Aromatic saturation

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. 

Catalyst choice is strongly influenced by the nature of the feedstock to be hydrotreated. Thus, whereas nickel-promoted and cobalt—nickel-promoted molybdenum catalysts can be used for desulfurization of certain feedstocks and operating conditions, a cobalt-promoted molybdenum catalyst is generally preferred in this appHcation. For denitrogenation and aromatics saturation, nickel-promoted molybdenum catalysts usually are the better choice. When both desulfurization and denitrogenation of a feedstock are required, the choice of catalyst usually is made so that the more difficult operation is achieved satisfactorily. 

Effect of Catalyst The catalysts used in hydrotreating are molybdena on alumina, cobalt molybdate on alumina, nickel molybdate on alumina or nickel tungstate. Which catalyst is used depends on the particular application. Cobalt molybdate catalyst is generally used when sulfur removal is the primary interest. The nickel catalysts find application in the treating of cracked stocks for olefin or aromatic saturation. One preferred application for molybdena catalyst is sweetening, (removal of mercaptans). The molybdena on alumina catalyst is also preferred for reducing the carbon residue of heating oils. 

Table 41.3 shows a performance comparison of Pt/Pd TUD-1 with a commercial Pt/Pd catalyst (26). The feedstock is a typical straight run gasoil ( SRGO ), a distillate precursor to diesel fuel. Under identical test conditions, the TUD-1 catalyst achieved 75% aromatics saturation versus 50% for the same volume of commercial catalyst. This superior result is particularly interesting because the TUD-1 catalyst had a much lower density than the commercial material, so that less catalyst by weight was required in the reactor. 

Aromatics, olefins and in general, unsaturated compounds undergo hydrogenation reactions, usually unwanted due to their detrimental effect on the operating costs, derived from an excessive consumption of hydrogen. Aromatic saturation, however, is used in jet fuel to improve the smoke point and in diesel for cetane enhancement. In the case of gasoline, extreme hydrogenation leads to a deterioration of the fuel performance parameters. 

Aromatic saturation reactions are reversible and exothermic, and at typical reaction conditions, do not attain 100% conversion. Furthermore, increasing the temperature to favor conversion of the other concurrent reactions disfavor aromatic hydrogenation. The kinetics studies indicate that they are fast reactions, indicating that equilibrium is reached under HDT conditions. 

NiW catalysts are the most active for hydrogenation and are best suited for aromatic saturation and hydrocracking. Accordingly, the poisoning effect of H2S and NH3 is significant in these catalysts. However, their HDS and HDN performance is less attractive than that obtained from NiMo and CoMo catalysts. 

Certain catalyst manufacturers claims to have optimized the preparation (CoMo catalysts), the formulation or the promotion (aromatic saturation) of their catalysts to achieve an appropriate balance of the hydrogenation function to desulfurize the sterically hindered compounds and yield the 15 ppm S fuel. However, the actual trend is to use NiMo catalyst for the treatment of the more refractory compounds, below 200 ppm S [22],... 

Precious metal catalysts have shown to be effective for the desulfurization of the steri-cally hindered compounds. One example is given with a commercial catalyst using both, palladium and platinum [23]. The high activity of these metals towards hydrogenation would result in aromatic saturation reactions, and consequently an increase in operating costs (not only for the catalyst cost but also for the increase in hydrogen uptake). 

The aromatic hydrogenation reactions are reversible and at normal hydrotreating conditions, the equilibrium limits to achieve complete conversion. Low temperatures and higher pressures favor the aromatic saturation. The carbon atoms of a multi-ring system are hydrogenated in sequential steps, each one being equilibrium limited, as well. 

In this equation, B stands for adsorption coefficients and C for concentrations. The thermodynamic control imposes the use of very high pressures, low space velocities, and very active catalysts. For the specific case of aromatic saturation and in the presence of H2S or any other sulfur compound, NiW is the recommended catalyst [66], However, in those cases where a precious metal catalyst may be used then, it becomes the preferred choice [67],... 

On sulfided metallic phases the hydrotreatment reactions also takes place. Noble metal catalysts usually include a zeolitic support. They are particularly used for fulfilling two different objectives, in the case of a gasoline oriented HCK their cracking and isomerization activity is the most important (increasing high octane and conversion yield). In a diesel HCK unit, the noble metal catalyst is mainly oriented to aromatic saturation and cetane improvement. However, in this latter case, also sulfided metal catalysts are used, especially NiW. 

Arosat [Aromatics saturation] A hydroprocessing process developed by C-E Lummus. 

The presence of metal may catalyze demethylation and can occur to some extent in catalysts where the metal function is under-passivated, as by incomplete sulfiding. This would convert valuable xylenes to toluene. The demethylation reaction is usually a small contributor to xylene loss. Metal also catalyzes aromatics saturation reactions. While this is a major and necessary function to facilitate EB isomerization, any aromatics saturation is undesirable for the process in which xylene isomerization and EB dealkylation are combined. Naphthenes can also be ring-opened and cracked, leading to light gas by-products. The zeolitic portion of the catalyst participates in the naphthene cracking reactions. Cracked by-products can be more prevalent over smaller pore zeolite catalysts. 

RDX, Cyclonite, Hexahydro-l,3,5-trinitro-l,3,5-triazine under Secondary Aliphatic Amines Ring-Substituted Aromatics Saturated Alkyl Halides Secondary Alcohols... 

Alicyclic hydroxylation. Hydroxylation of saturated rings yields monohydric and dihydric alcohols. For instance, cyclohexane is metabolized to cyclohexanol, which is further hydroxylated to frcms-cyclohexane-l,2-diol (Fig. 4.11). With mixed alicyclic/aromatic, saturated and unsaturated systems, alicyclic hydroxylation appears to predominate, as shown for the compound tetralin (Fig. 4.12). 

Funk, E. W, and J. M. Prausnitz. 1970. Thermodynamic properties of liquid mixtures Aromatic-saturated hydrocarbon systemtod. Eng. Chem62 8-15. 

In this Diels-Alder reaction with inverse electron demand the overlap of the LUMO of the 1-oxa-l,3-butadiene with the HOMO of the dienophile is dominant. Since the electron-withdrawing group of the oxabutadiene at the 3-position lowers its LUMO dramatically, both the cycloaddition and the condensation usually take place at room temperature. The reaction can be performed as a two-, three- or four-component transformation. There is actually no restriction on the aldehydes thus, aromatic, hetero-aromatic, saturated aliphatic and unsaturated aliphatic aldehydes may be used. In addition, ketones such as a-oxocarbocylic esters can also be employed. As 1,3-dicarbonyl compounds cyclic substances such as Meldrum s acid, barbituric acid and derivates, coumarines, any type of cycloalkane-1,3-dione and / -ketoesters, as well as their phosphorus, nitrogen or sulfur analogues and acyclic... 

Oxidation 1)H- 2) NalO Aromatic Saturated, Aliphatic Zwitterion ... 

These heavy gas oils were processed under conditions of 1300 psig, 3000 SCF Ha/bbl., 1 LHSV, and temperatures of 625°, 675°, and 725°F. In addition to sulfur and nitrogen removals, hydrogen consumption and aromatics saturation monitoring was attempted. 

---