Detection of the Adulteration of Motor Oil by Laser Induced Fluorescence Spectroscopy and Chemometric Techniques.

Petroleum products are the target of fraudulent practices due to their high commercial value. The aim of this study is to provide a new analysis system to assess motor oil adulteration. For this purpose, Laser Induced Fluorescence (LIF) spectroscopy was exploited coupled with chemometric tools to detect motor oil adulteration by three types of cheap motor oils. Principal Component Analysis (PCA) was able to distinguish samples in three groups according to the type of adulterant. Besides, Partial Least Squares Regression (PLSR) was exploited to determine the percentage of adulteration. The best model was obtained with a regression coefficient of 0.96, Root Mean Square Error of Prediction (RMSEP) of 2.83, Standard Error of Prediction (SEP) of 2.83 and Bias of 0.40. The main results of this work provide new analysis system using the combination of LIF spectroscopy combined to PCA and PLS as an efficient and fast method for motor oil analysis.

A Reaction-Based Optical Fingerprinting Strategy for the Recognition of Fat-Soluble Samples: Discrimination of Motor Oils.

Optical "fingerprints" are widely used for chemometrics-assisted recognition of samples of different types. An emerging trend in this area is the transition from obtaining "static" spectral data to reactions analyzed over time. Indicator reactions are usually carried out in aqueous solutions; in this study, we developed reactions that proceed in an organic solvent, thereby making it possible to recognize fat-soluble samples. In this capacity, we used 5W40, 10W40, and 5W30 motor oils from four manufacturers, with six samples in total. The procedure involved mixing a dye, sample, and reagents (HNO3, HCl, or tert-butyl hydroperoxide) in an ethanolic solution in a 96-well plate and measuring absorbance or near-infrared fluorescence intensity every several minutes for 20-55 min. The obtained photographic images were processed by linear discriminant analysis (LDA) and the k-nearest neighbors algorithm (kNN). Discrimination accuracy was evaluated by a validation procedure. A reaction of oxidation of a dye by nitric acid allowed us to recognize all six samples with 100% accuracy for LDA. Merging of data from the four reactions that did not provide complete discrimination ensured an accuracy of 93% for kNN. The newly developed indicator systems have good prospects for the discrimination of other fat-soluble samples. Overall, the results confirm the viability of the kinetics-based discrimination strategy.

High-pressure injection injury of the hand: Clinical usefulness of ultrasound as an early diagnostic tool.

High-pressure injection injuries of the hand are uncommon accidents with potentially catastrophic complications. We present a case of a 49-years-old male with a high-pressure injection of motor oil in his left hand. Ultrasound accurately demonstrated soft tissue infiltration and late complications, playing a fundamental role in the treatment choice.

A Green Approach to Oil Spill Mitigation: New Hybrid Materials for Wastewater Treatment.

This study focuses on the development of adsorptive materials to retain degraded 5w40 motor oil. The materials were prepared using xanthan (XG) and XG esterified with acrylic acid (XGAC) as the polymeric matrix. LignoBoost lignin (LB), LB esterified with oleic (LBOL), stearic acid (LBST) and montmorillonite (CL) were added into XG and XGAC matrices to obtain the adsorbents. Adsorption experiments revealed that XG/CL/LBOL had the highest adsorption capacity at 46.80 g/g, followed by XGAC/CL at 45.73 g/g, and XG/CL at 37.58 g/g. The kinetic studies, employing the pseudo-second-order (PSO) model, indicated rapid sorption rates with a good correlation to experimental data. FTIR spectra analysis have evidenced the physical nature of adsorption process, involving interactions such as hydrogen bonding, van der Waals forces, and π-π interactions. Equilibrium data fitting to the Henry, Freundlich, and Temkin isotherm models showed that the adsorption occurs within materials diverse pore structures, enhancing oil retention. Structural parameters like density, porosity, and surface area were pivotal, with XG/CL/LBOL showing the most favorable properties for high oil adsorption. Additionally, it was found that the adsorption efficiency was influenced by the material's morphology and the presence of chemical modifications. This comprehensive evaluation highlights the potential of these novel adsorptive materials for environmental remediation applications, offering an efficient and sustainable approach to reducing degraded motor oil pollution.

Optimization and screening of process parameters for the robust co-pyrolytic study of waste motor oil and rice stubble toward sustainable waste-to-fuel generation.

The current study explores the co-pyrolysis of waste motor oil (WMO) and rice stubble in a designed lab-scale pyrolyzer to produce alternative energy fuels. The parameter screening was followed by optimization utilizing the Box-Behnken design (BBD). Reactor temperature (TR), mixing ratio (M), and holding time (t) affected the co-pyro-oil yield substantially. A maximum co-pyro-oil yield of 90.3% was achieved at a TR = 485 °C, t = 12.5 min, and M = 5% rice stubble to waste motor oil, which was further characterized and compared with the commercial diesel fuel properties. The highest research octane number of 76.15 was obtained for the co-pyro-oil (Co-PO), followed by the pyro-oil generated from only waste motor oil (POWMO). Consequently, the paraffin content increased to 64.34 wt% from 27.66 wt % for PO RS. The carbon number varied from C7-C17 for PO WMO and Co-Po, aligning with the diesel fuel requirements. Furthermore, a substantial enrichment in the physio-chemical properties of the produced Co-PO with reduced moisture content and enhancement in higher heating value (HHV) was also noticed. Hence, the generated Co-PO could be utilized as transport-grade fuel.

Composition and source identification of deposits forming in landfill gas (LFG) engines and effect of activated carbon treatment on deposit composition.

Compositions of deposits forming on engines parts operated with landfill gas (LFG) were analyzed. The deposit compositions were compared before and after the installation of activated carbon system for treatment of LFG. Deposits forming on the spark plugs had significantly higher levels of calcium, chromium, and nickel in comparison to those forming on the engine heads. The LFG contained about 9.5 ± 0.4 mg/m(3) total siloxanes, majority of which were octamethylcyclotetrasiloxane (D4) (5.0 ± 0.2 mg/m(3)), decamethylcyclopentasiloxane (D5) (2.9 ± 0.1 mg/m(3)) and hexamethyldisiloxane (L2) (1.6 ± 0.1 mg/m(3)). The samples collected from the engine heads before the activated carbon treatment of LFG had significantly high levels of silicon (149,400 ± 89,900 mg/kg) as well as calcium (70,840 ± 17,750 mg/kg), sulfur (42,500 ± 11,500 mg/kg), and zinc (22,300 ± 7200 mg/kg). After the activated carbon treatment, silicon levels decreased significantly; however, deposits had higher sulfur content (104,560 ± 68,100 mg/kg) indicating that the activated carbon released some sulfur during treatment. The analyses indicate that zinc and calcium originated from the additives in the lube oil while lead, aluminum, copper, nickel, iron, chromium were due to the engine wear.

Influence of bioaugmentation in crude oil contaminated soil by Pseudomonas species on the removal of total petroleum hydrocarbon.

This study aimed to carry out the bioaugmentation of crude oil/motor oil contaminated soil. The mixture of novel strains Pseudomonas aeruginosa PP3 and Pseudomonas aeruginosa PP4 were used in this bioaugmentation studies. The four different bioaugmentation systems (BS 1-4) were carried out in this experiment labelled as BS 1 (Crude oil contaminated soil), BS 2 (BS 1 + bacterial consortia), BS 3 (Motor oil sludge contaminated soil), and BS 4 (BS 3 + bacterial consortia). The total petroleum hydrocarbon (TPH) was investigated for monitor the effectiveness of bioaugmentation process. The highest TPH removal rate was recorded on BS 4 (9091 mg Kg -1) was about 67% followed by 52% on BS 2 (8584 mg Kg -1) respectively. The percentage of biodegradation efficiency (BE) of residual crude and motor oil contaminated soil were evaluated by GCMS analysis and the results showed that 65% (BS 2) and 83% (BS 4) respectively. Further the bioaugmented soil was subjected to the plant cultivation (Lablab purpureus) and the results revealed that the L. purpureus was rapidly grown in the systems BS 4 and BS 2 than the system BS 1 and BS 2 which was due to the lesser biodegradation of the crude oil contents. In resultant, it can be concluded that the soil was suitable for the cultivation of plant. Overall, this study revealed that the selected bacterial consortia were effectively degraded the hydrocarbon and act as a potential bioremediator in the hydrocarbon polluted soil in a short period.

Effects of terminal electron acceptors on the biodegradation of waste motor oil using Chlorella vulgaris-Rhodococcus erythropolis consortia: Kinetic and thermodynamic windows of opportunity analysis.

The Chlorella vulgaris-Rhodococcus erythropolis consortia was constructed for the biodegradation of waste motor oil (WMO), combined with thermodynamic calculations and stoichiometric analyses. The microalgae-bacteria consortium was constructed as C. vulgaris: R. erythropolis = 1:1 (biomass, cell/mL), pH = 7, 3 g/L WMO. Under the same condition, the terminal electron acceptors (TEAs) play a crucial role in the WMO biodegradation, which follows Fe3+ >SO42- > none. The biodegradation of WMO fitted well with the first-order kinetic model under experimental temperatures with different TEAs (R2 >0.98). The WMO biodegradation efficiency reached 99.2 % and 97.1 % with Fe3+ and SO42-as TEAs at 37 °C, respectively. Thermodynamic methanogenesis opportunity windows with Fe3+ as TEA are 2.72 times fold as large as those with SO42-. Microorganism metabolism equations demonstrated the viability of anabolism and catabolism on WMO. This work lays the groundwork for the implementation of WMO wastewater bioremediation and supports research into the biochemical process of WMO biotransformation.

Kinetic study of the catalytic cracking of waste motor oil using biomass-derived heterogeneous catalysts.

Herein, biochar from biomass residues is demonstrated as active materials for the catalytic cracking of waste motor oil into diesel-like fuels. Above all, alkali-treated rice husk biochar showed great activity with a 250% increase in the kinetic constant compared to the thermal cracking. It also showed better activity than synthetic materials, as previously reported. Moreover, much lower activation energy (185.77to293.48kJmol) for the cracking process was also obtained. According to materials characterization, the catalytic activity was more related to the nature of the biochar's surface than its specific surface area. Finally, liquid products complied with all the physical properties defined by international standards for diesel-like fuels, with the presence of hydrocarbons chains between C10-C27 similar to the ones obtained in commercial diesel.

Pyrolytic oil blended gasoline as future fuel: pyrolysis mechanism, fuel properties, and composition analysis.

In this investigation, waste motor oil (WMO) was pyrolyzed at 550 °C which yielded about 76.73 wt.% of pyrolytic oil (PO). To study the effect of blending with gasoline on the fuel properties and composition, the PO was blended at 5-30% with an augmentation of 5% by volume. The respective fuel properties of all the blends were determined and compared with gasoline. The prime blending percentage of WMO pyrolytic oil (WMOPO) was established based on the gross calorific value obtained. Among all the blends, 5% blending PO (B5) ensued the highest calorific value about 45.63 MJ kg-1 which was adjacent to gasoline. The B5 oil was also having an analogous density as gasoline. The composition analysis visualized that B5 comprised of alkenes (1.25%), cycloalkanes (3.88%), cycloalkenes (2.43%), aromatics (25.38%), and alkanes (53.75%). The results also confirmed the occurrence of 50.52% of C4-C12 compounds. Since the fuel properties and composition of the B5 oil were comparable to the untainted gasoline, it can be a suitable proportion to consider as future fuel if the engine performance and emission analysis show any positive effects.

Waste surgical masks to fuels via thermochemical co-processing with waste motor oil and biomass.

In this work, the co-processing of waste surgical masks, waste motor oil, and biomass was investigated to reduce the environmental impacts of the increasing medical-derived plastic pollution as well as to elucidate its effect on the production of chemicals . The results showed high yields towards an oily product with an interesting hydrocarbon content in the diesel range. Furthermore, although the initial waste motor oil had a high sulfur content, the oily products showed a low sulfur content, that was logically distributed in the solid and gas phases. In addition, all oily products presented HHVs ​​higher than 44 MJ/Kg, with cetane indices, densities, and viscosities lower than those of petroleum-derived diesel. This work could impact on the management of waste surgical masks and the joint recovery of everyday waste towards high value-added products.

Base oil recovery from waste lubricant oil by polar solvent extraction intensified by ultrasound.

This paper proposes a greener approach to the intensification of base oil recovery for truck engines (32,500 km of use) using ethanol, propan-2-ol, 2-methylpropan-1-ol, and butan-1-ol as solvents for the extraction of base oil, combining mechanical stirring (220 rpm) and ultrasound (25 °C, 24 kHz, and 400 W). The results indicated that the recovery yields of the base oil, using the mechanical stirring and ultrasound (MS-US) system, for ethanol, propan-2-ol, 2-methylpropan-1-ol, and butan-1-ol were approximately 3.1, 25.6, 71.6, and 85.5%, respectively. By contrast, the recovery yields using only mechanical stirring were 8.8, 28.9, 58.9, and 76.1%, respectively. The system with pre-extraction could effectively remove Ca (85.3-93.0%), Mg (67.2-82.9%), Na (31.7-62.5%), and Zn (0.0-71.7%). Finally, the results showed a reduction of almost 100% for the concentrations of Al, Cr, Fe, and Mo in the pre-extraction system. The mechanical stirring (5 min) and ultrasound (5 min) system were able to intensify the extraction process using environmentally friendly solvents.

Investigation of the usage potential of calcium alginate beads functionalized with sodium dodecyl sulfate for wastewater treatment contaminated with waste motor oil.

In this study, calcium alginate (Ca-Alg) beads, an inexpensive, easily available, biodegradable material, were activated with anionic surfactant and used for the treatment of wastewater contaminated with waste motor oil. First, polyethyleneimine (PEI) was used to bind sodium dodecyl sulfate (SDS) onto the Ca-Alg beads' surface. Three different SDS concentrations (25, 50, & 100 mg/L) were prepared and treated with Ca-Alg beads for 1, 2, 4, 6, and 24 h. SDS binding yield reached equilibrium at the end of the 24 h, and the binding efficiencies of 25, 50, and 100 mg SDS/L were determined 84%, 72%, and 48%, respectively. The effect of pH between 2 and 10 was also investigated on oil adsorption. Maximum adsorption efficiency (77%) was obtained in the range of pH 6-8. After determining the optimum pH value for oil adsorption, the effect of beads amount (2.5-30 g/L) was also investigated on oil removal efficiency. When the amount of beads increased from 2.5 to 30 g/L, the oil adsorption efficiency increased from 77% to 95%. It was also observed that the oil adsorption efficiency increased when the size of the beads decreased from 4 to 1 mm. For the kinetic calculation, three different concentrations (250, 500, &1000 mg/L) of oily solution were prepared, and oil adsorption was investigated versus time. The kinetic studies for the adsorption of the oily solution using SDS functionalized Ca-Alg beads showed the second-order kinetics. When the initial oil concentration increased from 250 to 1000 mg/L, the amount of adsorbed oil molecules increased from 8.34 to 22.12 mg/g. Langmuir and Freundlich isotherm models were used to explain the relationship between adsorbent and adsorbate, and Langmuir isotherm was the most suitable model because of its high regression coefficient (r2 ) value. Column studies were also carried out, and it was concluded that the proposed adsorbent can be used effectively in the treatment of oily wastewater. PRACTITIONER POINTS: Although there are numerous adsorption studies and studies on the use of alginate beads in various fields in the literature, its use in oil treatment has not been found to our knowledge. The study aims to produce a selective adsorbent for the removal of oil from water by functionalizing the surface of the alginate beads with active agents. In conventional adsorption studies, pollutants are transported from liquid phase to solid phase. With the proposed new adsorbent material, oils will be specifically removed from wastewater and used as fuel. Thus, obtaining an organic origin adsorbent with high calorific value constitutes the original value of the study. In addition, no secondary pollutants will emerge after the adsorption process.

Management of adsorbent content in waste motor oil regeneration by spectrophotometrical study and effective acidification in production of nano-porous clay.

In the present work the application of novel technique was highlighted for reduction of adsorbent content in recovery process of waste motor oil by effective acidification. The effects of acidification factors such as acid proportions, adsorbent dose, powder/acid ratio and residence time were analyzed on removal of contaminates from waste oil. Acetic, hydrochloric and sulfuric acids were mixed according to the statistical mixture design algorithm to prepare acidification agents. The dry original clay was submitted into the prepared acidic solutions. The designed instrumental setup allowed the preparation of nano-porous powders where the controlled factors were residence time. The distillation of waste oil was carried out in the industrial scale. The significance of independent variables and their interactions were tested by blending the obtained powders with distillated oil and then the adsorption was evaluated, spectrophotometrically. The experimental results revealed the region in which the optimum regeneration of waste oil is obtainable. In order to well understand the role of nano-structured material on regeneration, the adsorbents were characterized through X-ray diffraction, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller surface area measurement and scanning electron microscopy. The employment of acetic acid in combination with sulfuric acid plays an effective role in development porous structure and improvement of contaminant adsorption. The powder produced in optimum condition contains nano-pores with diameter about 11 nm. The employment of this technique provides a potential for reduction of adsorbent content, 33.3 wt%. Finally, it was demonstrated that the efficiency of prepared adsorbent supports further development for commercial application purpose.

Remoção da fração oleosa de embalagens de lubrificantes automotivos pós-consumo por drenagem gravitacional / Residual oil removal from used automotive lubricant packages by gravitational drainage

RESUMO: Este trabalho aborda a questão do gerenciamento de embalagens pós-consumo de lubrificantes automotivos, considerando as dificuldades inerentes à implementação do sistema de logística reversa - prática compulsória por força de lei (Brasil, Lei 12.305/2010) - e a ineficácia dos atuais métodos utilizados para remoção da fração oleosa residual, necessária ao reprocessamento do material plástico por reciclagem mecânica direta. Para determinar metodologia apropriada para limpeza dos frascos de lubrificantes foram conduzidos experimentos para avaliar a influência do aquecimento e da posição das embalagens durante o processo de drenagem gravitacional. O procedimento analítico realizado proporcionou a escolha de uma combinação de variáveis capaz de assegurar remoção de elevado teor do resíduo oleoso com menor gasto energético. A otimização foi feita utilizando um planejamento experimental do tipo composto central com triplicata no ponto central. Os dados obtidos nos ensaios foram analisados com recursos estatísticos e demonstraram que ambos os parâmetros avaliados interferem, de forma significativa, no processo em estudo. Os resultados apontaram aumento da eficácia do processo quando a drenagem é realizada em temperaturas superiores a 35ºC e com a embalagem inclinada em ângulos próximos a 70º em relação à horizontal. Nessas condições, percentuais de remoção de óleo residual superaram 95% após 35 minutos de drenagem.

ABSTRACT: This work addresses the management of automotive lubricants packages after lubricant use, considering the difficulties of implementing reverse logistics system - compulsory practice by virtue of Law (Brazil, Law 12,305/2010) - and the poor effectiveness of the current methods for removing residual oil from packages, which is required before reprocessing plastic material in direct mechanical recycling. Experiments were conducted in order to determine the appropriate methodology for cleaning the lubricant bottles, evaluating the influence of temperature and package position in the gravitational drainage. This analytical procedure elicited a combination of variables and conditions capable of improving the removal of oily residue with less energy. The experimental optimization was performed using a central composite model with triplicate center point. The test results were statistically analyzed and showed that both parameters have significant influence on the separation process. The data indicated that the process is more effective when the drainage is performed above 35ºC and the packaging inclined at angles close to 70º relative to horizontal. Under these conditions, the oil removal is greater than 95% after 35 minutes of drainage.

Removal of transition metals from motor oil using ion exchange resins.

A variety of polystyrene-divinylbenzene resins functionalized with such groups as SO3H, N(CH2COOH)2, and SH were tested in the slurry batch mode for the removal of transition metals from used motor oil. Naturally occurring materials such as coal and clay were also tested. The N(CH2COOH)2 resin (Chelex 100) and the SH resin (Duolite GT-73) were found effective removing on the average 70 and 78% of metals such as Fe, Pb, Zn, Cu, Ni, and Mn, respectively. About 700 mLs of hot oil when pumped through a 37 × 0.9 cm column packed with the Duolite resin could be demetalized to the extent of about 80% if the column was first washed with hexane.

Comparison of biostimulation and bioaugmentation techniques for the remediation of used motor oil contaminated soil

This study was carried out on the bioremediation of used motor oil contaminated soil artificially contaminated to a pollutant level of 40,000ppm using biostimulation and bioaugmentation remediation techniques for 42 days. Four treatment options were investigated in wooden microcosms: Control (T1), water amended (T2), biostimulation (T3) and hybrid of biostimulation and bioaugmentation (T4). The effectiveness of bioremediation processes were monitored using the total petroleum hydrocarbon removal (TPH) and total bacterial count (TBC). T3 had the highest TPH removal rate (69.2±0.05 percent), followed by T4 (65.2±0.25 percent) and T2 (58.4±0.5 percent); the control (T1) had the lowest TPH removal rate (43.2±1.5 percent). TBC revealed that bioremediation actually took place; T4 had the highest maximum bacterial growth of 9.6E+07CFU/g, followed by T3 (7.2E+07CFU/g), T2 (1.7E+05CFU/g) and T1 (1.65E+05CFU/g). In addition, T3 had the highest metal removal rate (2.172 percent) and T4 had the lowest metal removal rate (0.203 percent).

O presente estudo trata da biorremediação usandose solo contaminado artificialmente com óleo de motor a um nível de poluente de 40.000 ppm usando técnicas de remediação por bioestimulação e por bioagumentação durante 42 dias. Quatro opções de tratamento foram investigadas no microcosmo de madeira: Controle (T1), água alterada (T2), bioestimulação (T3) e híbrido de bioestimulação e bioaugmentação (T4). A eficácia dos processos de biorremediação foram monitoradas usando a remoção de hidrocarbonetos totais petróleo (TPH) e contagem bacteriana total (TBC). T3 teve a maior taxa de remoção de TPH (69,2 ±; 0,05 por cento), seguido por T4 (65,2 ±; 0,25 por cento) e T2 (58,4 ±; 0,5 por cento); o controle (T1) apresentou a menor taxa de remoção de TPH (43,2 ±; 1,5 por cento). TBC revelou que a biorremediação efectivamente ocorreu; T4 teve o maior crescimento de bactérias 9,6E+07CFU/g, seguido pelo T3 (7.2E+07CFU/g), T2 (1.7E+05CFU/g) e T1 (1.65E+05CFU/g). Além disso, T3 apresentou a maior taxa de remoção metal (2,172 por cento) e T4 teve a mais baixa taxa de remoção metal (0,203 por cento).