Catalytic methods for associated petroleum gas pretreatment and processing

Two groups of technologies, specifically those for pretreatment and for processing of associated petroleum gases, were described. One group includes technologies based on deep adsorptive drying and desulfurization. The other group integrates technologies used for processing of associated petroleum gas into aromatic hydrocarbons, synthetic motor fuel (the Fischer-Tropsch process), and carbon nanomaterials. Basic process parameters were indicated for each of the technologies. The results of pilot (semicommercial) testing were presented for some of the processes.     

New catalytic methods for obtaining cellulose and other chemical products from vegetable biomass

Experimental data concerning the effects of catalysts are discussed for the oxidative destruction of wood lignin in the acetic acid-hydrogen peroxide-water medium, for lignin oxidation with oxygen into aromatic aldehydes in aqueous alkali, for the acid-catalyzed conversion of carbohydrates into esters of levulinic acid and 5-hydroxymethylfurfural in the two-phase system butanol-water, and for α-angelicalactone polymerization into biodegradable polymers.     

Forensic differentiation of biogenic organic compounds from petroleum hydrocarbons in biogenic and petrogenic compounds cross-contaminated soils and sediments

“Total petroleum hydrocarbons” (TPHs) or “petroleum hydrocarbons” (PHCs) are one of the most widespread soil pollutants in Canada, North America, and worldwide. Clean-up of PHC-contaminated soils and sediments costs the Canadian economy hundreds of million of dollars annually. Much of this activity is driven by the need to meet regulated levels of PHC in soil. These PHC values are legally required to be assessed using standard methods. The method most commonly used in Canada, specified by the Canadian Council of Ministers of the Environment (CCME), measures the total hydrocarbon concentrations in a soil by carbon range (Fraction 1: C₆–C₁₀; Fraction 2: C₁₀–C₁₆, Fraction 3: C₁₆–C₃₄: and Fraction 4: C₃₄+). Using the CCME method, all of the materials extractible by a mixture of 1:1 hexane:acetone are considered to be petroleum hydrocarbon contaminants. Many hydrocarbon compounds and other extractible materials in soil, however, may originate from non-petroleum sources. Biogenic organic compounds (BOCs) is a general term used to describe a mixture of organic compounds, including alkanes, sterols and sterones, fatty acids and fatty alcohols, and waxes and wax esters, biosynthesized by living organisms. BOCs are also produced during the early stages of diagenesis in recent aquatic sediments. BOC sources could include vascular plants, algae, bacteria and animals. Plants and algae produce BOCs as protective wax coating that are released back into the sediment at the end of their life cycle. BOCs are natural components of thriving plant communities. Many solvent-extraction methods for assessing soil hydrocarbons, however, such as the CCME method, do not differentiate PHCs from BOCs. The naturally occurring organics present in soils and wet sediments can be easily misidentified and quantified as regulated PHCs during analysis using such methods. In some cases, biogenic interferences can exceed regulatory levels, resulting in remediation of petroleum impacts that are not actually present. Consequently, reliance on these methods can trigger unnecessary and costly remediation, while also wasting valuable landfill space. Therefore, it is critically important to develop new protocols to characterize and differentiate PHCs and BOCs in contaminated sediments. In this study, a new reliable gas chromatography–mass spectrometry (GC–MS) method, in combination with a derivatization technique, for characterization of various biogenic compounds (including biogenic alkanes, sterols, fatty acids and fatty alcohols) and PHCs in the same sample has been developed. A multi-criteria approach has been developed to positively identify the presence of biogenic compounds in soil and sediment samples. More than thirty sediment samples were collected from city stormwater management (SWM) ponds and wetlands across Canada. In these wet sediment samples, abundant biogenic n-alkanes, thirteen biogenic sterols, nineteen fatty carboxylic acids, and fourteen fatty alcohols in a wide carbon range have been positively identified. Both PHCs and BOCs in these samples were quantitatively determined. The quantitation data will be used for assessment of the contamination sites and toxicity risks associated with the CCME Fraction 3 hydrocarbons.     

Coloured products from thiophene and aromatic 1,2-diketones

Thiophene and phenanthrene-9,10-quinone react in acidic solution to produce the deep blue extended quinone (Z,Z)-2,5-di(9-oxo-9,10-dihydro-10-phenanthrylidene)-2,5-dihydrothiophene the structure of which is confirmed by X-ray crystallography. Other aromatic 1,2-diketones give rise to related products.     

Sub-micro methods for the analysis of organic compounds

Summary A new technique is described which enables organic compounds to be analysed for elements and functional groups using sample weights of 30–50 micrograms (0.03 to 0.05 mg). These amounts are only just visible to the naked eye. The accuracy is similar to that of the microscale, and the technique is fairly simple.It is expected that these methods will be of value in biochemistry and associated fields where amounts of sample are often limited. The new technique is not intended to replace micro-methods. Investigations are still proceeding to develop further methods for the determination of functional groups and to refine earlier procedures.     

Determination of basic nitrogen-containing polycyclic aromatic compounds (azaarenes) in petroleum and petroleum products

Summary After a selective enrichment including liquid-liquid-partition (dimethylformamide/water/cyclohexane, 9110; DMF/water/benzene, 3710) and ion-exchange chromatography (SP Sephadex C 25), a basic fraction of a crude oil sample was analysed by capillary gas-chromatography. The enrichment procedure results in an azaarene fraction consisting exclusively of nitrogen-containing compounds as confirmed by a comparison of the chromatograms recorded by FID and a nitrogen-specific detector (N-FID). The coefficients of variation for a series of a several times (n=5) repeated analysis of 8 selected azaarenes from an Arabian Light sample were found to be between 4.7 and 6.7%.

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Bestimmung basischer Stickstoff-haltiger polycyclischer aromatischer Verbindungen (Azaarene) in Erdöl und Mineralölprodukten

Zusammenfassung Nach einer selektiven Anreicherung durch Flüssig-Flüssig-Verteilung (Dimethylformamid/ Wasser/Cyclohexan, 9110; DMF/Wasser/Benzol, 3710) und Ionenaustauscher-Chromatographie (SP Sephadex C 25) wurde die basische Fraktion einer Ölprobe capillargas-chromatographisch getrennt. Das Anreicherungsverfahren liefert eine Azaarenfraktion, die ausschließlich aus Stickstoff-haltigen Verbindungen besteht, was durch einen Vergleich der mit dem FID und N-FID registrierten Gas-Chromatogramme gezeigt werden konnte. Die Variationskoeffizienten einer mehrfach wiederholten Probenserie (Arabian Light, n=5) ergab für 8 ausgewählte Azaarene Werte zwischen 4,7 und 6,7%.

     

Development of a species-specific isotope dilution GC-ICP-MS method for the determination of thiophene derivates in petroleum products

A species-specific isotope dilution technique for accurate determination of sulfur species in low- and high-boiling petroleum products was developed by coupling capillary gas chromatography with quadrupole ICP-MS (GC-ICP-IDMS). For the isotope dilution step ³⁴S-labeled thiophene, dibenzothiophene, and mixed dibenzothiophene/4-methyldibenzothiophene spike compounds were synthesized on the milligram scale from elemental ³⁴S-enriched sulfur. Thiophene was determined in gasoline, ‘sulfur-free’ gasoline, and naphtha. By analyzing reference material NIST SRM 2296, the accuracy of species-specific GC-ICP-IDMS was demonstrated by an excellent agreement with the certified value. The detection limit is always limited by the background noise of the isotope chromatograms and was determined for thiophene to be 7 pg absolute, which corresponds to 7 ng sulfur/g sample under the experimental conditions used. Dibenzothiophene and 4-methyldibenzothiophene were determined in different high-boiling petroleum products like gas oil, diesel fuel, and heating oil. In this case a large concentration range from about < 0.04 to more than 2,000 μg g⁻¹ was covered for both sulfur species. By parallel GC-ICP-MS and GC-EI-MS experiments (EI-MS electron impact ionization mass spectrometry) the substantial influence of co-eluting hydrocarbons on the ICP-MS sulfur signal was demonstrated, which can significantly affect results obtained by external calibration but not those by the isotope dilution technique.     

原油中有机硫化物成因的硫酸盐热化学还原反应模拟研究

原油中部分有机硫化物来源于硫酸盐热化学还原反应。利用高压釜在高温高压含水条件下对正戊烷 硫酸镁反应体系进行了热模拟实验研究。通过气相色谱仪、微库仑仪、毛细管气相色谱/脉冲火焰光度检测器、红外光谱仪及X射线衍射仪,对气、油、固三相产物进行了分析。结果表明,硫酸盐热化学还原反应在425℃~525℃可以进行,主要生成氧化镁、炭、硫化氢、二氧化碳以及硫醇、硫醚和噻吩类等有机硫化物。根据动力学模型计算出该反应活化能为58.0kJ/mol。     

Extractive refining of high-sulfur diesel fraction to remove organic sulfur compounds and aromatic hydrocarbons

The results of seven-step extractive refining of high-sulfur diesel fraction to remove organic sulfur compounds and arenes using dimethylformamide, furfuryl alcohol, phenol, and the extraction systems dimethylformamide-hexane and phenol-hexane are reported.     

Newer acylation methods for the determination of organic hydroxyl and amino compounds

A critical review of certain acylation methods for the determination of organic hydroxyl and amino compounds is presented. Esterification methods developed after 1955, involving seven anhydrides and five acid chlorides, are discussed. A brief survey is given of acid-catalysed acetylation and of colorimetric methods based on the esterification reactions.     

Determination of individual sulfur-containing compounds in liquid hydrocarbon raw materials and their processing products by gas chromatography

The publications dedicated to the determination of individual sulfur-containing compounds in liquid hydrocarbon raw materials and their processing products by gas chromatography are summarized. In the analysis of petroleum raw materials, the preliminary separation of sulfur-containing compounds and a hydrocarbon matrix is usually performed. In the analysis of liquid oil refining products and gas condensate, the direct determination of individual sulfur-containing compounds can be frequently conducted. The use of currently available sulfur-selective chemiluminescence and atomic emission detectors in combination with nonpolar or slightly polar capillary columns and also two-dimensional chromatography is the most promising.     

Catalytic systems for reduction of nitro compounds involving cerium complexes with organic ligands

Conclusions Effective catalytic systems were developed for the reduction of aromatic nitro compounds, which consist of a heterogeneous palladium catalyst and cerium complexes with organic ligands.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp.1104–1107, May, 1979.     

New iodometric methods for the microdetermination of arsenic in organic compounds

New methods are described for the iodometric microdetermination of arsenic in organic compounds after wet digestion or oxygen flask combustion. After evaporation of the arsenic solution to dryness and dissolution of the residue in water, acetone is added and the solution is treated with iodide-iodate and the iodine liberated (by the interfering acids and the first dissociation step of arsenic acid) is reduced with thiosulphate. The KH(2)AsO(4) left is then reacted with zinc sulphate in presence of excess of KI and KIO(3). Acetone is added and the liberated iodine is titrated with thiosulphate. This titration corresponds to the second and third dissociation steps of arsenic acid and is used to calculate the arsenic content of the compound. When arsenicals not containing sulphur are decomposed by the oxygen flask method, the arsenic acid solution obtained is reacted directly with zinc sulphate in presence of KI and KIO(3) and the iodine released is titrated with thiosulphate. In this case, the titration corresponds to all three dissociation steps of arsenic acid. The average recoveries obtained by the two methods are 99.5 and 99.9%, respectively.     

Adsorptive interaction between nitrogen compounds and organic and/or mineral phases in subsurface rocks. Models for compositional fractionation of pyrrolic nitrogen compounds in petroleum during petroleum migration

The results are reported of a range of laboratory chromatographic fractionation experiments with synthetic model compounds and a petroleum pyrrolic nitrogen fraction. Reversed phase separation of pyrrolic nitrogen compounds was governed mainly by the number of carbon atoms in the molecule, with little selectivity toward different positional isomers, whereas normal phase separation of the compounds could be explained in terms of steric effects related to alkylation position. Comparison of experimental results from model compounds with observations made previously using sets of natural samples taken from sedimentary basins clearly suggests adsorptive interactions between organic and mineral phases are involved in the compositional fractionation of pyrrolic nitrogen compounds in petroleum during migration. Detailed studies of the effects of petroleum migration on the molecular distribution of petroleum pyrrolic nitrogen compounds may provide useful, quantifiable, migration-related geochemical parameters.