Pyrolysis of Canarium schweinfurthii hard-shell: Thermochemical characterisation and pyrolytic kinetics studies.

Canarium schweinfurthii fruit used in food and cosmetics produces waste nuts with a hard shell (hard-shell) and kernel. The hard-shell contained lignin and holocellulose, besides 51.99 wt% carbon, 6.0 wt% hydrogen, 41.68 wt% oxygen, and 70.97 wt% volatile matter. Therefore, this study commenced thermochemical investigations on the hard-shell through extensive intermediate pyrolysis and kinetic studies. During the active stage of thermogravimetric pyrolysis, the hard-shell lost a maximum of 56.45 wt%, and the activation energies obtained by the Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, and Starink methods were 223, 221 and 217 kJ/mol, respectively. The Flynn-Wall-Ozawa method depicted the degradation process accurately, where the Coat-Redfern method's contraction and diffusion mechanisms governed the pyrolysis reactions at activation energies of 16.62 kJ/mol and 38.83 kJ/mol, respectively. The pyrolysis process produced 25 wt% biochar and 25 wt% bio-oil under optimum conditions. The calorific values of the bio-oils with 6.81-7.11 wt% hydrogen and 68.01-71.12 wt% carbon was 26.32-27.83 MJ/kg, with phenolics and n-hexadecanoic and oleic acids as major compounds. Biochar, by contrast, has a high carbon content of 75.11-79.32 wt% and calorific values of 25.45-28.61 MJ/kg. These properties assert the biochar and bio-oils among viable bioenergy sources.

Effect of laser irradiated silver doped polystyrene/polyethylene terephthalate (PET) thin film for solar cell applications.

In the current research, the resist action of silver-doped polystyrene/polyethylene terephthalate (PET) solar thin film towards laser irradiation was observed. Moreover, silver-doped polystyrene nanoparticles were synthesized via a chemical technique while the PET film was purchased from the commercial market. Nd:YAG pulsed laser has been used to irradiate the samples at 2 minutes, 4 minutes, and 6 minutes respectively. The XRD (X-ray diffraction) pattern shows that silver-doped polystyrene peak at around angle θ = 26° tends to decrease after the bombardment of Nd:YAG pulsed laser. This indicates that the crystallinity of PET film decreased after laser irradiation. The Raman spectra have revealed the zwitter characteristics of silver-doped polystyrene are shifting of bands at 1380 cm-1 and 1560 cm-1 upon laser irradiation. For PET film, the Raman spectra showed that the exposed regions tend to change to cross-linking/chain-scissoring at 2 minutes and 4 minutes of irradiation. The surface roughness first increases and decreases upon irradiation. These results indicate that silver-doped polystyrene/polyethylene terephthalate (PET) thin film is appropriate for solar cell applications.

Effect of Sulfate-Based Scales on Calcite Mineral Surface Chemistry: Insights from Zeta-Potential Experiments and Their Implications on Wettability.

Scale formation and deposition in the subsurface and surface facilities have been recognized as a major cause of flow assurance issues in the oil and gas industry. Sulfate-based scales such as sulfates of calcium (anhydrite and gypsum) and barium (barite) are some of the commonly encountered scales during hydrocarbon production operations. Oilfield scales are a well-known flow assurance problem, which occurs mainly due to the mixing of incompatible brines. Researchers have largely focused on the rocks' petrophysical property modifications (permeability and porosity damage) caused by scale precipitation and deposition. Little or no attention has been paid to their influence on the surface charge and wettability of calcite minerals. Thus, this study investigates the effect of anhydrite and barite scales' presence on the calcite mineral surface charge and their propensity to alter the wetting state of calcite minerals. This was achieved vis-à-vis zeta-potential (ζ-potential) measurement. Furthermore, two modes of the scale control (slug and continuous injections) using ethylenediaminetetraacetic acid (EDTA) were examined to determine the optimal control strategy as well as the optimal inhibitor dosage. Results showed that the presence of anhydrite and barite scales in a calcite reservoir affects the colloidal stability of the system, thus posing a threat of precipitation, which would result in permeability and porosity damage. Also, the calcite mineral surface charge is affected by the presence of calcium and barium sulfate scales; however, the magnitude of change in the surface charge via ζ-potential measurement is insignificant to cause wettability alteration by the mineral scales. Slug and continuous injections of EDTA were implemented, with the optimal scale control strategy being the continuous injection of EDTA solutions. The optimal dosage of EDTA for anhydrite scale control is 5 and 1 wt % for the formation water and seawater environments, respectively. In the case of barite, in both environments, an EDTA dosage of 1 wt % suffices. Findings from this study not only further the understanding of the scale effects on calcite mineral systems but also provide critical insights into the potential of scale formation and their mechanisms of interactions for better injection planning and the development of a scale control strategy.

Effect of Native Reservoir State and Oilfield Operations on Clay Mineral Surface Chemistry.

An understanding of clay mineral surface chemistry is becoming critical as deeper levels of control of reservoir rock wettability via fluid-solid interactions are sought. Reservoir rock is composed of many minerals that contact the crude oil and control the wetting state of the rock. Clay minerals are one of the minerals present in reservoir rock, with a high surface area and cation exchange capacity. This is a first-of-its-kind study that presents zeta potential measurements and insights into the surface charge development process of clay minerals (chlorite, illite, kaolinite, and montmorillonite) in a native reservoir environment. Presented in this study as well is the effect of fluid salinity, composition, and oilfield operations on clay mineral surface charge development. Experimental results show that the surface charge of clay minerals is controlled by electrostatic and electrophilic interactions as well as the electrical double layer. Results from this study showed that clay minerals are negatively charged in formation brines as well as in deionized water, except in the case of chlorite, which is positively charged in formation water. In addition, a negative surface charge results from oilfield operations, except for operations at a high alkaline pH range of 10-13. Furthermore, a reduction in the concentrations of Na, Mg, Ca, and bicarbonate ions does not reverse the surface charge of the clay minerals; however, an increase in sulfate ion concentration does. Established in this study as well, is a good correlation between the zeta potential value of the clay minerals and contact angle, as an increase in fluid salinity results in a reduction of the negative charge magnitude and an increase in contact angle from 63 to 102 degree in the case of chlorite. Lastly, findings from this study provide vital information that would enhance the understanding of the role of clay minerals in the improvement of oil recovery.

Feature Ranking and Modeling of Mineral Effects on Reservoir Rock Surface Chemistry Using Smart Algorithms.

Reservoir rock minerals and their surface charge development have been the subject of several studies with a consensus reached on their contribution to the control of reservoir rock surface interactions. However, the question of what factors control the surface charge of minerals and to what extent do these factors affect the surface charge remains unanswered. Also, with several factors identified in our earlier studies, the question of the order of effect on the mineral surface charge was unclear. To quantify the mineral surface charge, zeta potential measurements and Deryaguin-Landau-Verwey-Overbeek (DLVO) theories, as well as surface complexation models, are used. However, these methods can only predict a single mineral surface charge and cannot approximate the reservoir rock surface. This is because the reservoir rock is composed of many minerals in varying proportions. To address these drawbacks, for the first time, we present the implementation of machine learning models to predict reservoir minerals' surface charge. Four different models namely the Adaptive Boosting Regressor, Random Forest Regressor, Support Vector Regressor, and the Gradient Boosting tree were implemented for this purpose with all the model predictions over 95% accuracy. Also, feature ranking of the factors that control the mineral surface charge was carried out with the most dominant factors being the mineral type, salt type, and pH of the environment. Findings reveal an opportunity for accurate prediction of reservoir rock surface charge given the enormous amount of data available.

Impact of Asphaltene Precipitation and Deposition on Wettability and Permeability.

Asphaltene precipitation and deposition have been a formation damage problem for decades, with the most devastating effects being wettability alteration and permeability impairment. To this effect, a critical look into the laboratory studies and models developed to quantify/predict permeability and wettability alterations are reviewed, stating their assumptions and limitations. For wettability alterations, the mechanism is predominantly surface adsorption, which is controlled by the asphaltene contacting minerals as they control the surface chemistry, charge, and electrochemical interactions. The most promising wettability alteration evaluation techniques are nuclear magnetic resonance, ζ potential, and the use of high-resolution microscopy. The integration of such techniques, which is still missing, would reinforce the understanding of asphaltene interaction with rock minerals (especially clays), which holds the key to developing a strategy for modeling wettability alteration. With regard to permeability impairment, surface deposition, pore plugging, and fine migration have been identified as the dominant mechanisms with several models reporting the simultaneous existence of multiple mechanisms. Existing experimental findings showed that asphaltene deposition is non-uniform due to mineral distribution which further complicates the modeling process. It also remains a challenge to separate changes due to adsorption (wettability changes) from those due to pore size reduction (permeability impairment).

A Surface Charge Approach to Investigating the Influence of Oil Contacting Clay Minerals on Wettability Alteration.

Reservoir rock wettability has been linked to the adsorption of crude fractions on the rock, with much attention often paid to the bulk mineralogy rather than contacting minerals. Crude oil is contacted by different minerals that contribute to rock wettability. The clay mineral effect on wettability alterations is examined using the mineral surface charge. Also, the pH change effect due to well operations was investigated. Clay mineral surface charge was examined using zeta potential computed from the particle electrophoretic mobility. Clay minerals considered in this study include kaolinite, montmorillonite, illite, and chlorite. Results reveal that the clay mineral charge development is controlled by adsorption of ionic species and double layer collapse. Also, clay mineral surface charge considered in this study shows that their surfaces become more conducive for the adsorption of hydrocarbon components due to the presence of salts. The salt effect is greater in the following order: NaHCO3 < Na2SO4 < NaCl < MgCl2 < CaCl2. Furthermore, different well operations induce pH environments that change the clay mineral surface charge. This change results in adsorption prone surfaces and with reservoir rock made up of different minerals, and the effect of contacting minerals is critical as shown in our findings. This is due to the contacting mineral control wettability rather than the bulk mineralogy.

Impact of Iron Minerals in Promoting Wettability Alterations in Reservoir Formations.

Asphaltene adsorption and deposition onto rock surfaces are predominantly the cause of wettability and permeability alterations which result in well productivity losses. These alterations can be induced by rock-fluid interactions which are affected by well operations such as acidizing, stimulation, gas injections, and so forth. Iron minerals are found abundantly in sandstone reservoir formations and pose a problem by precipitation and adsorption of polar crude components. This is due to rock-fluid interactions, which are dependent on reservoir pH; thus, this research work studied the surface charge development of pyrite, magnetite, and hematite. To ascertain conditions that will result in iron mineral precipitation and adsorption of asphaltene on iron mineral surfaces, zeta potential measurement was carried out. This is to determine the charge and colloidal stability of the iron mineral samples across wide pH values. Experimental results show that the charge development of iron minerals is controlled by mineral dissolution, the formation of complexes, adsorption of ions on the mineral surface, and the collapse of the double layer. The findings provide insights into the implications of iron mineral contacting crude oil in reservoir formations and how they contribute to wettability alterations due to different well operations.