US3907667A - Process for producing a lubricating oil from a residue feed - Google Patents

Process for producing a lubricating oil from a residue feed Download PDF

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US3907667A
US3907667A US390360A US39036073A US3907667A US 3907667 A US3907667 A US 3907667A US 390360 A US390360 A US 390360A US 39036073 A US39036073 A US 39036073A US 3907667 A US3907667 A US 3907667A
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Prior art keywords
catalyst
stage
feed
sulfur
hydrogen
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Jr Harry C Murphy
Robert A Plundo
Harry C Stauffer
Jr Herman Taylor
Stephen J Yanik
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Chevron USA Inc
Gulf Research and Development Co
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Gulf Research and Development Co
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Assigned to CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A CORP. OF DE. reassignment CHEVRON RESEARCH COMPANY, SAN FRANCISCO, CA. A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GULF RESEARCH AND DEVELOPMENT COMPANY, A CORP. OF DE.
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • ABSTRACT A multiple stage process is described for the catalytic hydrodesulfurization and hydrodemetallization of a residual petroleum oil boiling above the gasoline range.
  • the product of the process comprises essentially material boiling above the gasoline range and comprises little material boiling below the initial boiling point of the residual oil feed.
  • the hydrodesulfurization-demetallization process comprises an initial stage involving relatively high hydrogen pressure in the presence of a catalyst comprising a relatively low proportion of catalytically active hydrogenation metals.
  • the process employs a final stage in series having a relatively lower hydrogen pressure and a catalyst comprising a relatively higher proportion of hydrogenation metals.
  • the stream entering the final stage contains an amount up to 10, 20 or even 25 weight percent of the asphaltene content of the charge to the first stage while the effluent from the final stage is essentially free of asphaltenes.
  • the final stage effluent is therefore suitable as a residual lubricating oil feedstock without requiring a solvent deasphalting step.
  • FIGURE I EFFECT OF HYDROGEN PRESSURE ON DEMETALLIZATION WITH UNAGED CATALYST psi 800 I000 I200 I400 I600 I800 2000 2200 2300 (70Kg/ (a4Kg/ (seKg/ (
  • FIGURE 2 Sheet 2 of 9 FIGURE 2 7 2 ⁇ o H Porho
  • FIGURE 9 98 -PREACTOR EFFLUENT CYCLONE VESSEL FLUE GAS STRIPPER 94 STRIPPING STEAM REGENERATOR RISER REACTOR ZSTEAM UPPER FEED RECYCLE INJECTION COMBUSTION AIR AIR HEATER LOWER FEED INJECTION DISPERSION I LY4 STEAM 78 US Patant Sept. 23,1975
  • Sheet 7 of 9 FIGURE i0 ow etals tuly (Stag l) i h Met ls utoly (Stag Catalyst Requirements For 6 Month Cycle Life PROCESS FOR PRODUCING A LUBRICATING OIL FROM A RESIDUE FEED
  • This invention is based upon the hydrodesulfurization of asphaltene-containing residual petroleum oils having relatively high sulfur and metal contents.
  • the residual oils boil above the gasoline range and can have a boiling point of 375F.+ (191C.+), 400F.+ (204C.+), 650F.+ (343C.+) or even lO50F.+ (565C.+).
  • the present invention is based upon a multiple stage hydrodesulfurization process wherein the effluent from the final hydrodesulfurization stage is essentially free of asphaltenes as determined by pentane extraction and contains less than about 1, generally, or preferably less than about 0.6 ppm of nickel equivalent (nickel equivalent is equal to the ppm by weight of nickel plus 1/5 the ppm by weight of vanadium which is present).
  • the metals content from the effluent of the final hydrodesulfurization stage is so low that the total final stage effluent without dilution can be employed as the entire stream to a fluid catalytic cracking (FCC) process employing a zeolite catalyst in a riser wherein the catalyst and hydrocarbon flow at about the same velocity without catalyst build-up due to catalyst slippage within the riser and without an increase in catalyst to oil ratio in the riser.
  • FCC fluid catalytic cracking
  • the build-up of nickel and vanadium on the zeolite catalyst is so low when charging undiluted hydrodesulfurization effluent that the zeolite catalyst make-up rate is no more than about 0.2 pounds of zeolite catalyst per barrel of feed (571 g/m") to the FCC riser.
  • This zeolite catalyst make-up rate level is no higher than the normally required zeolite catalyst make-up rate in an FCC riser operation employing a distillate gas oil as the entire feed stream.
  • the total hydrodesulfurization effluent can be blended with other streams prior to FCC.
  • the present invention can'be employed for desulfurization of a full crude oil in the same unit or in separate units.
  • a 650F.+ (343C.+) metals containing residual oil can be hydrodesulfurized in a first unit according to the present invention while the lighter distillate or a portion thereof canbe hydrodesulfurized separately without the problems of metals contamination and high catalyst deactivation.
  • the desulfurized distillate or a portion thereof and the desulfurized residuum can be reblended to provide a total desulfurized crude for use as a fuel oil or to provide a blended residual and distillate oil low in sulfur .and boiling above the gasoline range for feeding to an
  • This is an important feature of the present process since cracking of feed oil in the hydrodesulfurization operation involves the consumption of hydrogen which is wasteful, whereas, if cracking is deferred until the stream reaches the FCC unit, gasoline is produced without consumption of hydrogen and without addition of extraneous hydrogen to the FCC unit.
  • gasoline produced in the FCC unit without added by drogen has a higher octane value than gasoline produced by cracking in the presence of added hydrogen. Therefore, the function of the hydrodesulfurization unit is confined to the removal of sulfur, metals and asphaltenes rather than the production of gasoline and the function of the FCC unit is confined predominantly to the production of gasoline and also to low-sulfur fuel oil with a greater gasoline selectivity based on feed than if a distillate gas oil feed only were charged to FCC; although the zeolite catalyst to feed ratio requirement in the FCC riser is not increased to obtain this greater gas oline selectivity in spite of the fact that the entire bottoms portion is being processed in the FCC riser.
  • the hydrodesulfurization process is essentially free of hydrocracking of feed components boiling above the gasoline range feed to material boiling within or below the gasoline range feed.
  • not more than 20 percent, generally, of feed components boiling above the gasoline range, or preferably, not more than 10 percent, and most preferably, not more than 2 to 5 percent of feed components to the hydrodesulfurization process boiling abovethe gasoline range are converted to gasoline range or lighter materials.
  • the hydrodesulfurization process is so free of hydrocracking to lighter materials that when charging atmospheric tower bottoms, i.e.
  • the hydrodesulfurization process is capable of hydrodesulfurization to produce an effluent wherein or percent by volume of the feed is recovered having a boiling point at least as high as the initial boiling point of the hydrodesulfurization feed oil.
  • the weight percentage of demetallization increases generally uniformly with increases in hydrogen partial pressure. Since most of the metal content of the residual oil is generally present in the asphaltenes present in the residual oil (the residual oil comprising relatively low boiling saturates and aromatics plus higher boiling resins and asphaltenes) this means that as the hydrogen partial pressure is increased and the asphaltene content of the hydrodesulfurization effluent decreases the metals content of the residue also decreases.
  • the present invention employs a hydrodesulfuriza tion catalyst having essentially no cracking activity.
  • the hydrodesulfurization catalyst comprises at least one Group VIII metal and at least one Group VI metal on an alumina support containing less than 1 weight percent silica.
  • the support contains less than 0.5 weight percent silica, and most preferably, the support contains as low as 0.1 weight percent silica.
  • the support can be essentially alumina. It is important that the support be sufficiently free of silica so that the catalyst is essentially devoid of ability to hydrocrack the feed below its initial boiling point.
  • the present invention is based upon the surprising discovery that in hydrodesulfurization the increase in weight percent demetallization in a residue oil feed with increases in hydrogen partial pressure is a transitory phenomenon only.
  • the unexpected discovery is disclosed that as the catalyst ages the reverse situation rapidly occurs. That is, at the higher hydrogen partial pressures, whereat at the beginning of the run the weight percentage of demetallization is the highest, catalyst aging tends to reduce this high ratio so that the longer the catalyst ages at a high hydrogen partial pressure the greater the fall off in weight ratio of demetallization to desulfurization.
  • relatively low hydrogen partial pressures which at start of run conditions produce a reduced weight percentage of demetallization, exhibit an increase in weight ratio of demetallization to desulfurization in the feed upon catalyst aging.
  • the hydrogen partial pressure should not be so low in a hydrodesulfurization stage of this invention that excessive and continual coke build-up on the catalyst is permitted to occur which would lead to an excessively short cycle life in the catalyst.
  • the hydrogen partial pressure can be sufficiently low to permit appreciable catalyst coke formation whereby when equilibrium is achieved the level of coke on the catalyst stabilizes so that catalyst coke is removed by hydrogenation and leaves the catalyst surface at about the same rate that new coke forms on the catalyst surface.
  • the present multiple stage hydrodesulfurization process requires that the initial stage have a hydrogen partial pressure which is higher than the hydrogen partial pressure of the final stage.
  • This is in direct contrast to US. Pat. No. 3,155,608 which is a prior art hydrodesul furization patent employing multiple stages, which disposes hydrogen recycle and fresh hydrogen streams to be so low that a continual build-up of coke is permitted but also that the catalyst in the final stage have a different composition to impart a higher hydrogenation activity as compared to the catalyst in the first stage.
  • the first stage catalyst Since the catalyst in the first stage is relatively protected against excessive coke formation and coke build-up with aging due to elevated hydrogen partial pressure and since its desulfurization rate is also assisted by relatively high hydrogen partial pressure, the first stage catalyst requires a lower Group VI and Group VIII metal content than the content of Group VI and Group VIII metal on the catalyst in the final stage of the hydrodcsulfurization process to balance the aging cycles between the stages and to avoid needlessly excessive active metals deposit on the first stage catalyst, which is economically wasteful.
  • the activity of the final stage catalyst must be protected in accordance with this invention against excessive aging caused by coke build-up by continuous or periodic injection of a sulfur-containing material such as hydrogen sulfide or hydrogen sulfideproducing hydrocarbon not present in the final stage feed stream to serve as a catalyst sulfiding agent in the final stage to replace loss of sulfur from the catalyst and to maintain high hydrogenation activity in the catalyst in the presence of relatively low hydrogen partial pressures.
  • a sulfur-containing material such as hydrogen sulfide or hydrogen sulfideproducing hydrocarbon not present in the final stage feed stream to serve as a catalyst sulfiding agent in the final stage to replace loss of sulfur from the catalyst and to maintain high hydrogenation activity in the catalyst in the presence of relatively low hydrogen partial pressures.
  • the maximum hydrogen partial pressure to be employed in the first catalyst stage should not exceed 2300 to 2500 psi (161.0 to 175.0 Kg/cm and preferably should not exceed 1900 to 2000 psi (133.0 to 140.0 Kg/cm If higher hydrogen partial pressures are employed in the first stage an economic waste will result because as the catalyst ages its initial advantage in demetallization activity is lost more rapidly at high hydrogen partial pressures than at lower hydrogen partial pressures so that the highest hydrogen partial pressure to be employed in the first hydrodesulfurization stage can be correlated with the length of the cycle so that maximum total metals removal can be achieved in the first stage considering the entire length of the catalyst cycle.
  • the catalyst cycle should be at least 5 and preferably at least 8 and more preferably at least 10 or 12 barrels of feed per pound of catalyst (at least 0.00175 and preferably at least 0.00280 and more preferably at least 0.00350 or 0.00420 m /g).
  • the catalyst system is balanced so that the high and low pressure hydrodesulfurization stages are capable of about the same cycle life before requiring catalyst regeneration or discard.
  • the quantity and composition of catalyst employed in each stage is established to provide as long a cycle life as possible with a minimum total quantity of catalyst per barrel of feed, considering the catalyst in each stage.
  • Each stage of the hydrodesulfurization process can provide a cycle life with the available catalyst of at least 4, 5 or 6 months or even at least 11 or 12 months.
  • the hydrogen pressure in the final stage must be balanced so that on the one hand it is low enough that with increasing catalyst age it tends to maintain or, preferably, to increase the ratio of demetallization to desulfurization which is achieved in the final stage as compared to the first stage and so that it provides an effluent which is essentially free of asphaltenes.
  • the hydrogen partial pressure in the final stage must be sufficiently high so that there is not an excessive and continual build-up of coke on the catalyst during the run.
  • the hydrogen partial pressure in the final hydrodesulfurization reactor should be high enough to at least achieve an equilibrium so that after an initial period of operation the build-up of asphaltene particles upon the catalyst surface stabilizes whereby hydrogenation accompanied by sulfur and metal removal from the asphaltene particle occurs at about the same rate as acceptance of a fresh asphaltene particle at the catalyst site.
  • an asphaltene particle might have to move from one catalyst site to another before it is able to accept hydrogen and become demetallized or desulfurized or the reaction may occur at a single site whereby the asphaltene particle becomes demetallized or desulfurized and accepts hydrogen at only one catalyst site and becomes converted to either a resin, an aromatic or a saturate and leaves the catalyst making the site on the catalyst available for a fresh asphaltene molecule.
  • an increased number of catalyst sites are required, and to provide this the weight percentage of active metals in the final stage catalyst is greater than in the initial stage catalyst.
  • the lowest pressure as well as the optimum pressure for the aforementioned functions in the final catalyst stage of this invention is at least 1300 or 1350 psi (91.0 or 94.5 Kglcm hydrogen partial pressure and preferably 1400 up to 1600 or even 1700, 1800 or 1900 psi (98.0 up to 112.0 or even 119.0, 126.0 or 133.0 Kg/cm hydrogen partial pressure.
  • psi 91.0 or 94.5 Kglcm hydrogen partial pressure and preferably 1400 up to 1600 or even 1700, 1800 or 1900 psi (98.0 up to 112.0 or even 119.0, 126.0 or 133.0 Kg/cm hydrogen partial pressure.
  • an advantageous balance is reached in ratio of weight percent demetallization to weight percent desulfurization coupled with a stabilization of asphaltene level on the catalyst surface so that the asphaltene level on the catalyst reaches a plateau at which it is removed and replaced at about the same rate.
  • the efiluent from the final stage is essentially free of asphaltenes.
  • the hydrogen pressures in the initial and final stages can be established in a number of ways. For example, by the hydrogen compressor pressure setting, the amount of diluents in the hydrogen stream and by the amount and locale of recycle hydrogen injection into the system or by the amount and location of fresh hydrogen injection into the system.
  • the hydrogen pressures are preferably balanced so that the length of the catalyst cycle before reaching catalyst deactivation in each of the stages is about the same. Catalyst deactivation occurs when the average temperature in any stage must be raised from a minimum of about 650 or 690F. (343 or 365C.) to a maximum of from about 790 or 800F. (421 or 427C.) or even 850F.
  • the temperatures are continually or intermittently raised in each reactor during a catalyst cycle to maintain the desired constant sulfur level in the effluent. For example, the temperatures will be adjusted upwardly continually in the reactors so that if a residual feed containing about 4 weight percent sulfur is charged to a three reactor system of this invention, with the reactors in series, the effluent from the first reactor will contain about 1 weight percent sulfur, the effluent from the second reactor will contain about 0.2 to about 0.5 weight percent sulfur and the effluent from the third reactor will contain about 0.05 to 0.1 weight percent sulfur.
  • the effluent from the third reactor will contain less than 1 and preferably less than 0.6 weight percent nickel equivalent (which is the ppm of nickel plus 1/5 of the ppm of vanadium) when the feed to the first reactor contains ppm of nickel plus vanadium, or more.
  • the effluent from the third reactor will be essentially free of asphaltenes, as measured by conventional means, i.e. no normal pentane insolubles will be detected in a normal pentane extraction of the effluent.
  • the total catalyst quantity required to achieve the hydrodesulfurization results of this invention will be sharply minimized by employing a higher Group V1 and Group Vlll metals weight level catalyst in the final stage than is employed in the catalyst in the first stage.
  • the sulfur addition to the final stage can be received directly by hydrogen sulfide injection, by injection of a hydrogen sulfide producing organic material not present in the feed oil or can be produced from the feed stream in an earlier and higher pressure hydrodesulfurization stage and transmitted to the final low pressure stage by passing the effluent from an earlier higher hydrogen pressure hydrodesulfurization stage containing hydrogen sulfide undiluted by fresh or make-up hydrogen to the final hy drodesulfurization stage without any flashing or hydrogen sulfide absorption step prior to the final hydrodesulfurization stage.
  • the catalyst in all phases comprises at least one Group V1 and at least one Group Vlll metal in sulfided condition, such as nickel-cobalt-molybdenum on alumina.
  • Group Vlll metal in sulfided condition
  • nickel-cobalt-molybdenum on alumina many metals combinations can be employed, such as a cobaltmolybdenum, nickel-tungsten and nickel-molybdenum.
  • a noncracking alumina support must be employed, such as an alumina containing less than 1 weight percent silica, preferably less than 0.5 weight percent silica and most preferably no more than 0.1 percent silica.
  • the metals content on the catalyst is higher in the final stage than in the initial stage. Whatever, metals content is employed, the weight percent of active Group Vl-Group Vlll hydrogenation metals in the final stage is higher than in the initial stage.
  • the present invention is directed towards the hydrodesulfurization of a residual oil containing substantially the entire asphaltene fraction of the crude from which it is derived and which therefore contains 95 to 99 weight percent or more of the nickel and vanadium content of the full crude.
  • the nickel, vanadium and sulfur content of the liquid charge can vary over a wide range.
  • nickel and vanadium can comprise 0.0005 to 0.05 weight percent (5 to 500 parts per million) or more of the feed oil while sulfur can comprise about 2 to 6 weight percent or more of the charge oil.
  • the hydrodesulfurization process of this invention it is the partial pressure of hydrogen rather than total reactor pressure which determines hydrodesulfurization and demetallization activity. Therefore, the hydrogen stream should be as free of other gases as possible.
  • the gas circulation rate can be between about 2000 and 20,000 standard cubic feet per barrel (between about 36.0 and 360.0 SCM/100L), generally, or preferably about 3000 to 10,000 standard cubic feet per bar rel of gas (54.0 to 180.0 SCM/lOOL), and preferably contains 80 percent or more of hydrogen.
  • the mol ratio of hydrogen to oil can be between 8:1 and 80:1.
  • Reactor temperatures can range between about 650 and 900F. (343 and 482C), generally, and between about 680 and 800F. (360 and 427C.), preferably. The temperature should be low enough so that not more than about 10, 15 or 20 percent of a 650F. (343C.+) residual oil charge will be cracked to furnace oil or lighter. At reactor outlet temperatures of 800 to 850F.
  • the liquid hourly space velocity in 0 each reactor of this invention based on hydrocarbon oil feed to the first stage can be between about 0.2 and 10, generally, between about 0.3 and 3, preferably, or between about 0.5 and 1.5, most preferably.
  • the catalyst employed in the process comprises sulfided Group VI and Group Vlll metals on a support, such as sulfided nickel-cobaltmolybdenum or cobalt-molybdenum on alumina.
  • sulfided Group VI and Group Vlll metals on a support such as sulfided nickel-cobaltmolybdenum or cobalt-molybdenum on alumina.
  • Hy-' drodesulfurization catalyst compositions suitable for use in the present invention are described in U.S. Pat.
  • an advantageous feature of the catalyst particles of the present invention is that the smallest diameter of these particles is broadly between about 1/20 and H40 or 1/50 inch (0.127 and 0.0635 or 0.051 cm), preferentially between 1/25 and H36 inch (0.102 and 0.071 cm), and most preferably between about l/29 and l/34 inch (0.081 and 0.075 cm). Particle sizes below the range of this invention would induce a pressure drop which is too great to make them practical.
  • the catalyst can be prepared so that nearly all or at least about 92 or 96 percent of the particles are within this size range.
  • the catalyst can be in any suitable configuration in which the smallest particle diameter is within this size range, such as roughlycubical, needleshaped or round granules, spheres, cylindrically-shaped extrudates, etc.
  • smallest particle diameter is meant the smallest surface to surface dimension through the center or axis of the catalyst particle, regardless of the shape of the particle.
  • the cylindrical extrudate form having a length between about 1/10 and 1/4 inch (0.254 and 0.635 cm) is highly suitable.
  • the catalyst is essentially free of dehydrogenation activity to prevent formation of severely hydrogen deficient coke on the catalyst. It is to be emphasized that the hydrocarbon build-up in the final stage catalyst is not a severely hydrogendeprived material initially but is essentially an asphaltene or coke precursor material as received in the feed stream containing somewhat higher than the feed hydrogen to carbon ratio.
  • the asphaltene is capable of undergoing desulfurization and demetallization accompanied by a reception of hydrogen to convert the feed asphaltene to a more hydrogen-rich molecule such as a resin, an aromatic, or a saturate, which can then leave the catalyst site by dissolving into the main flow stream in the final reactor, thereby stabilizing the asphaltene content on the catalyst.
  • a hydrocracking or coke forming (i.e. a hydrogen depriving) catalyst is illustrated by the fact that increasing hydrogen pressures with the catalyst does not result in any detectable or significant increased hydrogen consumption.
  • the amount of hydrocracking experienced with the catalyst of the present invention is about the same as that experienced with inert solid particles.
  • the various stages in series of the hydrodesulfurization process of the present invention are balanced with respect to hydrogen partial pressure, relative catalyst volume and catalyst activity in order to encourage balancing of relative metals removal in each of the stages.
  • the quantity of asphaltenes and metals will be greatest in the first stage, intermediate in the second and smallest in the third stage.
  • the percent reduction of asphaltenes and metals in the first stage will be the lowest, will be intermediate in the second stage and will be the highest in the third stage.
  • the sulfur concentration is highest in the higher boiling product fractions of the FCC prod net. It is an important advantage of this invention that the sulfur content of the hydrodesulfurization effluent is so low that even the fuel oil range (400 to 650F. [204 to 34 C]) product of FCC has a sulfur content below 0.25 weight percent, preferably below 0.20 weight percent, which meets commercial specifications for home heating oil in the U.S., so that further desulfurization of the fuel oil is not required. This is unusual since usually furnace oil range product from FCC operations must be desulfurized to meet home heating oil sulfur commercial specification.
  • the hydrodesulfurization-F CC combination process of this invention accomplishes all required desulfurization requirements in advance of the FCC step with no desulfurization operation required after the FCC operation.
  • a further and important advantage of this fact is that, because the sulfur is removed from the feed in advance of FCC, rather than following FCC, the sulfur dioxide in the FCC regenerator off-gas which comes from sulfur-containing coke on the zeolite catalyst, is minimized to a level meeting commercial requirements without scrubbing of sulfur dioxide from the regenerator flue gas. It is extremely difficult to scrub sulfur dioxide in a flue gas stream and high sulfur dioxide levels in FCC regenerators are rapidly becoming an unacceptable source of air pollution. in accordance with this invention this difficulty is obviated.
  • FIG. 1 shows the effect of hydrogen partial pressure upon the ratio of weight percent demetallization, using demetallization at 1,400 psi (98.0 Kg/crn hydrogen partial pressure as a base, of a residual oil employing a fresh (unaged) relatively low active metals level hydrogenation catalyst of the first hydrodesulfurization reaction stage of this invention.
  • FIG. 1 data taken with an unaged low metals catalyst show that an increase of hydrogen partial pressure results in an increase in demetallization. Since most of the metals present in the feed are present in the asphaltene fraction of the feed, an increase in demetallization represents a decrease in asphaltene content of the stream passing through the reactor.
  • F165. 2 and 3 illustrate the discovery of the present invention indicating that the data of FIG.
  • FIGS. 2 and 3 illustrate residual oil hydrodesulfurization data with a relatively low hydrogenation metals catalyst of the first hydrodesulfurization stage of this invention under high pressure conditions including a run at 2,300 psi 161.0 Kg/cm hydrogen partial pressure and a lower pressure run at 1950 psi (136.5 Kg/cm hydrogen partial pressure.
  • FIG. 2 shows that at the higher hydrogen partial pressure of 2,300 psi (161.0 Kg/em asphaltene content diminishes at a relatively rapid rate whereas at 1950 psi (136.5 Kg/cm hydrogen partial pressure there is substantially no change in asphaltene content.
  • the runs of FIGS. 2 and 3 were made with a catalyst that had been aged and not with the fresh catalyst.
  • FIG. 3 represents the same tests as shown in FIG.
  • the dashed line in FIG. 2 indicates that at a much higher hydrogen partial pressure of 3,000 psi (210.0 Kg/cm asphaltenes could be completely removed in a single reactor at a space time of about 1, completely removing the problem of asphaltene sulfur content in the oil in one stage.
  • FIGS. 2 and 3 Although the solid line data of FIGS. 2 and 3 appear to be contradictory, they illustrate the underlying discovery of the present invention and show the unexpected nature of this discovery. Referring to FIG. 2, at
  • FIG. 3 shows that at the 1950 psi (136.5 Kg/cm hydrogen partial pressure test condition the lack of extensive hydrocracking permitted the asphaltene molecule to remain at the catalyst site sufficiently long to become more extensively desulfurized, specifically because it was not first hydrogenated or hydrocracked and thereby enabled to readily leave the catalyst site. Therefore, at the lower pressure the catalytic effect tends to become controlling in preference to the asphaltene adsorption effect caused by the change in pressure.
  • the longer residence time at the 1950 psi does not diminish the asphaltene content in the stream but it does substantially reduce the sulfur level in the feed asphaltenes, which feed asphaltenes tend to remain as asphaltenes.
  • the hydrogen pressure effect tends to become controlling over the catalytic effect, causing the residence time at the catalyst site to be so brief the sulfur content of the asphaltenes that remained in the stream was diminished very little.
  • FIGS. 2 and 3 An important feature of the showing of FIGS. 2 and 3 is that the hydrocracking and/or hydrogenation (i.'e. hydrogenolysis) that occurred at the 2300 psi (161.0 Kglcm hydrogen partial pressure, while it diminished asphaltene content in the flowing stream, merely produced products containing only a slightly reduced quantity of sulfur and metals in the asphaltenes.
  • the hydrogen partial pressure in the first stage of the hydrodesulfurization process of the present invention need not be too high, resulting in lower costs for equipment.
  • the data indicate that much greater sulfur removal from the asphaltenes is accomplished at 1950 psi (136.5 Kg/cm than is accomplished at 2300 psi 161.0 Kg/cm Therefore, the hydrogen partial pressure in the first stage of the present invention with the relatively low Group VI-Group VIII metal content catalyst of this invention should be less than 2300 psi (161.0 Kg/cm and preferably less than 2100 or 1900 psi (147.0 or 133.0 kg/cm hydrogen partial pressure.
  • the hydrogen partial pressure to be employed will generally be dependent upon feed properties.
  • FIG. 4 illustrates another unexpected discovery related to the effect of hydrogen partial pressure upon 13 catalyst aging.
  • the data shown in FIG. 4 also illustrate a catalyst aging effect opposite to the effect shown in the data of FIG. 1.
  • FIG. 4 shows the results of pilot plant agingtests conducted in the initial reactor of applicants hydrodesulfurization process with a 50 percent reduced Kuwait crude residual feed employing an alumina-supported hydrodesulfurization catalyst hav ing the relatively low Group VI-Group Vlll metals content of this invention.
  • the data of FIG. 4 show the effect of aging on the ratio of percent demetallization to percent desulfurization at various hydrogen partial pressures.
  • FIG. 4 shows that a zero catalyst age the higher the hydrogen partial pressure the higher is the ratio of percent demetallization to percent desulfurization.
  • FIG. 4 shows that although the data curve for a 2300 psi (161.0 Kg/cm hydrogen partial pressure test initially exhibits the highest ratio of all the tests, the decline in selectivity for metals over sulfur removal with increasing age is the steepest at this high pressure.
  • FIG. 4 shows that although the data for the 1830 psi 128.
  • the test at 1400 psi (98.0 Kg/cm shows the highest ratio of percent demetallization to percent desulfurization of all the tests made.
  • the test made at 1400 psi (98.0 Kglcm achieves this high ratio because of two factors. First, its initial activity at this pressure is not so exceedingly low that it cannot be overcome by a positive aging slope. Secondly, the aging slope is sufficiently steep so that, combined with the relatively high initial catalyst activity, the 1400 psi (98.0 Kglcm pressure achieves high demetallization rates very early in the run.
  • the demetallization ratio in the 1400 psi (98.0 Kg/cm run exceeds the demetallization ratio for the 1830 psi 128.1 Kglcm run at a catalyst age of only 1 barrel per pound (0.00035 m lg). After this catalyst age, the 1400 psi (98.0 Kg/cm run far exceeds the 1830 psi (128.1 Kg/cm run in demetallization activity.
  • the final phase reactor is best operated at a pressure of about 1400 psi (98.0 Kg/crn of hydrogen and generally between 1300 psi (91.0 Kg/cm and 1600 psi (112.0 Kg/cm or 1700 psi( 1 19.0 Kg/cm of hydrogen.
  • An optimum pressure range would be about between 1300 psi (91.0 Kg/cm or 1350 psi (94.5 Kg/cm and 1500 psi (105.0 Kg/cm hydrogen pressure. Best results are obtained when the first and final stage hydrogen pressures pass the threshold values wherein the percent demetallization/percent desulfurization v. catalyst age is slightly negative in the first stage whereas this same slope is positive in the final stage.
  • FIG. 4 shows runs conducted at a sufficiently low pressure that the controlling feature in the reactor is the absorption and residence time of asphaltene at a catalyst site or sites.
  • the controlling feature in the reactor is the absorption and residence time of asphaltene at a catalyst site or sites.
  • significant hydrocracking or hydrogenation activity does not occur and therefore an asphaltene molecule contacting a catalyst site tends to reside at the site or to move to another catalyst site for a significant total catalyst residence time before reaction can occur.
  • Due to the lengthened on-catalyst residence time at low hydrogen partial pressures, the reaction that occurs is not apt to by hydrocracking or simple hydrogenation but is more apt to be removal of metals and sulfur accompa nied by an acceptance of hydrogen to provide a loss of metal and sulfur from the asphaltene molecule.
  • the residence time required is sufficiently great that a significant build-up of asphaltene molecule occurs upon the surface of the catalyst.
  • the asphaltene content on the catalyst may reach about 20 to 40 percent by weight of catalyst, as compared with a coke level on the catalyst in the first or high pressure hydrodesulfurization stage of only about 5-15 weight percent.
  • the asphaltenes do not tend to dehydrogenate and form what is known as carbon or coke of very low hydrogen content. Instead, they tend to remain as asphaltenes and to reside at the catalyst site while they slowly desulfurizc and dcmetallize.
  • the very high percentage metals removal level is only useful in the final reactor where the total asphaltene and metals concentration in the stream is already low and not in the initial reactor where the total asphaltene and metals level is high where high percentage removal of metals would result in excessively rapid catalyst aging. Therefore, in the balanced hydrodesulfurization system of this invention, the life of the catalyst in the initial stage is metals-limited while the life of the catalyst in the final stage is coke-limited, with the life cycles being essentially balanced.
  • FIG. 4 shows that in a lengthy commercial operation of at least 10 or 12 barrels of feed oil per pound of catalyst (0.00350 or 0.00420 m /g), the only runs that achieved a weight ratio of demetallization to desulfurization of greater than 1 at both start-of-run and end of-run were the 1400, 1660 and 1830 psi (98.0, 116.2 and 128.1 Kg/cm runs.
  • a ratio greater than 1 indicates the reactor is primarily an asphaltene removal re actor since most metals are concentrated in the asphaltenes.
  • FIG. 4 shows catalyst life cycles of 4, 5, 6 or even 11 or 12, or more, months is possible before regeneration or discarding of the catalyst.
  • FIG. 5 shows a typical aging run in a first stage reactor of this invention in terms of catalyst age versus increases in reaction temperature to reduce a 650F.+ (343+C.+) residue from about 4 weight percent sulfur to about 1 weight percent sulfur at about 1830 psi 128.1 Kg/cm partial pressure of hydrogen with a relatively low hydrogenation metals content catalyst of the present invention.
  • FIG. 6 shows similar aging runs at various space velocities (as reflected by cycle lengths) wherein the effluent from the test of FIG. 5, after being flashed to remove hydrogen sulfide and light hydrocarbons, and after receiving fresh hydrogen to be repressurized to about nearly the same hydrogen pressure as the hydrogen pressure in the first reactor, and employing a similar low hydrogenation metals catalyst as employed in the first reactor, is further treated in a second reactor to reduce the sulfur content from about 1 weight per cent down to either 0.3 or 0.5 weight percent sulfur.
  • FIG. 7 shows the results of aging runs made in the third and final hydrodesulfurization reactor of this invention.
  • a comparison of FIG. 7 with FIGS. 5 and 6 shows that the aging rate of the third reactor (FIG. 7) is much more rapid than the aging rate in the earlier reactors and the catalyst in the third reactor cannot last the ffill cycle reached in the earlier reactors unless special steps are taken in the third reactor, as described, which are not required in the first two reactors.
  • the third reactor was operated at 1700 psi I 19.0 Kg/cm hydrogen partial pressure and contained a catalyst having a higher Group VI-Group VIII metals content than the catalyst of the first two reactors.
  • the feed to the final reactor after having its sulfur content reduced to 0.3 0.5 weight percent, has remaining in it the most refractory sulfur and also the most refractory metals present in the feed oil.
  • This remaining sulfur and metals content is probably most refractory because, for example, it is the feed sulfur and metals content which is the most deeply embedded within the interior of the feed asphaltene or resin molecules.
  • the stream reaches the final stage most of the sulfur and metals content of the total stream is present in the remaining asphaltenes. Most of the less refractory sulfur and metals, i.e. the metals closest to the fringe of the asphaltene molecule, are more readily removed and are extracted in the first two stages.
  • the asphaltenes in the stream require the longest residence time at a catalyst site. They also require a catalyst which is enhanced in hydrogenation activity as compared to the catalyst used to remove less refractory sulfur and metals. While the reaction in the initial stage tends to by hydrogen pressure limited, the reaction in the final stage tends to be catalyst contact-time limited and low hydrogen pressure in the final stage tends to encourage lengthy contact time of the most refractory species, such as asphaltenes, at acatalyst site, just as high hydrogen pressure in an initial stage tends to inhibit asphaltene residence time at a catalyst site.
  • the sulfur level in the feed in the final stage is so low, even the removal of said sulfur as hydrogen sulfide is insufficient to maintain sufficient sulfur in the atmosphere to permit the catalyst in the final stage to be maintained in a fully or start-of-run sulfided condition, as required to prevent its rapid deactivation. Therefore, there is no flashing step between the second and third stages of the present invention and the hydrogen sulfide produced in the sec- 0nd stage is passed to the third stage and is used as a source of sulfur for maintaining the third stage catalyst in a highly sulfided condition, as is required for maintaming its activity.
  • the lack of hydrogen sulfide in the third reactor causes the catalyst to lose sulfur so as to maintain an equilibrium, with respect to hydrogen sulfide, between the catalyst, the liquid and the gas phases. If the cata lyst is to be maintained in an adequately sulfided state, it is necessary for the reactionstream to contain a sufficient quantity with hydrogen sulfide by maintaining a hydrogen sulfide atmosphere in the gases in contact with reaction stream. If there is insufficient hydrogen sulfide gas in contact with the stream to the reactant liquid saturated with hydrogen sulfide, the feed liquid will drain sulfur from the catalyst. But is there is sufficient gaseous hydrogen sulfide to saturate the feed liquid, the liquid will not tend to reduce the sulfur level of the catalyst.
  • the test made in FIG. 7 illustrates the importance of external addition of sulfur to the final stage catalyst, whether this sulfur comes from the previous stage, is injected as hydrogen sulfide or is injected as an extraneous organic sulfur-containing compound which is easily convertible to hydrogen sulfide.
  • the data illustrated by the triangle data points in FIG. 7 were taken to simulate the final stage of the hydrodesulfurization process of the invention except that no hydrogen sulfide from any source was added with the feed. As shown, the aging slope was steep throughout the run. However, the data in FIG. 7 illustrated by the square shaped points show a feed also devoid of hydrogen sulfide from any source until the region A denoted by hexanethiol addition was reached.
  • the aging curve was just as steep until reaching region A.
  • region A the sulfur containing compound hexanethiol was added with the feed in order to contribute sulfur for sulfiding of the catalyst.
  • the aging rate became stabilized and the curve became relatively flat, indicating essentially no further catalyst aging during the sulfiding of the catalyst.
  • the aging rate again increased, indicated by the region of the curve B, illustrating the criticality in the final stage of the present invention of maintaining the high Group VI-Group VIII metals-content catalyst in a sulfided condition.
  • the dearth of hydrogen sulfide is not noticed early in a test but depends upon the length of the test and the amount of catalyst present.
  • a lack of hydrogen sulfide in the third reactor atmosphere results in initial desulfurization of the top of the third stage catalyst bed coupled with a covering of catalyst sites with hydrogendeficient hydrocarbons, shifting the reaction burden to progressively deeper regions of the bed which are not yet desulfided. It is only when the desulfurization of the catalyst and covering of the catalyst sites with hydrogen deficient hydrocarbons reaches sufficiently deeply into the catalyst bed leaving insufficient fully sulfidcd and non-coated catalyst remaining, that the lack of hydrogen sulfide becomes apparent.
  • FIG. 8 schematically illustrates a preferred three stage hydrodesulfurization process of this invention.
  • a reduced crude such as a 650F.+ (343C.+) Kuwait reduced crude from an atmospheric tower bottoms is charged through line it through a filter 12 wherein salts and solids are removed.
  • the feed then passes into line l4 and is heated in furnace 16 from which it passes to the first high pressure reactor 18 through line 20.
  • the catalyst in the first stage stabilizes at a coke level of about 14 weight percent throughout substantially an entire six month test.
  • the effluent from reactor 18 is flashed to remove hydrogen sulfide and light hydrocarbons in flash chamber 20. These light materials pass through line 22 to line 24 and into a recycle gas treatment apparatus 26 from which hydrogen sulfide is recovered through line 28 and light hydrocarbons are recovered through line 30. Purified hydrogen is then available for recycle through line 52.
  • the flashed liquid from reactor 18 containing about 1 percent sulfur is passed through line 32 and admixed with purified hydrogen entering through line 34.
  • the repressurized stream in line 36 enters the second reactor 38.
  • Reactors l8 and 38 have the same type of low Group Vl-Group VIII metals catalyst.
  • the effluent from the second reactor 3% in line 20 contains about 0.5 0.3 weight percent sulfur and contains all the hydrogen sulfide produced in reactor 38. It enters the third reactor 42 through line 40 without being flashed for removal of hydrogen sulfide, whereby the hydrogen partial pressure in reactor 42 is lower than the hydrogen partial pressure in reactors 18 and 33.
  • line 40 introduces a pressure drop between reactors 38 and 42 to further lower the hydrogen pressure in reactor 42 and so that, in terms of pressure drop, re actor 42 is not equivalent to merely an elongated combination reactor 38-42.
  • Fresh hydrogen is not added to the charge to reactor 42 in order to maintain a low hydrogen partial pressure in reactor 42.
  • Reactor 42 contains a catalyst comprising a higher proportion of Group VI and Group VIII metals than the catalyst of the first two reactors and operates at a lower pressure than does the first two reactors.
  • additional hydrogen sulfide is required to maintain catalyst activity in reactor 42, it can be supplied from an extraneous source, not shown, or can be a slip-stream of hydrogen sulfidecontaining low hydrogen partial pressure gases from the first reactor which is charged to third reactor feed line 40 through line 23.
  • the coke level on the third stage catalyst stabilizes at about 20-40 weight percent based on original catalyst throughout substantially an entire six month test but contains only about 0.5 weight percent of metals from the feed at the end of a 6 month test. Unless extraneous sulfur is added, the NiS catalyst can be reduced to was while the M05 can be reduced to M0 8
  • the feed to the third reactor may contain a finite amount from less than about 1 to as high as 3 weight percent asphaltenes, which is reduced to about zero percent, and clearly below 0.1 weight percent asphaltenes in the third reactor depending upon the feed to the process.
  • the product being asphalt-free constitutes a lubricating oil feedstock in a suitable boiling range without a solvent deasphalting step required.
  • the asphaltenes have an affinity for the catalyst sites and therefore move through the third stage at a lower space velocity than the lighter saturates and aromatics, which do not require as much desulfurization or demetallization, which lighter materials tend to be less attracted to the catalyst sites, moving through the third stage at a much higher space velocity than the asphaltenes.
  • the effluent from reactor 42 passes through line 44 into flash chamber 46 from which light gases are re moved through line 48 and from which liquid is removed through line 50.
  • the light gases in line 48 are admixed with the light gases in line 22 and pass to the recycle gas treatment chamber 26.
  • Recycle hydrogen is recovered from chamber 26 through line 52 and is repressurized in compressor 54 for recycle to the feed stream through line 56 for feeding to the first reactor 18 or through line 58 for charging to the second reactor through heater 60.
  • Make-up hydrogen is added through line 62.
  • Product liquid from flash chamber 46 is passed through line 50 to a fractionator 64 from which low sulfur, low metals, fuel oil suitable for feeding to an FCC cracking unit is removed as bottoms through line 66.
  • a separate gas oil fuel can be removed through line 68.
  • a small amount of naphtha, if produced, is removed through line 70 and off-gas is removed through line 72.
  • the process converts less than 20 percent, preferably less than l percent and most preferably less than 5 or even less than 2 percent of the feed in line to material boiling in the naphtha range or below.
  • the middle stage 38 of the three hydrodesulfuriza- .tion stages of the present invention is pivotal to improved operation in the first stage 18 and to improved operation in the third stage 42. Since the middle stage 38 is a relatively high pressure stage and employs the same catalyst as the first stage 18, it provides a combination relatively high pressure process with the first stage 18, wherein less catalyst is required for a given amount of sulfur removal in high pressure stages 18 and 42, than if the same amount of sulfur were removed in a single stage without intermediate flashing. This advantageous effect is the subject of Ser. No. 206,083,
  • the middle or second stage 38 also cooperates with the final and relatively low pressure stage 42 utilizing the more highly active hydrogenation catalyst by providing hydrogen sulfide required in the low pressure stage by virtue of the facts that there is no flashing step between the second and third stages, there is no high pressure purified hydrogen injection between the second and third stages and the line 40 between the second and third stages introduces a pressure drop between the stages.
  • the second stage provides hydrogen sulfide to the third stage and thereby helps to keep the third stage catalyst in an active, sulfided state, and also helps to reduce the hydrogen partial pressure in the gases entering the third stage in order to advantageously lower the hydrogen pressure in the third stage.
  • the third stage catalyst is more preferential to metal removal than sulfur removal as compared to the first stage catalyst.
  • the first stage catalyst removes weight percent of both feed sulfur and feed metals while the third stage catalyst removes 73 weight percent of its feed sulfur but 89 weight percent of its feed metals.
  • the low sulfur material in line 66 of FIG. 8 is charged -to the FCC system shown in FIG. 9 through line 74 and possibly also line 76 of FIG. 9.
  • the total feed to the riser is preferably the hydrodesulfurized residual oil but distillate can also be added to the riser, if desired.
  • Dispersion steam is added to the FCC riser through lines 78 and 80.
  • Hot regenerated zeolite catalyst is added through line 82 while recycle oil is added through line 84. All catalyst fed to the riser is fed to the riser inlet to provide as high a flash equilibrium vaporization temperature as possible at the reactor inlet to vaporize the maximum possible quantity of residue to prevent coke formation due to nonvaporization of high boiling feed oil.
  • Deactivated catalyst passes through line 100 to regenerator 102 wherein it is regenerated by burning with combustion gas such as air which enters through line 104 and heater 106. Flue gas from the regenerator is discharged through line 107.
  • FIG. 10 illustrates the savings in hydrodesulfurization catalyst (especially in active metals content on the catalyst) made possible by employing higher and lower ac-

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US4657663A (en) * 1985-04-24 1987-04-14 Phillips Petroleum Company Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage
US5122257A (en) * 1986-12-10 1992-06-16 Shell Internationale Research Maatschappij B.V. Process for the manufacture of kerosene and/or gas oils
US20090129998A1 (en) * 2007-11-19 2009-05-21 Robert S Haizmann Apparatus for Integrated Heavy Oil Upgrading
US8894838B2 (en) 2011-04-29 2014-11-25 E I Du Pont De Nemours And Company Hydroprocessing process using uneven catalyst volume distribution among catalyst beds in liquid-full reactors
US9126174B2 (en) 2010-03-31 2015-09-08 Uop Llc Hydroprocessing method, or an apparatus relating thereto

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US4657663A (en) * 1985-04-24 1987-04-14 Phillips Petroleum Company Hydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage
US5122257A (en) * 1986-12-10 1992-06-16 Shell Internationale Research Maatschappij B.V. Process for the manufacture of kerosene and/or gas oils
US20090129998A1 (en) * 2007-11-19 2009-05-21 Robert S Haizmann Apparatus for Integrated Heavy Oil Upgrading
US9126174B2 (en) 2010-03-31 2015-09-08 Uop Llc Hydroprocessing method, or an apparatus relating thereto
US8894838B2 (en) 2011-04-29 2014-11-25 E I Du Pont De Nemours And Company Hydroprocessing process using uneven catalyst volume distribution among catalyst beds in liquid-full reactors

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