Petroleum Phenols

The principal oxygen compounds are phenols and naphthenic acids. These are present only in particular crude oils in significant amounts. By-product petroleum phenols have been industrial products ih America since the 1930 s, but the literature on their composition is limited. Naphthenic acids were found in considerable quantities in the early days of the oil industry in crude oils from Roumania and from Russia. These have, therefore, been worked upon in Europe before the first world war this work is associated with the name of von Braun. 

Cresylic Acids. Cresylic acids, or petroleum phenols, are obtained from cracked distillates, such as heavy catalytic naphtha and cracked heating oil. They usually exist in these distillates in amounts up to about 0.2% and are removed by extraction with a 10 to 40% sodium hydroxide solution (77). The extract is subsequently steamed, then... 

L-Aspartyl-L-Phenylalanine Methyl Ester Luminol Menthol Methane Methyl Alcohol Methyl Mercaptan Methyl-t-butyl Ether Monosodium Glutamate N,N-Diethyl-3-Methyl-benzamide Naphthalene Naproxen Niacin Nicotine Nitroglycerin Nylon 6 and Nylon 66 Oxalic Acid Pectin Penicillin Petrolatum Petroleum Phenol... 

Benzene was first isolated by Faraday in 1825 from the liquid condensed by compressing oil gas. It is the lightest fraction obtained from the distillation of the coal-tar hydrocarbons, but most benzene is now manufactured from suitable petroleum fractions by dehydrogenation (54%) and dealkylation processes. Its principal industrial use is as a starting point for other chemicals, particularly ethylbenzene, cumene, cyclohexane, styrene (45%), phenol (20%), and Nylon (17%) precursors. U.S. production 1979 2-6 B gals. 

R NHa + C.HjNCO = RNH CO NHC,Hj Traces of water will contaminate the product with diphenylurea (p. 336) if the solution is boiled hence the need for anhydrous conditions. i-Naphthylisocyanate reacts more slowly with water, and the i-naphthyl-urea derivative can often be obtained using a cold aqueous solution of an aliphatic amine it is particularly necessary in such cases to purify the product by recrystallisation from, or extraction with, boiling petroleum, leaving behind any insoluble di i-naphthylurea. Note that the amine must also be free from alcohols (p. 335) and phenols (p. 337). 

Dissolve 0 -5 g. of the phenol in 4-5 ml. of dry p ridine, add 1 - 3 g. of 3 5-dinitrobenzoyl chloride and reflux for 25-30 minutes. Pour the cold reaction mixture into 40 ml. of ca. 2N hydrochloric acid. Decant the supernatant aqueous hquid from the precipitated sohd or oil and stir it vigorously with about 10 ml. of N sodium carbonate solution. Filter off the sohd derivative and wash it with water. RecrystaUise from alcohol, dilute alcohol, benzene - acetone or benzene - light petroleum (b.p. 60-80 ),... 

Dissolve 0-5 g. of the phenol in 2 -5 ml. of pyridine, and add one equivalent of dlphenylcarbamyl chloride (or 0- 0-5 g. if the molecular weight is uncertain). Reflux the mixture for 30-60 minutes on a boiling water bath, and then pour into about 25 ml. of water. Filter the derivative, wash with a little sodium bicarbonate solution, and recrystallise from alcohol benzene, light petroleum (b.p. 60-80°) or carbon tetrachloride. 

The following alternative method may be used. Dissolve 0 01 mol of the phenol and 0 01 mol of a-naphthyl wo-cyanate in 20 ml. of light petroleum (b.p. 60-80°), add 2 drops of triethylamine (or, less satisfactorily, 2 drops of pyridine), reflux for 5 minutes, and allow to crystallise. Filter oflF the crystalline sohd through a sintered glass funnel. 

The Phenox process (254) removes phenol (qv) from the efduent from catalytic cracking in the petroleum industry. Extraction of phenols from ammoniacal coke-oven Hquor may show a small profit. Acetic acid can be recovered by extraction from dilute waste streams (255). Oils are recovered by extraction from oily wastewater from petroleum and petrochemical operations. Solvent extraction is employed commercially for the removal of valuable... 

Naphthalene, anthracene, carbazole [86-74-8] phenol [108-95-2] and cresyUc acids are found in the tar. Phenol and cresyUc acids are useful as chemical and resin intermediates. The aromatic chemicals are useful in the manufacture of pharmaceuticals, dyes, fragrances, and pesticides. Various grades of pitch are made from residues of tar refining. Coal-tar pitch is used for roofing and road tar, and as a binder mixed with petroleum coke to produce anodes for the aluminum industry. 

Triaryl phosphates are produced from the corresponding phenols (usually mixtures) by reaction with phosphoms oxychloride, usually in the presence of a catalyst (94—96). They are subsequently distilled and usually washed with aqueous bases to the desired level of purity. Tricresyl phosphate was originally made from petroleum-derived or coal-tar-derived cresyflc acids, ie, cresols, variously admixed with phenol and xylenols. Discovery of the toxicity of the ortho-cresyl isomers led manufacturers to select cresols having very Httle ortho-isomer. 

Table 8 shows that the naphthas produced by the EDS process have higher concentrations of cycloparaffins and phenols than do petroleum-derived naphthas, whereas the normal paraffins are present in much lower concentrations. The sulfur and nitrogen concentrations in coal naphthas are high compared to those in petroleum naphthas. 

Heteroatom functionalized terpene resins are also utilized in hot melt adhesive and ink appHcations. Diels-Alder reaction of terpenic dienes or trienes with acrylates, methacrylates, or other a, P-unsaturated esters of polyhydric alcohols has been shown to yield resins with superior pressure sensitive adhesive properties relative to petroleum and unmodified polyterpene resins (107). Limonene—phenol resins, produced by the BF etherate-catalyzed condensation of 1.4—2.0 moles of limonene with 1.0 mole of phenol have been shown to impart improved tack, elongation, and tensile strength to ethylene—vinyl acetate and ethylene—methyl acrylate-based hot melt adhesive systems (108). Terpene polyol ethers have been shown to be particularly effective tackifiers in pressure sensitive adhesive appHcations (109). 

Pour-Point Depressants. The pour point of alow viscosity paraffinic oil may be lowered by as much as 30—40°C by adding 1.0% or less of polymethacrylates, polymers formed by Eriedel-Crafts condensation of wax with alkylnaphthalene or phenols, or styrene esters (22). As wax crystallizes out of solution from the Hquid oil as it cools below its normal pour point, the additive molecules appear to adsorb on crystal faces so as to prevent growth of an interlocking wax network which would otherwise immobilize the oil. Pour-point depressants become less effective with nonparaffinic and higher viscosity petroleum oils where high viscosity plays a dominant role in immobilizing the oil in a pour-point test. 

Triaryl phosphates are produced by reaction of phosphoms oxychloride with phenoHc compounds at 100—200°C with magnesium or aluminum chloride catalyst. Past use of cresols and xylenols from coal tar or petroleum is replaced for lower toxicity and cost by synthetic phenoHcs, primarily isopropyl phenol, /-butyl phenol, and phenol itself A range of viscosities is achieved by selection and proportioning of the phenols and their isomers used for the starting material. 

Solvent Treatment. Solvent processes can be divided into two main categories, solvent extraction and solvent dewaxing. The solvent used in the extraction processes include propane and cresyHc acid, 2,2 -dichlorodiethyl ether, phenol (qv), furfural, sulfur dioxide, benzene, and nitrobenzene. In the dewaxing process (28), the principal solvents are benzene, methyl ethyl ketone, methyl isobutyl ketone, propane, petroleum naphtha, ethylene dichloride, methylene chloride, sulfur dioxide, and iV-methylpyrroHdinone. 

Methylphenol. This phenol, commonly known as o-cresol, is produced synthetically by the gas phase alkylation of phenol with methanol using modified alumina catalysis or it may be recovered from naturally occurring petroleum streams and coal tars. Most is produced synthetically. Reaction of phenol with methanol using modified zeoHte catalysts is a concerted dehydration of the methanol and alkylation of the aromatic ring. 2-Methylphenol [95-48-7] is available in 55-gal dmms (208-L) and in bulk quantities in tank wagons and railcars. 

Toluenesulfonic Acid. Toluene reacts readily with fuming sulfuric acid to yield toluene—sulfonic acid. By proper control of conditions, /)i7n7-toluenesulfonic acid is obtained. The primary use is for conversion, by fusion with NaOH, to i ra-cresol. The resulting high purity i7n -cresol is then alkylated with isobutylene to produce 2 (i-dii-tert-huty -para-cmso (BHT), which is used as an antioxidant in foods, gasoline, and mbber. Mixed cresols can be obtained by alkylation of phenol and by isolation from certain petroleum and coal-tar process streams. 

In the petroleum (qv) industry hydrogen bromide can serve as an alkylation catalyst. It is claimed as a catalyst in the controlled oxidation of aHphatic and ahcycHc hydrocarbons to ketones, acids, and peroxides (7,8). AppHcations of HBr with NH Br (9) or with H2S and HCl (10) as promoters for the dehydrogenation of butene to butadiene have been described, and either HBr or HCl can be used in the vapor-phase ortho methylation of phenol with methanol over alumina (11). Various patents dealing with catalytic activity of HCl also cover the use of HBr. An important reaction of HBr in organic syntheses is the replacement of aHphatic chlorine by bromine in the presence of an aluminum catalyst (12). Small quantities of hydrobromic acid are employed in analytical chemistry. 

Chromium is highly acid-resistant and is only attacked by hydrochloric, hydrofluoric, and sulfuric acids. It is also resistant to other common corroding agents including acetone, alcohols, ammonia, carbon dioxide, carbon disulfide, foodstuffs, petroleum products, phenols, sodium hydroxide, and sulfur dioxide. 

Ethyleneamines are used in certain petroleum refining operations as well. Eor example, an EDA solution of sodium 2-aminoethoxide is used to extract thiols from straight-mn petroleum distillates (314) a combination of substituted phenol and AEP are used as an antioxidant to control fouling during processing of a hydrocarbon (315) AEP is used to separate alkenes from thermally cracked petroleum products (316) and TEPA is used to separate carbon disulfide from a pyrolysis fraction from ethylene production (317). EDA and DETA are used in the preparation and reprocessing of certain... 

In addition to coal tar, petroleum has been a source of the same chemicals, and many of the individual phenols have been produced in the pure state by synthetic processes. 

The general proportions may be varied from one end of the tower to the other to accommodate changing liquid volumes and physical properties. These towers have been used in diameters ranging from a few inches for laboratory work up to 2.4 m (8 ft) in diameter by 12.2 m (40 ft) tall for purposes of deasphalting petroleum. Other commercial services include furfural extraction of lubricating oils, desulfurization of gasoline, phenol recoveiy from wastewaters, and many others. Columns up to 4.5 m in diameter and up to 50 m in height have been constructed. 

---