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.     

Reactions of carbon monoxide with unsaturated fatty acids and derivatives: A review

The important reactions of carbon monoxide with unsaturated fatty derivatives that are reviewed in this paper include hydroformylation (the oxo reaction), Koch carboxylation and Reppe carbonylation. With oleic acid as a substrate, the products are C₁₉ bifunctional compounds e.g., formyl- or carboxy-stearic acid. Double bond isomerization before carbon monoxide addition is characteristic of these catalytic reactions; additionally, rearrangement to introduce methyl branching occurs in the Koch carboxylation. Isomerization does not occur when a rhodium-triphenylphosphine catalyst replaces cobalt in the oxo reaction. Properties of the C₁₉ dicarboxylic acids differ and depend upon method of preparation: Many areas of application have been reported for C₁₉ compounds-lubricants, plasticizers, polyurethanes, epoxy resins, leather and other coatings, unsaturated polyester resins and transparent polyamide plastics. Presented at the AOCS Meeting, Los Angeles, April 1972. N. Market. Nutr. Res. Div., ARS, USDA.     

Composition of the ozonolytic degradation products of the organic matter of Barzasskii sapromyxite coal

The ozonization of Barzasskii sapromyxite coal in chloroform and the composition of ozonolytic degradation products were studied. Water-insoluble high-molecular-weight products were predominant among the ozonization products. A half of water-soluble substances consisted of aliphatic C₅–C₁₂ dicarboxylic acids and benzenedicarboxylic acid derivatives.     

Copolyamides derived from brassylic acid

Polyamides were prepared from C₆ to C₁₂ diamines with brassylic acid, a linear C₁₃ dicarboxylic acid, derived from Crambe seed oil. One distinct characteristic of these polymers is their low moisture adsorption as compared to nylon 66 and nylon 6. To modify the properties of these nylons, multi-component copolyamides were prepared from hexamethylene diamine and mixtures of brassylic acid with adipic, terephthalic, or isophthalic acids. It was found that the melting points of the co-polyamides were changed by the choice and the levels of the diacids used. The melting point-composition curves all show a eutectic minimum. The glass transition temperature of nylon 6,13 is also changed by the incorporation of other diacids. Water adsorption of nylon 6,13 increases with increased substitution of brassylic acid by other diacids in the order of adipic > isophthalic ≥ terephthalic. Mechanical properties of some copolyamides are in the same range as the commercial nylon 11 and nylon 12. The low moisture absorption, reduced fabrication temperature, and the wide range of properties obtainable through copolymerization make copolyamides derived from brassylic acid potentially suitable as specialty tubing, powder coatings, and molded machine parts. They will be commercially viable when brassylic acid becomes available on a large scale and is competitively priced.     

Heterocyclen aus o-Aminoketonen. XXIII [1]. Umsetzung von o-Aminoketonen mit Dicarbonsäuren

Heterocyclic Compounds from 2-Aminoketones. XXIII. Reaction of o-Aminoketones with Dicarboxylic Acids Saturated aliphatic dicarboxylic acids (C₄ C₇ and C₁₀) react with 2-aminobenzophenones in polyphosphoric acid (PPA) to form substituted derivatives of partial hydrogenated benzo[b][1,8]naphthyridines 2a–d and 2-anilino-quinoline-3-alkanoic-acids 5a–h . The heterologous derivatives of glutaric acid — containing S or N instead of β-CH₂ — with aminoketon undergo ring closure to give thiazino- and oxazino[3,2-b]quinolines 2e–h . Aromatic o-dicarboxylic acids with a –CH₂ CO- group react with aminoketones to yield anilinosubstituted 5i or pyrano[b]-condensed quinolines 6 . N,N′-Di-(2-benzoylphenyl)-dicarboxylicacid-diamides 3 with ammonia undergo cyclisation to α,ω-di-(4′phenyl-quinazolinyl-(2′))-alkanes 4 .     

Isomerization studies: III. decarbonylation of oleoyl chloride preparation of C19 dicarboxylic acids

Mixtures of siomeric C₁₇ diene hydrocarbons were obtained when oleoyl chloride was decarbonylated in the presence of a transition metal catalyst. The choice of catalyst determined the composition of diene mixture produced. Diene mixtures were characterized as a mixture of conjugated and 1,4- dienes, or as a mixture of isolated double bond dienes. Carboxylation of the conjugated C₁₇ diene by hydroformylationoxidation procedure gave a C₁₈ monocarboxylic acid as the major product, whereas with nonconjugated C₁₇ diene, the major product was a C₁₉ dicarboxylic acid. Application of the Koch carboxylation procedure to C₁₇ diene mixtures gave a C₁₉ dicarboxylic acid mixture as the major product. This latter acid mixture was structurally different from diacids obtained from the hydroformylation-oxidation procedure.     

Characterization of Aluminum Powders: II. Aluminum Nanopowders Passivated by Non‐Inert Coatings

Results of DTA‐TG investigation and chemical analysis of electro‐exploded aluminum nanopowders, passivated and/or coated with the non‐inert reagents: nitrocellulose (NC), oleic acid (C₁₇H₃₃COOH) and stearic acid (C₁₇H₃₅COOH), which were suspended in kerosene and ethanol, amorphous boron, nickel, fluoropolymer, ethanol and air (for comparison), are discussed. Surface protection of aluminum nanopowders by coatings of different origin results in significant advantages in the energetic properties of the powders. Aluminum nanopowders with a protecting surface show increased stability to oxidation in nitrogen, air and in water during storage period. On the basis of the experimental results, a diagram of the formation and stabilization of the coatings is proposed. The kinetics of the interaction of aluminum nanopowders with nitrogen, air and water is discussed. Recommendations concerning the efficiency of non‐inert reagent passivation are proposed on the basis of comprehensive analysis of the experimental data.     

Fabrication of Cr‐Cr23C6/Cr2N Composite Coatings: Change in the Phase Structure and Effect on the Corrosion Properties

Cr‐C composite coatings were electro‐codeposited in sulfuric acid‐based solutions containing submicrometer‐sized carbon black particles. The effect of heat‐treatment conditions on the carbide phase formation in the composite coatings and their corrosion behaviors were investigated. The obtained results showed that the Cr‐C composite coatings can be fabricated successfully and with an additional heat treatment, it is possible to obtain a Cr‐Cr₂₃C₆/Cr₂N composite structure. Therefore, the increase in corrosion potential suggests improvement in corrosion resistance due to the formation of Cr₂₃C₆/Cr₂N. This implies that Cr‐Cr₂₃C₆ and/or Cr₂N composite coatings have potential application to industrial fields in many respects.     

The chemistry of dibasic and polybasic fatty acids

Current processes to produce dibasic and polybasic fatty acids including azelaic, sebacic, dodecanedioic, C₂₁ diacid, fatty dimer and trimer acids are discussed. A number of alternative routes to produce azelaic, sebacic and fatty dimers are also discussed, includeding the preparation of azelaic and sebacic acids from butadiene and sebacic acid from adipic acid. Physical properties of the various dibasic acids are compared. Preparation of important derivatives and their applications is discussed, including: (a) esters and polyesters as vinyl plasticizers and as base stocks for synthetic lubricants; (b) polyamide resins in coatings, fibres, inks and adhesives; (c) salts as surfactants; and (d) amido amines and imidazolines as corrosion inhibitors. Dimer acids have found application in the petroleum industry as drilling mud thickeners in oil recovery.     

Microstructure and mechanical properties of hafnium carbide coatings synthesized by reactive magnetron sputtering

Hafnium carbide coatings with different carbon contents were synthesized in Ar–C₂H₂ mixture by reactive magnetron sputtering. Energy-dispersive X-ray, X-ray diffraction, scanning electron microscopy, atomic force microscopy, and nanoindentation were employed to characterize their microstructure and mechanical properties. The effects of C₂H₂ partial pressure on the composition, phase, microstructure, and mechanical properties of the coatings were investigated. The results show that hafnium carbide coatings can be synthesized at a low partial pressure of C₂H₂. The single-phase HfC coating with columnar crystal and favorable mechanical properties is obtained when the proportion of C₂H₂ partial pressure is only about 3.0% in the mixture, and the highest hardness and modulus are 27.9 and 255 GPa, respectively. The coating contains metal Hf and HfC phases and obtains low hardness under lower C₂H₂ partial pressure. When the C₂H₂ partial pressure is higher, the hardness and elastic moduli of acquired amorphous coatings decrease significantly.     

Bio‐based adipic acid from renewable oils

Adipic acid (hexanedioic acid, C₆H₁₀O₄) is a high‐volume dicarboxylic acid used as a chemical intermediate in the commercial manufacture of nylon 6,6, thermoplastic polyurethane resins, plasticizers, adhesives and synthetic lubricants, with an estimated global market worth approximately $6.3 billion. We report here the development of a robust industrial yeast strain and fermentation process for production of bio‐based adipic acid at high yield and selectivity from any vegetable oil, regardless of its fatty acid composition. Bio‐based adipic acid could alleviate many of the drawbacks associated with adipic acid produced from petrochemical sources and offer a sustainable alternative to benzene price swings as well as a significant reduction in greenhouse gas emissions.     

The preparation of C19 dicarboxylic acid by the koch reaction

This paper describes the preparation of C₁₉ dicarboxylic acid by the Koch reaction with carbon monoxide and sulfuric acid of oleic, tall oil fatty, and partially hydrogenated tall oil fatty acids. The effects of changing reaction conditions upon the yield and purity of the product were examined. With the best conditions, it was possible to prepare light-colored, heat-stable C₁₉ dicarboxylic acid in 83% overall weight yield at 96% purity, containing 75% tertiary isomers and 25% secondary.     

Microbial Synthesis of Medium‐Chain α,ω‐Dicarboxylic Acids and ω‐Aminocarboxylic Acids from Renewable Long‐Chain Fatty Acids

Biotransformation of long‐chain fatty acids into medium‐chain α,ω‐dicarboxylic acids or ω‐aminocarboxylic acids could be achieved with biocatalysts. This study presents the production of α,ω‐dicarboxylic acids (e.g., C₉, C₁₁, C₁₂, C₁₃) and ω‐aminocarboxylic acids (e.g., C₁₁, C₁₂, C₁₃) directly from fatty acids (e.g., oleic acid, ricinoleic acid, lesquerolic acid) using recombinant Escherichia coli‐based biocatalysts. ω‐Hydroxycarboxylic acids, which were produced from oxidative cleavage of fatty acids via enzymatic reactions involving a fatty acid double bond hydratase, an alcohol dehydrogenase, a Baeyer–Villiger monooxygenase and an esterase, were then oxidized to α,ω‐dicarboxylic acids by alcohol dehydrogenase (ADH, AlkJ) from Pseudomonas putida GPo1 or converted into ω‐aminocarboxylic acids by a serial combination of ADH from P. putida GPo1 and an ω‐transaminase of Silicibacter pomeroyi. The double bonds present in the fatty acids such as ricinoleic acid and lesquerolic acid were reduced by E. coli‐native enzymes during the biotransformations. This study demonstrates that the industrially relevant building blocks (C₉ to C₁₃ saturated α,ω‐dicarboxylic acids and ω‐aminocarboxylic acids) can be produced from renewable fatty acids using biocatalysis.

     

C-21 dicarboxylic acids in soap and detergent applications

A unique polycarboxylic acid, 5(6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, has been available commercially for over 15 years. A new high-purity (>97%), light-color version of the C-21 dicarboxylic acid has been developed recently. Soaps of the C-21 dicarboxylic acid can be used as hydrotropes to increase the solubility of nonionic surfactants in aqueous solutions containing builders and/or anionic surfactants. Since these soaps are anionic fatty acid derivatives, they reduce the surface tensions of formulations, thus improving detergency. The nontoxic and biodegradable nature of this dicarboxylic acid makes it an attractive formulation component. This paper outlines application evaluations of the soaps prepared from the C-21 dicarboxylic acids. These evaluations demonstrate how the soaps interact with nonionic surfactants or pine oil to provide clear formulations, how they wet cotton skeins in neutral to highly alkaline solutions, and how they inhibit gel formation when preparing high-solids fatty acid soap solutions. Furthermore, the preparation and characterization of the soaps of the C-21 dicarboxylic acid products are discussed. Mass-balance equations describe the preparation of aqueous soap solutions at any given concentration. Characterization of the resulting soap solutions includes acid number, pH, color, color stability, foam stability, surface tension as a function of concentration, and hard-water compatibility.     

Ultrasensitive and reversible room-temperature resistive humidity sensor based on layered two-dimensional titanium carbide

The nanostructured two-dimensional (2D) materials for humidity sensing applications have become increasingly attractive. However, 2D materials have negative aspects of easily stacking and agglomerating multilayers. Here, a novel resistive-type humidity sensor utilizing multi-layer titanium carbide (Ti₃C₂T_x) films as sensitive material is demonstrated. The humidity sensor exhibits an ultrasensitive and reversible sensing performance in a wide relative humidity range. Furthermore, the ultrafast response and recovery properties are achieved at room temperature. The Fourier transform infrared spectroscopy is used to investigate the adsorption of water vapor on Ti₃C₂T_x surfaces. A rapid capillary condensation of water vapor on the unique accordion-like microstructures and the hierarchical nanostructures of hydroxyl-riched Ti₃C₂T_x surface are supposed to be responsible for the super adsorption capability for water vapor. The electrostatic field induced by adsorbed water molecules is proposed to explain the resistance change of the titanium carbide humidity sensor. This work highlights the unique advantages of humidity sensor with layered 2D materials of Ti₃C₂T_x MXenes, including ultrasensitive, good reversibility and fast recovery at room temperature.     

Kinetics of reaction of C21 cycloaliphatic dicarboxylic acid and ethylenediamine

Kinetic studies were carried out on the reaction between ethylenediamine and C₂₁ cycloaliphatic dicarboxylic acid, prepared from dehydrated castor oil fatty acids and acrylic acid, in melt phase. The reaction was performed at six different temperatures ranging from 210 to 260°C and followed by determining the acid value of the product. The polyamidation reaction was found to follow an overall third order kinetics with an activation energy of 15.5 kcal/g mol.     

Optimization of the mechanical properties of magnetron sputtered diamond-like carbon coatings

Diamond-like carbon coatings containing hydrogen, a-C:H, were deposited by use of reactive DC magnetron sputtering with an industrial deposition system. The reactive gas C₂H₂ was used in combination with carbon targets. Using Raman spectroscopy, nanoindentation and Rockwell C indentation, the mechanical properties of the coatings were optimized. Excessively high compressive stresses, which were measured with Raman spectroscopy, were found in the coatings with high hardness, resulting in poor adhesion to the substrates. By thermal annealing, these compressive stresses were reduced without altering the hardness, resulting in diamond-like carbon coatings with good adhesion.     

Microstructure,mechanical and electrochemical properties of Ti3AlC2 coatings prepared by filtered cathode vacuum arc technology

Ti₃AlC₂ MAX phases have attracted increasing attention due to their unique properties. However, high synthesis temperatures of Ti₃AlC₂ bulk materials limit their further development. In this work, Ti₃AlC₂ coatings were prepared by a two-step method with filtered cathode vacuum arc (FCVA) deposition at room temperature and annealing at 800 °C for 1 h. The structure and properties of coatings were investigated. The results showed that the formation of Ti₃AlC₂ phase in the annealed coating depended on the C₂H₂ flow rate during deposition. At low C₂H₂ flow rates (≤ 9 sccm), almost no Ti₃AlC₂ phase was formed. As the C₂H₂ flow rate increased, the annealed coatings mainly exhibited Ti₃AlC₂ phases, the texture of which transformed from (104) to (105) planes. Meantime, the hardness of Ti₃AlC₂ coatings continuously increased to a maximum of 20.7 GPa, and the corrosion resistance first increased and then decreased with the increase of C₂H₂ flow rate.     

The water curing of a polyurethane resin used as a wool fiber coating

In the industrial application of polyurethane resins to form surface coatings on wool fabrics, the prepolymer resin Synthappret is curred by reaction with water, either as steam or as atmoshpheric water vapor, to form the rubber network. This paper examines changes in the mechanical properties of the resin with cure conditions. It is shown for steam-cured resin that the initial modulus, the equilibrium swelling in tetrachloroethylene, the Mooney-Rivlin constant C₁, and the average molecular weight of chain segments between crosslinks all reach constant values after 1 hr. However, the resin density and the Mooney-Rivlin constant C₂ show a linear dependence on cure time with no indication of reaching an equilibrium value. It is concluded that although the network is substantially complete after 1 hr of steam cure, there is a continuing pattern of reorganization. The mechanical properties of resin produced by air curing, a much slower process, are consistent with those of a network which has had a longer period of reorganization. The density of air-cured resin is significantly higher than that of resin prepared by steam curing. Stereoscan electron micrographs of the resin surface reveal a texture which coarsens with prolongation of cure time and also reveal a difference for the two methods of cure.     

Synthesis of amphiphilic amino acid C60 derivatives and their protective effect on hydrogen peroxide-induced apoptosis in rat pheochromocytoma cells

Water-soluble fullerene derivatives have often been used as effective scavengers for reactive oxygen species. Three amphiphilic amino acid C₆₀ derivatives, β-alanine C₆₀ derivative, cystine C₆₀ derivative and arginine C₆₀ derivative have been synthesized and characterized. Because of the hydrophobic interaction, the amino acid C₆₀ derivatives could self-assemble to form spherical aggregates. Moreover, the cystine C₆₀ derivative and arginine C₆₀ derivative could further form multilayer vesicles because of hydrogen bonding. Experiments demonstrate that the aggregate morphology could impact the protective effect of amino acid C₆₀ derivatives on apoptosis. These compounds were able to penetrate the cell membrane and reduce the accumulation of reactive oxygen species and cellular damage caused by hydrogen peroxide in PC12 cells. The results suggest that amino acid C₆₀ derivatives have the potential to prevent oxidative stress-induced cell death without evident toxicity. Hence, we hypothesize that the protective effect of amino acid C₆₀ derivatives on hydrogen peroxide induced apoptosis is related to many factors, such as scavenger activity and morphology of the aggregate.