In crude oil

The rings most frequently encountered in crude oils are those having five or six carbon atoms. In these rings, each hydrogen atom can be substituted by a paraffinic alkyl chain that is either a straight chain or branched. 

There are little or no olefins in crude oil or straight run (direct from crude distillation) products but they are found in refining products, particularly in the fractions coming from conversion of heavy fractions whether or not these processes are thermal or catalytic. The first few compounds of this family are very important raw materials for the petrochemical Industry e.g., ethylene, propylene, and butenes. 

Normally absent or in trace amounts in crude oil, products of conversion processes such as diolefins, acetylenes, etc., are encountered. Table 1.4 gives the physical properties of some of them. Noteworthy is 1-3 butadienerC ( l)... 

Sulfur is the heteroatom most frequently found in crude oils (see Table 1.5). Sulfur concentrations can range from 0.1 to more than 8 weight percent moreover, this content is correlated with the gravity of the crude oil and, therefore, its quality (light or heavy). 

In crude oil, nitrogen is found mostly in fractions boiling over 250°C and is particularly concentrated in resins and asphaltenes. Nitrogen takes the following forms / to). ... 

Other techniques such as X-ray diffusion or small angle neutron diffusion are also used in attempts to describe the size and form of asphaltenes in crude oil. It is generally believed that asphaltenes have the approximate form of very flat ellipsoids whose thicknesses are on the order of one nanometer and diameters of several dozen nanometers. 

The petroleum industry faces the need to analyze numerous elements which are either naturally present in crude oil as is particularly the case for nickel and vanadium or those elements that are added to petroleum products during refining. 

This method has a very general application range analysis for metals in crude oils, in their various distillation cuts, and in their residues as well as for metals contained in spent lubricating oils, water, lubricants, etc. 

Note, however, the particular cases of sulfur in crude oil from Rozel Point (Utah, USA) 13.95% in crudes from Etzel (Germany) 9.6% or crude from Gela... 

These reactions can explain the absence of olefins in crude oil, their presence being detected only in the crudes of low sulfur content. The sulfur content in crude from Bradford which is the one of the rare crudes containing olefins is about 0.4%. 

Practically, one measures the quantity of total sulfur (in all its forms) contained in crude oil by analyzing the quantity of SO2 formed by the combustion of a sample of crude, and the result is taken into account when evaluating the crude oil price. When they are present, elementary sulfur and dissolved H2S can also be analyzed. 

Free sulfur is rarely present in crude oils, but it can be found in suspension or dissolved in the liquid. The crude from Goldsmith (Texas, USA.) is richest in free sulfur (1% by weight for a total sulfur content of 2.17%). It could be produced by compounds in the reservoir rock by sulfate reduction (reaction 8.2). 

Of the general formula, R - S — H, where R represents an aliphatic or cyclic radical, the thiols —also known as mercaptans— are acidic in behavior owing to their S—H functional group they are corrosive and malodorous. Their concentration in crude oils is very low if not zero, but they are created from other sulfur compounds during refining operations and show up in the light cuts, as illustrated in Table 8.6. 

Table 8.7 gives some of the mercaptans identified in crude oils. 

Table 8.8 gives some examples of sulfides identified in crude oils. 

The presence of thiophene and its derivatives in crude oils was detected in 1899, but until 1953, the date at which the methyl-thiophenes were identified in kerosene from Agha Jari, Iran crude oil, it was believed that they came from the degradation of sulfides during refining operations. Finally, their presence was no longer doubted after the identification of benzothiophenes and their derivatives (Table 8.9), and lately of naphthenobenzothiophenes in heavy cuts. 

Water, Sediment, and Salt Contents in Crude Oils... 

The presence of such substances in crude oil is highly undesirable because they can plug piping and contaminate the products. 

The presence of salts in crude oils has several disadvantages ... 

The presence of these acids in crude oils and petroleum cuts causes problems for the refiner because they form stable emulsions with caustic solutions during desalting or in lubricating oil production very corrosive at high temperatures (350-400°C), they attack ordinary carbon steel, which necessitates the use of alloy piping materials. 

Mercaptans are naturally present in crude oil (Chapters 1 and 8), or they result from the decomposition of other sulfur compounds during thermai or catalytic cracking operations. 

Rail, H.T., C.J. Thompson, H.J. Coleman and R.L. Hopkins (1972), "Sulfur compounds in crude oil". Bureau of Mines Bull. No. 659. Distributed by National Technical Information Service (NTIS), US Dpt of Commerce, Springfield, VA. 

Alkanes from CH to C4gFlg2 typically appear in crude oil, and represent up to 20% of the oil by volume. The alkanes are largely chemically inert (hence the name paraffins, meaning little affinity), owing to the fact that the carbon bonds are fully saturated and therefore cannot be broken to form new bonds with other atoms. This probably explains why they remain unchanged over long periods of geological time, despite their exposure to elevated temperatures and pressures. 

Olefins are uncommon in crude oils due to the high chemical activity of these compounds which causes them to become saturated with hydrogen. Similarly, acetylene is virtually absent from crude oil, which tends to contain a large proportion of the saturated hydrocarbons, such as the alkanes. 

Some of the common aromatics found in crude oil are the simple derivatives of benzene in which one or more alkyl groups (CHg) are attached to the basic benzene molecule as a side chain which takes the place of a hydrogen atom. These arenes are either liquids or solids under standard conditions. 

Other compounds which may be found in crude oil are metals such as vanadium, nickel, copper, zinc and iron, but these are usually of little consequence. Vanadium, if present, is often distilled from the feed stock of catalytic cracking processes, since it may spoil catalysis. The treatment of emulsion sludges by bio-treatment may lead to the concentration of metals and radioactive material, causing subsequent disposal problems. 

An important industrial example of W/O emulsions arises in water-in-crude-oil emulsions that form during production. These emulsions must be broken to aid transportation and refining [43]. These suspensions have been extensively studied by Sjoblom and co-workers [10, 13, 14] and Wasan and co-workers [44]. Stabilization arises from combinations of surface-active components, asphaltenes, polymers, and particles the composition depends on the source of the crude oil. Certain copolymers can mimic the emulsion stabilizing fractions of crude oil and have been studied in terms of their pressure-area behavior [45]. 

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