Heavy Hydrocracking

For all of the hydrocracker operations, the feed properties are those of the heavy naphtha from the base crude mix blended with a specified fraction of light cycle oil from the base FCC operation. For all of the motor reformer operations, the feed properties are those of the motor naphtha from the base crude mix blended with heavy hydrocrackate from the base hydrocracker operation. For all of the BTX reformer operations, the feed properties are those of the BTX naphtha from the base crude mix blended with light hydrocrackate from the base hydrocracker operation. Finally, for each process unit, the process simulator computes the change in plant performance associated with a fixed perturbation of each feed property about the base operation. 

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. 

Processing heavy oils and bitumens represents a challenge for the current refinery processes, because heavy oils and bitumens poison the metal catalysts used m the refineries. In our research at the Loker Institute, we found the use of superacid catalysts, which are less sensitive to heavy oils, an attractive solution to their processing, particularly hydrocracking. 

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. 

Shell Gas B.V. has constructed a 1987 mVd (12,500 bbhd) Fischer-Tropsch plant in Malaysia, start-up occurring in 1994. The Shell Middle Distillate Synthesis (SMDS) process, as it is called, uses natural gas as the feedstock to fixed-bed reactors containing cobalt-based cat- yst. The heavy hydrocarbons from the Fischer-Tropsch reactors are converted to distillate fuels by hydrocracking and hydroisomerization. The quality of the products is very high, the diesel fuel having a cetane number in excess of 75. 

Heavy naphtha from atmospheric distillation units or hydrocracking... 

Feed hydrotreating or hydrocracking reduces SOj, emissions and the sulfur content of FCC products. As discussed earlier in this chapter, many benefits are associated with FCC feed hydrotreating. It is important to note that most of the sulfur in a hydrotreated feed is in heavy organic compounds and will be concentrated in the decanted oil and coke. Consequently, for a given sulfur in the feed, more SO, will be produced with hydrotreated feed. 

Van Driesen and Stewart (V4) have reported temperature measurements for various locations in commercial gas-liquid fluidized reactors for the large-scale catalytic desulfurization and hydrocracking of heavy petroleum fractions (2500 barrels per day capacity). The hydrogenation was carried out in two stages the maximum and minimum temperatures measured were 774° and 778°F for the first stage and 768° and 770°F for the second. These results indicate that gas-liquid fluidized reactors are characterized by a high effective thermal conductivity. 

Heavy fractions (e.g., vacuum gas oils) and residues HDP might involve both, hydrotreatment and hydrocracking operations. HDT, in this case, is a feed pretreatment, for preparation to another process unit, which might be a HCK unit. This process combination, HDT-HCK can be used on Cycle Oil (FCC, coker), VGO (SR and coker) and SR residues (atmospheric and vacuum). It can be carried out in a single reactor with more than one catalyst, or in more than one reactor. 

There are commercial processes for the direct upgrading of residues under high severe hydroconversion conditions. Other alternatives consider the previous hydrotreatment of the residue, so that the hydrocracking stage does not need to be so harsh. Otherwise, residue conversion could also proceed via carbon rejection methods, these processes fall out the scope of the present book and will not be considered here. However, it is important to mention than VR coking is seen as a more economical alternative than HDP, especially for the more heavy crudes, for which concentrations of metals and nitrogen would require the toughest conditions. 

Products Company and Davison (W.R. Grace) Catalysts) and Hydrocarbon Technologies, Inc. ART provides non-zeolitic catalysts for ebullating residue hydrocracking and fixed bed pretreating HDT [140], A nanoscale iron based, slurry catalyst is recommended for coal liquefaction, while a molecule-sized and chemically in situ generated catalyst is employed for the high conversion of asphaltenic fractions or heavy oils [141],... 

Product yields and qualities obtained from HCK of heavy Safaniya VR are compared in Table 12 [142], As can be seen, higher yields on slurry and ebullated beds are associated with poorer product quality, besides the asphaltene concentration in the hydrocracked VR makes almost impossible any further improvement by further processing. 

Fukuyama, H., Development of Carbon Catalyst for Heavy Oil Hydrocracking in NPRA Annual Meeting, 2002. 02-14. San Antonio, TX, Mar. 17-19. AM-, 10pp. 

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