Petroleum alteration

Sofer Z. (1984) Stable carbon isotope compositions of crude oils application to sourc e depositional environments and petroleum alteration. Am. Assoc. Petrol. Geol. Bull. 68(1),... 

The major portion of sait is found in residues as these streams serve as the bases for fuels, or as feeds for asphalt and petroleum coke production, the presence of salt in these products causes fouling of burners, the alteration of asphalt emulsions, and the deterioration of coke quality. Furthermore, calcium and magnesium chlorides begin to hydrolyze at 120°C. This hydrolysis occurs rapidly as the temperature increases (Figure 8.1) according to the reaction i. ... 

An alternative procedure is to leave the syrupy residue in a vacuum desiccator over anhydrous calcium chloride and siUca gel, and to Alter ofl the successive Crops of crystals as they separate. These are washed with light petroleum, b.p. 40-60°, spread on a porous tile and recrystallised. 

A solution of 1 (1.032 g, 4 mmol) in PhMe was heated to reflux for 17 h. Alter removing the solvent the residue was recrystallized Irom petroleum ether and gave 0 928 g ol 3 (90%). 

Amlno-6 bromopyrldlne ( ) Qlutacononitrile 1 (12 5 g 27 mmol) was added dropwise lo a solution of HBr in AcOH (30 g of 30%) in 5 mm with cooling and stimng The yellow precipiiale alter filtration and washing (NaHCOs sol) was extracted with EI2O and recrystallized from EtaO petroleum ether to give 2 7 g of 2 (60%) mp 88 89°C... 

Phenylpftenanttirldlne (3).3 Amine hydrochloride 1 (2.72 g, 9 28 mmol) in EtOH (75 mL) was treated with 0 926 N cold solution of KCXI. Colorless crystals appear The mixture was shaken lor 30 mtn in ice, water was added and the product was filtered and dryed (PaOs) to afford 2.7 g of 2 (100%), rnp 102°C (hexane) 2 (2 0 g, 6 6 mmol) in anh pyndine (20 mL) was treated with an excess of NaOCHa (exothermc) Alter 20 h the solvent was removed In vacuum, the residua triturated with EtaO and the extract treated with dry HCI to obtain the hydrochlonda of 3, mp 107-108°C (from petroleum ether), mp 95-100° (Irom water) Olphenylmethyieneanlllna (5). To a suspension of lead tetraacetate (4.9 g, fO mmol) in PhH (100 mL) under Na was added a solution of tnphenyhnethylamine 4 (2 6 g, 10 mmol) in PhH (100 mL) dropwise under stirring The mixture was refluxed for 1 h, cooled, filtered, washed and the solvent evaporated The residue was crystallized from EtOH to give 2 2 g of 5 (85%), mp 111-112°C. 

Gross adulteration w-itb up la lO per cunt, cf petroleum Oil was found in a number ot samples a few years ago. hot the great alteration in Lhe phyeicKJ characters of the oil rftnjer this easy of detection. 

Crystallization from acetone-petroleum ether gave 13 mg of colorless needles of A. -pregna-diene-9a-fluoro-11/3,16a,17a,21-tetrol-3,20-dione 16,21-diacetate melting point (Kbfier block) about 150° to 240°C with apparent loss of solvent at 150°C. Recrystallization from acetone-petroleum ether did not alter the melting point. 

Another emerging area m biofuels is pyrolysis, which is the decomposition of biomass into other more usable fuels using a high-temperature anaerobic process. Pyrolysis converts biomass into charcoal and a liquid called biocrude. This liquid has a high energy density and is cheaper to transport and store than the unconverted biomass. Biocrude can be burned in boilers or used in a gas turbine. Biocrude also can be chemical by altered into other fuels or chemicals. Use of pyrolysis may make bioenergy more feasible in regions not near biomass sources. Biocrude is about two to four times more expensive than petroleum crude. 

The salts content of soils may be markedly altered by man s activities. The effect of cathodic protection will be discussed later in this section. Fertiliser use, particularly the heavy doses used in lawn care, introduces many chemicals into the soil. Industrial wastes, salt brines from petroleum production, thawing salts on walks and roads, weed-killing salts at the base of metal structures, and many other situations could be cited as examples of alteration of the soil solution. In tidal areas or in soils near extensive salt deposits, depletion of fresh ground-water supplies has resulted in a flow of brackish or salty sea water into these soils, causing increased corrosion. 

A mixture of monolauryl phosphate sodium salt and triethylamine in H20 was treated with glycidol at 80°C for 8 h to give 98% lauryl 2,3-dihydro-xypropyl phosphate sodium salt [304]. Dyeing aids for polyester fibers exist of triethanolamine salts of ethoxylated phenol-styrene adduct phosphate esters [294], Fatty ethanolamide phosphate surfactant are obtained from the reaction of fatty alcohols and fatty ethanolamides with phosphorus pentoxide and neutralization of the product [295]. A double bond in the alkyl group of phosphoric acid esters alter the properties of the molecule. Diethylethanolamine salt of oleyl phosphate is effectively used as a dispersant for antimony oxide in a mixture of xylene-type solvent and water. The composition is useful as an additive for preventing functional deterioration of fluid catalytic cracking catalysts for heavy petroleum fractions. When it was allowed to stand at room temperature for 1 month it shows almost no precipitation [241]. 

Many of the phenols which are used in household and other commercial disinfectant products are produeed from the tar obtained by distillation of coal or more recently petroleum. They are known as the tar acids. These phenols are separated by fractional distillation according to their boiling point range into phenol, cresols, xylenols and high boiling point tar acids. As the boiling point increases the properties of the products alter as shown ... 

Alteration of Viscous Crude Oils", Annu. Fall Meeting of Soc. Petroleum Engrs, SPE paper No 14225 (Sept. 19 5) ... 

Increasing the water-wet surface area of a petroleum reservoir is one mechanism by which alkaline floods recover incremental oil(19). Under basic pH conditions, organic acids in acidic crudes produce natural surfactants which can alter the wettability of pore surfaces. Recovery of incremental oil by alkaline flooding is dependent on the pH and salinity of the brine (20), the acidity of the crude and the wettability of the porous medium(1,19,21,22). Thus, alkaline flooding is an oil and reservoir specific recovery process which can not be used in all reservoirs. The usefulness of alkaline flooding is also limited by the large volumes of caustic required to satisfy rock reactions(23). 

Engineered biocatalysts with altered specificity have been developed. A Rhodococcus strain capable of DBT as well as BT desulfurization has been developed by cloning dsz genes into a strain-containing BT desulfurization pathway. The variety of sulfur compounds in petroleum feedstocks and complexity of the problem may require use of a consortium rather than a single bacterial strain. Alternately, use of multiple bioreactors each with a single dominant strain may be employed to achieve maximum desulfurization [299],... 

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