Naphthenic acids resins

The aqueous sodium naphthenate phase is decanted from the hydrocarbon phase and treated with acid to regenerate the cmde naphthenic acids. Sulfuric acid is used almost exclusively, for economic reasons. The wet cmde naphthenic acid phase separates and is decanted from the sodium sulfate brine. The volume of sodium sulfate brine produced from dilute sodium naphthenate solutions is significant, on the order of 10 L per L of cmde naphthenic acid. The brine contains some phenolic compounds and must be treated or disposed of in an environmentally sound manner. Sodium phenolates can be selectively neutralized using carbon dioxide and recovered before the sodium naphthenate is finally acidified with mineral acid (29). Recovery of naphthenic acid from aqueous sodium naphthenate solutions using ion-exchange resins has also been reported (30). 

To mitigate the effects of corrosion resulting from the presence of salts, it is advantageous to reduce the salt concentration to the range of 3 to 5 ppm. Typically, brine droplets in crude oil are stabilized by a mixture of surface-active components such as waxes, asphaltenes, resins, and naphthenic acids that are electrostatically bound to the droplets surface. Such components provide an interfacial film over the brine droplet, resulting in a diminished droplet coalescence. Adding water to the crude oil can decrease the concentration of the surface-active components on the surface of each droplet, because the number of droplets is increased without increasing component concentration. 

Distillate fuel fractions can contain naphthenic acids, sulfonic acids, and other hydrophilic compounds. If these hydrophilic compounds are present as sodium salts due to caustic washing of fuel, they become powerful emulsifying agents. Also, heavy resinous compounds in fuel can act to stabilize existing emulsions. 

Black oil should be a pure petroleum product free from fatty oils, fatty acids, resins, soaps, or other nonhydrocarbons. Sediment and sludge, insoluble in paraffin naphtha, should not exceed 12% when determined by the methods of the American Association of State Highway Officials. The product should be a distilled or fractionated oil, and should contain no oil-well water or residue therefrom. The product should be free of or contain no more than traces of naphthenic acids, naphthenes, mercaptans, soluble sulfide, and volatile sulfur derivatives. The oil should flow freely from the tank car at temperatures above 32 F. 

Another market application for naphthenic acid is the lire industry, where cobalt naphthenate is used as an adhesion promoter. Naphthenic acid esters have been repeatedly cited as surfactants, lubricants, and replacements for phthalates as plasticizers for PVC resins. 

Dodd [68] measured the rheological properties of interfacial films in a semiquanti-tative manner by employing an interfacial shear rotational viscometer to study crude-water interfaces with NaCl, acid, and basic additives in the water phase. He concluded that the film must be comprised of naphthenic acids, naphthenic acid soaps, and naphthenic acid anions, in combination with resins, asphaltenes, and waxes. Furthermore, the acidic species must desorb from the interface under basic conditions and partition into the aqueous phase, rendering the interface considerably less rigid. Subsequent researchers have shown that acidic asphaltenes are more effective at emulsion stabilization than their neutral counterparts. 

To date there are thousands of products appearing in directories and patent literature. Generally, the compounds with EO/PO copolymers are exceptionally surface active and they migrate and spread readily at the interface. The fatty amines and quaternary cationics adhere to all surfaces including asphaltenes, resins, naphthenic acids, paraffin waxes, inorganic clays, carbons, and silica (288). 

Naphthenic acid n, A carboxylic acid derived from petroleum refining and usually one of a mixture of similar compounds. The mixed acids and some of their soaps, e.g., cobalt naphthenate and calcium naphthenate, are useful as catalysts or accelerators in curing polyester resins and as drying agents in paints and varnishes. Commercial naphthenic acids are not pure compounds, but consist of a mixture of acids based on cyclopentane rings. 

Demulsifiers synthesized by polycondensation of an ethylene oxide-propylene oxide block copolymer, an oxalkylated fatty amine, and a dicarboxylic acid are known as polyester amines. These demulsifiers have the ability to adhere to natural substances that stabilize emulsions, such as organic materials formed by asphaltenes, oil resins, naphthenic acids, paraffins, and waxes they also adhere to inorganic particles formed by clays, carbonates, silica, and metallic salts. These properties increase the demulsification efficiency of the polyester amines [2, 5]. The availability of a variety of building blocks allows for the preparation of demulsifiers for specific applications. With this chemicd arsenal it is possible to tailor demulsifiers for nearly all problems posed by stable emulsions, including crude oil dehydration and desalting. 

The most common accelerators for methyl ethyl ketone peroxide and cyclohexanone peroxide are salts of metals which exhibit more than one valency. The most widely used metal of this kind is cobalt, although salts of cerium, iron, manganese, tin and vanadium also find some application. In order to be effective as an accelerator a metal salt must be soluble in the polyester resin. The most commonly used salts are naphthenates, which are readily soluble octoates also may be used. (Naphthenic acid is extracted from the gas oil and kerosene fractions of petroleum and consists of a complex mixture of carboxylic acids of substituted cyclopentanes and cyclohexanes. ) The decomposition of a hydroperoxide (ROOH) by a metal salt such as cobalt naphthenate to give free radicals proceeds according to the following chain reaction ... 

Sulfuric acid also removes or dissolves resinous or asphaltic substances that may be present because of poor fractionation, entrainment, or cracking. These materials tend to inhibit the crystallization of wax, and hence acid treatment often raises the pour point. Oxygen compounds, such as naphthenic acids and ketones, and substances such as alcohols mid aldehydes that are formed by high-temperature oxidation are dissolved by sulfuric acid, but when diluted with oil their removal is never complete. Nitrogen bases similar to quinoline or pyridine, which are produced in small quantities during distillation, are easily dissolved in dilute add. 

Crude oil containing brine generally results in the formation of stable water-in-oil (W/O) emulsions when turbulent mixing conditions are encountered during the transportation process. The dispersion of water droplets in oil is facilitated by the presence of interfacial active agents in the crude oil such as asphaltenes, waxes, resins and naphthenic acid (Schramm, 1992). The quantity of these natural emulsifiers is more abundant in heavy than in light crude oils and, thus, the formation of more stable emulsions in heavy crude oils (Kokal, 2005). 

The physical and chemical properties, as well as exact chemical composition of heavy crude oil, vary from one source to another. Crude oils, especially the heavy crude oils, contain large quantities of asphaltenes (high-molecular-weight polar components). Other crude oil components are resins, fatty acids such as naphthenic acids, porphyrins, wax crystals, etc., which can associate to asphaltenes and affect the oil stability. Particles such as silica, clay, iron oxides, etc., can be present in crude oils. 

Cobalt in Driers for Paints, Inks, and Varnishes. The cobalt soaps, eg, the oleate, naphthenate, resinate, Hnoleate, ethyUiexanoate, synthetic tertiary neodecanoate, and tall oils, are used to accelerate the natural drying process of unsaturated oils such as linseed oil and soybean oil. These oils are esters of unsaturated fatty acids and contain acids such as oleic, linoleic, and eleostearic. On exposure to air for several days a film of the acids convert from Hquid to soHd form by oxidative polymeri2ation. The incorporation of oil-soluble cobalt salts effects this drying process in hours instead of days. Soaps of manganese, lead, cerium, and vanadium are also used as driers, but none are as effective as cobalt (see Drying). 

Assist the widely dissimilar ingredients used in a rubber compound to coalesce and mix into a homogeneous uniform processable mass. Homogenisers are low-MW polymeric resin blends. The homogenising resin blend contains portions that are compatible with aliphatic, naphthenic and aromatic parts of the elastomers in a blend and higher-MW homologues of the plasticisers. They have a wetting effect. Fatty acid derivatives and phenolic resins are used. 

Unsaturated polymers such as alkyd resins can be cured or dried in the presence of oxygen, a heavy metal, and an organic acid called a drier. The most common organic acids are linoleic, abietic, naphthenic, octoic, and tall oil fatty acids. 

A whole lubricating oil fraction consists of four major classes of hydrocarbons—namely (a) asphalts and resins, (b) aromatics, (c) naphthenes and branched paraffins, and (d) paraffin wax. Sulfuric acid is remarkably effective for removing undesirable constituents a and b by a combination of reaction and extraction and has little or no effect on wax (which must be removed by other means) or the naphthenic-type materials which comprise a good lubricating oil. 

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