Petroleum hydrocarbons bitumen

Asphalt [8052-42-4] is defined by the American Society for Testing and Materials (ASTM) (1) as a dark brown to black cementitious material in which the predominating constituents are bitumens that occur in nature or are obtained in petroleum processing. Bitumen is a generic term defined by ASTM as a class of black or dark-colored (soHd, semisoHd, or viscous) cementitious substances, natural or manufactured, composed principally of high molecular weight hydrocarbons, of which asphalts, tars, pitches, and asphaltites are typical. 

Advances in petroleum characterization at the molecular structure level by GC-MS methods renewed interest in OSC. Within the past few years, at least one-thousand new and novel OSC that previously were not known to be present in petroleum and bitumens have been reported. Tentative molecular structures inferred from GC-MS and other techniques have been confirmed in many cases by synthesis of authentic reference-compounds. The difficult and time-consuming synthetic work has been crucial in validating many of the novel structures. Another key finding has been that immature bitumens and crude oils (samples that have not received significant thermal stress) differ markedly from the previously known OSC in that they have carbon-skeletons resembling ubiquitous biomarker hydrocarbons (e.g., n-alkanes, isoprenoid alkanes, steranes, and hopanes). This similarity, of course, suggests that the hydrocarbons and OSC have common biogenic precursors. 

Asphaltenes are dark brown to black friable solids that have no definite melting point, and when heated, usually intumesce, then decompose leaving a carbonaceous residue. They are obtained from petroleums and bitumens by addition of a nonpolar solvent (such as a hydrocarbon) with a surface tension lower than 25 dynes cm-1 at 25°C (such as liquefied petroleum gases, the low-boiling petroleum naphthas, petroleum ether, pentane, isopentane, and hexane) but are soluble in liquids having a surface tension above 25 dynes cm-1 (such as pyridine, carbon disulfide, carbon tetrachloride, and benzene) (6, 7). 

Asphaltenes are, by definition, a solubility class (8, 9, 10) that is precipitated from petroleums and bitumens by the addition of a minimum of forty volumes of the liquid hydrocarbon. In spite of this, there are still reports of asphaltenes being isolated from crude oil by much lower proportions of the precipitating medium (II), which leads to errors not only in the determination of the amount of asphaltenes in the crude oil but also in the determination of the compound type. For example, when insufficient proportions of the precipitating medium are used, resins (a fraction isolated at a later stage of the separation procedure by adsorbtion chromatography) also may appear within the asphaltene fraction by adsorbtion onto the asphaltenes from the supernatant liquid and can be released by reprecipitation in the correct manner (12). Thus, questionable isolation techniques throw serious doubt on any conclusions drawn from subsequent work done on the isolated material. 

Hydrocarbon Structures. Early postulates of asphaltene structure centered around a variety of polymer structures based on aromatic systems (36, 37). More recent information has related to the structural parameters and carbon skeleton of petroleum fractions, and asphaltenes structures have been derived from spectroscopic studies of asphaltenes isolated from various petroleum and bitumen (38-46). 

Oil sands are unconsolidated sandstone deposits of a very heavy hydrocarbon bitumen. Bitumen is chemically similar to conventional oil but has comparatively high density (low gravity per American Petroleum Institute standards) and high viscosity. Based on United Nations Institute for Training and Research discussions aimed at establishing definitions for heavy crude oil and oil (tar) sands (1-3), bitumen can be placed in the context of other crude oils as shown in Table I. 

Most terpene (Cio) hydrocarbons have double bonds, hence their analysis can be approached as the analysis of cycloalkenes. However, some saturated terpanes were found in petroleum and bitumens. 

Tar Sands. Tar sands (qv) are considered to be sedimentary rocks having natural porosity where the pore volume is occupied by viscous, petroleum-like hydrocarbons. The terms oil sands, rock asphalts, asphaltic sandstones, and malthas or malthites have all been appHed to the same resource. The hydrocarbon component of tar sands is properly termed bitumen. 

Asphalt (qv) is prepared from petroleum and often resembles bitumen. When asphalt is produced simply by distillation of an asphaltic cmde, the product can be referred to as residual asphalt or straight-mn petroleum asphalt. If the asphalt is prepared by solvent extraction of residua or by light hydrocarbon (propane) precipitation, or if blown or otherwise treated, the term should be modified accordingly to qualify the product, eg, propane asphalt. 

A number of types of bituminous material exist and terminology is still somewhat confusing. The term bitumens in its widest sense includes liquid and solid hydrocarbons but its popular meaning is restricted to the solid and semisolid materials. The bitumens occur widely in nature and may be considered to be derived from petroleum either by evaporation of the lighter fraction under atmospheric conditions or by a deeper seated metamorphism. The purer native bitumens are generally known as asphaltites and include Gilsonite, extensively used for moulding, which occurs in Utah. 

By far the most widespread use of NMR in an on-line production environment is the utilization of downhole exploration tools by petroleum service companies such as Schlumberger, Halliburton, and Baker Hughes. Articles on these unilateral NMR systems are found in the patent databases, " academic literature, and on-line resources provided by the exploration companies. The references provided here are just a few examples in a very prolific field. The technique is applied in high-temperature and pressure situations and currently is used down to a depth of about 10 km (6 miles) to produce a picture of water/oil content in the adjacent rock formations as well as to derive permeability, diffusivity, and hydrocarbon chemistry information. Mobile unilateral NMR systems such as the NMR-MOUSE are also being developed in order to take benchtop NMR systems into the field to perform analysis of geological core samples at the drill site. NMR analyzers are also being developed to determine the bitumen content and properties in tar sand production and processing. " " ... 

Bitumen is the geological equivalent of lipids, consisting in the widest sense of any sedimentary hydrocarbon ranging in state from tarry (asphalt) through viscous to liquid (petroleum). 

BITUMEN. Natural flammable substances of a wide range of color, hardness, and volatility, constituted mainly of a mixture of hydrocarbons and essentially free from oxygenated bodies. Petroleums, asphalts, natural mineral waxes, and asphaltites arc considered bitumens. See also Tar Sands. 

Bitumen. Naturally occurring, solid or semisolid, hydrocarbons including asphalt, mineral pitch, petroleum and naphtha. The ASTM designates them as the fraction of hydrocarbons which are sol in CS2. They are rich in C and H and burn with a sooty flame... 

After removal of the asphaltene fraction, further fractionation of petroleum is also possible by variation of the hydrocarbon solvent. For example, liquehed gases, such as propane and butane, precipitate as much as 50% by weight of the residuum or bitumen. The precipitate is a black, tacky, semisolid material, in contrast to the pentane-precipitated asphaltenes, which are usually brown, amorphous solids. Treatment of the propane precipitate with pentane then yields the insoluble brown, amorphous asphaltenes and soluble, near-black, semisolid resins, which are, as near as can be determined, equivalent to the resins isolated by adsorption techniques. 

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