Petroleum naphthenes

The techniques of preparation and of separation of hydrocarbons were improved. New construction materials led to cracking being conducted under more severe conditions, to increase the amount of olefins produced.. This also permitted a change from propane to ethane as the raw material for ethylene synthesis. Aromatics became available from petroleum naphthenes. Diolefins and acetylene were also manufactured from petroleum sources. 

At the same time as the lower paraffins were being pressed into service, the second world war led to the manufacture of aromatics from petroleum. New methods of isolating, isomerizing, and dehydrogenating petroleum naphthenes were devised on the basis of petroleum techniques. During the war, manufacture of toluene and xylene was established since then, benzene has been added, because the growing demands of the chemical industry could not be met from the conventional source, coke-oven tar. 

Synonyms CNC Naphthenic acid copper salt Definition Copper salt of petroleum naphthenic acids Empirical C13H25CUO2... 

Definition Copper salt of petroleum naphthenic acids... 

It is produced from petroleum fractions rich in naphthenes by catalytic reforming in the presence of hydrogen (hydroforming) in this process dehydrogenation .nd dealkylation... 

Group the component in a petroleum fraction, which is possible if the normal boiling temperature and the standard specific gravity are known. This method gives correct results when the chemical structure is simple as in the case of a paraffin or naphthene. 

The major part of the sulfur contained in crude petroleum is distributed between the heavy cuts and residues (Table 8.10) in the form of sulfur compounds of the naphthenophenanthrene or naphthenoanthracene type, or in the form of benzothiophenes, that is, molecules having one or several naphthenic and aromatic rings that usually contain a single sulfur atom. 

Hydrocarbons, compounds of carbon and hydrogen, are stmcturally classified as aromatic and aliphatic the latter includes alkanes (paraffins), alkenes (olefins), alkynes (acetylenes), and cycloparaffins. An example of a low molecular weight paraffin is methane [74-82-8], of an olefin, ethylene [74-85-1], of a cycloparaffin, cyclopentane [287-92-3], and of an aromatic, benzene [71-43-2]. Cmde petroleum oils [8002-05-9], which span a range of molecular weights of these compounds, excluding the very reactive olefins, have been classified according to their content as paraffinic, cycloparaffinic (naphthenic), or aromatic. The hydrocarbon class of terpenes is not discussed here. Terpenes, such as turpentine [8006-64-2] are found widely distributed in plants, and consist of repeating isoprene [78-79-5] units (see Isoprene Terpenoids). 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

Naphthenic acids have been the topic of numerous studies extending over many years. Originally recovered from the petroleum distillates to minimise corrosion of refinery equipment, they have found wide use as articles of commerce in metal naphthenates and other derivatives. A comprehensive overview of the uses of naphthenic acid and its derivatives can be found in References 1 and 2. A review of the extensive research on carboxyUc acids in petroleum conducted up to 1955 is available (3), as is a more recent review of purification, identification, and uses of naphthenic acid (4). 

The name naphthenic acid is derived from the early discovery of monobasic carboxyUc acids in petroleum, with these acids being based on a saturated single-ring stmcture. The low molecular weight naphthenic acids contain alkylated cyclopentane carboxyUc acids, with smaller amounts of cyclohexane derivatives occurring. The carboxyl group is usually attached to a side chain rather than direcdy attached to the cycloalkane. The simplest naphthenic acid is cyclopentane acetic acid [1123-00-8] (1, n = 1). 

Naphthenic acid corrosion has been a problem ia petroleum-refining operations siace the early 1900s. Naphthenic acid corrosion data have been reported for various materials of constmction (16), and correlations have been found relating corrosion rates to temperature and total acid number (17). Refineries processing highly naphthenic cmdes must use steel alloys 316 stainless steel [11107-04-3] is the material of choice. Conversely, naphthenic acid derivatives find use as corrosion inhibitors ia oil-weU and petroleum refinery appHcations. 

The acid content of cmde petroleum varies from 0—3%, with cmdes from California, Venezuela, Russia, and Romania having the highest content. Smaller amounts are found ia U.S. Gulf Coast cmdes, whereas Httie or no naphthenic acids are found ia Pennsylvania, Iraq, or Saudi Arabia cmdes. Typical concentrations are shown ia Table 2. Minor amounts of naphthenic acids are also found ia bituminous oil sands, but these are not economically recoverable. Identification of naphthenic acids ia water from oil-beating strata is being examined as a potential method of petroleum exploration (18). 

Naphthenic acids occur ia a wide boiling range of cmde oil fractions, with acid content increa sing with boiling point to a maximum ia the gas oil fraction (ca 325°C). Jet fuel, kerosene, and diesel fractions are the source of most commercial naphthenic acid. The acid number of the naphthenic acids decreases as heavier petroleum fractions are isolated, ranging from 255 mg KOH/g for acids recovered from kerosene and 170 from diesel, to 108 from heavy fuel oil (19). The amount of unsaturation as indicated by iodine number also increases in the high molecular weight acids recovered from heavier distillation cuts. 

Oil field uses are primarily imidazolines for surfactant and corrosion inhibition (see Petroleum). Besides the lubrication market for metal salts, the miscellaneous market is comprised of free acids used ia concrete additives, motor oil lubricants, and asphalt-paving applications (47) (see Asphalt Lubrication AND lubricants). Naphthenic acid has also been studied ia ore flotation for recovery of rare-earth metals (48) (see Flotation Lanthanides). 

In the other market areas, lead naphthenates are used on a limited basis in extreme pressure additives for lubricating oils and greases. Sodium and potassium naphthenates are used in emulsiftable oils, where they have the advantage over fatty acid soaps of having improved disinfectant properties. Catalyst uses include cobalt naphthenate as a cross-linking catalyst in adhesives (52) and manganese naphthenate as an oxidation catalyst (35). Metal naphthenates are also being used in the hydroconversion of heavy petroleum fractions (53,54) and bitumens (55). 

Within the VGO saturates, distribution of paraffins, isoparaffins, and naphthenes is highly dependent on the petroleum source. The naphthenes account for roughly 60% of the saturates in a normal cmde oil. However, samples can be found having paraffins from <20 to >80%. In most samples, the / -paraffins from C2Q—are still present in sufficient quantity to be detected as distinct peaks in gc analyses. Some cmde oils show a nearly symmetric pattern of peaks such that each carbon number is present in regular progression up to a maximum around C -j. Other cmde oils show a similar distribution, but have preference for odd-numbered alkanes. Both the distribution and the selectivity toward odd-numbered hydrocarbons are considered to reflect differences in petrogenesis of the cmde oils. Although / -paraffins are distinct in the gc, these usually account for only a few percent of the saturates measured by gc. 

Process Oils, Plasticizers. Petroleum-based mbber process oils generally contain a mixture of paraffinic, naphthenic, and aromatic components. These oils vary in composition from grade to grade, but most contain some unsaturated moieties and this unsaturation can compete with the polymer for curatives. Therefore, state of cure can be decreased. This is not easily detected because oil softens the compound which masks the loss of state of cure. 

The petroleum oils are of three basic types aromatic, naphthemic, and paraffinic. Aromatic oils contain hazardous materials that require special handling precautions. Naphthenic oil does not contain hazardous levels of polynuclear aromatics (PNAs) and is less hysteretic. Because of these considerations the naphthenic oil is gaining in usage at the expense of more utilized aromatics. Paraffinic oil is only used modestly in tire compounds. The... 

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