Naphthalene refining

In the late 1980s, Brodie crystalHsers were installed in the United Kingdom and in France for upgrading phthaHc-grade naphthalene to 99% purity or better. This apparatus, developed by Union Carbide Corporation, AustraHa, for separating o- and -dichlorobensene, was adapted for naphthalene refining. The one installed in the United Kingdom, however, has been closed (21) (see Naphthalene). 

Figure 89. Flow diagram of old process of chemical naphthalene refining by treatment with sulfuric acid and sodium hydroxide soiu-tion... 

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. 

Approximately 50—55% of the product from a coal-tar refinery is pitch and another 30% is creosote. The remaining 15—20% is the chemical oil, about half of which is naphthalene. Creosote is used as a feedstock for production of carbon black and as a wood preservative. Because of modifications to modem coking processes, tar acids such as phenol and cresyUc acids are contained in coal tar in lower quantity than in the past. To achieve economies of scale, these tar acids are removed from cmde coal tar with a caustic wash and sent to a central processing plant where materials from a number of refiners are combined for recovery. 

However, since the naphthalene produced from petroleum is of high purity and quaUty, the production of refined naphthalene by such chemical treatments essentially has ceased in the United States. Not only are such treatments expensive, but they also generate a significant amount of waste sludge, which creates additional costs for appropriate waste-disposal faciUties. 

Another sulfur dioxide appHcation in oil refining is as a selective extraction solvent in the Edeleanu process (323), wherein aromatic components are extracted from a kerosene stream by sulfur dioxide, leaving a purified stream of saturated aHphatic hydrocarbons which are relatively insoluble in sulfur dioxide. Sulfur dioxide acts as a cocatalyst or catalyst modifier in certain processes for oxidation of o-xylene or naphthalene to phthaHc anhydride (324,325). 

In the case of low temperature tar, the aqueous Hquor that accompanies the cmde tar contains between 1 and 1.5% by weight of soluble tar acids, eg, phenol, cresols, and dihydroxybenzenes. Both for the sake of economics and effluent purification, it is necessary to recover these, usually by the Lurgi Phenosolvan process based on the selective extraction of the tar acids with butyl or isobutyl acetate. The recovered phenols are separated by fractional distillation into monohydroxybenzenes, mainly phenol and cresols, and dihydroxybenzenes, mainly (9-dihydroxybenzene (catechol), methyl (9-dihydtoxybenzene, (methyl catechol), and y -dihydroxybenzene (resorcinol). The monohydric phenol fraction is added to the cmde tar acids extracted from the tar for further refining, whereas the dihydric phenol fraction is incorporated in wood-preservation creosote or sold to adhesive manufacturers. Naphthalene Oils. Naphthalene is the principal component of coke-oven tats and the only component that can be concentrated to a reasonably high content on primary distillation. Naphthalene oils from coke-oven tars distilled in a modem pipe stiU generally contain 60—65% of naphthalene. They are further upgraded by a number of methods. 

In the Sulser-MWB process the naphthalene fractions produced by the crystallisation process are stored in tanks and fed alternately into the crystalliser. The crystalliser contains around 1100 cooling tubes of 25-mm diameter, through which the naphthalene fraction passes downward in turbulent flow and pardy crystallises out on the tube walls. The residual melt is recycled and pumped into a storage tank at the end of the crystallisation process. The crystals that have been deposited on the tube walls are then pardy melted for further purification. Following the removal of the drained Hquid, the purified naphthalene is melted. Four to six crystallisation stages are required to obtain refined naphthalene with a crystallisation point of 80°C, depending on the quaHty of the feedstock. The yield is typically between 88 and 94%, depending on the concentration of the feedstock fraction. 

Creosote. In coal-tar refining, the recovery of tar chemicals leaves residual oils, including heavy naphtha, dephenolated carboHc oil, naphthalene drained oil, wash oil, strained anthracene oil, and heavy oil. These are blended to give creosotes conforming to particular specifications. 

The carbonization by-products are usually refined, within the coke plant, into commodity chemicals such as elemental sulfur (qv), ammonium sulfate, benzene, toluene, xylene, and naphthalene (qv) (see also Ammonium compounds BTX processing). Subsequent processing of these chemicals produces a host of other chemicals and materials. The COG is a valuable heating fuel used mainly within steel (qv) plants for such purposes as firing blast furnace stoves, soaking furnaces for semifinished steel, annealing furnaces, and lime kilns as well as heating the coke ovens themselves. 

Figure 22-8 shows the features of a horizontal center-fed column [Brodie, Au.st. Mech. Chem. Eng. Tran.s., 37 (May 1979)] which has been commercialized for continuous purification of naphthalene and p-dichlorobenzene. Liquid feed enters the column between the hot purifying section and the cold freezing or recovery zone. Ciystals are formed internally by indirect cooling of the melt through the walls of the refining and recovery zones. Residue liquid that has been depleted or product exits from the coldest section of the column. A spiral conveyor controls the transport of solids through the unit. 

Zone refining purified naphthalene from anthracene, 2,4-dinitrophenylhydrazine, methyl violet, benzoic acid, methyl red, chrysene, pentacene and indoline. 

Carbazole, A-methylcarbazole, IV-ethylcarbazole, dibenzofuran, dibenzothiophene, fluorene, dibenzo-p-dioxin, phenoxathiin, phenoxazine, phenothiazine, xanthene, biphenyl, naphthalene, phenanthrene, anthracene, and fluoranthene could be transformed by E. coli, [314] which was transformed using a plasmid bearing the carAa, Ac, and Ad genes, and expressing only the carA-encoded proteins. Further work is needed to develop a final biocatalyst and to prove the advantages that this degradative pathway would incorporate in a refining bioprocess. 

UNIDAK A process for extracting naphthalene from reformer residues in petroleum refining. It includes a dealkylation stage to convert the naphthalene homologues to naphthalene. 

Naphthalene and its homologs are less acutely toxic than benzene but are more prevalent for a longer period during oil spills. The toxicity of different crude oils and refined oils depends not only on the total concentration of hydrocarbons but also the hydrocarbon composition in the water-soluble fraction (WSF) of petroleum, water solubility, concentrations of individual components, and toxicity of the components. The water-soluble fractions prepared from different oils wiU vary in these parameters. Water-soluble fractions (WSFs) of refined oils (e.g.. No. 2 fuel oil and bunker C oil) are more toxic than water-soluble fraction of crude oil to several species of fish (killifish and salmon). Compounds with either more rings or methyl substitutions are more toxic than less substituted compounds, but tend to be less water soluble and thus less plentiful in the water-soluble fraction. 

Note Impurities identified in refined ingots of commercially available ex-coal tar include naphthalene, 2-methylnaphthalene, fluorene, and methyldibenzofuran (Marciniak, 2002). 

Several refineries in Europe employ the Pro-Abd refiner to upgrade whizzed naphthalene to phthalic-grade quality or to convert the latter into the purer chemical grade. The device consists of a rectangular tank fitted with a nest of coils through which either steam or water circulates. The tank is filled with the feedstock, which is crystallized by circulating cold water in the coils. When the contents of the tank have solidified, a tap at the base is opened and hot water is circulated until the temperature is just below the desired crystallizing point of the product. This condition is maintained until no more oil drains from the base. The bottom tap is then closed and the contents of the tank are melted by steam circulation and drained. 

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