Refinery catalysts distillate conversion

A modern refinery is a complicated collection of conversion processes, each tailored to the properties of the feed it has to convert. The scheme shown in Fig. 9.1 summarizes the most important operations some reasons for these processes are given in Tab. 9.2, along with relevant catalysts. First the crude oil is distilled to separate it into fractions, varying from gases, liquids (naphtha, kerosene and gas oil), to the heavy residue (the so-called bottom of the barrel ) that remains after vacuum distillation. 

Superficially the Oryx GTL refinery design has much in common with the SMDS process, but there are important differences. There is no separate hydrotreater, which limits production of chemicals, such as waxes. The hydrocracker employs the Chevron Isocracking technology, which is based on a sulfided supported base-metal catalyst that was designed for crude oil conversion. The operating conditions of the hydrocracker are also more severe (>350°C, 7 MPa) than those required by the SMDS process (300-350°C, 3-5 MPa). Only intermediate products are produced (Table 18.13),5 with the naphtha slated as cracker feed and the distillate as blending component for diesel fuel. 

The high-boiling distillates, such as the atmospheric and vacuum gas oils, are not usually produced as a refinery product but merely serve as feedstocks to other processes for conversion to lower-boiling materials. For example, gas oils can be desulfurized to remove more than 80% of the sulfur originally in the gas oil with some conversion of the gas oil to lower-boiling materials (Table 6-11). The treated gas oil (which has a reduced carbon residue as well as lower sulfur and nitrogen contents relative to the untreated material) can then be converted to lower-boiling products in, say, a catalytic cracker where an improved catalyst life and volumetric yield may be noted. 

The Mizushima Oil Refinery of Japan Energy Corporation first implemented a high conversion operation of vacuum residue, versus a constant desulfurization operation, in the commercial residue hydrodesulfurization unit equipped with fixed-bed reactors, to produce more middle distillates as well as fuel oil with lower viscosity. The catalysts will be replaced when the sulfur content in the product oil reaches the allowable limit. Since we have believed that an increase in the residue conversion decreases the catalyst activity by coke deposition, we have been interested in controlling the coke deactivation to maximize the residue conversion during a scheduled operating period. 

The Mizushima Oil Refinery of Japan Energy Corporation first implemented an operation of vacuum residue hydrodesulfiirization in the conventional fixed bed reactor system in 1980. We have also conducted a high conversion operation to produce more middle distillates as well as lower the viscosity of the product fuel oil to save valuable gas oil which is used to adjust the viscosity. Vacuum residue hydrodesulfurization in fixed bed reactors mvolves the characteristic problems such as hot spot occurrence and pressure-drop build-up. There has been very little literature available discussing these problems based on commercial results. JafiFe analyzed hot spot phenomena in a gas phase fixed bed reactor mathematically, assuming an existence of the local flow disturbance region [1]. However, no cause of flow disturbance was discussed. To seek for appropriate solutions, we postulated causes ofhot spot occurrence and pressure-drop build-up by conducting process data analysis, chemical analysis of the used catalysts, and cold flow model tests. This paper describes our solutions to these problems, which have been demonstrated in the commercial operations. 

Compared to SMDS, this simplified process employs a different catalyst in the synthesis stage and does not include a Heavy Paraffinic Conversion stage for producing the finished middle distillate fractions. The syncrude product is a broad boiling range of hydrocarbons (Table 4), and the relative amounts of individual products can be varied by adjusting the reaction conditions. Alternatively, syncrude products can be processed in existing refineries into finished transportation fuels. 

Normal Paraffin-Based Olefins, Detergent range -paraffins are currently isolated from refinery streams by molecular sieve processes (see ADSORPTION, LIQUID separation) and converted to olefins by two methods. In the process developed by Universal Oil Products and practiced by Enichem and Mitsubishi Petrochemical, a -paraffin of the desired chain length is dehydrogenated using the Pacol process in a catalytic fixed-bed reactor in the presence of excess hydrogen at low pressure and moderately high temperature. The product after adsorptive separation is a linear, random, primarily internal olefin. Shell formedy produced olefins by chlorination—dehydrochlorination. Typically, C —C14 -paraffins are chlorinated in a fluidized bed at 300°C with low conversion (10—15%) to limit dichloroalkane and trichloroalkane formation. Unreacted paraffin is recycled after distillation and the predominant monochloroalkane is dehydrochlorinated at 300°C over a catalyst such as nickel acetate [373-02-4]. The product is a linear, random, primarily internal olefin. 

---