating due to the accumulation of organic species in aqueous system. Domestic, industrial and commercial activities comprise the biggest source of organic pollutants in municipal water. The increase of water pollution by these organics has led to the development of several water purification measures. Among others, water treatment technologies that are in place consist of ion exchange, activated carbon adsorption, reverse osmosis, molecular sieves and zeolites. However, none of these techniques have been reported to remove organic pollutants to parts-per-billion (ppb) or microgram-per-litre (ìg/L) levels. Recently, it has been reported that cyclodextrin nanoporous polymers are capable of absorbing these pollutants from water to such desirable levels. Cyclodextrins (CDs), basically starch derivatives, are cyclic oligomers consisting of glucopyranosyl units linked together through á-1,4-glycosidic linkages. They behave as molecular hosts capable of interacting with a range of guest molecules in a noncovalent manner within their cylindrical hydrophobic cavities. These interactions are a basis for the inclusion of various organic species. However, the high solubility of cyclodextrins in aqueous medium limits their application in the removal of organic pollutants from water. To make them insoluble, they are converted into highly cross-linked polymers. This is achieved by polymerizing the cyclodextrins with suitable difunctional linkers. In this project, a wide variety of monofunctionalized CDs have been effectively prepared using efficient modification strategies and successfully characterized by Infra-red (IR) and Nuclear Magnetic Resonance (NMR) spectroscopy. From these monofunctionalized CDs and corresponding linkers, insoluble nanoporous polymers with different physical properties were synthesized (Scheme 1).
Dr. B.B. Mamba

Over the last decade, endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs) have been detected in drinking water at very low levels, mostly ng/L concentrations, suggesting that these compounds resisted removal through water treatment processes. Concerns have been raised regarding the effectiveness of common drinking water treatment technologies to remove these emerging contaminants. Adsorption processes were suggested to play an important role in the removal of PhACs and EDCs, based on the assumption that these compounds are similar to other conventional micropollutants such as pesticides in both physicochemical properties and concentration levels present in water. However, this remains to be demonstrated since the availability of adsorption data for PhACs and EDCs is extremely limited and their environmental concentrations are typically much lower than the ones for pesticides. The primary objective of this research was to evaluate in detail the removal of representative EDCs and PhACs at environmentally relevant concentrations by granular activated carbon (GAC) adsorption. In the first stage of this study, EDCs (15) were screened separately from the PhACs (86) with two different sets of assessment criteria due to the different nature and the availability of information for these two groups of compounds. As a result, 6 EDCs and 12 PhACs were selected for further evaluation. Subsequently, a multi-residue analytical method based on gas chromatography/mass spectrometry (GC/MS) was developed for the simultaneous determination of the selected PhACs and EDCs. Two key analytical steps - solid phase extraction and derivatization - were systematically optimized using full factorial design and a central composite design, respectively. The statistical experimental design in combination with the concept of the total desirability was demonstrated to be an effective tool for developing a multi-residue analytical method. The application of the developed method to Grand River water, a local raw water source, and finished drinking water from this source indicated that PhACs such as naproxen, carbamazepine, salicylic acid, ibuprofen, and gemfibrozil, and EDCs such as estrone (E1) and nonylphenol mono-ethoxy carboxylate (NP1EC) were the most common contaminants. Based on these results, the quality of the analytical data, and the physicochemical properties relevant to the adsorption on activated carbon, two PhACs (naproxen, carbamazepine) and one EDC (nonylphenol (NP)) were finally chosen for the adsorption studies. Adsorptions of the selected target compounds were evaluated on two types of activated carbon (coal-based Calgon Filtrasorb® 400 (F400) and coconut shell-based PICACTIF TE (PICA) by first investigating their isotherms at environmentally relevant concentrations (equilibrium liquid phase concentration ranging from 10 to 1000 ng/L). The single-solute isotherm data determined for both carbons showed that the relative adsorbabilities of the three target compounds were not in agreement with expectations based on their log Kow values. Overall, in this low concentration range, carbamazepine was most easily removed, and NP was least adsorbable. The adsorption of naproxen was negatively influenced by its dissociation in water. Comparison of single-solute isotherms on F400 carbon for the target compounds to those for other selected conventional micropollutants showed that naproxen and carbamazepine have generally comparable isotherms to 2-methylisoborneol (MIB) and geosmin. The isotherm tests in a post-sedimentation (PS) water from a full-scale plant demonstrated that the presence of background natural organic matter (NOM) significantly reduced the adsorption of all three target compounds, among which.NP was the least impacted compound. Based on the quantification of the direct competition using the ideal adsorbed solution theory (IAST) in combination with the equivalent background compound (EBC) approach, the minimum carbon usage rates (CURs) for removing 90% of the target compounds in PS water were calculated at two environmentally relevant concentrations (50 and 500 ng/L). This work confirmed that the percentage removal of the trace level target compound at a given carbon dosage was independent of the initial target compound concentration. Isotherm experiments were conducted for the target compound on GACs preloaded with PS water for various time intervals (up to 16 weeks) at the Mannheim Water Treatment Plant (Region of Waterloo, ON, Canada). The results indicated that the adsorption of all target compounds were subject to significant negative impacts from preloading of NOM, albeit to different extents. Among the three target compounds, reduction in adsorption capacity for naproxen was most severe, followed by carbamazepine and then NP. The three target compounds followed quite different patterns of decrease in adsorption capacity with increasing preloading time, thus revealing different competitive mechanisms at work for the different compounds. For naproxen, the change in heterogeneity of the carbons due to preloading suggests that some pre-adsorbed NOM could not be replaced by naproxen. However, both direct competitive and pore blockage mechanisms could successfully explain the adsorption performance of naproxen and carbamazepine. The removal of NP even at prolonged preloading times could be explained by absorption or partitioning in the NOM matrix on the surface of, or inside the carbons. The kinetic parameters for each target compound-virgin carbon pair were determined using the short fixed bed (SFB) approach based on the pore and surface diffusion model (PSDM). The SFB results and sensitivity analyses indicated that, under the very low influent concentration conditions, film diffusion (indexed as βL) exerts a much greater effect on breakthrough profiles than internal diffusion. The SFB tests on preloaded GACs showed that mass transport of all the target compounds decreased with increasing preloading time. Similar to the impact of preloading on adsorption capacity, naproxen was subject to the most deteriorative effect, followed by carbamazepine and then NP. In addition, potential mechanisms for the decay of the film diffusion coefficient with increased preloading time were discussed based on scanning electron microscope (SEM) images of virgin and preloaded GAC. Electrostatic interactions between the NOM/bio film formed on the preloaded carbon and dissociated naproxen may have contributed to the enhanced reduction in its film diffusion. Sensitivity analyses and subsequent calculations of the Biot numbers confirmed that film diffusion was also the predominant mechanism controlling the mass transport on preloaded carbon, in particular for naproxen. This suggests that the early breakthrough prediction of the target compounds at their environmentally relevant concentrations could be further simplified by only considering film diffusion and adsorptive capacity. Kinetic and isotherm parameters were used as input for modeling using time-variable PSDM. It was found that the varying trends for Freundlich KF and 1/n, and βL could be generally depicted by a corresponding empirical model. Pilot scale treatability tests were performed for the target compounds which subsequently validated the time-variable PSDM results thus demonstrating its effectiveness and robustness to model GAC adsorber performance for PhAC and EDC removal at environmentally relevant concentrations. The time-variable approach was further improved by adjusting for NOM surface loading differences between the preloading and the pilot columns, which successfully compensated for the prediction errors at the early phase. The validated NOM surface loading associated time variable PSDM was used to predict performances of hypothetical F400 and PICA full-scale adsorbers. Both adsorbers were expected to provide satisfactory performance in achieving 90% removals for the neutral target compounds (carbamazepine and NP). Naproxen was predicted to break through fast since both, capacity and kinetic parameters decay quickly due to carbon fouling by NOM and the physicochemical properties of this compound. Initial recommendations on the choice of adsorption process (GAC vs. PAC) for removing EDCs and PhACs can be made based on the comparison of carbon usage rates (CUR) which were calculated for a GAC adsorber using the validated improved PSDM and for PAC using the minimum applied dosages predicted by the IAST-EBC model.