Extractable metal salts of carboxylic acids in Green River oil shale

A study of solvent-extractable metal salts of carboxylic acids from Colorado Green River oil shale is presented. Sodium was found to be the most abundant cation present in these acid metal salts. Identification of individual components is based on combined gas Chromatographic and mass spectrometric results obtained for their respective volatile methyl esters. Normal acid salts (C₁₁ to C₃₄), isoprenoid acid salts (C₁₅ to C₁₇, C₁₉ to C₂₂), nonisoprenoid branched acid salts (C₁₄ to C₁₉), terpenoid acid salts (C₃₀ to C₃₂), and α,ω-dicarboxylic acid salts (C₁₁ to C₂₉) were identified. Small concentrations of cyclohexyl acid salts and aromatic acid salts were also found. The high even-odd predominance for the distribution of normal acid salts indicates a mild thermal history for Green River oil shale. Some acid salts (45.6 wt%) were not identified because of nonvolatility of their methyl esters.     

Gas chromatographic identification of fatty acids,fatty alcohols,and hydrocarbons ofConvolvulus pluricaulis (chois)

Convolvulus pluricaulis (Chois) (Family: Convolvulaceae) (Hindi: Shankhapushpi), widely grown in the northern part of India, was analyzed for its fatty acids and waxy constituents. Straight chain hydrocarbons (C₂₂–C₃₃), fatty acids (C₁₄–C₂₈), and fatty alcohols (C₂₄–C₃₂) were found in the whole plant 95% aqueous ethanol extract. Hydrocarbons (C₂₇, C₃₁, and C₃₃), fatty acids (C₁₄, C₁₆, and C_18:2), and alcohols (C₂₆, iso-C₂₈, iso-C₃₀, and C₃₂) were the major components.     

Branched fatty acids from the caustic oxidation of isotridecyl oxo bottoms

Caustic oxidation has been used to convert the complex residue from the isotridecyl alcohol process (“C₁₃ oxo bottoms”) to simpler mixtures of highly branched, liquid carboxylic acids in about 65% combined yield. One of the products, produced in 34% yield, was a mixture of isotridecanoic acids formed mainly from C₁₃ alcohol and its ester. It was composed of 85% primary carboxylic acids and 15% secondary. The high boiling acids were largely C₂₆ secondary car-boxylic acids formed by oxidation of aldol dimers. The relative rates of esterification were stearic:C₁₃ acid:high boiling acids—1:0.35: 0.05. In addition, a 22% combined yield of neutrals consisting of saturated and unsaturated hydrocarbons and ethers was obtained. Presented at the ISF-AOCS World Congress, New York, April 1980.     

Degradation of combustible shale kerogen from the Dmitrievskoe deposit by ozonolysis

The process characteristics and the composition of products of the ozonolytic degradation of combustible shale kerogen from the Dmitrievskoe deposit (Kuznetsk Basin) in chloroform were studied. The soluble products of combustible shale ozonization mainly consisted of aliphatic C₉-C₂₂ n-monocarboxylic and C₂-C₁₁ dicarboxylic acids. Among the constituents of water-insoluble products, C₇-C₂₅ higher fatty acids were predominant with an impurity of unsaturated and aromatic compounds.     

Fingerprinting and characterization of carboxylic acids in in-situ oil shale retort and process waters by capillary column gas chromatography-mass spectrometry

Six important in-situ oil shale retort and process waters have been analysed for carboxylic acids by capillary column gas chromatography-mass spectrometry. A fingerprint or profile was obtained for Occidental boiler blowdown process water, retort water and heater-treater process water; Geokinetics retort water, and Laramie Energy Technology Center Omega-9 and 150 Ton retort waters. The results clearly show significant differences in that each retort or process water contains various mono-, di-, branched, keto-aliphatic and aromatic carboxylic acids. The Occidental retort and process waters contained straight-chain monocarboxylic acids from C₂–C₁₃ and C₂–C₁₄, whereas the Geokinetics retort water contained C₂–C₁₀, the 150 Ton retort water C₂–C₁₀, and Omega-9 retort water C₂–C₁₄ acids. Variations among the retort waters and process waters were more important for the normal dicarboxylic acids. The Occidental retort and process water contained no C₂–C₇ straight-chain dicarboxylic acids, but those from C₈–C₁₂ were present. The Omega-9 retort water contained all the straight-chain dicarboxylic acids, C₂–C₁₂, that were identified, whereas the 150 Ton sample contained only C₂ and C₄ dicarboxylic acids, and the Geokinetics sample C₂–C₄ and C₈–C₁₂ acids. The implications of the results in pyrolysis of oil shale kerogen are discussed.     

Oxidation of cyclopentene catalyzed by phosphotungstic quaternary ammonium salt catalysts

A series of phosphotungstic quaternary ammonium salts, Q₃ (PW₁₂O₄₀) and Q₃(PW₄O₁₆) [Q = (C₅H₅)N⁺(C₁₆H₃₃), (C₁₆H₃₃)N⁺(CH₃)₃, (C₄H₉)₄N⁺, and (CH₃)₄N⁺], were used as the catalysts in oxidation of cyclopentene. The catalysts [(C₅H₅)N(C₁₆H₃₃)]₃(PW₄O₁₆) and [(C₁₆H₃₃)N(CH₃)₃]₃(PW₄O₁₆) showed high catalytic activity in the selective oxidation of cyclopentene while using H₂O₂ (50%) as an oxidant and 2-propanol as a solvent. The oxidation products mainly consisted of glutaraldehyde, cis-1,2-cyclopentanediol and trans-1,2-cyclopentanediol. The above-mentioned two catalysts were dissolved completely in the reaction medium during the catalysis process and precipitated themselves from the reaction system after reaction, showing the characteristics of reaction-controlled phase-transfer catalysis. The types of quaternary ammonium cations and the phosphotungstic anions in phosphotungstic quaternary ammonium salts affected catalytic activity.     

Correlation of chemical constitution and boiling point with separation behaviour during distillation of coal liquid

The separation behaviour of coal hydrogenation liquids during distillation was clarified using correlations between chemical structural factors (R_a, R_n and C_al) and boiling points of narrow cut distillation fractions. The separation order according to chemical structure at given distillation temperatures was represented on a three-dimensional R_aR_nC_al diagram. In this diagram, one axis represents the number of aromatic rings in the structure of a compound (R_a), one represents the number of naphthenic rings (R_n), and the third axis represents the number of alkyl carbons (C_al). This diagram is believed to be an appropriate way to handle the analysis of molecules in coal liquids, which are extremely complicated mixtures. Kerosene, light oil and heavy oil from coal liquid were also characterized on this diagram. The distribution ranges of components during separation in distillation agree fairly well with their corresponding distillation temperature range on the R_a R_nC_al diagram proposed. The distillation curve was predicted from the structural analyses with h.p.l.c./g.c.-m.s. and constitution-boiling point correlation as shown in the R_aR_nC_al diagram.     

Chemical composition of the wax secreted by a scale insect (Ceroplastes pseudoceriferus Green)

The wax material in the secretion of a scale insect,Ceroplastes pseudoceriferus Green was analyzed chemically with special interest to the composition of higher fatty acids and higher alcohols. The wax consists of 34.2% fatty acids, 27.1% unsaponifiable matter and 29.5% resin acids. The fatty acids were found to be a complex mixture of 15 normal acids ranging from C₈ to C₃₂. Of these, octacosanoic, triacontanoic and dotriacontanoic acids comprise over 30% of the wax. Presence of relatively large amount of unsaturated fatty acids of the C₁₈ series (2.8% of the wax) is of particular interest. From the unsaponifiable fraction, only one saturated straight chain aleohol, bexacosanol, was detected (2.7% of the original wax). The other unsaponifiable matter was considered to be cyclic or branched carbon chain, and consisted of at least 12 to 20 compounds. The resin acid fraction was also found to be a complex mixture of at least 13 to 14 components.     

Characterization of pyrolysis products of harbolite and Avgamasya asphaltites: comparison with solvent extracts

The products of pyrolysis at 525 and 840 °C of two asphaltites from South-Eastern Turkey have been analysed and compared with the bitumen obtained by solvent extraction. The yield of oil product is reasonably similar for all three treatments, with gas (hydrogen, ethene, C₁C₄ alkanes and hydrogen sulphide) being liberated during pyrolysis. Greater percentages of alkanes with shorter chain lengths (along with some alkenes), and of pentane-soluble aromatic oils with reduced molecular masses, are generated during pyrolysis, at the expense of asphaltenes. The extra alkanes are generated partly by the cracking of aromatic side-chains and also from kerogen. Pyrolysis reduces the number of sulphur linkages in the oil, but nitrogen- and oxygen-containing structures are liberated from kerogen during heating.     

Comparison of the chemical structure of coal hydrogenation products,athabasca tar sand bitumen and Green River shale oil

Coal hydrogenation products, Athabasca tar sand bitumen, and Green River shale oil produced by retorting were analyzed by the Brown—Ladner method and the Takeya et al. method on the basis of elemental analysis and ¹H-NMR data, by ¹³C-NMR spectroscopy and by FT-IR spectroscopy. Structural characteristics were compared.The results show that the chemical structure of oils from Green River shale oil and Athabasca tar sand bitumen, and the oils produced in the initial stage of hydrogenation of Taiheiyo coal and Clear Creek, Utah, coal is characterized as monomers consisting of units of one aromatic ring substituted highly with C_3–6 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from Green River shale oil and Athabasca tar sand bitumen is characterized by oligomers consisting of units of 1–2 aromatic rings substituted highly with C_3–5 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from coal hydrogenation is characterized by dimers and/or trimers of unit structures of 2 to 5 condensed aromatic rings, substituted moderately with C_2–5 aliphatic chains and heteroatom-containing functional groups.The close agreement between fa(¹H-NMR) and fa(¹³C-NMR) for Green River shale oil derivatives and Athabasca tar sand derivatives indicates that the assumption of 2 for the atomic H/C ratio of aliphatic structures is reasonable. For coal hydrogenation products, a value of 1.6–1.7 for the H/C ratio of aliphatic structures would be more reasonable.     

Treatment of Green River oil shale by carbon dioxide and water: evidence for association of bitumen and carbonate materials

The use of CO₂ under pressure to disaggregate the mineral matrix of Green River oil shale has been studied. The degree of disaggregation was measured by changes in particle size distribution and the amount and constituency of the bitumen released after treatment. Although the effectiveness of this technique was minimal, it did afford greater insight into the physical and chemical characteristics of Green River oil shale, and provided further evidence for the strong association of bitumen, kerogen, and minerals through carboxylic acids, acting as coupling agents.     

Aliphatic,Isoprenoid and Aromatic Acids from an Israeli Shale

Normal fatty acids (C₉-C₁₉); isoprenoid acid (C₁₀); aromatic acids (C₁₁-C₁₃) of the general formula C_nH_{2 n-8} O₂, and two aromatic acids (C₁₁, C₁₂) of the formula C_nH_{2 n-14} O₂, were identified in a bitumen obtained from shale of Nebi Musa (near Jericho), using chromatographic (GLC) and spectroscopic (MS) methods.     

Characterization of skin-surface lipids from the monkey (Macaca fascicularis)

Skin-surface lipids from the monkeyMacaca fascicularis are composed of sterol esters (38%), cholesterol (4%) and two types of wax diesters, identified as Type II (IIa and IIb, 17% and 40%, respectively). Type IIa contained diesters of 1,2-alkanediols esterified with two molecules of long-chain (C₁₄−C₃₄) fatty acids having straight and branched chains. In the diesters IIa, fatty acids shorter than C₁₉ predominated in position 1, and fatty acids longer than C₂₀ predominated in position 2. Type IIb contained diesters of 1,2-alkanediols esterified with C₄ and C₅ branched-chain fatty acids (predominantly isovaleric acid) at position 1 and long-chain (C₁₄−C₂₇) acids, having straight and branched chains, at position 2. The shortchain acids were converted to 2-nitrophenylhydrazides and analyzed by high-performance liquid chromatography (HPLC). Ammonia chemical ionization (CI)-gas chromatography (GC)-mass spectrometry (MS) resolved the intact diesters IIb into 12 peaks corresponding to molecular weights ranging from 597 to 748, and showed that the molecular species, such as C₂₁−C₁₆−C₅ (diol, fatty acid in position 2, fatty acid in position 1), C₂₂−C₁₆−C₅ and C₂₃−C₁₆−C₅, were prevalent. The fatty acids from both diesters were mostly (>98%) saturated. The 1,2-alkanediols from both diesters consisted of C₁₆−C₂₆ saturated straight- and branched-chain components. The acyl groups of sterol esters contained 86% C₁₄−C₃₄ branched-chain acids. The unsaturated fatty acids (5.4%) belonged to a straight-chain monoenoic series having extremely long chains (C₁₈−C₃₄). The branched-chain structures in the fatty acids and diols were iso and anteiso. These results show the species-specific profile for the skin-surface lipid synthesis.     

Composition of Cuticular Waxes on Osmunda regalis Fronds

The chemical composition of rodlet-shaped wax crystals on fronds of Osmunda regalis was analyzed. In all, 139 compounds belonging to 14 homologous series were detected in the surface extract. They included typical plant wax constituents: alkanes (C₂₅–C₃₃), alkyl esters (C₃₈–C₅₀), primary alcohols (C₂₂–C₃₂), secondary alcohols (C₂₇ and C₂₉), ketones (C₂₇–C₃₃), aldehydes (C₂₄–C₃₄), fatty acids (C₂₄–C₃₂), and -sitosterol. Additionally, bifunctional C₂₉ compounds (-diketone, ketols, diols) were identified. Nonacosan-10-one as the most abundant single compound, together with its bifunctional derivatives, is likely to form the wax crystals found on O. regalis fronds. Hence, a new type of wax crystals is defined morphologically and chemically. The occurrence of comparable wax aggregates on surfaces of higher plants is discussed.     

Über die Zusammensetzung der Braunkohle XIV Bitumen einer lignitischen Kohle

Composition of Lignite XIV: Bitumen of a Lignitic Coal The bitumen of a Slowakian coal was isolated by extraction with various solvents and the chemical composition of the wax portion was determined. Using spectroscopic and chromatographic methods, homologous series of the following classes of substances were identified: n-monocarboxylic acids (C₁₀–C₃₀), ω-hydroxycarboxylic acids (C₁₀–C₃₀) and n-alcohols (C₁₂–C₃₀). The waxes constitute approximately one-half of the benzene extract. Chemical composition of the wax portion is similar to those of other crude montana waxes.     

Separation of some light monocarboxylic acids from water inbinary solutions in a reverse osmosis pilot plant

The separation of formic (C₁), acetic (C₂), propionic (C₃), and n-valeric (C₅) acids in binary water solutions has been studied using a reverse osmosis (RO) membrane pilot plant operating at different temperatures and pressures (usually 21 °C and 1.72 MPa). The RO membrane, which is composite, polyamide and spiral-wound, having a surface area of 2.6 m², was fed by a solution of 0.5 M of C₁, C₂ and C₃ acids and 0.146 M of C₅. The pilot plant was used to simulate a cascade series of RO modules by recycling the permeate flux at the end of each semi-batch run. The influence on the retention coefficient, R, of molecular weight and molar volume, pK_a of the different acids was determined. For acetic acid the influence of temperature (T) and transmembrane pressure (ΔP) was also studied, obtaining an inverse and direct good linear correlation for R vs. T and R vs. ΔP, respectively. The results are particularly interesting for acetic acid-water separation, which is an open question in industrial applications.     

A comparison of the dissolution of model compounds and the kerogen of Green River oil shale by oxidation with perchloric acid — A model for the kerogen of Green River oil shale

A stepwise degradation of a kerogen concentrate of Green River oil shale was effected by oxidation with perchloric acid of varying boiling point and concentration. Dissolution of the kerogen concentrate occurred between 160 and 170°C. Several model compounds were also oxidized with perchloric acid. The model compounds were polyethylene, graphite, nylon, and polyethylene oxide. The results indicated that the kerogen was similar to polyethylene oxide. The results of this study and previous work were used to present a model for the structure of the kerogen of Green River oil shale.     

The steryl ester and phospholipid fatty acids of the spongeAgelas conifera from the Colombian Caribbean

The steryl ester and phospholipid fractions of the marine spongeAgelas conifera were isolated and analyzed. The fatty acyl components of the steryl ester and phospholipid fractions as determined by gas chromatography and gas chromatography/mass spectrometry were very similar and consisted of 56.8 and 62.7% of C₁₄−C₂₀ acids (normal; branched, especiallyiso andanteiso; and monounsaturated, particularly Δ⁹ and Δ¹¹ acids) and of 43.1 and 35.5% of C₂₄−C₂₆ acids (Δ^5,9 diunsaturated acids), respectively. The major constituent fatty acids detected were 13-methyltetradecanoic,n-hexadecanoic, 10-methylhexadecanoic, 11-octadecenoic, 12-methyloctadecanoic, 5,9-pentacosadienoic and 5,9-hexacosadienoic acids. The phospholipids isolated were identified as phosphatidylcholine (37%), phosphatidylserine (34%), phosphatidylethanolamine (16%) and phosphatidylinositol (11%). The distribution of fatty acids within the phospholipid classes was also determined.     

Exocrine secretions of bees

The volatile components of Dufour's gland extracts were analyzed in four species of NearcticNomia bees;Nomia (Dieunomia)heteropoda, N. (Tetrazonata)tetrazonata, N. (Epinomia)nevadensis, andN. (Epinomia)triangulifera. A homologous series of five saturated macrocyclic lactones ranging from C₁₈ to C₂₆ was identified. A series of esters (branched C₅-alkenols and fatty acids) was also identified in all species investigated. Two of these esters are new natural products reported for bees. A discussion of the significance of the Dufour's gland secretion for halictid systematics and its function in the Halictidae is also presented.Exocrine Secretions of Bees: I. Duffield et al. (1980), II. Fernandes et al. (1981), III. Duffieldetal (1981).     

θ3 fatty acids in freshwater fish from south brazil

Lipid and fatty acid levels in the edible flesh of 17 freshwater fish from Brazil’s southern region were determined. Analyses of fatty acid methyl esters were performed by gas chromatography. Palmitic acid (C_16:0) was the predominant saturated fatty acid, accounting for 50–70% of total saturated acids. Oleic acid (C_18:1θ9) was the most abundant monounsaturated fatty acid. Linoleic acid (C_18:2θ6), linolenic acid (C_18:3θ3), and docosahexaenoic acid (C_22:6θ3) were the predominant polyunsaturated fatty acids (PUFA). The data revealed that species such as truta, barbado, and corvina were good sources of eicosapentaenoic acid (C_20:5θ3) and docosahexaenoic acid (C_22:6θ3), and that most freshwater fish examined were good sources of PUFA θ3.