Aromatics, hydrocracking

In ebullating bed reactor, such as the H-coal process, Ni-Mo or Co-Mo alumina catalysts have been used (96). The catalyst definitely improves the oil yields by accentuating aromatic hydrocracking, achieving conversions around 95% at catalyst make-up rates of 1 3%. 

Comparing the overall concentrations of these different carbons designated generally as structural patterns , measured before and after a process such as FCC or hydrocracking (see Chapter 10), enables the conversion to be monitored the simple knowledge of the percentage of condensed aromatic carbon of a feedstock gives an indication of its tendency to form coke. 

Properly speaking, steam cracking is not a refining process. A key petrochemical process, it has the purpose of producing ethylene, propylene, butadiene, butenes and aromatics (BTX) mainly from light fractions of crude oil (LPG, naphthas), but also from heavy fractions hydrotreated or not (paraffinic vacuum distillates, residue from hydrocracking HOC). 

This form of limited-conversion hydrocracking is a process that selectively prepares high quality residues for the special manufacture of base oils of high viscosity index or treating residues having low BMCl for the conversion of heavy fractions to ethylene, propylene, butadiene and aromatics. 

Diesel Fuel. Eederal diesel specifications were changed to specify a maximum of 0.05% sulfur and a minimum cetane index of 40 or a maximum aromatics content of 35 vol % for on-road diesel. Eor off-road diesel, higher sulfur is allowed. CARB specifications require 0.05% sulfur on or off road and 10% aromatics maximum or passage of a qualification test. Process technologies chosen to meet these specifications include hydrotreating, hydrocracking, and aromatics saturation. 

Catalysis. As of mid-1995, zeoHte-based catalysts are employed in catalytic cracking, hydrocracking, isomerization of paraffins and substituted aromatics, disproportionation and alkylation of aromatics, dewaxing of distillate fuels and lube basestocks, and in a process for converting methanol to hydrocarbons (54). 

Of the main reactions, aromatization takes place most readily and proceeds ca 7 times as fast as the dehydroisomerization reaction and ca 20 times as fast as the dehydrocyclization. Hence, feeds richest in cycloparaftins are most easily reformed. Hydrocracking to yield paraffins having a lower boiling point than feedstock proceeds at about the same rate as dehydrocyclization. 

Antimony trichloride is used as a catalyst or as a component of catalysts to effect polymerisation of hydrocarbons and to chlorinate olefins. It is also used in hydrocracking of coal (qv) and heavy hydrocarbons (qv), as an analytic reagent for chloral, aromatic hydrocarbons, and vitamin A, and in the microscopic identification of dmgs. Liquid SbCl is used as a nonaqueous solvent. 

Catalytic Reforming. Worldwide, approximately 30% of commercial benzene is produced by catalytic reforming, a process ia which aromatic molecules are produced from the dehydrogenation of cycloparaffins, dehydroisomerization of alkyl cyclopentanes, and the cycHzation and subsequent dehydrogenation of paraffins (36). The feed to the catalytic reformer may be a straight-mn, hydrocracked, or thermally cracked naphtha fraction ia the... 

Solvents are recovered from the oil stream through distillation and steam stripping in a fractionator. The stream extracted from the solvent contains high concentrations of hydrogen sulfide, aromatics, naphthenes and other hydrocarbons, and is often fed to the hydrocracking unit. 

All of the above reactions are reversible, with the exception of hydrocracking, so that thermodynamic equilibrium limitations are important considerations. To the extent possible, therefore, operating conditions are selected which will minimize equilibrium restrictions on conversion to aromatics. This conversion is favored at higher temperatures and lower operating pressures. 

Naphthas obtained from cracking units generally contain variable amounts of olefins, higher ratios of aromatics, and branched paraffins. Due to presence of unsaturated compounds, they are less stable than straight-mn naphthas. On the other hand, the absence of olefins increases the stability of naphthas produced by hydrocracking units. In refining operations, however, it is customary to blend one type of naphtha with another to obtain a required product or feedstock. 

Bond breaking can occur at any position along the hydrocarbon chain. Because the aromatization reactions mentioned earlier produce hydrogen and are favored at high temperatures, some hydrocracking occurs also under these conditions. However, hydrocracking long-chain molecules can produce Ce, C7, and Cg hydrocarbons that are suitable for hydrode-cyclization to aromatics. 

For more aromatics yield, the end point of the feed may be raised to include higher molecular weight hydrocarbons in favor of hydrocracking and dehydrocyclization. However, excessive hydrocracking is not desirable because it lowers liquid yields. 

Hydrodealkylation. Hydrodealkylation is a cracking reaction of an aromatic side chain in presence of hydrogen. Like hydrocracking, the... 

As in hydrocracking, this reaction increases the gas yield and changes the relative equilihrium distrihution of the aromatics in favor of benzene. Table 3-7 shows the properties of feed and products from Chevron Rheiniforming process. 

Catalytic reformers are normally designed to have a series of catalyst beds (typically three beds). The first bed usually contains less catalyst than the other beds. This arrangement is important because the dehydrogenation of naphthenes to aromatics can reach equilibrium faster than the other reforming reactions. Dehydrocyclization is a slower reaction and may only reach equilibrium at the exit of the third reactor. Isomerization and hydrocracking reactions are slow. They have low equilibrium constants and may not reach equilibrium before exiting the reactor. 

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