Residuum hydrodesulfurization catalysts

In Section III, commercial residuum hydroprocessing technology is discussed to establish the role and requirements of hydroprocessing in the overall refinery residuum conversion scheme. Commercial residuum hydroprocessing catalysts and residuum hydrodesulfurization (RDS)-hydrodemetallation (HDM) technology are reviewed briefly. 

RDSA RDS. RDS is used for attnospheric residuum hydrotreating, and VRDS for vacuum residuum hydrodesulfurization. The feedstock is put in contact with catalyst and hydrogen at moderate temperatures and pressures, consuming about 700-1300 SCF H2/bbl of feed (Lars et al., 1984 Otterstedt et al., 1986). 

Removal of the metal contaminants is not usually economical, or efficient, during rapid regeneration. In fact, the deposited metals are believed to form sulfates during removal of carbon and sulfur compounds by combustion that produce a permanent poisoning effect. Thus, if fixed-bed reactors are to be used for residuum or heavy oil hydrodesulfurization (in place of the more usual distillate hydro-desulfurization) it may be necessary to first process the heavier feedstocks to remove the metals (especially vanadium and nickel) and so decrease the extent of catalyst bed plugging. Precautions should also be taken to ensure that plugging of the bed does not lead to the formation of channels within the catalyst bed which will also reduce the efficiency of the process and may even lead to pressure variances within the reactor because of the distorted flow patterns with eventual damage. 

Figure 6-10 Carbon deposit on the catalyst as a function of time in the hydrodesulfurization of a residuum. 

Thus, any processing sequence devised to hydrodesulfurize a heavy oil or residuum must be capable of accommodating the constituents which adversely affect the ability of the catalyst to function in the most efficient manner possible. 

Residua and heavy oils contain impurities other than sulfur, nitrogen, and oxygen, and the most troublesome of these impurities are the organometallic compounds of nickel and vanadium. The metal content of a residuum or heavy oil can vary from several parts per million (ppm) to more than 1000 parts per million (Table 6-15), and there does seem to be more than a chance relationship between the metals content of a feedstock and its physical properties (Reynolds, 1997 Speight, 1999). In the hydrodesulfurization of the heavier feedstocks the metals (nickel plus vanadium) are an important factor since large amounts (over 150 ppm) will cause rapid deterioration of the catalyst. The free metals, or the sulfides, deposit on the surface of the catalyst and within the pores of the catalyst, thereby... 

RESID-fining [RESIDuum refining] A hydrodesulfurization process adapted for petroleum residues. Developed by Esso Research Engineering Company and licensed by them and Union Oil Company of California. A proprietary catalyst is used in a fixed bed. As of 1988, eight plants had been designed. 

A detailed description of a chromia-on-alumina catalyst prepared by impregnation has been given elsewhere . Another supported nonmetallic catalyst widely used commercially is cobalt molybdate-on-alumina. The preparation of this catalyst using an alumina support with controlled pore-size distribution is as follows. Silica-stabilized alumina, with greater than 50% of its surface area in 3-8 nm pores and at least 3% of the total pore volume in pores greater than 200 nm in diameter, is impregnated with an aqueous solution of cobalt and molybdenum. The finished oxysulfide catalyst was tested for hydrodesulfurization of petroleum residuum at 370°C and 100 atm for 28 days and compared with a convential cobalt-molybdate catalyst having a major portion of the surface area in 3-7 nm pores. The latter catalyst and controlled pore catalyst maintained 57 and 80% activity, respectively. 

---