Kinetics of thermal degradation of a Japanese oil sand

Thermal degradation characteristics of a Japanese oil sand at different heating rates (10, 20, and 30 °C/min), and 30 ml/min air flow rate have been investigated. The kinetic parameters have been calculated based on three stages of weight loss and/or the conversion of the sample. These include, stage 1 (SI): volatilization of moisture content and the light hydrocarbon (20–227 °C), stage 2 (SII): combustion of heavy hydrocarbon (227–527 °C), and stage 3 (SIII): oxidative decomposition of carbonaceous organic matter (502–877 °C). The results showed that the rate of change of the oil sand conversion with time $\left(\frac{d\alpha }{\mathit{dt}}\right)$ was affected by the heating rate. The time taken by the system to reach 0.99 conversion was observed as 85, 50, and 35 min at the heating rates of 10, 20, and 30 °C/min, respectively. The frequency factor, A, at SI was between 0.09 and 0.54 min^?1, while the activation energy, E_a, was 11.2–12.5 KJmol^?1 (the percentage weight loss, W_t, was 0–3.6 %w/w; and the conversion, α, was 0–0.2.). At SII, the values of A and E_a were 2.1–5.5 min^?1 and 17.6–19 KJmol^?1, respectively (W_t = 3.1–15.88 %w/w; α = 0.17–0.86.). The value of A at SIII was 5.5E11–1.1E13 min^?1, while E_a was 160–200 KJmol^?1 (W_t = 15.33–17.99 %w/w; and α = 0.84–0.99).     

Heat inactivation of Listeria innocua in broth and food products under non-isothermal conditions

The objective of this work was to study the effect of three linear temperature profiles (heating rates of 1.5, 1.8 and 2.6 °C/min, from 20 to 65 °C) on Listeria innocua inactivation in liquid medium. The inactivation was also analyzed in artificially contaminated parsley (heating rate of 1.8 °C/min) and throughout a frying process, using a pre-cooked frozen food as case study. Inactivation showed a sigmoidal behaviour and all data was fitted with a Gompertz-inspired model. Results demonstrated that, in liquid media, Listeria inactivation is influenced by the temperature profile used. As heating rate increases, the shoulder decreases and the tail effect disappears. If Listeria was in parsley, its heat resistance increased (for identical experimental conditions in broth). Besides model adequacy was proven in all studied situations, the heating rate affected parameters’ precision.     

Statistical optimization of biodiesel production from sunflower waste cooking oil using basic heterogeneous biocatalyst prepared from eggshells

A statistical design of experiments DOE was applied to investigate biodiesel fuel BDF production process from sunflower waste cooking oil SWCO using heterogeneous bio-catalyst produced from eggshells ES. It was based on 3 level D-optimal design involving as factors methanol:oil M:O molar ratio, catalyst concentration (wt%), reaction time (min) and mixing rate (rpm). Twenty runs were carried out. A predictive linear interaction model has been correlated finding out how significant the effects of these variables are in practice. LINGO software was used to find out the optimum values of the aforementioned variables for enhancing the process. According to the results obtained, the most dominant positive factor influencing the response variable (% BDF yield) was M:O molar ratio followed by catalyst concentration (wt%) and mixing rate in a decreasing order while the reaction time showed to have a negative effect on the yield. The maximum BDF yield (98.8% and 97.5%, predicted and experimental, respectively) was obtained at M:O 6:1 M ratio, catalyst concentration 3 wt%, reaction time 30 min, mixing rate 350 rpm and 60 °C. Also response surface methodology RSM has been applied to study the interactive effects of independent variables on BDF yield. It was found that, the interaction between M:O and catalyst concentration (wt%) has more significant effect than interaction between other variables. The activity of the produced bio-catalyst was comparable to that of chemical CaO and immobilized enzyme Novozym 435. All the physicochemical characteristics of the produced BDF using the prepared bio-catalyst and its blends with petro-diesel fuel PDF are completely acceptable and meet most of the required standard specifications.     

Non-thermal inactivation of Escherichia coli K12 in buffered peptone water using a pilot-plant scale supercritical carbon dioxide system with a gas–liquid porous metal contactor

This study evaluated the effectiveness of a supercritical carbon dioxide (SCCO₂) system, with a gas–liquid porous metal contactor, for reducing Escherichia coli K12 in diluted buffered peptone water. 0.1% (w/v) buffered peptone water inoculated with E. coli K12 was processed using the SCCO₂ system at CO₂ concentrations of 3.1–9.5 wt%, outlet temperatures of 34, 38, and 42 °C, a system pressure of 7.6 MPa, and a flow rate of 1 L/min. Increased CO₂ concentrations and temperatures significantly (P < 0.05) enhanced microbial reduction. A maximum reduction of 5.8-log was obtained at 8.2% CO₂ and 42 °C. To achieve a 5-log reduction of E. coli K12 in 0.1% buffered peptone water, minimum CO₂ concentrations of 9.5%, 5.5%, and 5.3% were needed at 34, 38, and 42 °C, respectively. Further reductions of cells were observed after storage for 7 days at 4 °C. But storage at 25 °C increased the number of viable cells to 8-log cfu/mL after 7 days. This study showed the potential of the pilot scale SCCO₂ system with a gas–liquid porous metal contactor for microbial inactivation in liquid food.     

A kinetic model for pyrolysis of petroleum residue under nonisothermal conditions

Kinetic study on pyrolysis of petroleum residue was carried out by an accurate Arrhenius type equation at heating rate of 0.5–30.0°C/min under nonisothermal conditions. The influence of some critical parameters including temperature, heating rate and activation energy on mass conversion was evaluated. The apparent activation energies for during the pyrolysis process were in the range of 198–361 kJ/mol at various mass conversions of 5–94%. The reaction temperature was introduced as the most important parameter for the improvement of mass conversion, compared to that of other parameters. The pyrolysis of petroleum residue was occurred in a broad temperature range, from 150–650°C, yielding 33 wt% unpyrolyzed residue. It also was found that an increase in heating rate has a minor impact in the process. Model predictions were compared with experimental data, which showed fully good agreement.     

Superheated steam reduction of deoxynivalenol in naturally contaminated wheat kernels

Contamination of wheat with the Fusarium mycotoxin deoxynivalenol (DON) is a concern to the ethanol industry as it is stable during most processing operations and will be concentrated in the spent grains, which are potentially a valuable feedstock. Superheated steam at four processing temperatures (110, 135, 160, and 185 °C), three steam velocities (0.65, 1.3, and 1.5 m/s), and processing times of 2–15 min were used to treat wheat kernels naturally contaminated with DON to find the best processing parameters for the reduction of DON. A commercial enzyme-linked immunosorbent assay (ELISA) kit was used to determine DON levels in the wheat samples. Samples became increasingly toasted, displaying a brown color with increasing processing temperatures and times, and became friable after processing at temperatures of 160 and 185 °C. Only samples processed at 185 °C and 1.3 m/s exhibited any starch gelatinization. Significant (P < 0.05) reductions in DON levels were seen at 160 and 185 °C but were not generally seen at 110 and 135 °C and the effect of velocity was not significant (P > 0.05). Reductions of up to 52% were achieved at 185 °C and 6 min processing time and were due only to thermal degradation and not to solubilization and extraction.     

Organic richness,kerogen types and maturity in the shales of the Dakhla and Duwi formations in Abu Tartur area,Western Desert,Egypt: Implication of Rock–Eval pyrolysis

The objective of this study is to assess the organic material for petroleum potential and characterize the relationships between organic material, thermal maturity, and the depositional environments. This is done using “14” samples from the shales of the Dakhla and Duwi formations in Abu Tartur area. The samples have been analyzed using the geochemical method of Rock–Eval pyrolysis. The analysis shows that the total organic carbon content lies between 0.56 and 1.96 wt%. It also shows that kerogen is a mixture of type II and III that is dominant, and is deposited in the shallow and restricted marine environment under prevailing reducing conditions. This type of kerogen is prone to oil and oil/gas production. The geochemical diagrams show that all the studied samples have good thermal maturation. The Dakhla and Duwi formations which have been divided into all zones are mature (have T_max over 435 °C), and have organic carbon content located at the oil window (T_max between 435 and 443 °C).     

Vipulanandan model for the rheological properties with ultimate shear stress of oil well cement modified with nanoclay

In this study, the effect of clay nanoparticles (NC) and temperature on the rheological properties with ultimate shear stress and weight loss of the oil well cement (class H) modified with NC was investigated. The NC content was varied between 0 and 1% by the weight of the cement. The total weight loss at 800 °C for the oil well cement decreased from 6.10% to 1.03%, a 83% reduction when the cement was mixed with 1% of NC. The results also showed that 1% of NC increased the rheological properties of the cement slurry. The NC modification increased the yield stress (τ_o) and plastic viscosity (PV) by 5%–65% and 3%–16% respectively based on the NC content and the temperature of the cement slurry. The shear thinning behavior of the cement slurry with and without NC has been quantified using the Vipulanandan rheological model and compared with the Herschel-Bulkley model. The Vipulanandan rheological model has a maximum shear stress limit were as the Herschel-Bulkley model did not have a limit on the maximum shear stress. Based on the Vipulanandan rheological model the maximum shear stress produced by the 0% and 1% of NC at the temperature of 25 °C were 102 Pa and 117 Pa respectively hence an increase of 15% in the ultimate shear stress due to the addition of NC. The addition of 1% of NC increased the compressive strength of the cement by 12% and 43% after 1 day and 28 days of curing respectively. The modulus of elasticity of the cement increased with the additional of 1% NC by 6% and 76% after 1 day and 28 days of curing respectively. Effects of NC content and the temperature on the model parameters have been quantified using a nonlinear model (NLM). The NLM quantified the effect of NC treatment on all the model parameters.     

Enhancing the performance of blown asphalt binder using waste EVA copolymer (WEVA)

Air blowing of asphalt generally decreases the penetration value of asphalt binder so that asphalt becomes more brittle and more susceptible to crack during thermal cycling. The aim of this study is to improve the elasticity of blown asphalt upon blending with 3%, 5%, and 7% by weight of thermoplastic waste EVA copolymer (WEVA). Physico-chemical characteristics of blended samples like (FTIR and TGA) were discussed. In addition, the physical properties including penetration test, softening point, ductility test, and elastic recovery were studied. The chemical constituents of asphalt binder including oils, resins, and asphaltenes fractions were investigated using solvent extraction technique. Also, the flow properties of dynamic viscometer at different shear rate were also measured. Moreover, the mechanical properties including storage modulus, tan δ, and stress relaxation were analyzed with dynamic mechanical analyzer at temperature range (20 °C–80 °C). The sample blended with 5%WEVA demonstrated an enhancement in storage modulus and elastic recovery and decrease in tan δ. Finally the prepared blends were applied on carbon steel panel, the paints showed an improvement in properties such as flexibility, hardness and drying times with good adhesion. The overall results approved that blending with 5 wt% (WEVA) improve the performance of blown asphalt binder.     

Characterization of biosurfactants produced by novel strains of Ochrobactrum anthropi HM-1 and Citrobacter freundii HM-2 from used engine oil-contaminated soil

Microbial surfactants are widely used for industrial, agricultural, food, cosmetics, pharmaceutical, and medical applications. In this study, two bacterial strains namely, Ochrobactrum anthropi HM-1 and Citrobacter freundii HM-2, previously isolated from used engine oil contaminated soil, and capable of producing biosurfactants, were used. Their cell-free culture broth showed positive results toward five screening tests (hemolysis in blood agar, drop collapse, oil displacement, emulsification activity (E₂₄), and surface tension (ST) reduction). They reduced the ST of growth medium (70 ± 0.9) to 30.8 ± 0.6 and 32.5 ± 1.3 mN/m, respectively. The biosurfactants were classified as anionic biomolecules. Based on TLC pattern and FT-IR analysis, they were designated as glycolipids (rhamnolipid). Waste frying oil was feasibly used as a cheap and dominant carbon source for biosurfactants production; 4.9 and 4.1 g/l were obtained after 96 h of incubation, respectively. Compared with non-irradiated cells, gamma-irradiated cells (1.5 kGy) revealed enhanced biosurfactant production by 56 and 49% for HM-1 and HM-2, respectively. The biosurfactants showed good stability after exposure to extreme conditions [temperatures (50–100 °C for 30 min), pH (2–12) and salinity (2–10% NaCl)], they retained 83 and 79.3% of their E₂₄, respectively, after incubation for a month, under extreme conditions. Biosurfactants effectively recovered up to 70 and 67% of the residual oil, respectively, from oil-saturated sand pack columns. These biosurfactants are an interesting biotechnological product for many environmental and industrial applications.     

Decontamination of fresh produce by the use of slightly acidic hypochlorous water following pretreatment with sucrose fatty acid ester under microbubble generation

Treatment by slightly acidic hypochlorous water (SAHW) in combination of pretreatment with sucrose fatty acid ester under microbubble generation was effective for decontamination of lettuce. Sufficient contact time of SAHW containing 30 mg/L of available chlorine on reduction of viable counts of lettuce was determined to be 5 min. For 5 min at 18–20 °C, treatment with 30 mg/L of available chlorine in SAHW appeared more effective in the reduction of bacteria on lettuce compared with 15 mg/L. The treatment of lettuce at 50 °C with SAHW at 30 mg/L of available chlorine showed a 2 log reduction of bacterial counts without injury in the tissue. The treatment at 50 °C, SAHW also delayed browning on cut lettuce for the first 5–6 days of subsequent storage at 6 °C. Among two sucrose fatty acid esters tested, sucrose monopalmitate at 100 mg/L had a higher efficacy for pretreatment under microbubble generation. After pretreatment for 5 min with 100 mg/L sucrose monopalmitate under microbubble generation and subsequent treatment with SAHW at 50 °C for 5 min, viable counts of lettuce were decreased by about 3–4 logs. After the same treatment, Pseudomonas sp. predominant on lettuce decreased drastically. These results indicate the effectiveness of the combined treatments of sucrose fatty acid ester under microbubble generation and SAHW at 50 °C for decontamination of fresh produce.     

Direct conversion of natural gas into COx-free hydrogen and MWCNTs over commercial Ni–Mo/Al2O3 catalyst: Effect of reaction parameters

A commercial hydrotreating nickel molybdate/alumina catalyst was used for the direct conversion of natural gas (NG) into CO_x-free hydrogen and a co-valuable product of multi-walled carbon nanotubes (MWCNTs). The catalytic runs were carried out atmospherically in a fixed-bed flow reactor. The effect of reaction temperature between 600 and 800 °C, and dilution of the NG feed with nitrogen as well as pretreatment of the catalyst with hydrogen were investigated. At a reaction temperature of 700 °C and dilution ratio of NG/N₂ = 20/30, the optimum yield of H₂ (～80%) was obtained with higher longevity. However, using the feed ratio of NG/N₂ = 30/20, the optimum yield of MWCNTs was obtained (669%). X-ray diffraction pattern for the catalyst after the reaction showed that the MWCNTs were grown on the catalyst at all reaction temperatures under study. TEM pictures revealed that the as-grown MWCNTs at 600, 650 and 800 °C are short and long with a low graphitization degree. At 700 °C a forest of condensed CNTs is formed, whereas both carbon nanofibers and CNTs were formed at 750 °C.     

NIR spectroscopy: A non-destructive fast technique to verify heat treatment of fish-meat gel

Attempts have been made to assess previous heat treatment of fish-meat gels prepared from walleye pollack and horse mackerel surimi, since surimi-based products have been gaining popularity for their protein quality, law fat content and convenience in consumption. Visible–NIR spectra of gels (30–90 °C) were collected from 650 to 1100 nm with a surface interactance fibre optic accessory. Partial least squares (PLS) and multiple linear regression (MLR) techniques were employed for data analysis. Spectral changes upon heat treatment were related to the heating temperature which reflected the changes in the environment of the secondary structure due to the denaturation of proteins, and to changes in the state of water. A promising linear relationship (R = 0.98) was observed between NIR-predicted temperatures and the actual heating temperatures with prediction error of 1.85 °C.     

Sensory quality and food safety of boneless chicken breast portions thawed rapidly by submersion in hot water

Boneless chicken breast portions were thawed by submersion in hot water (60 °C) and compared to refrigerator thawing. Thawing in hot water was significantly quicker (2–8.5 min) than refrigerator thawing (10–15.5 h). Thawing time in hot water increased with an increase in meat thickness. Sensory panelists could not distinguish a difference between hot water versus refrigerator thawed and subsequently grilled chicken breast portions. A model for Salmonella growth predicts that thawing chicken breast at the slowest rate in this study (0.5 °C/min) would result in a lower increase in the Salmonella concentration than that expected for room temperature storage for 4 h.     

Upgrading of coker distillate under variable hydrotreating operating conditions

Studies on hydrotreating coker distillates, produced from a delayed coker unit were done using a commercially available CoMo/γ-Al₂O₃ catalyst, on which 0.2 wt% P₂O₅ was added in order to improve its characteristics. The experimental studies were conducted in a fixed-bed continuous-reactor (cata-test unit) at temperatures (300–400 °C) and total hydrogen pressure (40–65 bar). These conditions have affected the feedstock characteristics and great reduction of sulfur, aromatics and boiling ranges. Other improvements were obtained in diesel index (DI) due to hydrogenation reaction of aromatics and desulfurization of its sulfur contents.     

Catalytic performance of dealuminated H–Y zeolite supported bimetallic nanocatalysts in Hydroizomerization of n-hexane and n-heptane

A series of dealuminated Y-zeolites impregnated by 0.5 wt% Pt catalysts promoted by different amounts of Ni, Pd or Cr (0.3 and 0.6 wt%) were prepared and characterized as hydrocracking catalysts. The physicochemical and structural characterization of the solid catalysts were investigated and reported through N₂ physisorption, XRD, TGA-DSC, FT-IR and TEM techniques. Solid catalysts surface acidities were investigated through FT-IR spectroscopy aided by pyridine adsorption. The solid catalytic activities were evaluated through hydroconversion of n-hexane and n-heptane employing micro-catalytic pulse technique directly connected to a gas chromatograph analyzer. The thermal stability of the solids was also investigated up to 800 °C. Crystallinity studies using the XRD technique of all modified samples proved analogous to the parent Y-zeolite, exhibiting nearly an amorphous and microcrystalline character of the second metal oxides. Disclosure of bimetallic catalysts crystalline characterization, through XRD, was not viable. The nitrogen adsorption–desorption isotherms for all samples concluded type I adsorption isotherms, without any hysteresis loop, indicating that the entire pore system is composed of micropores. TEM micrographs of the solid catalysts demonstrate well-dispersed Pt, Ni and Cr nanoparticles having sizes of 2–4 nm and 7–8 nm, respectively. The catalytic activity results indicate that the bimetallic (0.5Pt–0.3Cr)/D18H–Y catalyst is the most active towards n-hexane and n-heptane isomerization while (0.5Pt–0.6Ni)/D18H–Y catalyst can be designed as most suitable as a cracking catalyst.     

Catalytic para-xylene maximization. Part X: Toluene disproportionation on HF promoted H-ZSM-5 catalysts

H-ZSM-5 zeolite catalysts were doped with 2%, 3% and 4%HF to be used for investigating their activities and selectivities for xylenes production and for para-xylene maximization at temperatures of 300–500 °C via toluene disproportionation. This doping caused pore size modification of the H-ZSM-5 catalyst. The reaction was carried out in a fixed bed flow type reactor. The ratio of produced para-xylene relative to its thermodynamic composition reached as high as 3.29 at 300 °C on the 4%HF doped H-ZSM-5 catalyst although this catalyst possessed the lowest amount of the largest pores (3.0–5.7 nm) and the smallest pores (0.4–1.7 nm). The overall activities of the catalysts were decreased with an increase in HF doping because of diffusion restriction. The kinetics of the reaction were simply treated and found to give E_a and ΔS¹ values compatible with the characterization data of the catalysts.     

Investigation of directly suspended droplet micro extraction method for extraction of trihalomethane and halomethane in water samples

Simple and efficient directly suspended droplet micro extraction (DSDME) in conjunction with gas chromatography-electron capture detector (GC-ECD) has been developed for extraction and determination of Halomethane and Trihalomethane from water samples. In this technique a micro drop of n-hexane is delivered to the surface of an aqueous sample while being agitated by a stirring bar in the bulk of solution. Factors relevant to the extraction efficiency were studied and optimized. The optimized extraction conditions were extraction solvent: n- hexane; NaCl concentration: 1 M; solvent extraction volume: 50 μL; stirring rate: 720 rpm and the extraction time: 5 min. The detection limits of the method were in the range of 0.059–0.137 µg L^?1, relative standard deviation (n = 3) range were 0.019–0.048%. A good linearity (r² ≥ 0.997) and a relatively broad dynamic linear range (10–200 µg L^?1) were obtained and recoveries of method were in the range of 97.69–99.51%. Finally, the proposed method was successfully utilized for pre concentration and determination of halo methane in different real samples. Successfully DSDME technique combined with capillary GC-ECD for the analysis of THMs and HMs in the water investigated samples.     

Different outlet for preparing nano-TiO2 catalysts for the photodegradation of Black B dye in water

Two nano-titania catalysts were prepared using two economically varying titanium precursors: titanium tetrachloride (A) and titanium isopropoxide (B). The catalysts were calcined at temperatures of 500 °C, 600 °C and 700 °C and characterized using X-ray diffraction (XRD), electron diffraction (ED), BET surface properties and high resolution transmission microscopy (HRTEM). The calcined catalysts were found to differ markedly in their physical characters and TiO₂ phases produced as well as their photocatalytic activities. The anatase titania phase diminished from 100% to 83% in TiO₂A but from 64% to zero in TiO₂B via temperature increase from 500 °C to 700 °C, due to transforming anatase to rutile. The brookite TiO₂ phase only appeared (17%) in catalyst B500. In general, the catalyst of choice is A600 by virtue of many compositional, economical and catalytic advantages.     

Effect of organic acids,hydrogen peroxide and mild heat on inactivation of Escherichia coli O157:H7 on baby spinach

Minimally processed baby spinach contaminated with Escherichia coli O157:H7 has been associated with multiple outbreaks of foodborne illnesses recently. Chlorinated water is widely used to wash vegetables commercially, but this washing procedure has limited efficacy and can lead to the formation of carcinogenic substances. This study was conducted to determine the effects of organic acids and hydrogen peroxide alone and in binary combinations with or without mild heat (40 and 50 °C) on the inactivation of Escherichia coli O157:H7 on baby spinach. Baby spinach leaves were dip-inoculated with E. coli O157:H7 to a level of 6 log CFU/g and stored at 4 °C for 24 h before treatment. Individual washing solutions (1% and 2% lactic acid [LA], citric acid [CA], malic acid [MA], tartaric acid [TA], acetic acid [AA], hydrogen peroxide [H₂O₂] as well as binary combinations of LA, CA, MA and H₂O₂ at final concentrations of 1% were used to decontaminate spinach leaves at 22, 40 or 50 °C for 2–5 min to test their efficacy in reducing E. coli O157:H7. Chlorinated water (200 ppm free chlorine) decreased the population of E. coli O157:H7 on baby spinach by only 1.2–1.6 log CFU/g, which was not significantly different from DI water washing. Washing with 1% LA at 40 °C for 5 min was the most effective treatment achieving a 2.7 log reduction of E. coli O157:H7 which is significantly higher than chlorine washing. Washing with LA + CA or LA + HP at 40 °C for 5 min was equally effective against E. coli O157:H7, resulting in a 2.7 log reduction of E. coli O157:H7. The application of mild heat significantly enhanced the efficacy of washing solutions on the inactivation of E. coli O157:H7. There was, however, no significant difference between treatments at 40 °C for 5 min and 50 °C for 2 min. The results suggested that the use of organic acids in combination with mild heat can be a potential intervention to control E. coli O157:H7 on spinach.