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At least 541 records · Page 30

An improved Method for Determining Transient Fuel Dilution of Oil in an Internal-Combustion Engine Using Laser-Induced Florescence and Multivariate Least Square Calibration

An optical diagnostic, based on laser-induced fluorescence (LIF), has been developed for on-engine measurements of real-time fuel dilution of engine oil or fuel in oil (FIO). Fuel dilution of oil is broadly relevant to advancing engine technology including durability, calibration, and catalyst-system management, and believed to promote destructive stochastic pre-ignition (SPI) during high-load engine operations. While standard (e.g., ASTM D3524-90) methods are not capable of real-time transient measurements, the LIF technique resolves transient dilution on the minutes time scale. We have expanded on our original FIO instrument development by introducing an improved analysis based on multivariate least square chemometrics analysis. The measurement uses a fuel dye (180–1300 parts per million, by mass) and monitors for its presence in the oil using 532 nm excitation and LIF. While the original FIO instrument utilized a two-color ratio method for analysis, the improved chemometric analysis uses the fully resolved LIF dye spectra to provide better predictive FIO accuracy (>92%) over a wide FIO range (1.5–14%) typical of engine application. We also investigate the effect of oil temperature on the LIF signal. Limited engine applications for demonstrating and validating the improved FIO instrument are shown, and the related data used to quantify practical detection limit and sensitivity. The improved analysis is insensitive to laser power fluctuation and change in detector integration time, providing an excellent FIO sensitivity (1–2%) and detection limit (0.01 %FIO) over a wide range of loads and injection timings, illustrating this updated approach to be a promising tool for advancing engine technology.

42 ENGINEERING↗

Potential synergies of drop-in biofuel production with further co-processing at oil refineries

Drop-in biofuels have been defined as functionally equivalent to petroleum-based transportation fuels and are fully compatible with the existing petroleum infrastructure. They will be essential in sectors such as aviation if we are to achieve emission reduction and climate mitigation goals. Currently, 'conventional' drop-in biofuels, which are primarily based on upgrading of lipids / oleochemicals, are the only significant source of commercial volumes of drop-in biofuels. However, the necessary increased, future volumes will likely come from 'advanced' drop-in biofuels based on biomass feedstocks such as forest and agriculture residues. Biocrudes / bio-oils produced from lignocellulosic feedstocks using thermochemical technologies such as gasification, pyrolysis, and hydrothermal liquefaction need to be further upgraded to drop-in biofuels. However, advanced drop-in biofuels have been slow to reach commercial maturity due to significant technical challenges, high capital costs, and the challenge of generally lower oil prices. It is likely that the co-processing of drop-in biofuels with conventional petroleum refining could considerably reduce capital costs. Initially, co-processing is likely to be established through the upgrading of conventional / oleochemical feedstocks (lipids). Lipids are readily available in large volumes (global production in 2017 was ~185 million metric tonnes) and can be more easily integrated into oil-refinery processes. In contrast, lignocellulose-derived biocrudes / bio-oils are not yet available in significant volumes and are more complex to co-process in a refinery. The likely strategies for co-processing of oleochemicals (lipids) and bio-oil and biocrude feedstocks based on different insertion points within the refinery infrastructure are discussed.

09 BIOMASS FUELS↗

Effect of Heating Rate on Latent Heat of Fusion of Waxy Crystals in Crude Oil

Crude-oil transportation requires a study of the latent heat of phase transitions and the melting parameters of solid paraffin in the oil. The latent heat of fusion and the effect of the heating rate on melting were measured for Daqing oilfield waxy oil using differential scanning calorimetry. The peak melting ranges of the waxes were determined. The results showed that the total latent heats at heating rate 5°C/min from —20°C to the end of melting were 3035 and 39.26 J/g for two crude-oil samples. The latent heat maximum temperatures were 24.5 and 25.5°C The maximum latent heat for both samples was attained at heating rate 1°C/min. The relative deviation for the other heating rates was less than 3%. It was shown that the heating rate affected the position of the latent heat peak. The peak temperature shifted from 24 to 28°C for one sample and from 25.5 to 28.0°C for the other as the heating rate increased from I to 15°C/min. The results of the present work could be useful for further research on the paraffin precipitation mechanism during transportation of crude oil.

02 PETROLEUM↗

Measuring bio-oil upgrade intermediates and corrosive species with polarity-matched analytical approaches

Integrating biofuels with conventional petroleum products requires improvements in processing to increase blendability with existing fuels. This work demonstrates analysis techniques for more hydrophilic bio-oil liquids that give improved quantitative and qualitative description of the total acid content and organic acid profiles. To protect infrastructure from damage and reduce the cost associated with upgrading, accurate determination of acid content and representative chemical compound analysis are central imperatives to assessing both the corrosivity and the progress toward removing oxygen and acidity in processed biomass liquids. Established techniques form an ample basis for bio-liquids evaluation. However, early in the upgrading process, the unique physical phases and varied hydrophilicity of many pyrolysis liquids can render analytical methods originally designed for use in petroleum-derived oils inadequate. In this work, the water solubility of the organic acids present in bio-oils is exploited in a novel extraction and titration technique followed by analysis on the water-based capillary electrophoresis (CE) platform. The modification of ASTM D664, the standard for Total Acid Number (TAN), to include aqueous carrier solvents improves the utility of that approach for quantifying acid content in hydrophilic bio-oils. Termed AMTAN (modified Total Acid Number), this technique offers 1.2% relative standard deviation and dynamic range comparable to the conventional ASTM method. Furthermore, the results of corrosion product evaluations using several different sources of real bio-oil are discussed in the context of the unique AMTAN and CE analytical approaches developed to facilitate those measurements.

09 BIOMASS FUELS↗

An updated assessment of oil market disruption risks

The probability of the size and duration of another oil disruption is critical to estimating the value of any policies for reducing the economic damages from a sudden oil supply disruption. The Energy Modeling Forum at Stanford University developed a risk assessment framework and evaluated the likelihood of one or more foreign oil disruptions over the next ten years. Leading geopolitical, military and oil-market experts provided their expertise on the probability of different events occurring, and their corresponding link to major disruptions in key oil market regions. The study evaluated 5 primary regions of production: Saudi Arabia, Other Persian Gulf, Africa, Latin America, and Russian / Caspian States. Disruptions are defined as being net of offsets (e.g., OPEC spare capacity), with the notable exception that the SPR is not included as a source of offsets. Furthermore, at least once during the 10-year time frame (2016–2025), there exists approximately an 80% probability of a net (of offsets) disruption of 2 MMBD (million barrels per day) or more lasting at least 1 month.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Identification of engine oil-derived ash nanoparticles and ash formation process for a gasoline direct-injection engine

Engine oil-derived ash particles emitted from internal combustion (IC) engines are unwanted by-products, after oil is involved in in-cylinder combustion process. Since they typically come out together with particulate emissions, no detail has been reported about their early-stage particles other than agglomerated particles loaded on aftertreatment catalysts and filters. To better understand ash formation process during the combustion process, here differently formulated engine oils were dosed into a fuel system of a gasoline direct injection (GDI) engine that produces low soot mass emissions at normal operating conditions to increase the chances to find stand-alone ash particles separated from soot aggregates in the sub-20-nm size range. In addition to them, ash/soot aggregates in the larger size range were examined using scanning transmission electron microscopy (STEM)-X-ray electron dispersive spectroscopy (XEDS) to present elemental information at different sizes of particles from various oil formulations. The STEM-XEDS results showed that regardless of formulated oil type and particle size, Ca, P and C were always contained, while Zn was occasionally found on relatively large particles, suggesting that these elements get together from an early stage of particle formation. The S, Ca and P K-edge X-ray absorption near edge structure (XANES) analyses were performed for bulk soot containing raw ash. The linear combination approach & cross-checking among XANES results proposed that Ca 5 (OH)(PO 4 ) 2 , Ca 3 (PO 4 ) 2 and Zn 3 (PO 4 ) 2 are potentially major chemical compounds in raw ash particles, when combined with the STEM-XEDS results. Despite many reports that CaSO 4 is a major ash chemical when ash found in DPF/GFP systems was examined, it was observed to be rarely present in raw ashes using the S K-edge XANES analysis, suggesting ash transformation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

pH-Responsive crude oil-in-water Pickering emulsion stabilized by polyacrylamide nanogels

Oil-in-water (o/w) Pickering emulsions stabilized by polyacrylamide (PAM) and poly(acrylamide-co-acrylic acid) nano-sized crosslinked polymeric particles (nanogels) under various conditions are described herein. Nanogels with different crosslinking and charge degree were synthesized through suspension polymerization and characterized at various salinities and pH using dynamic light scattering (DLS) and scanning electron microscopy (SEM). The PAM nanogel-stabilized o/w Pickering emulsions were quickly demulsified in alkaline solutions whereas they showed markedly stability in brines and under acidic conditions. A small amount of nanogels were sufficient for the formation of Pickering emulsions. The average diameter of oil droplets was no longer decreasing with nanogel concentration increment above 1000 mg/L. In addition, the average diameter of oil drops was independent of sonication period in the range of 15–240 s. Interestingly, the string-like structures of nanogel aggregations were found in the aromatic hydrocarbons/water Pickering emulsions, which significantly enhanced the emulsion stability. Compared to the crude oil, the corresponding Pickering emulsions showed excellent flowability at various shear rates. The crude oil/water Pickering emulsions could be broken using alkali as a trigger, which suggests the potential utility for the recovery of crude oil.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Corrosion of stainless steels in the riser during co-processing of bio-oils in a fluid catalytic cracking pilot plant

Co-processing of bio-oils with conventional petroleum-based feedstocks is an attractive initial option to make use of renewable biomass as a fuel source while leveraging existing refinery infrastructures. But, bio-oils and their processing intermediates have high concentrations of organic oxygenates, which, among their other negative qualities, can result in increased corrosion issues. A range of stainless steel alloys (409, 410, 304L, 316L, 317L, and 201) was exposed at the base of the riser in a fluid catalytic cracking pilot plant while co-processing vacuum gas oil with pine-derived pyrolysis bio-oils that had been catalytically hydrodeoxygenated to ~ 2 to 28% oxygen. We studied the processing using a catalyst temperature of 704 °C, a reaction exit temperature of 520 °C, and total co-processing run times of 57–75 h. External oxide scaling 5–30 μm thick and internal attack 1–5 μm deep were observed in these short-duration exposures. The greatest extent of internal attack was observed for co-processing with the least stabilized bio-oil, and more so for types 409, 410, 304L, 316L, 317L stainless steel than for type 201. Finally, the internal attack involved porous Cr-rich oxide formation, associated with local Ni-metal enrichment and S-rich nanoparticles, primarily containing Cr or Mn. Implications for alloy selection and corrosion are discussed.

09 BIOMASS FUELS↗

Synthesis and characterization of methyl esters from non-edible plant species yellow oleander oil, using magnesium oxide (MgO) nano-catalyst

Highlights: • Introduction of new non-edible oil source for bioenergy industry. • Nano-particles MgO used as a heterogeneous catalyst. • Maximum conversion yield at optimum level achieved 93.1%. • Fuel properties were matched and found similar to ASTM standards. - Abstract: Synthesis and characterization of methyl esters from non-edible oil sources provide a distinctive and sustainable approach towards sustainable energy and the cleaner environment, in general. This study aims the synthesis of methyl esters from non-edible plant species yellow oleander seeds oil. The transesterification process was carried for the synthesis of methyl esters, using heterogeneous nano-catalyst magnesium oxide (MgO). A well known co-precipitation method was used for the synthesis of MgO nano-catalyst. The application of MgO nano-catalyst showed the maximum conversion (93.1%) of triacylglycerols to methyl esters. Different parameters affecting the conversion percentage; alcohol to oil molar ratio, temperature and catalyst concentrations were checked and optimized, accordingly. The optimum conditions for the maximum conversion noted; 1:5 oil to methanol molar ratio at 90 °C, using 0.2% (w/w) MgO nano-catalyst. The various analytical techniques; XRD, SEM-EDX and TEM-EDS spectroscopes were used to check out the nano-particle morphology and crystalline size, accordingly while, the FTIR, GC–MS & NMR were used to quantify and determine the structural measurements of synthesized methyl esters. The fuel properties of oleander methyl esters papered sample were checked, compared and found within accordance to the ASTM standards.

09 BIOMASS FUELS↗

Comprehensive Chemical Characterization of Hydrocarbons in NIST Standard Reference Material 2779 Gulf of Mexico Crude Oil

Comprehensive chemical information is needed to understand the environmental fate and impact of hydrocarbons released during oil spills. However, chemical information remains incomplete because of the limitations of current analytical techniques and the inherent chemical complexity of crude oils. In this study, gas chromatography (GC)-amenable C 9 -C 33 hydrocarbons were comprehensively characterized from the National Institute of Standards and Technology Standard Reference Material (NIST SRM) 2779 Gulf of Mexico crude oil by GC coupled to vacuum ultraviolet photoionization mass spectrometry (GC/VUV-MS), with a mass balance of 68 ± 22%. This technique overcomes one important limitation faced by traditional GC and even comprehensive 2D gas chromatography (GC×GC): the necessity for individual compounds to be chromatographically resolved from one another in order to be characterized. VUV photoionization minimizes fragmentation of the molecular ions, facilitating the characterization of the observed hydrocarbons as a function of molecular weight (carbon number, N C ), structure (number of double bond equivalents, N DBE ), and mass fraction (mg kg -1 ), which represent important metrics for understanding their fate and environmental impacts. Linear alkanes (8 ± 1%), bran ched alkanes (11 ± 2%), and cycloalkanes (37 ± 12%) dominated the mass with the largest contribution from cycloalkanes containing one or two rings and one or more alkyl side chains (27 ± 9%). Linearity and good agreement with previous work for a subset of >100 components and for the sum of compound classes provided confidence in our measurements and represents the first independent assessment of our analytical approach and calibration methodology. Another crude oil collected from the Marlin platform (35 km northeast of the Macondo well) was shown to be chemically identical within experimental errors to NIST SRM 2779, demonstrating that Marlin crude is an appropriate surrogate oil for researchers conducting laboratory research into impacts of the DeepWater Horizon disaster.

02 PETROLEUM↗

Recent advances in hydrotreating of pyrolysis bio-oil and its oxygen-containing model compounds

There is considerable world-wide interest in discovering renewable sources of energy that can substitute for fossil fuels. Lignocellulosic biomass, which is the most abundant and inexpensive renewable feedstock on the planet, has a great potential for sustainable production of fuels, chemicals, and carbon-based materials. Fast pyrolysis integrated with hydrotreating is one of the simplest, most cost-effective and most efficient processes to convert lignocellulosic biomass to liquid hydrocarbon fuels for transportation, which has attracted significant attention in recent decades. However, effective hydrotreating of pyrolysis bio-oil presents a daunting challenge to the commercialization of biomass conversion via pyrolysis-hydrotreating. Specifically, development of active, selective, and stable hydrotreating catalysts is the bottleneck due to the poor quality of pyrolysis bio-oil feedstock (high oxygen content, molecular complexity, coking propensity, and corrosiveness). Significant research has been conducted to address the practical issues and provide the fundamental understanding of the hydrotreating/hydrodeoxygenation (HDO) of bio-oils and their oxygen-containing model compounds, including phenolics, furans, and carboxylic acids. A wide range of catalysts have been studied, including conventional Mo-based sulfide catalysts and noble metal catalysts, with the latter being the primary focus of the recent research because of their excellent catalytic performances and no requirement of environmentally unfriendly sulfur. The reaction mechanisms of HDO of model compounds on noble metal catalysts as well as their efficacy for hydrotreating or stabilization of bio-oil have been recently reported. This review provides a survey of the relevant literatures of recent 10 years about the advances in the understanding of the HDO chemistry of bio-oils and their model compounds mainly on noble metal catalysts.

biomass, lignocellulose, pyrolysis bio-oil, hydrod↗

Role of Well Operations and Multiphase Geomechanics in Controlling Fault Stability During CO 2 Storage and Enhanced Oil Recovery

CO 2 injection in active oil fields is a technology proposed for industrializing carbon storage operations. However, monitoring CO 2 migration, oil recovery, and mechanical deformation within caprock and on faults is a challenging problem in large-scale storage-enhanced oil recovery operations due to intersecting faults, multiphase flow effects, and wells with complex production-injection schedule. We develop and demonstrate a methodology based on our coupled modeling framework to monitor the movement of CO 2 , hydrocarbons and water, and the associated evolution in mechanical stability of faults during CO 2 storage-enhanced oil recovery in the Farnsworth Unit oil field in Texas, United States. The methodology honors geological, geophysical, and production-injection data acquired in the field over six decades. Differential depletion from hydraulically isolated fault compartments followed by water and CO 2 injection-induced overpressure causes volumetric contraction and expansion of the reservoir, and changes in the total and effective stresses in the overburden-reservoir-underburden complex. CO 2 migrates upward to accumulate near top of the geologic structure, and water migrates downward to pressurize the faults. Three-dimensional changes in the pressure and stress fields in the system lead to changes in the shear and effective normal tractions on three major faults compartmentalizing the field. Evolution in fault tractions is used to compute the evolution in the Coulomb failure function of the faults to quantify induced-slip tendency under production and injection. We explain the spatial heterogeneity and time variability of Coulomb failure function in terms of well location heterogeneity and well rate variability.

58 GEOSCIENCES↗

Chapter 5: Non-Isocyanate Polyurethane from Vegetable and Microalgal Oil

In this chapter, vegetable oil, heterotrophic algal oil and phototrophic algal oil were used for NIPU development. NIPU properties were evaluated, and its promising performance was demonstrated, indicating that vegetable oils and algal oils with high functionalities are promising precursors for NIPU polymers.

BIOMASS FUELS↗

Electrocatalytic Hydrotreatment of Bio-Oil: Exploring Interactions Between Functional Groups

Electrocatalytic hydrotreatment (ECH) is being explored as a sustainable route for upgrading bio-oil to renewable fuels and chemicals. Bio-oil, produced by the fast pyrolysis of lignocellulosic biomass, is a complex mixture of compounds with various oxygen-containing functional groups, such as anhydrosugars, carboxylic acids, ketones, aldehydes, furans, phenols and alcohols. The ECH of several bio-oil model compound binary mixtures was conducted to investigate the interactions between these functional groups. Notably, phenolic compound reduction was significantly inhibited in the presence of aldehydes, particularly furfural. A strategy involving the reagent-based reduction of the aldehyde to an alcohol prior to ECH was shown to partially mitigate this inhibitory effect. Additionally, qualitative studies on the ECH of catalytic fast pyrolysis (CFP) oil with low aldehyde content showed promising results. These studies achieved the conversion of cyclopentenones and phenolic compounds present in the CFP oil to cyclopentanols and cyclohexanols, respectively.

09 BIOMASS FUELS↗

Soil burial biodegradation studies of palm oil-based UV-curable films

The palm oil-based ultraviolet (uv)-curable films were subjected to an outdoor soil burial test to investigate the biodegradation under natural environment. The films were burial in the soil experiment plot at the Nuclear Malaysia’s Dengkil complex. The uv-curable films were synthesized from the epoxidized palm oil acrylated (EPOLA) resin and the polyurethane palm oil (POBUA) resin, respectively. Biodegradation tests are more specific to burial film in soil experiments for 12 months under natural conditions. The biodegradability of palm oil resin based uv-curable films were investigated and compared with the petrochemical resin based film. The films properties were compared with respect to properties of the thermal characteristic, the crystallinity, the morphology and the weight loss which are analyzed using the thermogravimetric analysis (TGA), the differential scanning calorimetry (DSC), the scanning electron microscope (SEM), an optical microscope and the weight loss of film calculation. These findings suggested that the palm oil-based uv-curable films show quite satisfactory biodegradation levels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Friction and Wear Reduction Mechanism of Polyalkylene Glycol-Based Engine Oils

Polyalkylene glycols (PAG) have been explored as a possible base stock for engine oil formulation. The friction, wear, and load-carrying capacity of five different PAG chemistries were evaluated either as a base stock or as formulated oils in pure sliding and sliding-rolling conditions using various laboratory bench test rigs operating under boundary and mixed lubrication regimes. The results were compared against GF-5 SAE 5W-20 and a mineral-based oil. The wear surfaces were also characterized using various surface-sensitive techniques for analysis of tribofilms to understand the mechanism of friction reduction. The results indicated that PAG oils show lower friction/traction coefficients and improved load-carrying capability, depending on the formulation, than those of the GF-5 SAE 5W-20 and mineral-based oil. The adsorption of PAG molecules on the surface appeared to be responsible for the lower friction characteristics.

AES↗

Bioprocessing-Based Approach for Bitumen/Water/Fines Separation and Hydrocarbon Recovery from Oil Sands Tailings

Oil sands are a major source of oil, but their industrial processing generates tailings ponds that are an environmental hazard. The main concerns are mature fine tailings (MFT) composed of residual hydrocarbons, water, and fine clay. Tailings ponds include toxic contaminants such as heavy metals, and toxic organics including naphthenics. Naphthenic acids and polyaromatic hydrocarbons (PAHs) degrade very slowly and pose a long-term threat to surface and groundwater, as they can be transported in the MFT. Research into improved technologies that would enable densification and settling of the suspended particles is ongoing. In batch tests, BioTiger™, a microbial consortium that can metabolize PAHs, demonstrated improved oil sands tailings settling from a Canadian tailings pond. Results also showed, depending on the timing of the measurements, lower suspended solids and turbidity. Elevated total organic carbon was observed in the first 48 hours in the BioTiger™-treated columns and then decreased in overlying water. Oil sands tailings mixed with BioTiger™ showed a two-fold reduction in suspended solids within 24 hours as compared to abiotic controls. The tailings treated with BioTiger™ increased in microbial densities three orders of magnitude from 8.5 × 105 CFU/mL to 1.2 × 108 CFU/mL without any other carbon or energy source added, indicating metabolism of hydrocarbons and other available nutrients. Results demonstrated that bioaugmentation of BioTiger™ increased separation of organic carbon from particles in oil sands and enhanced settling with tailings with improved water quality.

04 OIL SHALES AND TAR SANDS↗

Increased expression of fatty acid and ABC transporters enhances seed oil production in camelina

Abstract Background Lipid transporters play an essential role in lipid delivery and distribution, but their influence on seed oil production in oilseed crops is not well studied. Results Here, we examined the effect of two lipid transporters, FAX1 ( fatty acid export1 ) and ABCA9 ( ATP-binding cassette transporter subfamily A9 ) on oil production and lipid metabolism in the oilseed plant Camelina sativa . Overexpression (OE) of FAX1 and ABCA9 increased seed weight and size, with FAX1 -OEs and ABCA9 -OEs increasing seed length and width, respectively, whereas FAX1 / ABCA9 -OEs increasing both. FAX1- OE and ABCA9- OE displayed additive effects on seed oil content and seed yield. Also, OE of FAX1 and ABCA9 affected membrane lipid composition in developing pods, especially on phosphatidylcholine, phosphatidylethanolamine, and phosphatidylglycerol. The expression of some genes involved in seed oil synthesis, such as DGAT2 , PDAT1 , and LEC1 , was increased in developing seeds of FAX1 - and/or ABCA9 -OEs. Conclusion These results indicate that increased expression of FAX1 and ABCA9 can potentially be applied to improving camelina oil production.

59 BASIC BIOLOGICAL SCIENCES↗