Paraffinic Petroleum Research Articles

THE USE OF BENZENE OXIDATION PRODUCT AS A COMPONENT OF AN INHIBITORY ADDITIVE FOR PARAFFINIC AND HIGHLY PARAFFINIC PETROLEUM

Results of the application of benzene oxidation product (BOP), formed in barrier discharge, as an improving component of the inhibiting additive for paraffinic and highly paraffinic petroleum are presented. The proposed additive consists of a copolymer of alkyl acrylates with dodecylamine acrylate and BOP at a ratio of 15:1 wt. %. Benzene oxidation by air in a barrier discharge proceeds predominantly to phenol (~77.3 wt. %), diatomic phenols, and an insignificant amount of macromolecular compounds. The effect of the additive (in combination with BOP) in the amount of 0.03-0.05 wt. was evaluated relying on changes in the rheological characteristics and freezing point of paraffinic and highly paraffinic petroleum with a high content of resins and asphaltene components. The composition containing polymer and BOP additionally reduces the amount of asphaltene-resin-paraffin deposits by 1.5-2.5 g, which gives an increase in inhibitory capacity by 10-12 %. The depression of the freezing point of petroleum is 46 °С on average. The dynamic viscosity of petroleum under study decreases in the presence of the additive by a factor of 2.2 on average.

The Use of Benzene Oxidation Product as a Component of an Inhibitory Additive for Paraffinic and Highly Paraffinic Petroleum

The Use of Benzene Oxidation Product as a Component of an Inhibitory Additive for Paraffinic and Highly Paraffinic Petroleum

Short-Term Biodegradation of Crude Petroleum Oil in Water by Photostimulated Janibacter terrae Strain S1N1.

Biodegradation is a sustainable green strategy that gives the opportunity for remediation of water contaminated with petroleum products. In this study, 12 bacterial isolates were recovered from River Nile, Egypt and screened for their potential to degrade a mixture of paraffinic petroleum crude oil. The most promising isolate was identified according to 16S rRNA sequencing as Janibacter terrae strain S1N1 (GenBank accession No. KX570955.1). In order to boost the biodegradation efficiency, the bacterial suspension was photostimulated by exposure to different irradiation doses using a low-power helium–neon (He–Ne) laser (λ = 632.8 nm). Maximum biodegradation was achieved after 4 min of exposure (134.07 J cm–2) at optimized pH value (6) and temperature (35 °C). The gas chromatography–mass spectrometry (GC-MS) analysis revealed the biodegradation of 96.5% of the substrate after only 48 h of incubation. The n-C17/Pr and n-C18/Ph ratios indicated a preferential biodegradation of iso-paraffines over normal ones. Meanwhile, pristane/phytane (Pr/Ph) ratios were indicative of selective biodegradation for pristane. The carbon preference index (CPI) was nearly around unity indicating the ability of Janibacter terrae to attack the odd and even n-alkanes simultaneously. These results support the superiority of irradiated bacteria in optimizing the biodegradation efficiency and shortening the time of treatment, thus proposing an eco-friendly technique in water bioremediation programs.

Depositional and organofacies influences on the petroleum potential of an unusual marine source rock: Waipawa Formation (Paleocene) in southern East Coast Basin, New Zealand

Abstract The Paleocene Waipawa Formation is a widespread, ∼2–80 m-thick marine mudstone that occurs in several New Zealand basins. It is relatively enriched in organic matter (OM) and is the inferred source of a sub-commercial oil discovery and several correlated oil seeps. To determine the organofacies and depositional influences on the petroleum potential of the formation, we have undertaken a high-resolution, multidisciplinary study of the Taylor White section in the central East Coast Basin. This section is the thickest stratigraphically coherent surface exposure of the formation and includes contacts with the bounding Whangai and Wanstead formations. Bathymetric indicators within the foraminiferal assemblages indicate a slope setting for the section, deepening from middle to lower bathyal through the Waipawa–Wanstead succession. Significantly, the Whangai Formation in this section is barren of foraminifera. Dinoflagellate and calcareous nannofossil biostratigraphy provides somewhat conflicting age control but a resulting age model indicates a tenfold increase in compacted sediment accumulation rate during Waipawa deposition (from ∼1 to ∼10 cm/ky). Our multivariate statistical analysis of geochemical and paleontological data reveals systematic variation in paleoenvironmental and source rock parameters within the section, with samples forming four distinct clusters or organofacies: OM-rich and OM-poor Waipawa organofacies, Whangai, and Wanstead organofacies. The two Waipawa organofacies are distinguished by enrichments in total organic carbon (TOC) and organic 13C, dominance of phytoclasts (mainly degraded woody plant matter; 66–98%), and low amounts of amorphous organic matter ( Whangai and Wanstead organofacies are characterised by a greater proportion of marine OM but are distinguished from each other by differences in OM preservation: OM is well-preserved with indications of hypoxia in the Whangai organofacies but is poorly preserved in the Wanstead organofacies. Geochemical fingerprinting identifies an interval of Whangai organofacies that separates two phases of Waipawa organofacies deposition. The lower phase comprises four alternations between OM-rich and OM-poor Waipawa organofacies and the upper phase comprises a single pulse of OM-rich Waipawa facies bounded by OM-poor intervals. Overall, Waipawa Formation in this section has TOC and pyrolysable hydrocarbon (S2) values of 0.2–4.6 (mean 2.2) wt% and 0.1–12.4 (mean 3.9) mg HC/g rock, respectively. One-third of S2 values exceed 5 mg HC/g rock, indicating good‒very good bulk petroleum potential, with the remainder having poor‒fair potential. Petroleum potential (S2) increases with increasing TOC (R2 = 0.85). Hydrogen index (HI) values range from 21 to 295 mg HC/g TOC, averaging just 147 mg HC/g TOC. In line with these modest HI values, quantitative pyrolysis-gas chromatography confirms that the petroleum potential is primarily for gas or gas-condensate, with relatively little oil potential. Of the total paraffinic petroleum yield, gas (n-C1–5) contributes 80–100%, whilst total (n-C6+) and non-volatile (n-C15+) paraffinic oil contribute ≤20% and ≤6%, respectively. Despite the low paraffinic oil potentials, n-C6+ and n-C15+ correlate relatively strongly with HI, and less strongly with TOC. The overall gas-condensate-prone nature of the Waipawa organofacies at Taylor White reflects the predominance of woody phytoclasts, which are unlikely to produce paraffinic oil. The small paraffinic oil component is instead more likely to be associated with the marine algal component. Although this component is volumetrically subordinate, the higher paraffinic oil potential appears to result from the combination of high productivity of specific marine algae (i.e., pelagophytes), hypoxic depositional conditions and, most importantly, increased preservation of OM, including through sulfurisation. This raises the possibility of more algal-rich, oil-prone facies existing within the Waipawa Formation in areas with higher TOC or, alternatively, in areas beyond the direct reach of the terrestrial influxes, yet still sufficiently influenced by low water-column oxygen levels and high sulfur contents that promote enhanced OM preservation.

A novel method for the separation of high-molecular-weight saturates from paraffinic petroleum based samples

The precise chromatographic isolation of saturates is a common problem of the characterization of highly paraffinic petroleum based samples. Incomplete elution of high-molecular-weight saturates (HMWS) or contamination of saturates by aromatics can occur when alumina or silica gel are used to separate highly paraffinic samples. Here, we present a precise, fast and simple method for the quantitative isolation of HMWS from samples of highly paraffinic crude oils, crude oil deposits, high-boiling petroleum distillates, distillation residues and waxes. The method is based on a direct chromatographic elution of HMWS with n-heptane at 80 °C on a column packed with silica gel modified with silver nitrate. The pre-separation of asphaltenes from samples is not necessary. This allowed for a quantitative elution of all present HMWS (up to C100) with no contamination by aromatics. As an example of a practical application to benefit from this efficient hydrocarbon fractionation procedure, is the analysis of crude oils and deposits. A detailed knowledge of the content of high-molecular-weight n-alkanes in these samples can help to prevent problems during crude oil transport and storage.

Simulation of the Supramolecular Structure of Petroleum Disperse Systems

The formation of predominant structures of supramolecular entities in highly dispersed colloidal systems, the dispersion phase of which is represented by hydrocarbons, has been studied using molecular mechanics (MM+) simulation. The character of structuring in both individual groups of molecules and their mixtures yielding energetically most stable associates of supramolecular structures has been investigated for compounds taken to model paraffinic, naphthenic, and asphaltenic petroleum components. It has been shown that the number of identical molecules (n) in the associates is limited. For example, asphaltene molecules form an associate with an ordered (graphite-like) supramolecular structure at n ≈ 5–10. Consideration of a mixture of three components with regard to the values of intermolecular interaction energy EIMI shows that in colloidal solutions, asphaltenes form a core to which naphthenic and paraffin hydrocarbons are coordinated.

High Technology of Production of Bitumen from Highly Paraffinic Crude

Background: The problem of manufacturing bitumen of high quality from oil residues is quite actual problem, as under conditions of depletion of oil reserves it is needed expansion of raw materials base. Methods: The analysis of oil processing state in the world determines the necessity of complex approach to solve the problem of using heavy oils, oil residues and natural bitumen, combining the further working the known processes and generating new alternative technological processes. The prospects of new effective processes development in oil processing are possible with application of different chemical and physical phenomena (mechano-chemical, plasma-chemical, ultrasonic actions and the others). Results: Currently, in practice in Russia, for refinement of final product of highly paraffinic crudes, which is production of highoctane benzine, diesel fuels, there are used pour-point depressants and inhibits, compounding with highly paraffinic crudes, processing by secondary processes – reforming, zeoforming, isomerization, viscosity breaking and coking. Practically, all these methods have restrictions on application of processing heavy oil stock. Therefore, the main objective is searching to find alternative methods on the basis of nontraditional technological processes1 . Facilities of bitumen production from goudron with paraffin carbohydrates about 15% of masses are considered2,3. It is rather problematic to obtain quality product from such raw materials. Conclusion: Therefore, the process of oxidation of goudron to bitumen is conducted in the presence of a catalytic complex, the action of which consists in reduction of paraffin carbohydrates and in reduction of process, So its presence is 2 times reducing preparation time of bitumen road marks. Also, results demonstrate that the reduction in the content of paraffinic hydrocarbons occurs by 2 times. Keywords: Bitumen, Catalystic Complex, Goudron, Highly Paraffin Petroleum Residue

Retention and efficacy of ultra-low volume pesticide applications on Culex quinquefasciatus (Diptera: Culicidae).

To combat mosquitoes and the public health hazards they present, spraying chemical adulticides is an efficient and timely control method for immediate reduction of adult populations. With the growing consciousness of environmental and public health concerns, effective mosquito control means not only maximizing the effectiveness (in terms of mosquito mortality rates) of the pesticide application, but also minimizing the unintended effects (health hazard and environmental pollution). A series of experiments was carried out to assess the efficacy and deposition of ultra-low volume (ULV) sprays on adult mosquitoes which included the influence of chemical type, spray volume, spray concentration, droplet size, and deposit location (where the droplets land on the mosquito). A modified Potter Tower was used to apply an extremely fine spray (volume median diameter ∼20 μm) on caged adult mosquitoes (Culex quinquefasciatus). Reslin (50 g/L bioresmethrin) was diluted in either water or D-C-Tron plus spray oil (782 g/L paraffinic petroleum oil), Twilight (89 g/L phenothrin) was diluted in D-C-Tron, and the mosquito mortality was assessed 24 h after spraying. A fluorescent tracer was added to the spray mixture to determine the amount of spray on mosquitoes. A fluorescent microscope was also used to view the deposit of droplets on mosquitoes. It was found that droplet retention and mortality were reduced with the larger droplet sizes. Large water-based droplets tend to bounce off adult mosquitoes. There is a tendency for droplets approximately 20 μm in size to be retained on the fine hairs on the mosquito. The largest spray deposit was found on the adult mosquito wings and the lowest deposit on the head. Mortality was higher for formulations diluted with oil compared to those diluted with water. ULV applications with ultra-fine sprays (VMD 20 μm) and oil-based products resulted in maximum target efficacy under laboratory conditions, at minimum cost, and with the minimum amount of chemical adulticides.

Thermodynamic and structural studies of the solid deposit formation in paraffinic petroleum cuts

A general review [1, 2] is presented concerning joi ntly the crystallographic structures and the transition physicochemical data (Tfus, �fusH, �fusS, �ebH, �subH, Cp) in the pure normal alkanes, as well as the structural and thermodynamic behavior of their synthetic binary, t ernary and multinary model mixtures and of real petroleum waxes, particularly the solubility and mixture prop erties [3-6]. A major part of the structural and thermodyn amic data of the literature and our experimental results are listed from methane up to the alkane with carbon at om number equal to 390 [1, 2] as well as their variati ons versus the atom carbon number. The experimental results [3] and those of literatur e concerning the pure n-alkane dissolution enthalpies allow to determine the enthalpy of the formation of one o r several crystallized solid solutions of the mixture s [4] and to highlight the influence of the characteristic pa rameters of the paraffinic distribution (theoretical average chain length, n-alkanes number, monophasic or polyphasic state) on the excess properties in the solid state. This data bank permits to test the predictive capacities of t he UNIQUAC thermodynamic model. After modifying the expression of the interaction energy to take into a ccount the effect of the size difference between the n-alk anes of the mixtures and the internal disorder induced by t he nalkane length distribution, this model give very go od results for the prediction of the excess enthalpy o f complex multialkane samples [4].

103 CHOLESTEROL-LOADED CYCLODEXTRIN ADDED TO FRESH BOAR EJACULATES AND SPERM CRYOSURVIVAL

Sperm cryosurvival is affected by altering the lipid composition of sperm plasma membranes and causes damage to spermatozoa during the cryopreservation process as loss of motile cells and functionality, compared with fresh sperm. Our objective was to compare the effect of adding cholesterol-loaded cyclodextrin (CLC) on sperm quality after freezing boar sperm. The CLC was prepared as described: 200 mg of cholesterol was dissolved in 1 mL of chloroform, and 1 g of methyl-β-cyclodextrin was dissolved in 2 mL of methanol. A 0.45-mL aliquot of the cholesterol solution was added to the cyclodextrin solution, after which the mixture was poured into a glass dish and the solvents removed using a hot plate for 24 h. The crystals were removed from the dish and stored at 22°C. A working solution of the CLC was prepared by adding 50 mg of CLC to 1 mL of BTS at 37°C. Thirty-five ejaculates from 5 boars were collected, diluted 1:1 in Beltsville thawing solution, and kept to 2 h at 22°C. The ejaculates were held at 15°C for 60 min and centrifuged at 15°C for 400g for 10 min; the pellet was suspended to 120 million cells in cooled diluent (80 mL of lactose solution 11%, 20 mL of egg yolk) and divided in 2 treatments: control and 1.5 mg of CLC/mL. The samples were incubated for 15 min at 15°C, cooled to 5°C over a 90-min period, and diluted 1:1 with freeze diluent (72.5 mL of lactose solution 11%, 6 mL of glycerol, 1.5 mL of Equex). Sperm were packaged into 0.5-mL straws, frozen in static liquid nitrogen vapor for 20 min before being plunged into liquid nitrogen. Straws were thawed in a water bath at 37°C for 30 sec, extended in Beltsville thawing solution, and analyzed by optic microscopy. Sperm were stained with 35 μg mL-1 of Hoechst 33342 and incubated for 15 min at 37°C, centrifuged at 400g for 5 min, and suspended in BTALP to a final concentration of 2 million spermatozoa/mL. A total of 10 000 spermatozoa (5 μL) from each sample were added to droplets containing 10 porcine oocytes. Porcine cumulus oocyte complexes were aspirated and placed in BTALP. The cumulus cells of the oocytes were removed by vortexing for 2 min at maximum speed. Denuded oocytes were washed 4 times in BTALP and incubated for 1 h at 38.5°C in an atmosphere of 5% CO2 in air, following which 10 oocytes per treatment were randomly placed into 45 μL droplets of BTALP, using a small bore fire polished glass pipette to remove loosely bound spermatozoa. Five oocytes were placed onto glass slides and covered with a cover slip supported by a mix of paraffin wax and petroleum jelly. Oocytes were viewed using an epifluorescence microscope, and the total number of spermatozoa bound to each zona pellucida (ZP) was determined at 400× magnification. Treatment differences for sperm motility and zona binding were determined using ANOVA. The addition of CLC to boar sperm before cryopreservation resulted in higher percentages of motile sperm and higher numbers bound to the ZP (35% and 67 sperm/ZP) compared with control cells (26% and 36 sperm/ZP; P < 0.01). In summary, adding CLC to boar sperm before cryopreservation improved cells. FAPEMIG, Piglandia, CNPq, FACEPE.

Transformer oils prepared from the vacuum distillates of Egyptian crude paraffinic petroleum

Vacuum gas oil and spindle oil obtained from the vacuum distillation of paraffinic crude oil from the Western Desert region of Egypt were utilized for transformer oils production. The vacuum gas oil, spindle oil and blends therefrom containing different percentages of these oils and were subjected to aromatic extraction, dewaxing catalytic hydrogenation processes. The aromatic extraction process used N-methyl-2-pyrrolidone as solvent, for a feed ratio of 0.7:1 (wt/wt) at an extraction temperature of 55 °C, while in the dewaxing process the wax is removed by chilling the raffinate at − 42 °C using MEK-toluene (60:40,vol/vol). The hydrofinishing process was achieved in a pilot plant using NiO–MoO 3/Al 2O 3 catalyst. These refining processes improved the viscosity indices and the pour points of the resulting oils and removed most of the polar impurities. It was found that, the transformer oil formulated from 7:3 b.w. vacuum gas oil:spindle oil respectively meets the IEC 60296-2003 standard specifications requirements. Its sulfur content is very low and non-corrosive. The gassing tendency is also low due to its low aromatic content. Further, the electrical properties which are significant for transformer oils fulfill the standard specifications as a result of the low water content and polar contaminants. Moreover, addition of 2,4-dimethyl-6-tertiary butyl phenol increases the oxidation stability of the produced oil, by acting as a free radical inhibitor.

Semi‐synthetic motor oils derived from high paraffinic petroleum base stock

PurposeTo prepare semi‐synthetic oils satisfying the classification API SF/CC and SAE 10W30 from mineral base oils derived from high paraffinic petroleum, synthetic alkylbenzenes base oils, and suitable additives.Design/methodology/approachThe mixtures of base mineral oils of deep hydro‐isomerization derived from high‐paraffinic petroleum (viscosity at 100°C is 12.5 cSt) and the mixtures of the synthetic alkyl aromatics oils with the naphthenic components (viscosity at 100°C of 8.0 cSt) were used as base oil. viscosity‐temperature properties, pour points, and flash points were modified by mixing of suitable additives. Octan M‐1, Octan M‐2, Octan M‐3, and Octan M‐4 oils were obtained by application of suitable additives into the prepared base oils B‐C. In order to get the SAE 10W30 requirements the viscous additive was added (0.4‐0.6 mass percent) to prepared base oils. For obtaining the API/SF/CC grade oils, package additive (Hitec 9229) additive was added (4.7 mass percent) to the mixture. The oil (Octan M‐1) was tested in the engine of Mercedes‐Benz model 230 car and positive results over 20,000 km running.FindingsIt was observed that, viscosities and pour points change linearly as the mass percent of alkylbenzenes the in the base oil mixture is changed. This realizes the possibility of the creation of semi‐synthetic motor oil of desired properties in the case of lack of other low‐viscosity synthetic component such as poly‐á‐olefins, diester and polyester oil. The obtained oils are useful for service in relatively mild climatic conditions (average temperature of the winter period −15 to −30°C).Research limitations/implicationsThe obtained oils cannot fully satisfy the requirements of the engines by pour point and low‐temperature characteristics in the absence of additives.Practical implicationsBecause of complexity of obtained mixture, it was impossible to study the structure and composition of the obtained products by modern techniques such as high field NMR spectroscopy.Originality/valueDetails practical information on preparation of four semi‐synthetic oils satisfying the classification API SF/CC are reported.

Surface Tensions of Hydrocarbons and Bitumens at High Temperatures and Pressures

AbstractA maximum bubble pressure apparatus, described in a previous publication, has been used at pressures to 13.9 MPa (2000 psig) and temperature to 623 K (350°C) to measure the static surface tension of several alkanes and paraffinic petroleum fractions, and two types of Alberta bitumens in contact with hydrogen, helium and hydrogen/methane mixtures. With hydrogen, the surface tensions of alkanes or mixtures of alkanes were nearly independent of pressure, whereas with helium surface tension increased significantly. With hydrogen/methane mixtures, the surface tension decreased in value as pressure increased, with the effect increasing at the higher methane concentrations. For the two bitumens used, the surface tension with hydrogen showed a 10–15% increase as pressure increased at constant temperature. Some discussion is also given concerning methods of predicting the effects of pressure and temperature in hydrogen/hydrocarbon systems.

ORGANIC FACIES, DEPOSITIONAL ENVIRONMENT AND PETROLEUM GENERATING CHARACTERISTICS OF THE LACUSTRINE SHAHEJIE FORMATION, ES4 MEMBER, WESTERN DEPRESSION, LIAOHE BASIN (NE CHINA)

Organic petrological and organic geochemical investigations have been carried out on Eocene lacustrine deposits from the Western Depression of the Liaohe Basin (NE China). The purpose was to conduct a systematic organofacies classification of these rocks, to determine their source rock potential and hydrocarbon characteristics, and to study depositional processes within this palaeo‐lake setting. Rock‐Eval data and molecular biomarkers indicate that samples analysed were immature in terms of thermal maturation.Three distinct organofacies have been identified within the ES4 member of the Shahejie Formation. The depositional model envisages the formation of good to excellent oil‐prone source rocks in a shallow saline‐alkaline lake with a stratified water column; of source rocks with moderate source potential in a deep and freshwater lake; and of poor quality source rocks towards the lake margins.The shallow lake organofacies is characterised by high total organic carbon contents (up to 17.6%) and high Hydrogen Index values (up to 908 mg HC/g TOC). The laminated sediments contain elevated amounts of fluorescing amorphous organic matter (OM) and lamalginite. High primary production dominated by cyanobacteria together with anoxic bottom waters and a paucity of terrestrial vegetation in an arid climate resulted in the deposition of Type I OM. The presence of monoaromatic carotenoids, typically derived from photosynthetic purple and green sulphur bacteria Chromatiaceae and Chlorobiaceae, suggests a water body in which an anoxic photic zone occurred at least periodically. The source rocks deposited in this type of lake have the potential to generate high‐wax paraffinic petroleum at high subsurface temperatures (up to 159°C at a heating rate of 5.3° C/million years).The quality and quantity of the OM within the freshwater organofacies (Shale I, Shale II) were determined to be lower. Petrologic observations point to the absence of laminations and the presence of Botryococcus braunil telalginite. The abundance of lycopane and its aromatised abundance of lycopane and its aromatised diagenetic analogues confirmed the presence of this algal species. Generally low concentrations of gammacerane and high pristane/phytane ratios indicate a low salinity, hydrologically open environment in which oxic conditions generally prevailed, resulting in relatively poor preservation of OM.Sediments of poor source rock quality deposited in the marginal fan‐delta setting (the Shu‐Du area) can be distinguished visually by the presence of terrigenous particles (vitrinite, inertinite and terrigenous liptinites), and geochemically by the presence of phenols in the pyrolysates.

Matrix Effects Affecting the Indirect Calibration of the Static Headspace-Gas Chromatographic Method Used for Dissolved Gas Analysis in Dielectric Liquids

To evaluate the effects of the density and polarity of the matrix on the dissolution of H2, O2, N2, CH4, CO, CO2, C2H2, C2H4, C2H6, C3H6, and C3H8 in various dielectric liquids, the gas−liquid partitioning coefficients (Ostwald coefficients) have been measured under the conditions of method C of ASTM D 3612-01 using a vapor−liquid-phase equilibrium technique. Altogether, 286 gas−liquid systems distributed throughout samples of mineral oils, vegetable oils, and synthetic oils were investigated with the aim of extending the scope of applicability of method C for dissolved gas analysis. The possibility of applying the method to a range of high-viscosity liquids (up to 120 cSt at 40 °C) was first demonstrated by measuring the equilibration of the species in the coexisting vapor phase of the samples. The effect of oil aging upon gas solubility was then addressed by assessing samples of a given mineral oil collected at different ages of in-service equipment. The oxidation of a weak polar dielectric was found to exert a negligible influence on the solubility of the nonpolar gas solutes, while for the only species with a permanent dipole moment (CO), an important reduction is seen in the solubility with the building up of oxidation products in the matrix. The Ostwald coefficients determined with samples of mineral oils (N = 13) obtained from naphthenic and paraffinic petroleum crudes showed that in the absence of strong intermolecular interactions, the solubility of the individual gases decreased with the matrix density as expected from the literature. Other measurements carried out with samples of vegetable oils (N = 7) revealed that solutes with highly polarizable π electrons (e.g., C2H2 and CO2) are susceptible to strong intermolecular interactions with some matrix polar components, which increase their ability to dissolve in this type of dielectrics. Last, the results collected with samples of synthetic oils (N = 6) were conclusive regarding the role played by some functional groups of the matrix components (carbonyl groups, conjugated double bonds, SiO bonds) in the intermolecular forces acting on the gas solutes. In light of these direct measurements of solubility data, the possibility of using a typical set of Ostwald coefficients for assessing mineral oils of various origins and as they age in the electrical apparatus was confirmed.

Upgrading of bitumen in supercritical fluids

An upgrading process for heavy oils and bitumens, based on the use of activated carbon catalysts, was investigated in a bench-scale plug flow reactor. Good results were obtained at pressures as low as 7.0 MPa at temperatures of 400–450°C. The process required the presence of hydrogen gas and a hydrogen-rich solvent in a supercritical state. If the solvent was a highly saturated alkane, very little solvent decomposition occurred. A number of n-alkanes were tested as solvents, as well as paraffinic petroleum cuts and donor solvents such as tetralin and decalin. A range of values of other operating parameters was also investigated. With an Athabasca bitumen coker feed, bitumen conversions to distillable liquids of 82–88% by weight (95–105% vol%) were achieved, with 6–8 wt% (coke+pitch) yields. Demetallization was almost 100%, and hydrodesulfurization and hydrodenitrification levels of over 80% also resulted. Under similar conditions, a conventional Co/Mo hydrotreating catalyst gave higher hydrogen uptake but lower pitch conversion, supporting the concept that carbon-based catalysts may give a unique product distribution and utilize hydrogen more effectively. It is postulated that four conditions must be met to obtain the favorable results found in this work: there must be a significant level of supercritical fluid; there must be a highly saturated or paraffinic supercritical solvent present; hydrogen gas must be present; and there must be an activated carbon catalyst used which may also have incorporated in it a catalytically active metal.

EVALUATION OF PARAFFINIC MATERIAL IN ASPHALTENES ISOLATED BY PRECIPITATION WITH LIGHT ALKANES

ABSTRACT The precipitation of paraffins by the methods usually employed for isolation and quantification of asphaltenes was verified by a brief characterization of n-alkane insoluble material from a paraffinic petroleum. So, a technique was sought to allow ready detection of these paraffins in n-pentane and n-heptane asphaltenes of heavy petroleum fractions of interest, and that was achieved by the use of differential scanning calorimetry. Liquid chromatography, which might yield material for further characterization, was also studied, with high temperature elutions, but it could not resolve groups with asphaltenes as the initial sample.

Grapevines to Hydrogen Cyanamide

The effects of surfactants on the efficacy of hydrogen cyanamide (H2CN2) applied to `Perlette' grapevines (Vitis vinifera L.) grown in the Coachella Valley of California were examined in 1994 and 1995. Vines were pruned in mid-December in both years and treatments applied at 1000 L·ha-1 the following day to dormant spurs and cordons using a hand-held spray wand. In 1994, H2CN2 was applied at 0.5%, 1%, or 2% by volume in combination with 0%, 0.5%, 1%, 2%, or 3% by volume of the amine-based surfactant Armobreak. In 1995, H2CN2 was applied at 0.5%, 1%, or 2% by volume in combination with Armobreak at 0% or 2% by volume. In 1994, budbreak rate was highly dependent upon H2CN2 concentration when 0% to 1% Armobreak was used; budbreak was generally most rapid for vines treated with 2% H2CN2 and slowest for vines treated with 0.5% H2CN2. When 2% or 3% Armobreak was used, however, little effect of H2CN2 concentration was observed. Results were similar in 1995, but the budbreak of vines treated with 2% H2CN2 + 2% Armobreak lagged behind that of vines treated with 1% H2CN2 + 2% Armobreak. The number of days after treatment required for 70% bud-break generally declined as the concentrations of H2CN2 and Armobreak were increased. A separate experiment conducted in 1995 revealed that several surfactants varying in chemical composition, Armobreak, Activator 90 and Agridex, had similar effects on H2CN2 efficacy. The results indicate that the addition of surfactants to H2CN2 solutions can significantly reduce the amount of active ingredient necessary for maximum efficacy on grapevines. Chemical names used: hydroxypolyoxyethylene polyoxypropylene ethyl alkylamine (Armobreak); alkyl polyoxyethylene ether (Activator 90); paraffin petroleum oil (Agridex).

99/00233 Thin layer chromatography study of heavy liquefaction products derived from two Chinese bituminous coals

Two Chinese bituminous coals, Yanzhou and Fenxi, were liquefied in the temperature range of 375--450 C and under a cold H{sub 2} pressure of 7 MPa without the presence of a solvent. An iron sulfide catalyst, prepared by in-situ precipitation, was used in the study. Heavy liquefaction products, a portion of toluene and trichloroethylene (TCE) solubles, were studied by thin layer chromatography (TLC) technique. Under most conditions, the conversions of catalytic liquefaction are about twice as much as that of thermal liquefaction. The yields to toluene solubles are similar to that of TCE solubles. The TLC results of the heavy liquefaction products are compared with petroleum derived highway asphalts and with a coal tar pitch. The results show that the liquefaction products of Yanzhou coal, under certain conditions, have similar composition as that of petroleum derived highway asphalts, but significantly different from that of coal tar pitch, paraffinic petroleum residue and building asphalt.

Grapevines to Hydrogen Cyanamide

The effects of surfactants on the efficacy of hydrogen cyanamide (H2CN2) applied to `Perlette' grapevines (Vitis vinifera L.) grown in the Coachella Valley of California were examined in 1994 and 1995. Vines were pruned in mid-December in both years and treatments applied at 1000 L·ha-1 the following day to dormant spurs and cordons using a hand-held spray wand. In 1994, H2CN2 was applied at 0.5%, 1%, or 2% by volume in combination with 0%, 0.5%, 1%, 2%, or 3% by volume of the amine-based surfactant Armobreak. In 1995, H2CN2 was applied at 0.5%, 1%, or 2% by volume in combination with Armobreak at 0% or 2% by volume. In 1994, budbreak rate was highly dependent upon H2CN2 concentration when 0% to 1% Armobreak was used; budbreak was generally most rapid for vines treated with 2% H2CN2 and slowest for vines treated with 0.5% H2CN2. When 2% or 3% Armobreak was used, however, little effect of H2CN2 concentration was observed. Results were similar in 1995, but the budbreak of vines treated with 2% H2CN2 + 2% Armobreak lagged behind that of vines treated with 1% H2CN2 + 2% Armobreak. The number of days after treatment required for 70% bud-break generally declined as the concentrations of H2CN2 and Armobreak were increased. A separate experiment conducted in 1995 revealed that several surfactants varying in chemical composition, Armobreak, Activator 90 and Agridex, had similar effects on H2CN2 efficacy. The results indicate that the addition of surfactants to H2CN2 solutions can significantly reduce the amount of active ingredient necessary for maximum efficacy on grapevines. Chemical names used: hydroxypolyoxyethylene polyoxypropylene ethyl alkylamine (Armobreak); alkyl polyoxyethylene ether (Activator 90); paraffin petroleum oil (Agridex).