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Water pollution is one of the major ecological threats people face around the world. Water contamination by organic and inorganic compounds is hazardous to both the environment and human health. Adsorption techniques have gained much attention in the field of water remediation due to their efficiency, simplicity in operation, and ease of implementation. However, the adsorbents currently being used are costly. The main objective of this work is to develop novel, low-cost adsorbents from waste material by modifying the adsorbent surface for water remediation. Adsorbent modifications involve various chemical and physical methods such as acid/base treatments, metal/metal oxide impregnation, functional group alteration, and steam/air activation. In chapter I, these modification methods are summarized along with characterization techniques and adsorption interactions available for contaminant removal. In chapter II, a novel activated carbon is introduced from the fruit of Garcinia cambogia with acid activation, for the removal of Pb(II) and Cd(II) from water. Activated carbon was prepared by soaking dried Garcinia cambogia pieces in 85% phosphoric acid and carbonizing at 650 °C in a muffle furnace for 1 h. Chapter III describes the modification of waste tire rubber as an adsorbent for heavy metal ion removal. This modification was done by mixing ground tire rubber (GTR) with chitosan dissolved acetic acid (2%) solution followed by NaOH treatment. Chitosan modified-GTR successfully removed more Pb(II) and Cu(II) ions than GTR, suggesting added amine groups on the GTR surface through chitosan modification enhanced the heavy metal ion adsorption. In chapter IV, caffeine, ibuprofen, and acetylsalicylic acid removals by hybrid magnetic Fe3O4/Douglas fir biochar adsorbent are discussed. Adsorptions were compared with non-magnetic Douglas fir biochar. The surface chemistry and composition of modified adsorbents were examined by SEM, SEM-EDX, TEM, PZC, XRD, XPS, FTIR, TGA, elemental analysis, and surface area measurements.

CG-4 H2S adsorbent, an iron oxide based solid, has high sulfur capacity (20-25% w/w) and thus finds favor in users eyes in North America. This product, imported from CLEAN Catalysis and Purification Technologies Development Company in Shanxi Province, China, is now being used in gas processing companies in Alberta, Canada and Texas, USA. However, due to the elemental sulfur deposition on the adsorbent, the recovered sulfur capacity by regeneration is only about 1/3 as that of fresh adsorbent. This limits the adsorbent use to be once, which results in higher operating cost due to the frequent changeover and cost for landfills. The problem of sulfur deposition is also the limitation to the utilization and regeneration of other desulfurization adsorbent or catalyst. <p>This study developed a process to recover the sulfur capacity of CG-4 adsorbent by ammonia leaching to remove elemental sulfur. The leaching was conducted in a stainless steel cylindrical reactor at room temperature and a pressure higher than the vapor pressure of liquid ammonia. The leaching process does not deleteriously change the physical strength, but improve the properties of surface area, pore volume and pore size distribution. The new regeneration process is able to recover over 90% sulfur capacity in the first adsorption-regeneration cycle. The sulfur capacity recovery declined when CG-4 had been leached for more than one time. Nonetheless, even after the third time leaching, the sulfur capacity was recovered by 60%. The conditions of leaching process were optimized in a laboratory-scale experiment. <p>Additionally, the elemental sulfur collected from leaching process has 91.5% w/w purity and can likely be used as an additive to asphalt or used as a soil amendment for agricultural applications. The separation of solid wash-offs and liquid ammonia was simply fulfilled by depressurizing the leaching vessel and vaporizing the ammonia. CG-4 adsorbent is verified capable of at least three times reuses, which results in 60% reduction in disposal amount per unit H2S being treated. This not only reduces the cost in disposal to landfills but also the cost in CG-4 adsorbent and brings the revenue from the recovered elemental sulfur. The vapor ammonia is recommended to be recycled and reused by compressing it back to liquid.

CG-4 H2S adsorbent, an iron oxide based solid, has high sulfur capacity (20-25% w/w) and thus finds favor in users eyes in North America. This product, imported from CLEAN Catalysis and Purification Technologies Development Company in Shanxi Province, China, is now being used in gas processing companies in Alberta, Canada and Texas, USA. However, due to the elemental sulfur deposition on the adsorbent, the recovered sulfur capacity by regeneration is only about 1/3 as that of fresh adsorbent. This limits the adsorbent use to be once, which results in higher operating cost due to the frequent changeover and cost for landfills. The problem of sulfur deposition is also the limitation to the utilization and regeneration of other desulfurization adsorbent or catalyst. <p>This study developed a process to recover the sulfur capacity of CG-4 adsorbent by ammonia leaching to remove elemental sulfur. The leaching was conducted in a stainless steel cylindrical reactor at room temperature and a pressure higher than the vapor pressure of liquid ammonia. The leaching process does not deleteriously change the physical strength, but improve the properties of surface area, pore volume and pore size distribution. The new regeneration process is able to recover over 90% sulfur capacity in the first adsorption-regeneration cycle. The sulfur capacity recovery declined when CG-4 had been leached for more than one time. Nonetheless, even after the third time leaching, the sulfur capacity was recovered by 60%. The conditions of leaching process were optimized in a laboratory-scale experiment. <p>Additionally, the elemental sulfur collected from leaching process has 91.5% w/w purity and can likely be used as an additive to asphalt or used as a soil amendment for agricultural applications. The separation of solid wash-offs and liquid ammonia was simply fulfilled by depressurizing the leaching vessel and vaporizing the ammonia. CG-4 adsorbent is verified capable of at least three times reuses, which results in 60% reduction in disposal amount per unit H2S being treated. This not only reduces the cost in disposal to landfills but also the cost in CG-4 adsorbent and brings the revenue from the recovered elemental sulfur. The vapor ammonia is recommended to be recycled and reused by compressing it back to liquid.

Aflatoxins are naturally occurring carcinogens found on grains, particularly in warmer climates. Because of their carcinogenic properties, they are strictly regulated and are only allowed in minimal amounts. Aflatoxin B1, the most potent naturally occurring carcinogen known, is metabolized in the liver to form aflatoxin M1, which is present in the milk of lactating animals. If aflatoxin concentrations are elevated above legal limits, the milk cannot be used for human consumption. Because of this, research has been conducted to evaluate ways to mitigate its absorption in the animal and prevent transfer to the milk. One such way is through the use of clay adsorbents. The current studies aimed to evaluate the efficacy of two different clay adsorbents at preventing aflatoxin transfer to the milk of Holsteins fed a known concentration of aflatoxin.

In response to the ever-increasing global energy demand and the need to move away from non-renewable and CO2-emitting fossil fuels as the primary energy production method, renewable energy sources have become more and more viable as energy production methods. However, given the unreliable and instantaneous nature of these energy sources, reliable, renewable energy storage methods are required. Hydrogen is an excellent candidate as a chemical energy store, as it is highly abundant, relatively easily produced as diatomic hydrogen (including from water electrolysis), and only produces water upon its complete combustion. Hydrogen also has the highest gravimetric energy density of any known chemical fuel, meaning that not very much of it is required relative to other chemical fuels. However, hydrogen gas is incredibly sparse, and therefore hydrogen has a very low volumetric energy density, making storage of the material a key challenge in the development of the so-called “hydrogen economy”. Most commonly, hydrogen is stored by compressing it to 70 MPa. However, this technique has a number of flaws, including the high expense of strong tanks (and in the case of light duty vehicles, lightweight materials are also required), and the inherent safety risks that high pressure, highly flammable gas poses. One of the alternatives to compression is to store hydrogen by adsorption, which uses high surface area materials to densify hydrogen via the formation of weak physical bonds. This research line is well developed, and a number of different materials has been created that show good potential as hydrogen storage materials, such as activated carbons and metal organic frameworks. However, the vast majority of materials developed for this purpose are tailored only with the hydrogen uptake in mind, which can cause issues as the focus of development shifts from small scale tests to full tank scale. One adsorptive that shows a number of highly useful engineering properties on the large scale, such as good thermal resistance and solution processability, is the polymer of intrinsic microporosity PIM-1. This material can be processed into a number of morphologies without losing porosity, and shows good thermal and mechanical resistance. However, its adsorption capacity is rather limited, with the BET surface area generally reported in the 700 – 800 m2 g-1 range, and hydrogen uptake of 1.45 wt% at 77 K and 1 MPa. This thesis presents two separate studies on attempting to improve the hydrogen uptake of PIM-1 without adversely affecting the material properties that make it attractive. The first of these was the creation of mixed-matrix-membrane style composite films solution cast from PIM-1 and the metal organic framework MIL-101. PIM-1 proved slightly difficult to synthesise consistently with high molecular weight, but MIL-101 is an easy hydrothermal synthesis. Film casting was successfully performed, producing flat, homogeneous films that maintained the MOF crystallinity. These materials were tested for their thermal properties – thermal decompositions proceeded according to the rule of mixtures of the two starting materials, whilst an increasing concentration of MOF was shown to decrease the specific heat capacity. Both PIM-1 and MIL-101 were shown to adsorb nitrogen as previously reported. The composites showed increasing uptake with MIL-101 content, but at a lower rate than the rule of mixtures. This was a common theme for the N2 (77 K), CO2 (293 K) and low pressure H2 isotherms performed. High pressure isotherms up to 17 MPa were performed on PIM-1 for the first time, showing a maximum excess uptake of 1.8 wt% on the powder and 1.6 wt% on the film, both at 77 K. The composites showed improved uptake with increasing MIL-101, but the maximum uptakes did not meet the rule of mixtures. The uptakes at the highest pressure did, however. Multiple temperature isotherm sets were performed on the PIM-1 film and powder, as well as the 30 wt% composite. These data sets were hampered largely by machine faults, but contained sufficient valuable data to be able to proceed with parameter fitting. The sensitivity of the isotherms produced in this study to the value of skeletal density is also examined closely. The second theme of improved H2 uptake in PIM-1 was to carbonise the material. TGA studies on PIM-1 showed good thermal stability in anoxic conditions, and TGA twinned with mass spectroscopy was able to confirm a previously proposed mechanism of thermal decomposition. Carbonised and activated PIM-1 film samples, and a carbonised powder, were produced using physical activation methods. The adsorption performance of the carbons was disappointing, as the uptakes of N2 and H2 (< 0.1 MPa) were reduced post-carbonisation, with little recovery in the activated film. CO2 uptakes were improved, however. High pressure H2 isotherms on both the carbonised and activated films showed unusual ‘stepping’ behaviour in the adsorption curve, but maximum uptakes for both (1.0 – 1.3 wt%) were less than that seen for PIM-1 alone. Parameter fitting was performed on all of the high pressure H2 isotherms performed in this study, using a method previously proposed by the Mays group. The parameter fits all showed effective hydrogen densification in the adsorbate layer, although the repeatability of parameter values, and the smoothness of the parameters as a function of temperature were undermined by the low quality of some of the isotherms. Using the parameters acquired, it was possible to calculate the isosteric enthalpy of adsorption for PIM-1 powder (-9.5 kJ mol-1), film (- 8.0 kJ mol-1) and the 30 wt% composite (-9.3 kJ mol-1). The stored and deliverable hydrogen contained within tanks featuring the tested materials were estimated, although only the MIL-101 powder on its own competes with other hydrogen storage adsorbents currently reported.

Microwave heating has unique advantages compared to convection-radiation heating methods including fast heating rate and selective heating of objects. This thesis studied two applications of microwave heating in the environmental field: adsorbent regeneration and oil sands coke activation. The thermal behavior during microwave heating of select adsorbents when dry or saturated with selected adsorbates was studied to assess the potential for using microwave heating to regenerate adsorbents. Strong microwave-absorbing adsorbents depicted faster heating rate when dry. Weakly microwave-absorbing adsorbents depicted faster heating rate when saturated with polar adsorbates. Fast activation of oil sands coke using microwave heating and KOH was successfully completed. The iodine number of the activated delayed coke obtained after 10 minutes of microwave activation was 1130 mg/g. The short activation time and simplicity of the process demonstrate that microwave-activation is a promising approach to convert oil sands coke into activated carbon adsorbent with high adsorption capacity. / Environmental Engineering

The overall goal of this study is to evaluate the ability of novel nanostructured adsorbent media (NTAs, iron sulfides (FeS2 and FeS)) to remove arsenic, selenium and mercury from ash and scrubber pond effluents. The NTAs aim to enhance arsenic removal from solution compared to conventional adsorbents. The iron sulfides are expected to produce stable residuals for ultimate disposal after removing As, Se and Hg from solution, so that removal of these compounds from wastewaters will not result in contamination of soils and groundwaters. Methods for reliably and economically producing these materials were developed. The synthesized NTAs and iron sulfides were characterized by surface analysis techniques such as XRD, FT-IR, SEM-EDS, TEM, XPS, AFM and N2-adsorption. These analyses indicated that Ti(25)-SBA-15 has highly ordered hexagonal mesopores, MT has interparticle mesopores, pyrite (FeS2) forms crystalline, nonporous rectangular nanoparticles (<500 nm), and mackinawite (FeS) forms amorphous, nonporous nanoparticles (<100 nm). Kinetic and equilibrium tests for As(III, V) removal were conducted with NTAs over a range of pH (4, 7, 9.5). The rates of arsenic uptake were very fast and followed a bi-phasic sorption pattern, where sorption was fast for the first 10 minutes, and then slowed and was almost completed within 200 minutes. Distinct sorption maxima for As(III) removal were observed between pH 7 and pH 9.5 for MT and between pH 4 and pH 7 for Ti(25)-SBA-15. The amount of As(V) adsorbed generally decreased as pH increased. In addition, a surface complexation model (SCM) based on the diffuse layer model (DLM) was used to predict arsenic adsorption envelopes by NTAs under various environmental conditions. The SCM for As(III, V) adsorption by NTAs demonstrated the role of mono- and bidentate surface complexes in arsenic adsorption. A batch reactor system was employed in an anaerobic chamber to conduct experiments to characterize both the removal of As, Se, Hg from solution and their subsequent reactions with iron sulfides. Experiment variables for removal experiments included: contaminant valence state (As(V), As(III), Se(VI), Se(IV), Hg(II)); adsorbent/reactant type (FeS, FeS2); adsorbent/reactant concentration; pH (7, 8, 9, 10); and competing ion (SO42-) concentration (0, 1, 10 mM). Experimental variables for reaction experiments were reaction time (up to 30 days) at pH 8 and oxidation states of contaminants. In addition, the stability of iron sulfides (FeS2, FeS) combined with target compounds was investigated by measuring the ability of the target compounds to resist release to the aqueous phase after removal. These experiments showed that iron sulfides were good adsorbent/reactants for target contaminants in spite of the presence of sulfate. This was particularly true at intermediate concentrations of target compounds. The experiments also demonstrated that iron sulfides interacted with target contaminants in such a way to improve their resistance to being released back to solution as pH was changed. Therefore, this study demonstrates the ability of novel nanostructured adsorbent media to remove arsenic, selenium and mercury from ash and scrubber pond effluents and the ability of iron sulfides to produce residuals that are stable when disposed in landfills.

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abstract: Due to depletion of oil resources, increasing fuel prices and environmental issues associated with burning of fossil fuels, extensive research has been performed in biofuel production and dramatic progress has been made. But still problems exist in economically production of biofuels. One major problem is recovery of biofuels from fermentation broth with the relatively low product titer achieved. A lot of in situ product recovery techniques including liquid-liquid extraction, membrane extraction, pervaporation, gas stripping and adsorption have been developed and adsorption is shown to be the most promising one compared to other methods. Yet adsorption is not perfect due to defect in adsorbents and operation method used. So laurate adsorption using polymer resins was first investigated by doing adsorption isotherm, kinetic, breakthrough curve experiment and column adsorption of laurate from culture. The results indicate that polymer resins have good capacity for laurate with the highest capacity of 430 g/kg achieved by IRA-402 and can successfully recover laurate from culture without causing problem to Synechocystis sp.. Another research of this paper focused on a novel adsorbent: magnetic particles by doing adsorption equilibrium, kinetic and toxicity experiment. Preliminary results showed excellent performance on both adsorption capacity and kinetics. But further experiment revealed that magnetic particles were toxicity and inhibited growth of all kinds of cell tested severely, toxicity probably comes from Co (III) in magnetic particles. This problem might be solved by either using biocompatible coatings or immobilization of cells, which needs more investigation. / Dissertation/Thesis / M.S. Chemical Engineering 2012