Toluene and xylenes

The gas phase oxidation of toluene and xylene is not of practical importance except for the conversion of o-xylene into phthalic anhydride, which will be separately discussed in Sect. 2.5.3. 

The main products of partial oxidation are aromatic aldehydes and acids formed by oxidation of the reactive methyl group. However, the yields that can be obtained are rather poor, in contrast to the catalytic liquid phase oxidation, which is much more selective. The poor yields are due partly to further oxidation (combustion) of the primary products, and partly to direct oxidation of the aromatic nucleus (also mainly combustion). 

Catalyst Temp. (°C) Initial selectivity (%) with respect to benzaldehyde Maximum yield (%)  

Reddy and Doraiswamy [262] used 15% Mo03—5% W03 as a catalyst at 500° C and found a selectivity of 75% with respect to benzaldehyde by keeping the degree of conversion at a low level (5%). 

A formal reaction scheme, given by Germain and Laugier to describe the formation of all observed partial oxidation products, is shown below. This scheme comprises three reaction paths corresponding to side chain oxidation, oxidative coupling and direct oxidation of the nucleus as initiating reactions. In reality, an even more complex reaction network is to be expected. 

---

BTX A mixture of low boiling point aromatics, i.e. benzene, toluene and xylenes. 

Benzene, toluene and xylenes are used either as solvents or as basic intermediates for the chemical and petrochemical industries. 

Amm oxida tion, a vapor-phase reaction of hydrocarbon with ammonia and oxygen (air) (eq. 2), can be used to produce hydrogen cyanide (HCN), acrylonitrile, acetonitrile (as a by-product of acrylonitrile manufacture), methacrylonitrile, hen onitrile, and toluinitnles from methane, propylene, butylene, toluene, and xylenes, respectively (4). 

TURBINE fuels), are both in demand. Solvent extraction is also extensively used to meet the growing demand for the high purity aromatics such as ben2ene, toluene, and xylene (BTX) as feedstocks for the petrochemical industry (see BTX PROCESSING FEEDSTOCKS,PETROCHEMICALS). Additionally, the separation of aromatics from aUphatics is one of the largest appHcations of solvent extraction (see Petroleum, refinery processes survey). 

Anhydrous silver hexafluorophosphate [26042-63-7] AgPF, as well as other silver fluorosalts, is unusual in that it is soluble in ben2ene, toluene, and xylene and forms 1 2 molecular crystalline complexes with these solvents (91). Olefins form complexes with AgPF and this characteristic has been used in the separation of olefins from paraffins (92). AgPF also is used as a catalyst. Lithium hexafluorophosphate [21324-40-3] LiPF, as well as KPF and other PF g salts, is used as electrolytes in lithium anode batteries (qv). 

Solvents for A-type inks are aUphatic hydrocarbons, for example, hexane, textile spidts, Apco Thinner, lactane, VM P (varnish makers and painters ) naphtha, and mineral spirits. Aromatic hydrocarbons such as toluene and xylene are solvents for B-type inks. Generally, a blend of aUphatic and aromatic hydrocarbons is commonly used for this type of ink. 

Tetrahydronaphthalene dehydrogenates to naphthalene at 200—300°C in the presence of a catalyst thermal dehydrogenation takes place at ca 450°C and is accompanied by cracking to compounds, such as toluene and xylene. 

In general, when the product is a fraction from cmde oil that includes a large number of individual hydrocarbons, the fraction is classified as a refined product. Examples of refined products are gasoline, diesel fuel, heating oils, lubricants, waxes, asphalt, and coke. In contrast, when the product is limited to, perhaps, one or two specific hydrocarbons of high purity, the fraction is classified as a petrochemical product. Examples of petrochemicals are ethylene (qv), propylene (qv), benzene (qv), toluene, and xylene (see Btx processing). 

The mixed monocyclic aromatics are called BTX as an abbreviation for ben2ene, toluene, and xylene (see Btxprocessing). The benzene and toluene are isolated by distillation, and the isomers of the xylene are separated by superfractionation, fractional crystallisation, or adsorption (see Xylenes and ethylbenzene). Bensene is the starting material for styrene (qv), phenol (qv), and a number of fibers and plastics. Toluene (qv) is used to make a number of... 

Benzene, toluene, and xylene are made mosdy from catalytic reforming of naphthas with units similar to those already discussed. As a gross mixture, these aromatics are the backbone of gasoline blending for high octane numbers. However, there are many chemicals derived from these same aromatics thus many aromatic petrochemicals have their beginning by selective extraction from naphtha or gas—oil reformate. Benzene and cyclohexane are responsible for products such as nylon and polyester fibers, polystyrene, epoxy resins (qv), phenolic resins (qv), and polyurethanes (see Fibers Styrene plastics Urethane POLYiffiRs). 

Novolak Resins. In a conventional novolak process, molten phenol is placed into the reactor, foHowed by a precise amount of acid catalyst. The formaldehyde solution is added at a temperature near 90°C and a formaldehyde-to-phenol molar ratio of 0.75 1 to 0.85 1. For safety reasons, slow continuous or stepwise addition of formaldehyde is preferred over adding the entire charge at once. Reaction enthalpy has been reported to be above 80 kj /mol (19 kcal/mol) (29,30). The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent such as toluene. Toluene and xylene are used for azeotropic distillation. FoHowing decantation, the toluene or xylene is returned to the reactor. 

The solubiHty of phosphoms in water is about 3 ppm. However, process water used in phosphoms manufacture or handling often catties larger amounts of phosphoms as particulates or small droplets, depending on the water temperature. Phosphoms-contaminated water is commonly called phossy water. Phosphoms has low solubiHty in most common solvents, but is quite soluble in carbon disulfide and some other special solvents. The solubiHty in CS2 and benzene was formerly used in phosphoms analyses, but toxicity and increasing waste disposal costs have led to mote use of toluene and xylene, and mote tecentiy to the use of nonchemical turbidity measurements. 

The PMBs, as higher homologues of toluene and xylenes, ate handled in a similar manner, even though their flash points are higher (see Table 1). Containers are tightly closed and use areas should be ventilated. Breathing vapors and contact with the skin should be avoided. Toxicity and primary... 

Reformulating to reduce HAP solvents frequently means that solvent blend costs increase. The newer blends are generally not be as effective. For example, many coatings were usually formulated using ketones as the active solvents with aromatic hydrocarbons as diluents. This combination produced the most cost-effective formulations. However, when MEK, MIBK, toluene, and xylene became HAP compounds, less-effective solvents had to be used for reformulation. Esters are the most common ketone replacements, and aUphatic diluents would replace the aromatic hydrocarbons. In this situation, more strong solvent is required compared to the ketone/aromatic formulation and costs increase. The combination of reduced VOC emissions and composition constraints in the form of HAP restrictions have compHcated the formulator s task. 

Aromatic Hydrocarbons. Sulfolane is used principally as a solvent for extraction of benzene, toluene, and xylene from mixtures containing aHphatic hydrocarbons (33—37). The sulfolane process was introduced in 1959 by SheU Development Company, and that process is Hcensed by Universal OH Products. A sulfolane extraction process is also Hcensed by the Atlantic Richfield Company. In 1994, worldwide consumption was estimated at ca 6974 t/yr of sulfolane for 137 sulfolane extraction units (see Bix processes Extraction, liquid-liquid Xylenes and ethylbenzene). 

Toluene, Benzene, and BTX Reeoveiy. The composition of aromatics centers on the C - and Cg-fraction, depending somewhat on the boihng range of the feedstock used. Most catalytic reformate is used directiy in gasoline. That part which is converted to benzene, toluene, and xylenes for commercial sale is separated from the unreacted paraffins and cycloparaffins or naphthenes by hquid—hquid extraction or by extractive distillation. It is impossible to separate commercial purity aromatic products from reformates by distillation only because of the presence of azeotropes, although comphcated further by the closeness in boihng points of the aromatics, t/o-paraffin, and unreacted C -, C -, and Cg-paraffins. 

C and 5 kg/cm pressure (see Molecularsieves). Selectivity for toluene and xylenes peaks at 550°C but continues with increasing temperature for hensene. The Cyclar process (Fig. 6) developed joindy by BP and UOP uses a spherical, proprietary seoHte catalyst with a nonnoble metallic promoter to convert C or C paraffins to aromatics. The drawback to the process economics is the production of fuel gas, alow value by-product. BP operated a... 

Transall lation. Two molecules of toluene are converted iato one molecule of benzene and one molecule of mixed xylene isomers ia a sequence called transalkylation or disproportionation. Economic feasibiUty of the process strongly depends on the relative prices of benzene, toluene, and xylene. Operation of a transalkylation unit is practical only when there is an excess of toluene and a strong demand for benzene. In recent years, xylene and benzene prices have generally been higher than toluene prices so transalkylation is presendy an attractive alternative to hydrodealkylation (see also Btx... 

Rapid, simple, quaUtative methods suitable for determining the presence of benzene in the workplace or surroundings have been utilized since the 1930s. Many early tests offered methods for detection of aromatics but were not specific for benzene. A straightforward test allowing selective detection of benzene involves nitration of a sample to y -dinitrobenzene and reaction of the resultant ether extract with an ethanoHc solution of sodium hydroxide and methyl ethyl ketone (2-butanone), followed by the addition of acetic acid to eliminate interferences from toluene and xylenes. Benzene imparts a persistent red color to the solution (87). The method is claimed to be sensitive to concentrations as low as 0.27 ppm benzene from 10 mL air samples. 

Bismuth ttiiodide may be prepared by beating stoichiometric quantities of the elements in a sealed tube. It undergoes considerable decomposition at 500°C and is almost completely decomposed at 700°C. However, it may be sublimed without decomposition at 3.3 kPa (25 mm Hg). Bismuth ttiiodide is essentially insoluble in cold water and is decomposed by hot water. It is soluble in Hquid ammonia forming a red triammine complex, absolute alcohol (3.5 g/100 g), benzene, toluene, and xylene. It dissolves in hydroiodic acid solutions from which hydrogen tetraiodobismuthate(Ill) [66214-37-7] HBil 4H2O, may be crystallized, and it dissolves in potassium iodide solutions to yield the red compound, potassium tetraiodobismuthate(Ill) [39775-75-2] KBil. Compounds of the type tripotassium bismuth hexaiodide [66214-36-6] K Bil, are also known. 

Deep C t lytic Crocking. This process is a variation of fluid catalytic cracking. It uses heavy petroleum fractions, such as heavy vacuum gas oil, to produce propylene- and butylene-rich gaseous products and an aromatic-rich Hquid product. The Hquid product contains predorninantiy ben2ene, toluene, and xylene (see BTX processing). This process is being developed by SINOPEC in China (42,73). SINOPEC is currentiy converting one of its fluid catalytic units into a demonstration unit with a capacity of 60,000 t/yr of vacuum gas oil feedstock. 

Processes for hydrogen gasification, hydrogen pyrolysis, or coking of coal usually produce Hquid co-products. The Hygas process produces about 6% Hquids as benzene, toluene, and xylene. Substitution of petroleum residuum for the coal-derived process oil has been used in studies of coal Hquefaction and offers promise as a lower cost technology (104). 

Some catalysts exposed to air stripping off-gas were subject to deactivation. However, using a catalytic oxidizer at a U.S. Coast Guard faciUty (Traverse City, Mich.) for the destmction of benzene, toluene, and xylene stripped from the groundwater, the catalytic oxidization unit operated at 260 to 315°C, and was able to achieve 90% destmction efficiency (see Groundwatermonitoring). 

The main product, benzene, is represented by solute (B), and the high boiling aromatics are represented by solute (C) (toluene and xylenes). The analysis of the products they obtained are shown in Figure 12. The material stripped form the top section (section (1)) is seen to contain the alkanes, alkenes and naphthenes and very little benzene. The product stripped from the center section appears to be virtually pure benzene. The product from section (3) contained toluene, the xylenes and thiophen which elutes close to benzene. The thiophen, however, was only eliminated at the expense of some loss of benzene to the lower stripping section. Although the system works well it proved experimentally difficult to set up and maintain under constant operating conditions. The problems arose largely from the need to adjust the pressures that must prevent cross-flow. The system as described would be virtually impossible to operate with a liquid mobile phase. 

An electrostatic precipitator is used to remove more tar from coke oven gas. The tar is then sent to storage. Ammonia liquor is also separated from the tar decanter and sent to wastewater treatment after ammonia recovery. Coke oven gas is further cooled in a final cooler. Naphthalene is removed in a separator on the final cooler. Light oil is then removed from the coke oven gas and is fractionated to recover benzene, toluene, and xylene. Some facilities may include an onsite tar distillation unit. The Claus process is normally used to recover sulfur from coke oven gas. During the coke quenching, handling, and screening operation, coke breeze is produced. The breeze is either reused on site (e.g., in the sinter plant) or sold offsite as a by-product. 

---