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TABLE 34 Summary of Hydrocracking Process Operations Conditions Solid acid catalyst (silica-alumina with rare earth metals, various other options) Temperature: 260 450 C (500 842 F) (solid/liquid contact) Pressure: 1,000 6,000 psi hydrogen Frequent catalysts renewal for heavier feedstocks Gas oil: catalyst life up to 3 years Heavy oil/tar sand bitumen: catalyst life less than 1 year Feedstocks Refractory (aromatic) streams Coker oils Cycle oils Gas oils Residua (as a full hydrocracking or hydrotreating option) In some cases, asphaltic constituents (S, N, and metals) removed by deasphalting Products Lower molecular weight paraffins Some methane, ethane, propane, and butane Hydrocarbon distillates (full range depending on the feedstock) Residual tar (recycle) Contaminants (asphaltic constituents) deposited on the catalyst as coke or metals Variations Fixed bed (suitable for liquid feedstocks Ebullating bed (suitable for heavy feedstocks)
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Hydrotreating Hydrotreating (Fig 310) is carried out by charging the feed to the reactor, together with hydrogen in the presence of catalysts such as tungsten-nickel sulfide, cobalt-molybdenum-alumina, nickel oxide-silica-alumina, and platinum-alumina Most processes employ cobalt-molybdenum catalysts which generally contain about 10 percent of molybdenum oxide and less than 1 percent of cobalt oxide supported on alumina The temperatures employed are in the range of 260 to 345 C (500 653 F), while the hydrogen pressures are about 500 to 1000 psi
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Reactor Hydrogen make-up Hydrogen recycle
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FIGURE 310 A distillate hydrotreater for hydrodesulfurization
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Hydrocracking Hydrocracking is similar to catalytic cracking, with hydrogenation superimposed and with the reactions taking place either simultaneously or sequentially Hydrocracking was initially used to upgrade low-value distillate feedstocks, such as cycle oils (high aromatic products from a catalytic cracker which usually are not recycled to extinction for economic reasons), thermal and coker gas oils, and heavy-cracked and straight-run naphtha These feedstocks are difficult to process by either catalytic cracking or reforming, since they are characterized usually by a high polycyclic aromatic content and/or by high concentrations of the two principal catalyst poisons sulfur and nitrogen compounds A comparison of hydrocracking with hydrotreating is useful in assessing the parts played by these two processes in refinery operations Hydrotreating of distillates may be defined simply as the removal of nitrogen sulfur and oxygen-containing compounds by selective hydrogenation The hydrotreating catalysts are usually cobalt plus molybdenum or nickel plus molybdenum (in the sulfide) form impregnated on an alumina base The hydrotreated operating conditions are such that appreciable hydrogenation of aromatics will not occur 1000 to 2000 psi hydrogen and about 370 C (698 F) The desulfurization reactions are usually accompanied by small amounts of hydrogenation and hydrocracking The commercial processes for treating, or finishing, petroleum fractions with hydrogen all operate in essentially the same manner as single-stage or two-stage processes (Fig 311) The feedstock is heated and passed with hydrogen gas through a tower or reactor filled with catalyst pellets The reactor is maintained at a temperature of 260 to 425 C (500 797 F) at
Fresh gas
Quench gas Recycle gas compressor
1st stage
2nd stage
HP separator
LP separator Recycle
FIGURE 311 A single-stage or two-stage (optional) hydrocracking unit
pressures from 100 to 1000 psi, depending on the particular process, the nature of the feedstock, and the degree of hydrogenation required After leaving the reactor, excess hydrogen is separated from the treated product and recycled through the reactor after removal of hydrogen sulfide The liquid product is passed into a stripping tower where steam removes dissolved hydrogen and hydrogen sulfide and, after cooling the product is taken to product storage or, in the case of feedstock preparation, pumped to the next processing unit
336 Reforming Processes When the demand for higher-octane gasoline developed during the early 1930s, attention was directed to ways and means of improving the octane number of fractions within the boiling range of gasoline Straight-run (distilled) gasoline frequently had very low octane numbers, and any process that would improve the octane numbers would aid in meeting the demand for higher octane number gasoline Such a process (called thermal reforming) was developed and used widely, but to a much lesser extent than thermal cracking Thermal reforming was a natural development from older thermal cracking processes; cracking converts heavier oils into gasoline whereas reforming converts (reforms) gasoline into higher octane gasoline The equipment for thermal reforming is essentially the same as for thermal cracking, but higher temperatures are used Thermal Reforming In the thermal reforming process a feedstock such as 205 C (401 F) end-point naphtha or a straight-run gasoline is heated to 510 to 595 C (950 1103 F) in a furnace, much the same as a cracking furnace, with pressures from 400 to 1000 psi (27 68 atm) As the heated naphtha leaves the furnace, it is cooled or quenched by the addition of cold naphtha The material then enters a fractional distillation tower where any heavy products are separated The remainder of the reformed material leaves the top of the tower to be separated into gases and reformate The higher octane number of the reformate is due primarily to the cracking of longer chain paraffins into higher octane olefins The products of thermal reforming are gases, gasoline, and residual oil or tar, the latter being formed in very small amounts (about 1 percent) The amount and quality of the gasoline, known as reformate, is very dependent on the temperature A general rule is: the higher the reforming temperature, the higher the octane number, but the lower the yield of reformate Thermal reforming is less effective and less economic than catalytic processes and has been largely supplanted As it used to be practiced, a single-pass operation was employed at temperatures in the range 540 to 760 C (1004 1400 F) and pressures of about 500 to 1000 psi (34 68 atm) The degree of octane number improvement depended on the extent of conversion but was not directly proportional to the extent of crack per pass However at very high conversions, the production of coke and gas became prohibitively high The gases produced were generally olefinic and the process required either a separate gas polymerization operation or one in which C3 to C4 gases were added back to the reforming system More recent modifications of the thermal reforming process due to the inclusion of hydrocarbon gases with the feedstock are known as gas reversion and polyforming Gaseous olefins gases produced by cracking and reforming can be converted into liquids boiling in the gasoline range by heating them under high pressure Since the resulting liquids (polymers) have high octane numbers, they increase the overall quantity and quality of gasoline produced in a refinery Catalytic Reforming Like thermal reforming, catalytic reforming converts low-octane gasoline into high-octane gasoline (reformate) When thermal reforming could produce reformate with research octane numbers of 65 to 80 depending on the yield, catalytic
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