Aromatics Pyrolysis

Propane cracking is similar to ethane except for the furnace temperature, which is relatively lower (longer chain hydrocarbons crack easier). However, more by-products are formed than with ethane, and the separation section is more complex. Propane gives lower ethylene yield, higher propylene and butadiene yields, and significantly more aromatic pyrolysis gasoline. Residual gas (mainly H2 and methane) is about two and half times that produced when ethane is used. Increasing the severity... 

Enthalpies of formation and entropies of resonance stabilized radicals of importance in aromatic pyrolysis are estimated to a level of accuracy suitable for order of magnitude calculations. 

Krupp Uhde Aromatics Pyrolysis gasoline, reformate or light oils Extractive distillation process uses selective solvents to separate aromatics from feed streams 30 NA... 

Pyrolysis can be used for the thermal decomposition of waste materials that are predominantly organic in nature, e.g. scrap tyres, scrap cables, waste plastics, shredder wastes, and acid sludge. Rotary kilns are particularly suitable as universally applicable pyrolysis units for continuous operation. Highly aromatic pyrolysis oils for use as chemical raw materials are obtained at reactor temperatures of about 700 °G. Such pyrolysis oils could form the basis for the production of aromatics such as benzene, naphthalene, and their homologues, thermoplastic hydrocarbon resins and precursors of industrial carbon, when the proven processes for the refining of coal tar and crude benzene are applied. 

The refining of highly aromatic pyrolysis oils from waste yields the following range of products ... 

Anthracene dimers as well as dihydroanthracene have been identified as initial reaction products in all pyrolysis studies of anthracene. As shown in Chart I, 11 dimers from anthracene are possible. Because the 9-position is the most reactive, one might expect a predominance of the 9,9 -dimer. However the 2,9-dimer was reported as the major product in one study (18). Many of the other possible dimers were also obtained, depending on the reaction conditions employed. Both steric effects and reactivity factors must, therefore, be taken into account for considering the possible reaction products in aromatic hydrocarbon pyrolysis. The results for anthracene show how the lack of a functional group and the nonspecificity for molecular recombination lead to complex product mixtures in aromatic pyrolysis. 

Since coke is the terminal product of the aromatic pyrolysis pathway, it is of interest to explore the formation mechanism. Insight into this process in the range 800° to 1100°C is provided by the benzene pyrolysis data of Kiney and Delbel (5) in a flow reactor. The diphenyl concentration vs. time behavior reported is characteristic of an intermediate in a sequential reaction A B C where A (benzene) decreases and C... 

In the USA, and to some extent in Great Britain and Norway, ethane is the dominant feedstock for steam cracking. It is recovered from wet natural gas and gives high yields of ethylene, hydrogen and methane. From naphtha, the preferred feedstock in Europe and Japan, additional principal products are propylene, C4 hydrocarbons and pyrolysis naphtha as well as highly aromatic pyrolysis tar. 

The Kureha/ Union Carbide process operates at a higher temperature than the BASF method (Figure 3.46). It uses steam as a heat carrier, at a temperature of 2,000 °C. Preheated crude oil is fed into the superheated steam in an adiabatic reactor, from which 30% ethylene is recovered. Reaction time is only 15 to 20 msec. This process also produces an aromatics-rich oil of relatively high naphthalene content which boils above the pyrolysis gasoline. The aromatic pyrolysis tar concurrently produced can be used to manufacture medium-modulus carbon fibers. 

Pyrolysis gasoline is a by-product of the steam cracking of hydrocarbon feeds in ethylene crackers (see Ethylene). Pyrolysis gasoline typically contains about 50—70 wt % aromatics, of which roughly 50% is benzene, 30% is toluene, and 20% is mixed xylenes (which includes EB). 

Aromatic Hydrocarbons. These are the most toxic of the hydrocarbons and inhalation of the vapor can cause acute intoxication. Benzene is particularly toxic and long-term exposure can cause anemia and leukopenia, even with concentrations too low for detection by odor or simple instmments. The currendy acceptable average vapor concentration for benzene is no more than 1 ppm. PolycycHc aromatics are not sufftcientiy volatile to present a threat by inhalation (except from pyrolysis of tobacco), but it is known that certain industrial products, such as coal tar, are rich in polycycHc aromatics and continued exposure of human skin to these products results in cancer. 

Xylenes. The main appHcation of xylene isomers, primarily p- and 0-xylenes, is in the manufacture of plasticizers and polyester fibers and resins. Demands for xylene isomers and other aromatics such as benzene have steadily been increasing over the last two decades. The major source of xylenes is the catalytic reforming of naphtha and the pyrolysis of naphtha and gas oils. A significant amount of toluene and Cg aromatics, which have lower petrochemical value, is also produced by these processes. More valuable p- or 0-xylene isomers can be manufactured from these low value aromatics in a process complex consisting of transalkylation, eg, the Tatoray process and Mobil s toluene disproportionation (M lDP) and selective toluene disproportionation (MSTDP) processes isomerization, eg, the UOP Isomar process (88) and Mobil s high temperature isomerization (MHTI), low pressure isomerization (MLPI), and vapor-phase isomerization (MVPI) processes (89) and xylene isomer separation, eg, the UOP Parex process (90). 

An excess of crotonaldehyde or aUphatic, ahcyhc, and aromatic hydrocarbons and their derivatives is used as a solvent to produce compounds of molecular weights of 1000—5000 (25—28). After removal of unreacted components and solvent, the adduct referred to as polyester is decomposed in acidic media or by pyrolysis (29—36). Proper operation of acidic decomposition can give high yields of pure /n j ,/n7 j -2,4-hexadienoic acid, whereas the pyrolysis gives a mixture of isomers that must be converted to the pure trans,trans form. The thermal decomposition is carried out in the presence of alkaU or amine catalysts. A simultaneous codistillation of the sorbic acid as it forms and the component used as the solvent can simplify the process scheme. The catalyst remains in the reaction batch. Suitable solvents and entraining agents include most inert Hquids that bod at 200—300°C, eg, aUphatic hydrocarbons. When the polyester is spHt thermally at 170—180°C and the sorbic acid is distilled direcdy with the solvent, production and purification can be combined in a single step. The solvent can be reused after removal of the sorbic acid (34). The isomeric mixture can be converted to the thermodynamically more stable trans,trans form in the presence of iodine, alkaU, or sulfuric or hydrochloric acid (37,38). 

Superffex C t lytic Crocking. A new process called Superflex is being commercialized to produce predorninantiy propylene and butylenes from low valued hydrocarbon streams from an olefins complex (74). In this process, raffinates (from the aromatics recovery unit and the B—B stream after the recovery of isobutylene) and pyrolysis gasoline (after the removal of the C —Cg aromatics fraction) are catalyticaHy cracked to produce propylene, isobutylene, and a cmde C —Cg aromatics fraction. AH other by-products are recycled to extinction. 

Chlorobenzenes are stable compounds and decompose slowly only under excess heating at high temperatures to release some HCl gas and traces of phosgene. It is possible, under certain limited conditions of incomplete combustion or pyrolysis, to form polychlorinated dibenzo-/)-dioxins (PCDDs) and dibenzofurans (PCDFs) from chlorobenzenes (Cm OROCARBONS and cm OROHYDROCARBONS, toxic aromatics). 

Tetracyanoethylene is colorless but forms intensely colored complexes with olefins or aromatic hydrocarbons, eg, benzene solutions are yellow, xylene solutions are orange, and mesitylene solutions are red. The colors arise from complexes of a Lewis acid—base type, with partial transfer of a TT-electron from the aromatic hydrocarbon to TCNE (8). TCNE is conveniendy prepared in the laboratory from malononitrile [109-77-3] (1) by debromination of dibromoma1 ononitrile [1855-23-0] (2) with copper powder (9). The debromination can also be done by pyrolysis at ca 500°C (10). 

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