Residue-Containing Products

These products comprise whole crude oils, as well as bottom fractions of distilling units and (partly) converted materials. The common property of these products is the fact that they contain high-boiling material which is not amenable to gas chromatographic analysis. 

Nevertheless, a number of gas chromatographic applications exist, epecially those for the determination of crude oil indicators. Such indicators are used as geochemical parameters for the thermal history of the crude as well as to indicate the possible relationship between crudes from different wells. These indicators comprise a number of isomeric aromatic species, such as the individual alkylnaphthalenes (44, 45), the individual Cio-mono-aromatics or the individual C9-mono-aromatics. The ratio between these isomers gives a definite indication of the crude oil. In general, these systems use a Deans switching unit to make a heart-cut, which then is focused, reinjected and separated on a second column with a different polarity. 

1 A DETAILED HYDROCARBON ANALYTICAL SYSTEM COUPLED TO A SIMULATED DISTILLATION PROCESS 

2 AN SEC-LC-GC SYSTEM EOR THE ANALYSIS OE LOW BOILING MATERIALS IN RESIDUAL PRODUCTS 

A more complicated, but flexible, system has been reported by Blomberg et al. (46). Here, size exclusion chromatography (SEC), normal phase EC (NPLC) and GC were coupled for the characterization of restricted (according to size) and selected (according to polarity) fractions of long residues. The seemingly incompatible separation modes, i.e. SEC and NPLC, are coupled by using an on-line solvent-evaporation step. 

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With Stirring, hydrazine hydrate (4 ml in 30 ml of THh ) was added over 60 min. The reaction mixture was then cooled to room temperature and filtered through Celite. The filtrate was concentrated in vacuo and the residue purified by chromatography through silica gel using 10% ether in hexane for elution. The fractions containing product were combined and evaporated to give the product as a clear oil (2.94g, 50%). 

The high-chromium casting alloys (50% nickel, 50% chromium and 40% nickel, 60% chromium) are designated for use at temperatures up to 900 C in furnaces and boilers Ared by fuels containing vanadium, sulfur and sodium compounds (e.g., residual petroleum products). Alloys with lower chromium contents cannot be used with residual fuel oils at temperature above 6S0 C because the nickel reacts with the vanadium, sulfur and sodium -impurities to form compounds that are molten above 650 C [27]. 

The prognosis for bioremediation of residues containing polychlorinated anilines and their impurities is rather discouraging. Important factors include (a) limited biodegradability, (b) restricted bioavailability, and (c) the possible formation of oligomeric coupling products. 

V. E. Ignateva, A. G. Telin, N. I. Khisamutdinov, S. V. Safronov, V. N. Artemev, and Y. A. Ermilov. Composition for oil extraction—contains hydrocarbon- or alcohol-containing solvent, water and vat residue from production of glycerine or ethylene glycol. Patent RU 2065941-C, 1996. 

E. A. Konovalov, Y. A. Ivanov, T. N. Shumilina, V. F. Pichugin, and N. N. Komarova. Lubricating reagent for drilling solutions—contains agent based on spent sunflower oil, water, vat residue from production of oleic acid, and additionally water glass. Patent SU 1808861-A, 1993. 

Now, since each respective fraction shows a structural change along with the reaction course, it may be considered at the same time that it contains products from a higher molecular fraction. In other words, for instance i r A2 is produced from coal 2 which changes by hydrogenolysis and at the same time, the residue resultinq from the reaction from Fr Ai to Fr also appears in this fraction. 

The coal residue was separated into a THF-soluble fraction and a THF-insoluble residue. The wt % yields and atom % 2H compositions are given in Table I. The coal residue was 6 wt % soluble in tetrahydrofuran. The soluble fraction had 23 atom % 2H content. Evaluation of the 2H NMR data showed that 85 wt % of this fraction was derived from the coal and that its deuterium content was 10%. The chemically-bonded naphthalene-d8 content of the THF-soluble fraction, estimated from the 2H NMR data, was about 15 wt % or approximately 1 wt % of the coal. The insoluble residue had 6 atom % 2H content. This indicates that the residue contained approximately 1 wt % chemically-bonded naphthalene which was estimated from the difference in the atom % 2H content of the insoluble residue and recovered naphthalene-d8. This gives a total chemically-bonded naphthalene-d8 content of approximately 2 wt %. Similar results were obtained in extraction experiments made with phenanthrene (30), where it was found that 3-7 wt % of the phenanthrene was chemically linked to the coal product. 

Methylation was accomplished by direct conversion of the acetyl derivative as previously described. The final product contained 45% OCHs. Molecular weight determinations in benzene gave values representing 18 to 19 D-fructose residues. Hydrolytic products of the methyl derivative were separated by conversion to benzoyl derivatives. The trimethylfructose was identified as 3,4,6-trimethyl-D-fructofuranose by its phenylosazone. The authors conclude that the ratios 1 3 1 exist among the di-, tri-, and tetramethyl-D -fructoses produced by the hydrolysis. 

The extracts from the reaction are combined and shaken up with a little anhydrous magnesium sulfate (120 grams) and filtered. The filtrate is evaporated to dryness in the rotary vacuum evaporator, care being taken not to heat the extracts or the residual syrup above 55° C. A good mechanical vacuum pump and effective cold traps in the line are necessary to remove the residual dimethylformamide from the residue. A brown to black bubbly residue should remain when evaporation is complete. This residue contains the amide product and considerable impurities. A general method of purifying the amide follows. 

After the corrosion products had been removed from the surface of the metal to be analysed, a weighed sample was treated with moderately concentrated nitric acid and the reaction mixture was allowed to stand overnight... the supernatant liquid was poured off and saved, and any undissolved metal or insoluble residue again treated with nitric acid... If tin was present as shown by the continued presence of a residue insoluble in nitric acid, this was collected on filter paper... (this) was simply dried in an oven and weighed... a parallel control experiment was made with a known weight of pure tin. It was found from this that 100 parts of dried residue contained 71 parts metallic tin, in other words the gravimetric factor was 0.71. 

Monosaccharide residues containing vicinal hydroxyl groups are oxidized by periodate, and are subsequently removed in the reduction-hydrolysis step. Therefore, the positions to which such monosaccharide residues are linked can be located by methylation analysis performed before, and after, Smith degradation. Alternatively,59 the oxidized and reduced sample is methylated, the ether hydrolyzed, and the product realkylated with CD3I or CH3CH2I. This kind of procedure can have advantages over that first described. For example, methylation before the hydrolysis step hinders the acetal protection of hydroxyl groups that can occur in acid hydrolysis.7... 

The results from OILEQUIL can be converted to an active layer thickness in several ways. First, the total thickness of the zone shown to contain product could be used. This would overestimate the thickness of the recoverable product layer, because oil at low saturations is immobile. Second, one could follow Van Dam (1967) in assuming a residual oil saturation of 20% (or another value appropriate to the soil and LNAPL involved) and pick out the thickness of the zone with greater than 20% product saturation from the OILEQUIL tabular output. In equation form,... 

The mixture was left to cool to room temperature and the solid catalysts were removed by filtration. Toluene and the by-product, acetaldehyde, were removed under reduced pressure by using a rotary evaporator. The residue contains the desired product together with unreacted vinyl octanoate and traces of octanoic acid, which are formed by hydrolysis of the vinyl octanoate. The product can be purified by redissolving the residue in hexane (20 mL) and washing it with 0.1 M NaOH (20 mL x 3). The organic layer was dried with anhydrous Na2S04 and the hexane was removed by a rotary evaporator. 

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