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Research Hypothesis: The injection of a blend of rich hydrocarbon gas and CO2 into an oil reservoir will reduce molecular weight (MW) selectivity, lower minimum miscibility pressure (MMP) and viscosity of the oil, and improve gas solubility, resulting in an overall improvement in enhanced oil recovery (EOR) performance.
The movement to transfer from petroleum-based products and materials to renewables does not necessarily have to bypass the use of oil. A new type of "black-gold" is readily abundant from the earth's most abundant source of aromatic carbon: lignin. While fractionation of petroleum yields fuels and chemicals for a diverse set of industries, lignin fractionation using targeted catalysts has demonstrated the ability to generate monomers and oligomers rich in functional groups for polymer synthesis. This study explores the use of lignin-oil, generated from reductive catalytic fractionation of popular wood, to a hydroxyl-rich mixture of aromatics that is used to synthesize a thermoplastic non-isocyanate polyurethane. The lignin-oil is first converted to a cyclocarbonated derivative using a benign synthetic sequence and further polymerized with a diamine to yield the non-isocyanate TPU. While more work is underway to optimize the reaction conditions and meet typical mechanical properties of commercial materials, initial analysis shows thermoplastic behavior and flexible properties consistent with traditional thermoplastic polyurethanes.
Drop hammer tests with different shock strut models and shock strut oils were performed at temperatures ranging to -40 C. The various shock strut models do not differ essentially regarding their springing and damping properties at low temperatures; however, the influence of the different shock strut oils on the springing properties at low temperatures varies greatly.
Abstract The development of catalytic transformations and processes is essential to utilize bio‐oil and lignin derivatives. Metal nanoparticles (M‐NPs) stabilized in ionic liquids (ILs) are promising for the catalytic hydrotreatment of bio‐oil because the properties of the catalyst system can be customized by combining the appropriate IL and metal nanoparticles. Herein, we demonstrate an experimental approach to stabilize lignin‐derived phenolics isolated from bio‐oil with ruthenium NPs stabilized by an ionic copolymer in 1‐ethyl‐3‐methylimidazolium acetate ([C 2 C 1 Im][OAc]). The mild hydrotreatment of phenolic oligomers (POs) was performed with the synthesized M‐NP catalyst at 100 °C for 6 h. Hydrotreatment of the POs resulted in enhanced thermal stability of the POs by as much as a factor of three, as determined by the aging index and by reducing reactive functionalities, which was also confirmed by NMR spectroscopy and GC analysis. The results support our hypothesis that M‐NPs stabilized in ILs can effectively stabilize POs under mild conditions, which could be applicable to any lignin‐derived phenolic.
Abstract Valorization of humins, the polymeric byproducts formed during the acid‐catalyzed production of HMF (5‐hydroxymethylfurfural) or furfural, is necessary to improve process economics and make biorefineries viable. We report the one‐step catalytic hydrotreatment of humins in methanol to humin oil containing fully or partially deoxygenated compounds. First, we compare four commercial noble‐metal catalysts (Ru/C, Rh/C, Pt/C, and Pd/C). Aromatic hydrocarbons, phenols, and esters are the main products detected by GC. Rh/C achieves the best GC‐detectable oil yield and 75 % humins conversion in 3 h at 400 °C, 30 bar H 2 , and a catalyst‐to‐humins mass ratio of 1:10. High H 2 pressures and intermediate temperatures, reaction times, and catalyst loadings enhance GC‐detectable oil yields. In contrast, high temperatures and long reaction times enhance gasification. Aromatics and phenols are found at high temperatures and long reaction times, whereas esters are the major species at short reaction times and high catalyst loading. 13 C‐isotopic labeling studies confirm, for the first time, that methanol participates in the alkylation and esterification reactions to form aromatic, phenolic and ester products. The reactivity in isopropanol is also discussed.
Here, early motivation and use of energetic materials in the Western World by Alfred Nobel was intended to facilitate mining, construction, and demolition activities. The motivation for the work was the recognized need for a safer energetic material as an alternate to unstabilized nitroglycerine. The invention of dynamite by Nobel was widely adopted in the civilian world and brought a fortune to Nobel, resulting in the formation of the annual Nobel Prize awards, recognizing significant achievements across many fields of endeavour. Nonetheless, further development of energetics was primarily motivated by and funded for military purposes, rather than civilian usage. And indeed much investment has been given to the development and characterization of military energetics and their application. An example application is the precision shaped charge, primarily developed as a means of focusing energy in a narrow metallic jet for deep penetration of heavy armor. However, the largest costumer today and for many years for shaped charges is not the military, but rather the oil and gas industry, which has adapted the military technology for perforation of oil and gas wells. While there are similar aspects to desired penetration capabilities in both applications, there are enough differences to warrant energetics R & D focused on oil and gas industry needs.
PurposeTo evaluate the effect of previous transarterial iodized oil tissue marking (ITM) on technical parameters, three-dimensional (3D) computed tomographic (CT) rendering of the electroporation zone, and histopathology after CT-guided irreversible electroporation (IRE) in an acute porcine liver model as a potential strategy to improve IRE performance.MethodsAfter Ethics Committee approval was obtained, in five landrace pigs, two IREs of the right and left liver (RL and LL) were performed under CT guidance with identical electroporation parameters. Before IRE, transarterial marking of the LL was performed with iodized oil. Nonenhanced and contrast-enhanced CT examinations followed. One hour after IRE, animals were killed and livers collected. Mean resulting voltage and amperage during IRE were assessed. For 3D CT rendering of the electroporation zone, parameters for size and shape were analyzed. Quantitative data were compared by the Mann–Whitney test. Histopathological differences were assessed.ResultsMean resulting voltage and amperage were 2,545.3 ± 66.0 V and 26.1 ± 1.8 A for RL, and 2,537.3 ± 69.0 V and 27.7 ± 1.8 A for LL without significant differences. Short axis, volume, and sphericity index were 16.5 ± 4.4 mm, 8.6 ± 3.2 cm{sup 3}, and 1.7 ± 0.3 for RL, and 18.2 ± 3.4 mm, 9.8 ± 3.8 cm{sup 3}, and 1.7 ± 0.3 for LL without significant differences. For RL and LL, the electroporation zone consisted of severely widened hepatic sinusoids containing erythrocytes and showed homogeneous apoptosis. For LL, iodized oil could be detected in the center and at the rim of the electroporation zone.ConclusionThere is no adverse effect of previous ITM on technical parameters, 3D CT rendering of the electroporation zone, and histopathology after CT-guided IRE of the liver.
In this study, perfluoropolyether oil-based ferrofluid was prepared to satisfy special demands in applications which are too harsh to conventional ferrofluids. Fe{sub 3}O{sub 4} magnetic nanoparticles were synthesized by co-precipitation and modified by perfluoropolyether carboxylic acid surfactant in the atmosphere without protective gas. Perfluoropolyether oil-based ferrofluid was prepared with modified nanoparticles and perfluoropolyether by high-energy ball milling. Properties of ferrofluid fabricated were verified through a series of experiments. Ferrofluid stability was tested by interval point-density method; the average density change is merely 0.0077 g/ml, and change rate is 0.37% after 500 days. Saturation magnetization is 582.46 Gs, much larger than the other four ferrofluids. The average volatility rate is 7.4985*10{sup − 5} g/h/cm{sup 2} at 80 °C after 260 h. Viscosity increases to 1825.7 mPa⋅ s under − 20 °C and still have mobility at − 40 °C. The ferrofluid can resist air blast for 8 h under 200 °C without oxidation or decomposition. Perfluoropolyether oil-based ferrofluid cannot be damaged by water or organic solvents. In addition, the ferrofluid can survive in pH = 1 acid or pH = 14 alkali at least 279 days without corrosion.
Atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful tool for analysis of solid and liquid samples. It is an excellent alternative for crude oil analysis without any sample preparation step. Here, ASAP-MS in positive ion mode, ASAP(+)-MS, has been optimized for analysis of condensed aromatics (CA) standards, crude oil, and paraffinic fraction samples using a Synapt G2-S HDMS. Initially, two methodologies were used to access the chemical composition of samples: (1) using a temperature gradient varying from 150 to 600 °C at a heating rate of 150 °C min{sup –1}, and (2) with constant temperature of 300 and 400 °C. ASAP(+)-MS ionized many compounds with a typical petroleum profile, showing a greater signals range of m/z 250–1300 and 200–1400 for crude oil and paraffin samples, respectively. Such performance, mainly related to the detection of high molecular weight compounds (>1000 Da), is superior to that of other traditional ionization sources, such as ESI, APCI, DART, and DESI. Additionally, the CA standards were identified in both forms: radicals, [M]{sup +•}, and protonated cations, [M + H]{sup +}, with minimum fragmentation. Therefore, ASAP was more efficient in accessing the chemical composition of nonpolar and polar compounds. It is promising in its application with ultrahigh resolution MS instruments, such as FT-ICR MS and Orbitrap, since molecular formulas with greater resolution and mass accuracy (<1 ppm) would be assigned. .
Plant lipids are an essential energy source for diets and are a sustainable alternative to petroleum-based fuels and feedstocks. Fatty acid breakdown during seed germination is crucial for seedling establishment but unexpected during seed filling. Here, we demonstrate that the simultaneous biosynthesis and degradation of fatty acids begins early and continues across all phases of oil filling and throughout the photoperiod. Tests in camelina, rapeseed, and an engineered high-oil tobacco line confirmed that concomitant synthesis and breakdown in oil-producing tissues over development is the rule rather than the exception. Furthermore, we show that transgenics, designed to elevate fatty acid biosynthesis, failed to achieve anticipated increases in storage lipid levels due to increased degradation, potentially explaining the underperformance of engineered lines compared to expectations more generally.
With ever more challenging (T,p) environments for cementing applications in oil and gas wells, there is a need to identify the fundamental mechanisms of fracture resistant oil well cements. We report results from a multi-technique investigation of behavior and properties of API class G cement and silica-enriched cement systems subjected to hydrothermal curing from 30 °C to 200 °C; including electron probe microanalysis, X-ray diffraction, thermogravimetry analysis, electron microscopy, neutron scattering (SANS), and fracture scratch testing. The results provide a new insight into the link between system chemistry, micro-texture and micro-fracture toughness. We suggest that the strong correlation found between chemically modulated specific surface and fracture resistance can explain the drop in fracture properties of neat oil-well cements at elevated temperatures; the fracture property enhancement in silica-rich cement systems, between 110° and 175 °C; and the drop in fracture properties of such systems through prolonged curing over 1 year at 200 °C.
Managing produced water from oil and gas wells constitutes a significant portion of the costs of operating a well. Here, in this work, we have designed two different centralized water treatment facilities capable of managing produced water from oil and gas wells in Texas and Louisiana, both of which convert the produced water into the following valuable resources: ten-pound brine and fresh water. The two main designs each use commercially available technology with varying levels of establishment in treating produced water. Both treatment processes remove oil and grease and suspended solids, reduce the divalent ion concentrations, and concentrate the brines to a near-saturation state. The baseline design uses chemical precipitation to remove the divalent ions to meet the reuse specifications, whereas the advanced design uses nanofiltration (NF) membranes to separate divalent ions and uses reverse osmosis (RO) membranes to partially concentrate the brine. Both models use mechanical vapor recompression to concentrate the brine up to NaCl saturation. The baseline process is shown to be cost-effective for low-hardness brines. In the case of high hardness, the chemical precipitation step is cost-prohibitive. We find that NF membranes are a promising alternative to chemical precipitation as a means of separating monovalent and divalent ions.
The oil and gas sector is a key driver of the offshore economy. Yet, it is also associated with a number of unwanted environmental impacts which potentially threaten the long term economic and environmental viability of marine ecosystems. Environmental Impact Assessment (EIA) can potentially make a significant contribution to the identification and management of adverse impacts through the promotion of evidence based decision making. However, the extent to which EIA has been embraced by key stakeholders is poorly understood. On this basis, this paper provides an initial evaluation of EIA performance within the oil and gas sector. The methodology adopted for the paper consisted of the structured review of 35 Environmental Statements (ESs) along with interviews with regulators, operators, consultants and advisory bodies. The findings reveal a mixed picture of EIA performance with a significant number of ESs falling short of satisfactory quality and a tendency for the process to be driven by compliance rather than best practice. -- Highlights: • Concerns identified relating to impacts of offshore oil and gas industry. • Research assesses performance of EIA in addressing impacts. • Findings highlight weak quality standards and procedural deficiencies. • Institutional reforms identified in order to improve practice.
Ethylic transesterification process for biodiesel production without any chemical or biochemical catalysts at different subcritical thermodynamic conditions was performed using wet animal fat, soybean and palm oils as feedstock. The results indicate that 2 h of reaction at 240 °C with pressures varying from 20 to 45 bar was sufficient to transform almost all lipid fraction of the samples to biodiesel, depending on the reactor dead volume and proportions between reactants. Conversions of 100%, 84% and 98.5% were obtained for animal fat, soybean oil and palm oil, respectively, in the presence of water, with a net energy ration values of 2.6, 2.1 and 2.5 respectively. Finally, these results indicate that the process is energetically favorable, and thus represents a cleaner technology with environmental advantages when compared to traditional esterification or transesterification processes.
We report a detailed compositional characterization of a bio-crude oil and aqueous by-product from hydrothermal liquefaction of Nannochloropsis salina by direct infusion Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) in both positive- and negative-ionization modes. The FT-ICR MS instrumentation approach facilitates direct assignment of elemental composition to >7000 resolved mass spectral peaks and three-dimensional mass spectral images for individual heteroatom classes highlight compositional diversity of the two samples and provide a baseline description of these materials. Aromatic nitrogen compounds and free fatty acids are predominant species observed in both the bio-oil and aqueous fraction. Residual organic compounds present in the aqueous fraction show distributions that are slightly lower in both molecular ring and/or double bond value and carbon number relative to those found in the bio-oil, albeit with a high degree of commonality between the two compositions.
We demonstrated production of a superior performance biodiesel referred to here as fatty acid fusel alcohol esters (FAFE) – by reacting fusel alcohols (isobutanol, 3-methyl-1-butanol, and (S)-(-)-2-methyl-1-butanol) with oil (glyceryl trioleate) using lipase from Aspergillus oryzae. Reaction conditions corresponding to a molar ratio of 5:1 (fusel alcohols to oil), enzyme loading of 2% w/w, reaction temperature of 35 °C, shaking speed of 250 rpm, and reaction time of 24 h achieved >97% conversion to FAFE. Further, FAFE obtained from reacting a fusel alcohol mixture with corn oil were evaluated for use as a fuel for diesel engines. FAFE mixtures showed superior combustion and cold-flow properties, with the derived cetane numbers up to 4.8 points higher, cloud points up to -6 °C lower, and the heat of combustion up to 2.1% higher than the corresponding FAME samples, depending on the fusel mixture used. This represents a significant improvement for all three metrics, which are typically anti-correlated. Finally, FAFE provides a new opportunity for expanded usage of biodiesel by addressing feedstock limitations, fuel performance, and low temperature tolerance.
Although near-miscible CO 2 flooding has recently received considerable attention, no criteria are available to predict its applicability to a specific reservoir. Evaluating the viability of near-miscible flooding requires experimental exploration of a specific region in pressure–temperature space. The near-miscible pressure field is bounded on one side in P, T space by the MMP (minimum miscible pressure). This paper provides robust empirical correlations to estimate the MMP for both pure and impure CO 2 and for prediction of the near-miscible pressure region for CO 2 -oil. Many slim tube analyses, lacking high density data points, systematically underestimate the MMP, when the near miscible region is not accounted for. They are based on 147 published data sets that include: slim tube experimental determination of MMP; interfacial tension (IFT) between oil and CO 2 ; concentration of solution gas; and purity of the CO 2 . This paper is the first to begin a systematic exploration of the pressure-temperature space within which near-miscible effects characterize CO 2 floods. Our new correlations provide a basis for identifying and investigating the nature of near miscible effects associated with existing CO 2 floods. For a case study of an offshore field we determined that lower and upper pressure boundaries for effective near-miscible flooding, are 0.87 MMP and 1.07 MMP at reservoir temperatures. The proposed model is the first empirical correlation for the prediction of near-miscible pressure region, it will provide the basis for both screening the relative potential of oil reservoirs for economically viable miscible or near-miscible CO 2 -flooding.
CO 2 enhanced oil recovery (EOR) is a potential way for carbon capture, utilization and storage (CCUS). Though, the effect of CO 2 injection is greatly influenced by the reservoir conditions. Typically, Minimum miscible pressure (MMP) is selected as one of the key parameters for the screening and evaluation of prospective CO 2 flooding. Conventional slim tube test is both accurate and widely accepted but it is inefficient. Existing empirical formulas for MMPs are easy to be used but have been proved inaccurate and unreliable. Machine learning-based methods have great advantages in predicting MMP. However, only predication accuracy is discussed for most models without the screening of the main control factors and further validation of the model reliability. In this paper, a new prediction model based on support vector machine (SVM) was developed for pure/impure CO 2 and crude oil system. This study was based on 147 sets of MMP data from the literature with full information on reservoir temperature, oil composition and gas composition. The main control factors were screened by several statistical methods. Unlike the conventional prediction models that verified by only prediction accuracy, learning curve and single factor control variable analysis are further validated to obtain the optimum model.