Academic literature on the topic 'Enhanced bentonite'

AbstractThe mineral stability of two bentonites was studied in the presence of pyrite concentrate to simulate the possible reactions between the bentonite barrier used in a high-level nuclear waste (HLW) repository and host rock containing up to 5 wt.% of admixed pyrite. Smectite was the only bentonite mineral affected by pyrite treatment under the experimental conditions used. Bentonites reacted differently with pyrite due to the different nature of the smectites. The distinct crystal chemistry of the smectites controlled by the composition of the parent rocks influenced the smectite surface properties (cation exchange capacity and layer charge distribution) which resulted in a different response of the bentonites to pyrite treatment. A partial transformation of the original smectites into H-smectites represented the initial stage of smectite destabilization on acid attack. Rising non-equivalent isomorphous substitution in the octahedral sheets of the smectites enhanced smectite reactivity and thus the reaction between bentonite and pyrite, causing lower stability of the bentonite containing high-charge smectite.

Pilot sites are currently used to test the performance of bentonite barriers for sealing high-level radioactive waste repositories, but the degree of mineral stability under enhanced thermal conditions remains a topic of debate. This study focuses on the SKB ABM5 experiment, which ran for 5 years (2012 to 2017) and locally reached a maximum temperature of 250 °C. Five bentonites were investigated using XRD with Rietveld refinement, SEM-EDX and by measuring pH, CEC and EC. Samples extracted from bentonite blocks at 0.1, 1, 4 and 7 cm away from the heating pipe showed various stages of alteration related to the horizontal thermal gradient. Bentonites close to the contact with lower CEC values showed smectite alterations in the form of tetrahedral substitution of Si4+ by Al3+ and some octahedral metal substitutions, probably related to ferric/ferrous iron derived from corrosion of the heater during oxidative boiling, with pyrite dissolution and acidity occurring in some bentonite layers. This alteration was furthermore associated with higher amounts of hematite and minor calcite dissolution. However, as none of the bentonites showed any smectite loss and only displayed stronger alterations at the heater–bentonite contact, the sealants are considered to have remained largely intact.

The application of modified-bentonite-enhanced oil dispersion in water and oil–mineral aggregate (OMA) formation was studied in the laboratory. The effect of modification on the surface properties of bentonite was characterized. The hydrophobicity and surface electric properties of bentonite were significantly improved by attaching cetyltrimethyl ammonium bromide to its surface. The results showed that surface properties of bentonite played an important role in OMA formation. Spherical droplets of OMAs were formed with natural bentonite and elongated solid OMAs and flake OMAs were formed with modified bentonite as observed by fluorescence microscopy. The effects of shaking time, oil concentration and mineral content were also studied. It was suggested that oil concentration and mineral content were critical factors and OMA formed rapidly with both types of bentonite. Modified bentonite had better performance on OMA formation than hydrophilic natural bentonite.

Bentonite, a supplementary cementitious material for Portland cement, has greatly contributed to environmental sustainability. However, few studies have investigated mortar samples produced by substituting bentonite for cement, and cement strength may be adversely affected when cement is replaced with bentonite in larger proportions. Therefore, this paper investigates and discusses the effect of microbially induced calcium carbonate precipitation (MICP) on improving the strength of bentonite-amended cement. The bio-mineralization process of MICP was characterized by SEM-EDS, while the biominerals formed in bentonite-amended mortar were identified by FIIR and XRD analysis. The results showed that: at bentonite concentrations of 0%, 10%, 20%, 30%, and 40% in cement, the bacterial suspension and reaction solution enhanced the compressive strength of bentonite-amended cement by 17%, 20%, 79%, 78%, and 38%, respectively, after 28 days, compared to control specimens; With the increased bacterial concentration in the presence of the reaction solution, the strength of the bentonite-amended cement (20% bentonite) increased remarkably compared to the control specimen (without bacteria). When the bacterial concentration was OD600 2.0, the compressive strength of bentonite-amended cement (20% bentonite) increased by 80% after 28 days; MICP process has a great effect on improving the strength of bentonite-amended cement. It is a green and economical choice to use MICP to improve the strength of bentonite-amended cement.

Fluoride-contaminated drinking waters are known to cause severe health hazards such as fluorosis and arthritis. This paper presents the encapsulation of iron oxide nanoparticles in kaolin-bentonite composites adsorbents (KBNPs) for the removal of fluoride from drinking water by adsorption compared with kaolin-bentonite composite (KB). Adsorbents with an average weight of ∼200 mg and ∼7 mm diameter (granules) were prepared in the ratio of 10 : 10 : 0.1 for kaolinite, bentonite, and magnetite nanoparticles, respectively. The granules were air-dried and calcined at 750°C and contacted with 2 mg/L sodium fluoride solution at varying time periods. The adsorbents were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) formulation, and Brunauer–Emmett–Teller (BET), whereas the adsorption mechanism and the kinetics were explained using the Langmuir isotherm, Freundlich models, and pseudo-first-order and pseudo-second-order models. The results showed that the BET surface areas for the granules were 10 m2/g and 3 m2/g for KBNPs and KB, respectively. The SEM images for the adsorbents before and after adsorption confirm the plate-like morphology of kaolin and bentonite. The FTIR analyses of bentonite (3550 cm−1–4000 cm−1) and kaolin (400–1200 cm−1) correspond to the structural hydroxyl groups and water molecules in the interlayer space of bentonites and the vibrational modes of SiO4 tetrahedron of kaolin, respectively. The KBNPs composites also recorded a fluoride removal efficiency of ∼91% after 120 minutes compared with 64% for KB composites without Fe3O4 nanoparticles. The adsorptions of fluoride by the KBNPs and KB granules were found to agree with the Freundlich isotherm and a pseudo-second-order kinetic model, respectively. The results clearly show that the impregnation of clays with magnetite nanoparticles has significant effect in the removal of fluoride, and the implication of the results has been discussed to show the impact of clay-magnetite nanoparticles composites in the removal of fluoride from contaminated water.

Modification and characterization of bentonite from location Bogovina, Serbia was performed in order to obtain material applicable in wastewater purification. The <75?m bentonite fraction was used in organobentonite synthesis while the <2?m bentonite fraction, obtained by hydroseparation was used in pillaring procedure. Organo-modification of bentonite was performed with (1-hexadecyl)trimethylammonium bromide (HDTMA-Br). Pillared bentonite was obtained using standard procedure. Al3+ and Fe3+ ions were incorporated in pillars in 4:1 ratio and applied as catalyst in catalytic wet peroxide oxidation. Differences in structure of starting and modified bentonites were established by XRD analysis and nitrogen physisorption on -196 ?C. The (001) smectite peak around 2? = 6? shifts during the modification process. The Na-exchange process lowered d001 from 1.53 nm (2? = 5.78?) for starting clay to 1.28 nm (2? = 6.92?), but the clay retained its swelling properties. The pillaring process increased and fixed the basal spacing to 1.74 nm. Intercalation of HDTMA ions into smectite structure increased d001 to 2.00 nm for organobentonite. Specific surface area, SBET, was affected by particle size and type of modification. The samples with finer bentonite fraction had higher SBET due to increased smectite content. Na-exchanged bentonite samples had higher SBET value than starting clay samples of same granulation. Organomodification caused dramatic decrease in SBET value, while the pillaring process lead to an increase of SBET value. Adsorptive and catalytic purification of wastewaters containing dyes was tested using Acid Yellow 99 as a model dye. Na-exchanged bentonite had greater adsorption affinity for dye adsorption than raw bentonite owing to higher SBET. By organomodification this affinity was enhanced more than 70 times due to transition of bentonite surface from hydrophilic to organophilic. Al,Fe pillared bentonite was proven to be efficient in catalytic wet peroxide oxidation of Acid Yellow 99 dye at room temperature.

In this work, enhanced chitosan/bentonite composite was prepared by treating chitosan/bentonite composite with concentrated hydrochloric acid (HCl). The adsorption of fluoride ions from aqueous solution onto the enhanced chitosan/bentonite composite was investigated. Adsorption studies were performed in a batch system, and the effects of various parameters, such as the pH value of the solution, adsorbent dosage and initial fluoride concentration, were evaluated. The optimum operating conditions for fluoride removal by the enhanced chitosan/bentonite composite were pH = 7 or so, and adsorbent dosage =1.2 g. Increasing initial fluoride concentration reduced the adsorption of fluoride onto the enhanced chitosan/bentonite composite. Furthermore, the presence of other co-anions weakened the adsorption of fluoride onto this adsorbent. The equilibrium adsorption isotherms were well described by both the Freundlich and Langmuir models. The maximum monolayer adsorption capacity was 2.95 mg/g at 293 K.

Bentonite is characterized by the large specific surface, good adsorption, ion exchange ability, and nontoxicity. An enhanced bentonite base composite flocculant (BTA) can be prepared from treating the calcium base bentonite and compositing various functional additives. Bentonite was firstly treated by citric acid, then the talc and activated carbon turned to be acid part and simultaneously the part that was treated by sodium bicarbonate and calcium hydroxide turned to be alkaline part, and finally the acid bentonite part and alkaline bentonite part were mixed up with preground powder of polymeric chloride aluminium (PAC), cationic polyacrylamide (CPAM), ferrous sulfate, and aluminum sulfate, and after all of the processing flocculant BTA was obtained. The optimum preparation process of flocculant BTA has shown 29.5% acid bentonite part, 29.5% alkaline bentonite part, 15% PAC, 1% CPAM, 5% ferrous sulfate, and 20% aluminum sulfate. BTA was used to treat drinking water with high turbidity and metal ion in Karamay City, Xinjiang. The treated water was surely up to the drinking water standard of China in decolorization rate, deodorization rate, heavy metal ion removal rate, and so forth, and contents of residual aluminum ions and acrylamide monomer in drinking water were considerably decreased.

In this paper, a peroxide-tertiary amine oxidation-reduction initiator system was used to synthesize a cross-linked polyacrylamide/bentonite composite at room temperature. The composite could contain up to 50% bentonite. Performance studies showed that the salt tolerance of the composite was enhanced compared to bentonite. The structure of the composite was characterized and analyzed by XRD, FTIR, and TG. Other than a slight increase in the interlamellar spacing, the structure of bentonite did not change during its aggregation. The composite therefore had enhanced dispersion properties and improved thermal stability.

A dense nonaqueous phase liquid, o-dichlorobenzene (o-DCB) was removed by surfactant-enhanced electrokinetic remediation from saturated bentonite clay. The surfactant was Antarox BL-236, a nonionic surfactant with a solubilization capacity of 0.052 g DCB/g surfactant. The 9 cm long bed, which initially contained 10 wt % bentonite and a dispersion of o-DCB (2910 or 5821 ppm) in water, was placed in a horizontal cylinder (5 cm ID) and held at each end by a supported filter paper. Carbon disk electrodes were located in compartments at each end of the bed. Surfactant solution or distilled water was fed to the anode compartment and effluent was withdrawn from the cathode compartment to maintain liquid levels. A constant direct current of 1.53 mA/cm2 of bed cross sectional area was applied. The current generated hydrogen ions at the anode, hydroxyl ions at the cathode, and an electroosmotic flow from the anode to the cathode. Stainless steel pin electrodes placed in the bed and pH electrodes inserted into the bed and the electrode compartments gave continuous measurements of voltage differences and pH changes. Experimental runs were 48 to 96 hours in duration.
To prevent cracking of the bed, which increased the energy requirements, the cathode compartment was flushed continuously with 0.01 M HNO3, a procedure called cathode rinse. An anode feed of 10 wt % surfactant solution removed six times more DCB in 4 days than distilled water. About 20% of the solubilization capacity of the surfactant was utilized at 2910 ppm initial DCB, increasing to 34% for 5820 ppm. DCB was detected in the effluent after about 1.5 pore volumes of liquid passed through the bed; thereafter the rate of DCB removal was approximately constant. The effects of surfactant concentration and NAPL concentration on DCB removal and the energy expenditure were determined.

In this study, Nano clay suspo-emulsions rheologically characterized for the application in enhanced oil recovery. The impact of Bentonite Nano clay particles on the rheological properties of paraffin oil-water emulsion prepared using CTAB (a cationic surfactant) and DOSS (anionic surfactant), commonly used in petroleum and industrial applications as emulsifiers were investigated.

Surface tension and Rheological measurements of the two surfactants were determined using concentrations ranging from 10⁻⁶ moles/liter to 10⁻¹moles/liter (concentrations above and below the critical micelle concentration).

The bulk rheological behavior of emulsions was characterized without and with the addition of Bentonite Nano clay particles through rheological measurements. The emulsions were tested with varying concentrations of CTAB and DOSS ranging from 10⁻⁶ moles/liter to 10 ⁻¹ moles/liter. These bulk rheology tests included shear rate sweeps and oscillatory tests to determine the viscosity, yield stress, critical stress, storage, and loss modulus. For these rheological tests, the oil-water ratio was varied ranging from 10% v/v to 90% v/v to determine how these results might differ in different emulsion systems. The rheological result for 10/90 % v/v emulsion, prepared with CTAB and DOSS (with and without the addition of Bentonite Nano clay particles) was analyzed. The addition of Bentonite Nano clay led to an increase in the storage and loss modulus of the emulsions.

Interfacial shear rheology tests were further carried out in two runs to determine the strength and mechanical properties of the film at the oil-water interface. By varying concentrations of CTAB and DOSS from 10⁻⁶ moles/liter to 10⁻¹moles/liter in the first run and adding Bentonite Nano clay in the second run, interfacial viscosity measured at four different temperatures and the interfacial storage modulus measured at room temperature was obtained. A zero-loss modulus was recorded for each run confirming that the oil-water interface is more elastic (solid-like).

Author´s name: Bc. Stanislav Klimek School: Brno University of Technology, Faculty of Mechanical Engineering, Energy institute Title: Determining the life storage of a carbon steel cask Consultant: Prof. Ing. Oldřich Matal, CSc. Number of pages: 70 Year: 2009 The assignment of this diploma thesis is to estimate the lifetime of spent fuel container made from carbon steel grade. This container is designed for deep geological disposal of spent nuclear fuel. Basic mechanism of corrosion are described in detail in the first part. Further on, this work deals with the other specific phenomena and influences, which affect at corrosion of steel in conditions of a deep geological repository. Heat, radiation and surroundings are considered of particular importance. In the following part an estimate of the lifetime of model container is introduced, which is affected by temperature and radiation. Here recommendations for protection of container are introduced, arising from the model calculation. Finally, the relevancy of incidence of particular parameters is evaluated, which affect the corrosion.

Deep geological repository (DGR) for disposal of high-level radioactive waste (HLW) is designed to rely on successive superimposed barrier systems to isolate the waste from the biosphere. This multiple barrier system comprises the natural geological barrier provided by the repository host rock and its surrounding and an engineered barrier system (EBS). The EBS represents the synthetic, engineered materials placed within the natural barrier, comprising array of components such as waste form, waste canisters, buffer materials, backfill and seals. The buffer will enclose the waste canisters from all directions and act as a barrier between canisters and host rock of the repository. It is designed to stabilise the evolving thermo-hydro-mechanical-chemical stresses in the repository over a long period (nearly 1000 years) to retard radionuclides from reaching biosphere. Bentonite clay or bentonite-sand mix have been chosen as buffer materials in EBS design in various countries pursuing deep geological repository method. The bentonite buffer is the most important barrier among the other EBS components for a geological repository. The safety of repository depends to a large extent on proper functioning of buffer over a very long period of time during which it must remain physically, chemically and mineralogically stable. The long term stability of bentonite buffer depends on varying temperature and evolution of groundwater composition of host rocks in a complex way. The groundwater in the vicinity of deep crystalline rock is often characterized by high solute concentrations and the geotechnical engineering response of bentonite buffer could be affected by the dissolved salt concentration of the inflowing ground water. Also during the initial period, radiogenic heat produced in waste canisters would radiate into buffer and the heat generated would lead to drying and some shrinkage of bentonite buffer close to canister. This could alter the dry density, moisture content and in turn the hydro-mechanical properties of bentonite buffer in DGR conditions. India has variety of bentonite deposits in North-Western states of Rajasthan and Gujarat. Previous studies on Indian bentonites suggest that bentonite from Barmer district of Rajasthan (termed as Barmer-1 bentonite) is suitable to serve as buffer material in DGR conditions. Nuclear power agencies of several countries have identified suitable bentonites for use as buffer in DGR through laboratory experiments and large scale underground testing facilities. Physico-chemical, mineralogical and engineering properties of Kunigel VI, Kyungju, GMZ, FoCa clay, MX-80, FEBEX and Avonseal bentonites have been extensively studied by Japan, South Korea, China, Belgium, Sweden, Spain, Canada. It is hence essential to examine the suitability of Barmer-1 bentonite as potential buffer in DGR and compare its physico-chemical and hydromechanical properties with bentonite buffers identified by other countries. The significant factors that impact the long-term stability of bentonite buffer in DGR include variations in moisture content, dry density and pore water chemistry. With a view to address these issues, the hydromechanical response of 70 % Barmer-1 bentonite + 30 % river sand mix (termed bentonite enhanced sand, BES specimens) under varying moisture content, dry density and pore water salt concentration conditions have been examined. The broad scope of the work includes: 1) Characterise the physico-chemical and hydro-mechanical properties of Barmer-1 bentonite from Rajasthan, India and compare its properties with bentonite buffers reported in literature. 2) Examine the influence of variations in dissolved salt concentration (of infiltrating solution), dry density and moisture content of compacted BES specimens on their hydro-mechanical response; the hydro-mechanical properties include, swell pressure, soil water characteristic curve (SWCC), unsaturated hydraulic conductivity, moisture diffusivity and unconfined compression strength. Organization of thesis: After the first introductory chapter, a detailed review of literature is performed to highlight the need for detailed characterisation of physico-chemical and hydromechanical properties of Barmer-1 bentonite for its possible application in DGR in the Indian context. Further, existing literature on hydro-mechanical response of bentonite buffer to changes in physical (degree of saturation/moisture content, dry density) and physico-chemical (solute concentration in pore water) is reviewed to define the scope and objectives of the present thesis in Chapter 2. Chapter 3 presents a detailed experimental programme of the study. Chapter 4 characterises Barmer-1 bentonite for physico-chemical (cation exchange capacity, pore water salinity, exchangeable sodium percentage) and hydro-mechanical properties, such as, swell pressure, saturated permeability, soil water characteristic curve (SWCC) and unconfined compression strength. The properties of Barmer-1 bentonite are compared with bentonite buffers reported in literature and generalized equations for determining swell pressure and saturated permeability coefficient of bentonite buffers are arrived at. Chapter 5 describes a method to determine solute concentrations in the inter-lamellar and free-solutions of compacted BES (bentonite enhanced sand) specimens. The solute concentrations in micro and macro pore solutions are used to examine the role of osmotic flow on swell pressures developed by compacted BES specimens (dry density 1.50-2.00 Mg/m3) inundated with distilled water and NaCl solutions (1000-5000 mg/L). The number of hydration layers developed by the compacted BES specimens on inundation with salt solutions in constant volume swell pressure tests is controlled by cation hydration/osmotic flow. The cation hydration of specimens compacted to dry density of 2.00 Mg/m3 is mainly driven by matric suction prevailing in the clay microtructure as the number of hydration layers developed at wetting equilibrium are independent of the total dissolved solids (TDS) of the wetting solution. Consequently, the swell pressures of specimens compacted to 2.00 Mg/m3 were insensitive to the salt concentration of the inundating solution. The cation hydration of specimens compacted to dry density of 1.50 Mg/m3 is driven by both matric suction (prevailing in the clay micro-structure) and osmotic flow as the number of hydration layers developed at wetting equilibrium is sensitive to the TDS of the wetting solution. Expectedly, the swell pressures of specimens compacted to 1.50 Mg/m3 responded to changes in salt concentration of the inundating solution. The 1.75 Mg/m3 specimens show behaviour that is intermediate to the 1.50 and 2.00 Mg/m3 series specimens. Chapter 6 examines the influence of initial degree of saturation on swell pressures developed by the compacted BES specimens (dry density range: 1.40- 2.00 Mg/m3) on wetting with distilled water from micro-structural considerations. The micro-structure of the bentonite specimens are examined in the compacted and wetted states by performing X-ray diffraction measurements. The initial degree of saturation is varied by adding requisite amount of distilled water to the oven-dried BES mix and compacting the moist mixes to the desired density. The montmorillonite fraction in the BES specimens is responsible for moisture absorption during compaction and development of swell pressure in the constant volume oedometer tests. Consequently, it was considered reasonable to calculate degree of saturation based on EMDD (effective montmorillonite dry density) values and correlate the developed swell pressure values with degree of saturation of montmorillonite voids (Sr,MF). XRD measurements with compacted and wetted specimens demonstrated that if specimens of density series developed similar number of hydration layers on wetting under constant volume condition they exhibited similar swell pressures, as was the case for specimens belonging to 1.40 and 1.50 Mg/m3 series. With specimens belonging to 1.75 and 2.00 Mg/m3 series, greater number of hydration layers were developed by specimens that were less saturated initially (smaller initial Sr,MF) and consequently such specimens developed larger swell pressures. When specimens developed similar number of hydration layers in the wetted state, the compaction dry density determined the swell pressure. Chapter 7 examines the influence of salt concentration of infiltrating solution (sodium chloride concentration ranges from 1000- 5000 mg/L) on SWCC relations, unsaturated permeability and moisture diffusivity of compacted BES specimens. Analysis of the experimental and Brooks and Corey best fit plots revealed that infiltration of sodium chloride solutions had progressively lesser influence on the micro-structure and consequently on the SWCC relations with increase in dry density of the compacted specimens. The micro-structure and SWCC relations of specimens compacted to 1.50 Mg/m3 were most affected, specimens compacted to 1.75 Mg/m3 were less affected, while specimens compacted to 2.00 Mg/m3 were unaffected by infiltration of sodium chloride solutions. Variations in dry density of compacted bentonite impacts the pore space available for moisture flow, while, salinity of wetting fluid impacts the pore structure from associated physico-chemical changes in clay structure. Experimental results showed that the unsaturated permeability coefficient is insensitive to variations in dry density and solute concentration of wetting liquid, while, the effective hydraulic diffusivity is impacted by variations in these parameters. Chapter 8 summarises the major findings of the study.

Increasing nitrate concentration in ground water from improper disposal of sewage and excessive use of fertilizers is deleterious to human health as ingestion of nitrate contaminated water can cause methaemoglobinemia in infants and possibly cancer in adults. The permissible limit for nitrate in potable water is 45 mg/L. Unacceptable levels of nitrate in groundwater is an important environmental issue as nearly 80 % of Indian rural population depends on groundwater as source of drinking water. Though numerous technologies such as reverse osmosis, ion exchange, electro-dialysis, permeable reactive barriers using zero-valent iron exists, nitrate removal from water using affordable, sustainable technology, continues to be a challenging issue as nitrate ion is not amenable to precipitation or removable by mineral adsorbents. Tapping the denitrification potential of soil denitrifiers which are inherently available in the soil matrix is a possible sustainable approach to remove nitrate from contaminated drinking water. Insitu denitrification is a useful process to remove NO3–N from water and wastewater. In biological denitrification, nitrate ions function as terminal electron acceptor instead of oxygen; the carbon source serve as electron donor and the energy generated in the redox process is utilized for microbial cell growth and maintenance. In this process, microorganisms first reduce nitrate to nitrite and then produce nitric oxide, nitrous oxide, and nitrogen gas. The pathway for nitrate reduction can be written as: NO3-→ NO2-→ NO → N2O → N2. (i) Insitu denitrification process occurring in soil environments that utilizes indigenous soil microbes is the chosen technique for nitrate removal from drinking water in this thesis. As presence of clay in soil promotes bacterial activity, bentonite clay was mixed with natural sand and this mix, referred as bentonite enhanced sand (BES) acted as the habitat for the denitrifying bacteria. Nitrate reduction experiments were carried out in batch studies using laboratory prepared nitrate contaminated water spiked with ethanol; the batch studies examined the mechanisms, kinetics and parameters influencing the heterotrophic denitrification process. Optimum conditions for effective nitrate removal by sand and bentonite enhanced sand (BES) were evaluated. Heterotrophic denitrification reactors were constructed with sand and BES as porous media and the efficiency of these reactors in removing nitrate from contaminated water was studied. Batch experiments were performed at 40°C with sand and bentonite enhanced sand specimens that were wetted with nutrient solution containing 22.6 mg of nitrate-nitrogen and ethanol to give C/N ratio of 3. The moist sand and BES specimens were incubated for periods ranging from 0 to 48 h. During nitrate reduction, nitrite ions were formed as intermediate by-product and were converted to gaseous nitrogen. There was little formation of ammonium ions in the soil–water extract during reduction of nitrate ions. Hence it was inferred that nitrate reduction occurred by denitrification than through dissimilatory nitrate reduction to ammonium (DNRA). The reduction in nitrate concentration with time was fitted into rate equations and was observed to follow first order kinetics with a rate constant of 0.118 h-1 at 40°C. Results of batch studies also showed that the first order rate constant for nitrate reduction decreased to 5.3x10-2 h-1 for sand and 4.3 x10-2 h-1 for bentonite-enhanced sand (BES) at 25°C. Changes in pH, redox potential and dissolved oxygen in the soil-solution extract served as indicators of nitrate reduction process. The nitrate reduction process was associated with increasing pH and decreasing redox potential. The oxygen depletion process followed first order kinetics with a rate constant of 0.26 h-1. From the first order rate equation of oxygen depletion process, the nitrate reduction lag time was computed to be 12.8 h for bentonite enhanced sand specimens. Ethanol added as an electron donor formed acetate ions as an intermediate by-product that converted to bicarbonate ions; one mole of nitrate reduction generated 1.93 moles of bicarbonate ions that increased the pH of the soil-solution extract. The alkaline pH of BES specimen (8.78) rendered it an ideal substrate for soil denitrification process. In addition, the ability of bentonite to stimulate respiration by maintaining adequate levels of pH for sustained bacterial growth and protected bacteria in its microsites against the effect of hypertonic osmotic pressures, promoting the rate of denitrification. Buffering capacity of bentonite was mainly due to high cation exchange capacity of the clay. The presence of small pores in BES specimens increased the water retention capacity that aided in quick onset of anaerobiosis within the soil microsites. The biochemical process of nitrate reduction was affected by physical parameters such as bentonite content, water content, and temperature and chemical parameters such as C/N ratio, initial nitrate concentration and presence of indigenous micro-organisms in contaminated water. The rate of nitrate reduction process progressively increased with bentonite content but the presence of bentonite retarded the conversion of nitrite ions to nitrogen gas, hence there was significant accumulation of nitrite ions with increase in bentonite content. The dependence of nitrate reduction process on water content was controlled by the degree of saturation of the soil specimens. The rate of nitrate reduction process increased with water content until the specimens were saturated. The threshold water content for nitrate reduction process for sand and bentonite enhanced sand specimens was observed to be 50 %. The rate of nitrate reduction linearly increased with C/N ratio till steady state was attained. The optimum C/N ratio was 3 for sand and bentonite enhanced sand specimens. The activation energy (Ea) for this biochemical reaction was 35.72 and 47.12 kJmol-1 for sand and BES specimen respectively. The temperature coefficient (Q10) is a measure of the rate of change of a biological or chemical system as a consequence of increasing the temperature by 10°C. The temperature coefficient of sand and BES specimen was 2.0 and 2.05 respectively in the 15–25°C range; the temperature coefficients of sand and BES specimens were 1.62 and 1.77 respectively in the 25–40°C range. The rate of nitrate reduction linearly decreased with increase in initial nitrate concentration. The biochemical process of nitrate reduction was unaffected by presence of co-ions and nutrients such as phosphorus but was influenced by presence of pathogenic bacteria. Since nitrate leaching from agricultural lands is the main source of nitrate contamination in ground water, batch experiments were performed to examine the role of vadose (unsaturated soil) zone in the nitrate mitigation by employing sand and BES specimens with varying degree of soil saturation and C/N ratio as controlling parameters. Batch studies with sand and BES specimens showed that the incubation period required to reduce nitrate concentrations below 45 mg/L (t45) strongly depends on degree of saturation when there is inadequate carbon source available to support denitrifying bacteria; once optimum C/N ratio is provided, the rate of denitrification becomes independent of degree of soil saturation. The theoretical lag time (lag time refers to the period that is required for denitrification to commence) for nitrate reduction for sand specimens at Sr= 81 and 90%, C/N ratio = 3 and temperature = 40ºC corresponded to 24.4 h and 23.1 h respectively. The lag time for BES specimens at Sr = 84 and 100%, C/N ratio = 3 and temperature = 40ºC corresponded to 13.9 h and 12.8 h respectively. Though the theoretically computed nitrate reduction lag time for BES specimens was nearly half of sand specimens, it was experimentally observed that nitrate reduction proceeds immediately without any lag phase in sand and BES specimens suggesting the simultaneous occurrence of anaerobic microsites in both. Denitrification soil columns (height = 5 cm and diameter = 8.2 cm) were constructed using sand and bentonite-enhanced sand as porous reactor media. The columns were permeated with nitrate spiked solutions (100 mg/L) and the outflow was monitored for various chemical parameters. The sand denitrification column (packing density of 1.3 Mg/m3) showed low nitrate removal efficiency because of low hydraulic residence time (1.32 h) and absence of carbon source. A modified sand denitrification column constructed with higher packing density (1.52 Mg/m3) and ethanol addition to the influent nitrate solution improved the reactor performance such that near complete nitrate removal was achieved after passage of 50 pore volumes. In comparison, the BES denitrification column achieved 87.3% nitrate removal after the passage of 28.9 pore volumes, corresponding to 86 h of operation of the BES reactor. This period represents the maturation period of bentonite enhanced sand bed containing 10 % bentonite content. Though nitrate reduction is favored by sand bed containing 10 % bentonite, the low flow rate (20-25 cm3/h) impedes its use for large scale removal of nitrate from drinking water. Hence new reactor was designed using lower bentonite content of 5 % that required maturation period of 9.6 h. The 5 and 10 % bentonite-enhanced sand reactors bed required shorter maturation period than sand reactor as presence of bentonite contributes to increase in hydraulic retention time of nitrate within the reactor. On continued operation of the BES reactors, reduction in flow rate from blocking of pores by microbial growth on soil particles and accumulation of gas molecules was observed that was resolved by backwashing the reactors.

Thermoplastics are widely used advanced materials in various fields as an essential product. The increasing interest in replacing thermosets due to their advanced properties such as high toughness, manufacturing time and processing possibilities. Thermoplastics exhibit poor mechanical properties in several engineering applications; hence the use of nano clay minerals enhances the mechanical property of thermoplastics to be used in many engineering applications. The reinforcing effect of clay minerals (nano-clay) in various thermoplastics such as polycarbonate (PC), polypropylene (PP), Acrylonitrile butadiene styrene (ABS) and high-density polyethylene (HDPE), which are popularly known as commodity plastics and are widely used in fabricating automotive parts and household articles. The frequently used clay minerals such as montmorillonite, bentonite, hectorite, halloysites and kaolinite as filler material in thermoplastics make them suitable in many engineering applications with enhanced mechanical properties. The integration of clay minerals into a polymer matrix allows both properties from clay minerals and polymer to be combined so as to exploit entirely new functionalities. In recent years, owing to a number of practical applications in the field of opto-electronics, a great deal of interest has been paid to study optical, dielectric and conduction behaviours of various polymeric materials. This chapter is designed to be a source for nano-clay reinforced thermoplastic nano-composite research including synthesis, characterization, structure/property relationship and applications considering optical and electrical conductivity which are discussed.

In recent years, the application of nanomaterial has been attracting the oil and gas industry. Nanomaterials research results show an improving performance of cement, drilling fluid and enhanced oil recovery. In this paper, the effect of multi-walled carbon nanotube (MWCNT) and MWCNT functionalized with ligands–OH and - COOH nanoparticles on laboratory drilling fluids formulated from bentonite, KCL, Carboxymethyl cellulose (CMC) and xanthan gum (XG) was studied. The formulations and tests were performed at room temperature. The results show that addition of 0.0095wt.% of MWCNT, MWCNT-OH and MWCNT-COOH nanoparticles in CMC/bentonite system decreases the filtrate-loss by 8.6 %, 7.1 % and 17.9 % respectively. These particles also decreased the coefficient of friction by 34 %, 37 % and 33 % respectively. In xanthan gum drilling fluid, 0.019wt%. MWCNT reduced the friction coefficient by 38 %.

Recently the application of nanomaterial is attracting the oil and gas industry. The preliminary nanomaterials research results show an improving performance of cement, drilling fluid and Enhanced Oil Recovery. In this paper, the effect of nano Silicon dioxide (SiO2) on polymer (HV-CMC, Xanthan gum, LV-CMC) and salt (KCl, NaCl) treated bentonite drilling fluid systems has been studied at room temperature. The results show that the performance of nano SiO2 in bentonite mud system depends on its concentration and the types of salt and polymer systems used. In the considered fluid systems, it is also observed that the addition of about 0.06% SiO2 influences rheology, and filtrate loss of the drilling fluid systems. The viscoelasticity of the selected best system further studied and their hole -cleaning and hydraulics performances are simulated. The overall result shows that the formulated optimum concentration of nano-system shows good performances and rheological behavior.

Abstract Chemical flooding is one of enhanced oil recovery (EOR) methods. The primary mechanism of EOR of chemical flooding is interfacial tension reduction, mobility ratio improvement and wettability changes. Recent studies showed that enhancing emulsification performance was beneficial to improve oil displacement efficiency. The formation of Pickering emulsion by nanoparticles could greatly improve the emulsifying performance. Using nanoparticles stabilized emulsions for chemical EOR application is a novel method. In this study, six different types of nanoparticles were selected, including hydrophilic nano silica, modified nano silica, carbon nanotubes and bentonite, etc. The nanoparticle combine with petroleum sulfonate could form a stable emulsion. Particle wettability were measured by using contact angle measurement (OCA20). Emulsifying intensity index was measured for different nanoparticle-stabilized emulsions. The mechanisms of nanoparticle-stabilized emulsions and relationship between emulsion stability have been investigated. The influence of dispersant on nanoparticle-stabilized emulsions also has been investigated. Nanoparticles mainly play a role in improving the stability of emulsions while surfactant play a major role in enhancing the emulsifying dispersion. The wettability of solid particles was one of the most important factors that affects the stability of emulsions. Partial hydrophobic nanoparticles were much easier to form stable emulsions than hydrophilic nanoparticles. Nanoparticles could form a three-dimensional network structure, thereby the stability of the emulsion was improved. Use of surfactant to disperse nanoparticles could further improve the emulsion stability. Finally, three nanoparticles stabilized emulsion formulations were developed for chemical flooding EOR. Nanoparticle-stabilized emulsions could improve oil displacement efficiency in chemical combination flooding. This research was used to optimize chemical combination flooding formulation and has a guidance function for application of nanoparticles in chemical flooding EOR.

Abstract In a deep gas drilling project, the 22-in section across shallow fractured carbonates is drilled using an unweighted clay-water system incorporating up to 50-lbm/bbl bentonite. The main challenges comprise lost circulation, tight hole, and low penetration rates due to high clay content and lack of inhibition, resulting in geological complications and affecting the well delivery time. To seal off the large fractures in the lower-cretaceous limestones, the new drilling fluid was engineered with high thixotropic characteristics presenting a flat, shear-thinning rheological profile with low plastic viscosity, high yield point and flat gel strengths. The selection of candidate wells was supported by offset wells analysis considering drilling performance, penetration rate and footage achieved, and the likelihood of encountering losses. Fine-tuning of the fluid rheology was performed to effectively account for the probability of losses on each well and a fit-for-purpose drilling fluid formulation was designed. This innovative technology combining mixed-metal oxide with premium bentonite was run in a series of wells as a substitute to the previously used system. Due to its superior viscosity at low shear rates the fluid successfully prevented losses by gelling up in the interstices of the highly fractured limestone intervals. In addition, the fluid delivered higher drilling performance across the abrasive sandstone-clay intercalations and the hard carbonates toward the bottom of the section. By maintaining full circulation all way through and therefore avoiding the expenses associated with blind drilling and pumping mud cap, the initiative resulted in considerably lowering the fluid cost in this section. Significant operation time savings were also achieved by drilling the section faster to the intended casing point in a minimum number of runs. Enhanced wellbore condition that allowed the drill string to trip out on elevators instead of back-reaming also contributed to saving rig time. The casing could be run to bottom and cemented trouble free in one stage with cement returns to surface thus precluding the cost of stage collar tool in most of the wells. This paper unveils the facets of this versatile water-base fluid that was introduced as a solution to prevent losses and address poor drilling performance.

Abstract Well-designed formulations of drilling fluids are required for drilling operations to improve rheological and filtration properties. The rheological properties and fluid loss during the drilling process are severely affected at the deep well with high temperature and pressure conditions. This study investigates the comparison of zirconia nanoparticles and conventionally used silica nanoparticles on rheological and filtration properties at temperatures ranging from 76°F to 122°F. Sodium-bentonite dispersion in deionized water was used as the base drilling fluid. Rheological properties were determined at different temperatures using a Discovery Hybrid rheometer with various concentrations of nanoparticles from 0.2 wt.% to 0.75 wt.% concentrations. Steady shear rheology experiments were performed to study drilling formulations’ shear stress, viscosity, and yield stress. Temperature ramp rheology tests at 76°F and 122°F were performed to analyze the effect of increasing temperature on viscosity. The filtration tests were conducted to study the fluid loss properties of drilling fluids at various concentrations of nanoparticles. Linear swelling analysis of clay in the presence of drilling muds was performed to study the shale inhibition properties of prepared drilling formulations. The incorporation of nanoparticles significantly enhanced the rheological properties such as yield stress and viscosity at various concentrations and temperatures. Rheological properties of zirconia muds compared with silica muds for various concentrations of nanoparticles. Temperature ramp rheology tests showed that zirconia muds have enhanced viscosity at 0.75 wt.% compared to the counterpart of silica mud. A decrease in fluid loss was observed for zirconia muds compared to the base mud while fluid loss increases with increasing concentration of silica nanoparticles. The incorporation of nanoparticles in the drilling fluids significantly reduced the swelling of clay compared to the swelling of clay in deionized water. This research supports the extensive interpretation of water-based drilling fluids using zirconia nanoparticles and a comparison of drilling properties with silica-based fluids for high-temperature applications. The potential use of zirconia nanoparticles in drilling fluid formulations provides the way forward for the improvement of fluid loss characteristics, shale inhibition, and rheological properties.

RWMC and JGC have been running an all-round R&D program for the period of 2000–2010 to develop the concept of Vertical Emplacement for disposal of vitrified waste. The conceptual design of its basic equipment was worked out in 2000, followed by forming the large-scale bentonite block in 2001–2004. Study has also been conducted on a mechanism to convey and position the large-scale block using a vacuum suction device. Subsequent to these developments, various technologies necessary for designing the Vertical Emplacement equipment have been reviewed, which would enhance engineering feasibility and reliability. Full-scale demonstration program under a joint research program with JAEA (Japan Atomic Energy Agency) started in 2008 with the twin objectives i) supporting of public relations and ii) technical verification. The large-scale bentonite block and part of the full-scale Vertical Emplacement equipment are now on view at the Full-scale demonstration facility in Horonobe, Hokkaido, Japan.