Aromatics production

Aromatic compounds are the most widely used and one of the most important classes of petrochemicals. They are still an important constituent of high-octane gasoline, although because of their carcinogenic nature their application will decrease. FCC gasoline contains about 29% aromatics, whereas the aromatic content of reformates is about 63%. They also are excellent solvents and constitute an important component of synthetic rubbers and fibers. 

Historically aromatic compounds were produced from hard coal by coking. The polyaromatics present in coal are released under the pyrolytic conditions and are absorbed in oil or on activated charcoal to separate them from the other coal gases. The components are freed by codistillation with steam or by simple distillation. The contaminant nitrogen- and sulfur-containing compounds are removed by washing with sulfuric acid or by hydrogenation. 

Crude oil, however, has almost completely replaced coal as a source of aromatics. Crude oil contains several percents of benzene, toluene, and xylenes and their cycloalkane precursors. The conversion efficiency for preparing toluene or xylenes from their precursors is nearly 100%. For benzene this efficiency is slightly lower. Moreover, alkanes are also transformed to aromatics during refining processes, allowing efficient production of simple aromatic compounds. 

Catalytic reforming has become the most important process for the preparation of aromatics. The two major transformations that lead to aromatics are dehydrogenation of cyclohexanes and dehydrocyclization of alkanes. Additionally, isomerization of other cycloalkanes followed by dehydrogenation (dehydroisomerization) also contributes to aromatic formation. The catalysts that are able to perform these reactions are metal oxides (molybdena, chromia, alumina), noble metals, and zeolites. 

Liquefied petroleum gas (LPG), a mixture of propane and butanes, is catalytically reacted to produce an aromatic-rich product. The first step is 

Product yield from saturated LPG feed to the cyclar process  

Basis High-yield mode. Lower cost Cyclar units can be designed, but for lower overall yields. 

Interest in the use of lower-value light paraffins for the production of aromatics led to the introduction of two new processes similar to the Cyclar process, the Z-forming and the Aroformer processes, which were developed in Japan and Australia, respectively/  

Research is also being conducted in Japan to aromatize propane in presence of carhon dioxide using a Zn-loaded HZSM-5 catalyst/ The effect of CO2 is thought to improve the equilibrium formation of aromatics by the consumption of product hydrogen (from dehydrogenation of propane) through the reverse water gas shift reaction. 

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Donor substituents on the vinyl group further enhance reactivity towards electrophilic dienophiles. Equations 8.6 and 8.7 illustrate the use of such functionalized vinylpyrroles in indole synthesis[2,3]. In both of these examples, the use of acetyleneic dienophiles leads to fully aromatic products. Evidently this must occur as the result of oxidation by atmospheric oxygen. With vinylpyrrole 8.6A, adducts were also isolated from dienophiles such as methyl acrylate, dimethyl maleate, dimethyl fumarate, acrolein, acrylonitrile, maleic anhydride, W-methylmaleimide and naphthoquinone. These tetrahydroindole adducts could be aromatized with DDQ, although the overall yields were modest[3]. 

Separation of Aromatic and Aliphatic Hydrocarbons. Aromatics extraction for aromatics production, treatment of jet fuel kerosene, and enrichment of gasoline fractions is one of the most important appHcations of solvent extraction. The various commercial processes are summarized in Table 4. 

Alternatively the alkylated aromatic products may rearrange. -Butylbenzene [104-57-8] is readily isomerized to isobutylbenzene [538-93-2] and j Abutyl-benzene [135-98-8] under the catalytic effect of Friedel-Crafts catalysts. The tendency toward rearrangement depends on the alkylatiag ageat and the reaction conditions (catalyst, solvent, temperature, etc). 

C, 0.356—1.069 m H2/L (2000—6000 fU/bbl) of Hquid feed, and a space velocity (wt feed per wt catalyst) of 1—5 h. Operation of reformers at low pressure, high temperature, and low hydrogen recycle rates favors the kinetics and the thermodynamics for aromatics production and reduces operating costs. However, all three of these factors, which tend to increase coking, increase the deactivation rate of the catalyst therefore, operating conditions are a compromise. More detailed treatment of the catalysis and chemistry of catalytic reforming is available (33—35). Typical reformate compositions are shown in Table 6. 

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. 

A variety of ring syntheses have been devized which depend on carbanion addition to an activated double bond. The examples depicted in Scheme 74 illustrate the use of inter alia cyano and nitro groups which are subsequently eliminated. In appropriate instances the inclusion of additional eliminable groups ensures the formation of fully aromatized products. 

Where an N-methoxy group is present, as in l-methyl-3-methoxybenzimidazole, elimination of MeOH can give an aromatic product. 

Scheme 9.3. Correlation between for Retro-Diels-Alder Reaction and Resonance Stabilization of Aromatic Products...

Also of importance to the industry is the demand for aromatic products. The high octane reformate, which is rich in aromatics, is a major source of aromatics for petrochemical operations. Powerformers can produce aromatics such as benzene and toluene. 

For aromatics production, similar considerations apply. Maximum yields of xylenes and other heavy aromatics can be obtained in cyclic units, but, again, at somewhat higher investments. The process selection, thus, again requires the balancing of process credits versus debits for the specific application. For light aromatics (benzene-toluene) production, however, the situation tends to favor a... 

An unactivated aryl fluorine may be activated by complexauon with chro-mium(VI). Replacement of the fluonne in the complexed system occurs readily, and the uncomplexetl aromatic product can be generated by treatment with iodine [84] (equation 46)... 

Similarly, fluorinated ketones are prepared and react with enamines [50], This reaction involves the intermediacy of an a,P-ethylenic ketone and leads to annelation-aromatization products [5tJ] (Table 13) (equation 37). 

Although fluorocarbons are considered very stable compounds, they can be defluonnated to unsaturated denvatives under certain mild conditions. Hexa-decafluorobicyclo[4.4.0]dec-I(6)-ene reacts with activated zinc powder at 80-100 °C to yield partially and fully aromatized products [61] The final product composition depends on the solvent. Dioxane, acetonitrile, and dimethylform-amide, m this order, effect increasing unsaturation (equation 30). 

The Hurd-Mori synthesis of 1,2,3-thiadiazoles from a-methylene ketones developed in 1955 is, even today, the method of choice for a number of 1,2,3-thia-diazole derivatives. Both the mechanism and the regiochemistry have been extensively studied, but since the isolation of the intermediate by Hurd and Mori (84CHEC-I(6)460), there has been no further work supporting the formation of this intermediate or its conversion into the aromatization product. In 1995 Kobori and coworkers published the isolation of several 1,2,3-thiadiazolin-1-oxides 186, finally demonstrating their participation in the formation of 1,2,3-thiadiazoles. Substituents R and R play an important role in the isolation of 1,2,3-thiadiazolin-1-oxide (95H(41)2413). 

The alkylation with alkenes can be catalyzed by protons. The carbon-carbon double bond of the alkene is protonated according to Markow nikojfs rule, to give a carbenium ion 10, which then reacts by the above mechanism to yield the alkylated aromatic product 11 ... 

The electrophile 4 adds to the aromatic ring to give a cationic intermediate 5. Loss of a proton from 5 and concomitant rearomatization completes the substitution step. Subsequent hydrolysis of the iminium species 2 yields the formylated aromatic product 3. Instead of the highly toxic hydrogen cyanide, zinc cyanide can be used. The hydrogen cyanide is then generated in situ upon reaction with the hydrogen chloride. The zinc chloride, which is thereby formed, then acts as Lewis acid catalyst. 

Liquid solvents are used to extract either desirable or undesirable compounds from a liquid mixture. Solvent extraction processes use a liquid solvent that has a high solvolytic power for certain compounds in the feed mixture. For example, ethylene glycol has a greater affinity for aromatic hydrocarbons and extracts them preferentially from a reformate mixture (a liquid paraffinic and aromatic product from catalytic reforming). The raffinate, which is mainly paraffins, is freed from traces of ethylene glycol by distillation. Other solvents that could be used for this purpose are liquid sulfur dioxide and sulfolane (tetramethylene sulfone). 

Pollitzer, E. L., Hayes, J. C., and Haensel, V, The Chemistry of Aromatics Production via Catalytic Reforming, Refining Petroleum for Chemicals, Advances in Chemistry Series No. 97, American Chemical Society, 1970, pp. 20-23. 

Chlorine and iodine can be introduced into aromatic rings by electrophilic substitution reactions, but fluorine is too reactive and only poor yields of monofluoro-aromatic products are obtained by direct fluorinafion. Aromatic rings react with CI2 in the presence of FeCl3 catalyst to yield chlorobenzenes, just as they react with Bi 2 and FeBr3. This kind of reaction is used in the synthesis of numerous pharmaceutical agents, including the antianxiety agent diazepam, marketed as Valium. 

Loss of H+ from the carbocation gives the hydroxy-substituted aromatic product. 

Problem 16.19 1 What aromatic products would you obtain from the KMn04 oxidation of the following substances ... 

Numerous reactions have been described in which the oxygen of the oxepin system is removed to give benzene derivatives. The formation of the aromatic products can be rationalized by an arene oxide as intermediate. A suitable reagent for the elimination of an oxygen atom from this heterocycle is triphenylphosphane, e.g. formation of l,24 2a,12 and 2b.1,9... 

Direct aromatization of the quinonoid intermediates is a photochemically allowed but thermally forbidden rearrangement (Scheme 5.6). When phenylethyl radicals are generated photochemically at 20 °C there is evidence95 of a-o coupling by way of the aromatized product 7. The products derived from these pathways can be trapped in thermal reactions by radical98 or acid1 catalyzed... 

The Diels-Alder reaction of 2-vinylfurans 73 with suitable dienophiles has been used to prepare tetrahydrobenzofurans [73, 74] by an extra-annular addition these are useful precursors of substituted benzofurans (Scheme 2.29). In practice, the cycloadditions with acetylenic dienophiles give fully aromatic benzofurans directly, because the intermediate cycloadducts autoxidize during the reaction or in the isolation procedure. In the case of a reaction with nitro-substituted vinylbenzofuran, the formation of the aromatic products involves the loss of HNO2. 

Benzenediamine (185) and benzoin (186) gave a separable mixture of 2,3-diphenyl-1,2-dihydroquinoxaline (187, R = Ph) and 2,3-diphenylquinoxaline (188, R = Ph) (dry mixture, microwave irradiation under reflux, 4 min 21% and 67%, respectively) in contrast, similar treatment with m,m -dichloro-benzoin gave only the aromatized product, 2,3-bis(m-chlorophenyl)quinoxa-line (188, R = C6H4Cl-m) (94%). ... 

Industrial workers involved in chlorinated aromatic production including chlorophenol suffered dioxin-induced chloracne 2,3). Chloracne and other serious health disturbances have been attributed to polychloro-dibenzo-p-dioxins in workers involved in manufacturing 2,4,5-T 4, 5). Dioxins are toxic to chick embryos, guinea pigs, rabbits, and monkeys 6, 7, 8, 9, 10). 

AOPP has been used in many studies to examine the role of PAL in the synthesis of secondary aromatic compounds. The results summarized in Table I indicate that levels of AOPP that have little or no effect on growth can strongly affect production of secondary aromatic products. Other studies have shown rapid cessation of isoflavone synthesis in Cicer ariethinum by 0.3 mM AOPP (61). 

In the case of an excipient that contains a mixture of constituents, qualitative and quantitative details of the composition should be provided (other than for flavoring or aromatic products, which must state the information only qualitatively provided there is a suitable method for ensuring consistency of composition and of the presence of the main ingredients and any carriers, with relevant references to purity criteria such as those established by the World Health Organization Food and Agriculture Organization). 

Tris(trimethylsiloxy)-methoxy hexatriene undergoes with aliphatic imidazolides in the presence of a Lewis acid a 5C -f 1C cyclocondensation reaction leading t° aromatic products 18]... 

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