EP0323724A2 - Verfahren zur Stabilisierung von Hydroisomeraten - Google Patents

Verfahren zur Stabilisierung von Hydroisomeraten Download PDF

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Publication number
EP0323724A2
EP0323724A2 EP88311988A EP88311988A EP0323724A2 EP 0323724 A2 EP0323724 A2 EP 0323724A2 EP 88311988 A EP88311988 A EP 88311988A EP 88311988 A EP88311988 A EP 88311988A EP 0323724 A2 EP0323724 A2 EP 0323724A2
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Prior art keywords
catalyst
oil
wax
mild
alumina
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EP88311988A
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English (en)
French (fr)
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EP0323724B1 (de
EP0323724A3 (en
Inventor
Ian Alfred Cody
Donald T. Eadie
Glen Porter Hamner
John Mackillop Macdonald
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton

Definitions

  • the Group VIII metal component is preferably platinum.
  • the catalysts of choice are selected from Group VIII on halogenated alumina or material containing alumina support, preferably alumina or material consisting predominantly (i.e.
  • alumina catalyst preferively Group VIII on fluorided or chlorinated support, more preferably platinum on fluorided alumina support, most preferably platinum on fluorided ⁇ alumina catalyst.
  • platinum on fluorided alumina support most preferably platinum on fluorided ⁇ alumina catalyst.
  • These preferred catalysts are preferred hydro­somerization catalyst in which service they are employed under moderate to severe operating conditions.
  • Slack wax containing from 0% to 25% oil coming from the dewaxing of conventional petroleum crude oils is subjected to hydrotreating over conven­tional hydrotreating catalyst so as to reduce the sul­fur and nitrogen content levels of the wax.
  • This hydrotreating is necessary so as to avoid deactivation of the typical Group VIII on halogenated refractory metal oxide isomerization catalyst.
  • other, less sensitive isomerization catalyst, such as combination Group VI-Group VIII metal on refractory metal oxide catalysts are used, since such catalyst are usually sulfided prior to use, the need for prehydrotreating is lessened, if not eliminated.
  • the total liquid product of isomerized slack wax from the isomerization unit is then contacted with the Group VIII metal on refractory metal oxide catalyst or Group VIII on halogenated refractory metal oxide catalyst under mild hydrorefining conditions, which step is followed by a subsequent fractionation into various cuts boiling in the different lube basestock boiling ranges, dewaxing and final fractionation. While these steps can be practiced in different sequences it is preferred that the total liquid product from the isomerization unit be subjected to the herein described mild hydrorefining. It was unexpected that the mild hydrorefining can effectively treat this total liquid product since in the past it had been throught necessary to conduct such hydrofinishing procedures on fractions of oils and not on broad cuts of oils.
  • fractionated isomerized wax products can be hydrofined it has also been unexpectedly discovered that unfractionated isomerized wax product, the total liquid product from the isomerization unit can be hydrofined under mild conditions to produce a material of improved daylight stability.
  • lube oil base stocks or blending stock oils made by the isomerization of slack waxes can have their daylight stability markedly improved by a process comprising contacting the total liquid product from the isomerization unit with a Group VIII metal on refrac­tory metal oxide support catalyst or Group VIB-Group VIII metal on halogenated refractory metal oxide hydro­isomerization catalyst under mild conditions.
  • This mild condition hydrofinishing is performed at a temper­ature of about 170°C to 270°C, preferably about 180 to 220°C, a flow velocity of 0.25 to 10 V/V/hr, preferably 1 to 4 V/V/hr, a pressure of from 300 to 1500 psi H2, preferably 500 to 1000 psi H2 and a hydrogen gas rate of 500 to 10,000 SCF/bbl, preferably 1000 to 5000 SCF/bbl.
  • Temperatures at the high end of the range should be employed only when similarly employing pres­sures at the high end of their recited range. Tempera­tures in excess of those recited may be employed if pressures in excess of 1500 psi are used, but such pressures may not be practical or economic.
  • any necessary hydrotreating of the slack wax feed is performed employing commercial catalyst, such as Co/Mo-Ni/Mo on alumina, under standard commercially accepted conditions, e.g., temperature of 320°C to 400°C, space velocity of 0.1 to 2.0 v/v/hr, pressure of from 500 to 3000 psig H2, and gas rates of from 500 to 5000 SCF/B.
  • commercial catalyst such as Co/Mo-Ni/Mo on alumina
  • Isomerization is conducted over a catalyst containing a hydrogenating metal component typically one from Group VI or Group VIII or mixture thereof, preferably Group VIII, more preferably noble Group VIII most preferably platinum on a halogenated refractory metal oxide support.
  • the catalyst typically contains from 0.1-5.0 wt.% metal, preferably 0.1 to 1.0 wt.% metal, most preferably 0.2-0.6 wt.% metal.
  • the refrac­tory metal oxide support is typically a transition e.g. gamma or eta alumina and the halogen is most usually fluorine. Isomerization is accomplished under moderate to high temperature conditions of 270°C to 400°C, pre­ferably 300°C to 360°C.
  • Space velocity ranges from 0.10 to 10 v/v/hr, preferably 1.0 to 2.0 v/v/hr. Pres­sure ranges from 500 to 3000 psi H2, preferably 1000 to 1500 psi H2. Hydrogen gas rate ranges from 1000 to 10,000 SCF/B. Moderate levels of conversion of wax to isomerate are preferred. Conversions to a level such that about 40% or less unconverted wax remains in the 370°C+ fraction sent to the dewaxer, preferably 15-35% unconverted wax remains in the 370°C+ fraction sent to the dewaxer are preferred.
  • the prehydrotreating step can be dispensed with, but the isomerized wax product would still have to be freed of H2S and NH3 prior to being contacted with the second stage catalyst. This could be done by flashing or stripping of the product to remove H2S and NH3.
  • a preferred catalyst for use in the present process contains a hydrogenation metal component which is a Group VIII noble metal or mixture thereof, preferably noble Group VIII metal, most preferably platinum on a fluorided alumina or material containing alumina, preferably alumina or material consisting predominantly (i.e.
  • XRD X-ray diffraction
  • the fluoride content of the catalyst can be determined in a number of ways.
  • Fluoride concentration of the sample is determined by ion chromatography analysis of the combustion product solution. Calibration curves are prepared by combusting several concentrations of ethanolic KF standards (in the same manner as the sample) to obtain a 0-10 ppm calibration range. Fluoride concentration of the catalyst is calculated on an ignition-loss-free-basis by comparison of the sample solution response to that of the calibration curve. Ignition loss is determined on a separate sample heated to 800 degrees F for at least 2 hours. Ion chromatographic analysis uses standard anion conditions.
  • Fluo­ride distillation with a titrimetric finish. Fluo­rides are converted into fluorosilicic acid (H2SiF6) by reaction with quartz in phosphoric acid medium, and distilled as such using super heated steam. This is the Willard-Winter-Tananaev distillation. It should be noted that the use of super heated, dry (rather than wet) steam is crucial in obtaining accurate results. Using a wet steam generator yielded results 10-20% lower. The collected fluorosilicic acid is titrated with standardized sodium hydroxide solution. A correction has to be made for the phosphoric acid which is also transferred by the steam. Fluoride data are reported on an ignition-loss-free-basis after determination of ignition loss on a sample heated to 400 degree C for 1 hour.
  • Another preferred catalyst is a catalyst prepared by a process involving depositing a hydro­genation metal on an alumina or material containing alumina support, calcining said metal loaded support typically at between 350 to 500°C, preferably about 450 to 500°C for about 1 to 5 hours, preferably about 1 to 3 hours and fluoriding said metal loaded support using a high pH fluorine source solution to a bulk fluorine level of about 8 wt% or less (e.g., 2 to 8 wt%), preferably about 7 wt% or less, said high pH source solution being at a pH of 3.5 to 4.5 and preferably being a mixture of NH4H and HF followed by rapid drying/heat­ing in a thin bed or rotary kiln to insure thorough heating in air, an oxygen containing atmosphere or an inert atmosphere to a temperature between about 350 to 450°C in about 3 hours or less, preferably 375 to 400°C, and holding at the final temperature, if necessary, for a time sufficient to reduce
  • a low pH fluorine source solution having a pH of less than 3.5 using aqueous solutions of HF or appro­priate mixtures of HF and NH4F to a bulk fluorine level of about 10 wt% or less (e.g., 2 to 10 wt%), preferably about 8 wt% or less followed by drying/heating in a thin bed or rotary kiln to a temperature of about 350 to 450°C, preferably 375 to 425°C in air an oxygen containing atmosphere, or an inert atmosphere and holding for 1 to 5 hours.
  • aqueous solutions of HF or appro­priate mixtures of HF and NH4F to a bulk fluorine level of about 10 wt% or less (e.g., 2 to 10 wt%), preferably about 8 wt% or less
  • drying/heating in a thin bed or rotary kiln to a temperature of about 350 to 450°C, preferably 375 to 425°C in
  • the alumina or alumina containing support material is preferably in the form of extrudates, and are preferably at least about 1/32 inch across the longest cross-sectional dimension. If the low pH prepared catalyst is first charged to a unit, the catalyst must be held at the final activation tempera­ture for longer than 5 hours, preferably longer than 10 hours and preferably at temperatures of 400 to 450°C.
  • the above catalysts typically contain from 0.1 to 5.0 wt% metal, preferably 0.1 to 1.0 wt% metal, most preferably 0.2 to 0.6 wt% metal.
  • the dried/heated catalyst has a surface nitrogen content N/Al of 0.01 or less by X-ray photo­electron spectroscopy (XPS, preferably an N/Al of 0.007 or less, most preferably an N/Al of 0.004 or less by XPS.
  • XPS X-ray photo­electron spectroscopy
  • the catalyst following the above recited heating step can be charged to the isomerization reactor and brought quickly up to operating condi­tions.
  • the catalyst prepared using the pH 3.5 to 4.5 solution technique can be activated, preferably in pure or plant hydrogen (60 to 70% H2) at 350 to 450°C, care being taken to employ short activation times, from 1 to 24 hours, preferably 2 to 10 hours being sufficient. Long activation times (in excess of 24 hours) have been found to be detrimental to catalyst performance.
  • catalysts made using solutions of pH less than 3.5 can be activated in pure or plant hydrogen at 350 to 500°C for from 1 to 48 hours or longer.
  • catalyst prepared using solutions of pH less than 3.5 are not heated first, then it is preferred that they be subsequently activated at more severe conditions, i.e. for longer times and/or at higher temperatures. On the other hand, if they are heated first, then moderate activation condition procedures similar to those employed with catalysts made from higher pH solution techniques will suffice.
  • a typical activation profile shows a profile of 2 hours to go from room temperature with 100°C with the catalyst being held at 100°C for 0 to 2 hours then the temperature is raised from 100 to about 350 over a period of 1 to 3 hours with a hold at the final temperature of from 1 to 4 hours.
  • the catalyst can be activated by heating from room tem­perature to the final temperature of 350 to 450°C over a period of 2 to 7 hours with a hold at the final temperature of 0 to 4 hours. Similar activation can be accomplished by going from room temperature to the final temperature of 350 to 450°C in 1 hour.
  • Another preferred catalyst comprises a hydrogenating metal on fluorided alumina or material containing alumina support made by depositing the hydrogenation metal on the support and fluoriding said metal loaded support using acidic fluorine sources such as HF by any convenient technique such as spraying, soaking, incipient wetness, etc. to deposit between 2-10% F preferably 2-8%F.
  • acidic fluorine sources such as HF
  • the catalyst is dried, typically at 120°C and then crushed to expose inner surfaces, the crushed catalyst is double sieved to remove fines and uncrushed particles.
  • This sized catalyst is 1/32 inch or less and typically from 1/64 to 1/32 inch in size across its largest cross-sectional dimension.
  • the starting particle or extrudate may be of any physical configuration. Thus, particles such as cylinders, trilobes or quadrilobes may be used. Extrudates of any diameter may be utilized and can be anywhere from 1/32 of an inch to many inches in length, the length dimension being set solely by handling considerations. It is preferred that follow­ing sizing the particle have a length smaller than the initial extrudate diameter.
  • the particle or extrudate is crushed or fractured to expose inner surfaces.
  • metal loaded support particle which is already about 1/32 inch in size or smaller and fluoride it as described above using HF.
  • the sized material will range in size between about 1/64 to 1/32 inch in size.
  • the uncalcined catalyst is activated in a hydrogen atmosphere such as pure hydrogen or plant hydrogen containing 60 to 70 vol% H2 by heating to 350 to 500°C, preferably to 350 to 450°C for from 1 to 48 hours or longer.
  • a hydrogen atmosphere such as pure hydrogen or plant hydrogen containing 60 to 70 vol% H2 by heating to 350 to 500°C, preferably to 350 to 450°C for from 1 to 48 hours or longer.
  • the hydrogen activation profiles previously described may be used here.
  • This sized catalyst is unexpectedly superior for wax isomerization as compared to the uncrushed particle or extrudate starting material. It has also been discovered that 370°C+ oil products made using the sized catalyst as compared to the uncrushed or extrudate material starting with wax possessing about 5 to 10% oil exhibit higher VI's than do 370+ oil products made starting with wax possessing 0% oil (on the one hand) and about 20% oil (on the other). Therefore, to produce products having the highest VI one would isomerize wax having from 5 to 15% oil, preferably 7 to 10% oil using the "sized" catalyst produced using HF.
  • One desiring to maximize the production of lube oil having a viscosity in the 5.6 to 5.9 cSt/100°C range should practice the isomerization process under low hydrogen treat gas rate conditions, treat gas rates on the order or 500 to 5000 SCF/bbl, H2, preferably 2000 to 4000 SCF/bbl, H2, most preferively about 2000 to 3000 SCF/bbl, H2.
  • the isomerized max material is then subject­ed to second stage catalyst using a Group VIII metal on refractory metal oxide catalyst or Group VIII metal on halogenated refractory metal oxide catalyst.
  • the halogenated catalyst can be the same or different than the Group VIII metal on halogenated refractory metal oxide catalyst used in the prior isomerization reac­tor.
  • the process can be run in blocked sequence,, the reactor first used to produce isomerate by being run at severe conditions with the isomerate going to tankage, the stored isomerate being subsequent recycled through the unit now run under mild conditions to remove trace quanti­ties of polynuclear aromatics and other constituents deterimental to daylight and oxidation stability, but which conditions are not sufficient to effect further isomerization of the hydrocarbon components.
  • This second stage zone is run at a temperature of about 170°C to 270°C, preferably 180°C to 220°C, a flow velocity of 0.25 to 10 v/v/hr, preferably 1 to 4 v/v/hr, a pressure of from 300 to 1500 psi H2, preferively 500 to 1000 psi H2, and a hydrogen gas rate of 500 to 10,000 SCF/B, preferably 1000 to 5000 SCF/B. Higher temperatures may be employed if pressures in excess of 1500 psi are used, but such high pressures may not be practical.
  • the isomerate is fractionated into a lubes cut and fuels cut, the lubes cut being identified as that fraction boiling in the 330°C+ range, preferably the 370°C+ range and even higher.
  • This lubes fraction is then dewaxed to a pour point of about -21°C or lower. Dewaxing is accom­plished by techniques which permit the recovery of unconverted wax, since in the process of the present invention this unconverted wax is recycled to the isomerization unit. It is preferred that this recycle wax be recycled to the main wax reservoir and be passed through the hydrotreating unit to remove any quantities of entrained dewaxing solvent which solvent could be detrimental to the isomerization catalyst.
  • Solvent dewaxing is utilized and employs typical dewaxing solvents.
  • Solvent dewaxing utilizes typical dewaxing solvents such as C3-C6 ketones (e.g. methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C6-C10 aromatic hydrocarbons (e.g. toluene), mixtures of ketones and aromatics (e.g.
  • MEK/toluene autorefri­gerative solvents such as liquefied, normally gaseous C2-C4 hydrocarbons such as propane, propylene, butane, butylene and mixtures thereof, etc. at filter tempera­ture of -25 to -30°C.
  • the preferred solvent to dewax the isomerate, especially isomerates derived from heavier waxes (e.g. Bright Stock Waxes) under miscible conditions and thereby produce the highest yield of dewaxed oil at a high filter rate is a mixture of MEK/MIBK (20/80 v/v) used at a temperature in the range -25 to -30°C.
  • the fractionation bottoms are recycled by being sent first to the fresh feed reservoir and combined with the wax therein.
  • the isomerate from the second stage cata­lyst zone can be fractionated into narrow cuts and each cut individually dewaxed.
  • Figures 1 and 2 present schematic represen­tations of preferred embodiments of the wax isomeriza­tion process.
  • slack wax feed derived from for example a lighter oil such as 600N oil or lighter is fed from the reservoir (1) to a hydrotreater (3) via line 2 wherein heteroatom compounds are removed from the wax.
  • This hydrogenated slack wax is then fed via line 4 to the isomerization unit (5) after which the total liquid product is fed first via lines 6 and 6A to a low temperature, mild condition second stage treating unit (unit 7) wherein the TLP is contacted with the isomerization catalyst or simply a noble Group VIII metal on aluminum catalyst to produce a stream which is then sent via line 6B to the fraction­ator tower (unit 8).
  • the tube stream boiling in the 370°C+ range is then forwarded via line 9 to the solvent dewaxer (unit 10) for the separation of waxy constituents therefrom, the dewaxed oil fraction being recovered via line 11 and forwarded to other conven­tional treatment processes normally employed on base stock or blending stock oils.
  • the recovered wax is recycled either directly to the slack wax stream being fed to the isomerization unit or it is recycled to the wax reservoir (1) via line 12B for passage through the hydrotreater prior to being recycled to the isomeriza­tion unit.
  • Figure 2 the wax processing stream is much like that of Figure 1, the main difference being that Figure 2 represents the scheme for handling heavier slack wax feeds, such as a wax feed derived from Bright Stock oil
  • the wax from reservoir 1 is fed via line 2 to the hydrotreater (3) prior to being sent via line 4 to the isomerization unit (unit 5) after which it is fed via lines 6 and 6A to a low temperature mild condition second stage treating unit (unit 7) wherein it is contacted with a further charge of isomerization catalyst or simply noble Group VIII metal on alumina and fed via line 6B to the fractionator tower (unit 8).
  • the isomerate made using the heavy wax is fractionated into a light fraction boiling in the 370°C- (a fuels cut) a lube cut boiling in the 370°C+ range and bottoms fraction boiling in the 580°C+ range.
  • the lube fraction, a broad cut boiling in the 370°C to 580°C range is sent via line 9 to the dewaxer (unit 10) as previously described.
  • the 580°C+ bottoms fraction contains appreciable wax and is recycled via lines 13, 13A, 13B and 4 to the isomerization unit (5).
  • This bottoms fraction optionally can be combined via lines 13 and 13C with the wax in line 12 recovered from the dewaxing unit (10) in which case the total recycled stream can be fed directly to the isomeriza­tion unit via lines 12A, 13B and 4 or it can be sent to the wax reservoir (1) via line 12B for treatment of the hydrotreater prior to being fed to the isomeriza­tion unit.
  • the total liquid product (TLP) from the isomerization unit can be advantageously treated in a second stage at mild conditions using the isomerization catalyst or simply noble Group VIII on refractory metal oxide catalyst to reduce PNA and other contaminants in the isomerate and thus yield an oil or improved day­light stability.
  • the total isomerate is passed over a charge of the isomerization catalyst or over just noble Gp VIII on e.g. transition alumina.
  • Mild conditions are used, e.g. a temperature in the range of about 170-270°C, preferably about 180 to 220°C, at pressures of about 300 to 1500 psi H2, preferably 500 to 1000 psi H2, a hydrogen gas rate in the range of from about 500 to 10,000 SCF/bbl, preferably 1000 to 5000 SCF/bbl and a flow velocity of about 0.25 to 10 v/v/hr., preferably about 1-4 v/v/hr.
  • Temperatures at the high end of the range should be employed only when similarly employing pressures at the high end of their recited range. Temperatures in excess of those recited may be employed if pressures in excess of 1500 psi are used, but such high pressures may not be practical or economic.
  • the total isomerate can be treated under these mild conditions in a separate, dedicated unit or the TLP from the isomerization reactor can be stored in tankage and subsequently passed through the aforemen­tioned isomerization reactor under said mild condi­tions. It has been found to be unnecessary to frac­tionate the 1st stage product prior to this mild 2nd hold at 100°C for one hour; heat from 100°C to 400°C in three hours, hold at 450°C for four hours.
  • Platinum on fluorided ⁇ -alumina made by soaking a commercially available Pt/ ⁇ -Al2O3 base (Catalyst A) in NH4F/HF solution made up to a pH of about 4. The soaked material was washed, then dried then heated for two hours at 400°C in air. The catalyst was analyzed and had a bulk fluorine content of 6.9 wt%, platinum content of 0.62 wt%, surface N/Al ratio (by XPS) of 0.0040.
  • This catalyst was activated by heating to 350°C in H2 at 50 psi in the following manner; room tempera­ture to 100°C in two hours, hold at 100°C for one hour; heat from 100°C to 350°C in two hours, hold at 350°C for one hour.
  • Platinum on fluorided ⁇ -alumina made by soaking a commercially available Pt/ ⁇ -Al2O3 base (Catalyst A) in 10% HF. The soaked material was washed and dried at 150°C in air. The catalyst was analyzed and had a bulk fluorine content of 8.0%, platinum content of 0.62 wt%. The catalyst was activated by heating to 400°C in H2 at 300 psi in the following manner; room temperature to 100°C at 35°C per hour, hold at 100°C for 6 hours, heat from 100°C to 250°C at 10°C per hour, hold at 250°C for 12 hours; heat to 400°C at 10°C per hour; hold at 400°C for 3 hours.
  • platinum on ⁇ -alumina comprising 0.5% Pt on ⁇ -alumina from which halogen had been removed and activated by heating in 40 psi H2 as follows: room temperature to 100°C in 2 hours, hold at 100°C for 1 hour; heat to 350°C over 2 hours, hold at 350°C for 1 hour.
  • raw slack waxes from the dewaxing of petroleum oils were hydrotreated to remove polar materials, as well as heteroatomic compounds (sulfur and nitrogen containing compounds) which would deactivate the platinum on fluorided alumina hydroisomerization catalysts.
  • Any conven­tional hydrotreating catalyst can be used, e.g., Cyanamid's HDN-30; Katalco's NM-506; Ketjen's KF-840; etc.
  • the prime processing targets for the hydro­treated material are a sulphur content of about 10 ppm or less and a nitrogen content of 1 ppm or less.
  • Ketjen KF-840 was used in the form of 1/20 inch quadrilobes.
  • the catalyst as received from the manufacturer, had 4% NiO and 19.5% MoO3 on an alumina base, and had a surface area of 180 m2/gram, with an average pore volume of 0.35 cc/g, and an average pore radius of 38 ⁇ . Twelve liters of this catalyst was packed into a tubular fixed bed 189 cm long and 9.9 cm in diameter and sulfided by exposure to H2S in hydrogen and a sulfur containing vacuum distil­late.
  • the hydrotreating unit can be run in either up flow or down flow mode. Two different slack waxes were hydrotreated, a Western Canadian 600N slack wax, and an Augusta Bright Stock slack wax. Typical properties of each feed are given below in Table 1.
  • the 600N slack wax was hydrotreated in an up-flow mode at 0.5 v/v/hr, 1000 psig hydrogen pressure and a gas treat rate of 1500 SCF H2/B.
  • reaction temperature was held at 320°C and thereafter at 330°C.
  • the slack wax sulphur contents ranged from about 0.073 weight percent to 0.113 weight percent and nitrogen content ranged from 12 to 17 wppm.
  • Periodic analysis of the hydrotreated wax showed that sulphur contents were consistently 4 wppm and lower, while nitrogen contents were always 2 wppm or less.
  • the Bright Stock slack waxes feeds having different oil contents were hydrotreated in an up-flow mode at 380°C, 1000 psig hydrogen pressure and 1500 SCFH2/B treat gas rate.
  • the space velocity was varied from 0.42 to 0.5, in order to obtain the desired sulfur and nitrogen reduction. Inspections of the hydro­treated wax feeds used in the examples are given below in Table 2.
  • the hydrotreated Bright Stock slack wax (B) was isomerized at 320°C, 0.89 v/v/hr space velo­city, 1000 psi (H2) pressure and 5000 SCF/bbl, H2, gas rate over a 200 cc charge of Catalyst B.
  • the hydroconver­sion was conducted upflow mode and operated at a mass velocity was 160 pounds per hour/square foot (i.e. low mass velocity).
  • TLP isomerate total liquid product
  • Base oils were prepared from the total liquid product coming from the isomerization zone by fractionating said TLP into various lube fractions and dewaxing said lube fraction to a pour point of -21°C.
  • daylight stability was determined on the products from 1 through 5 (above) by exposing 5 ml samples in the presence of air contin­uously in a light box apparatus in which the lamp used was an Excella fluorescent tube from Sunburst Electric which simulated the intensity and frequency range of actual solar radiation. Samples were rated daily on the degree of haze, floc and sludge formation as to time exposed to air and radiation.
  • the dewaxed base stock oils above 1-5 were evaluated for daylight stability and found to exhibit the following: TABLE 3 Dewaxed Base Oil # Daylight Stability 1 Light haze, 48 hrs; distinct haze 96 hrs. 2 Haze/sludge ⁇ 24 hours 3 Haze/sludge ⁇ 24 hours 4 Haze/sludge ⁇ 24 hours 5 Haze/sludge ⁇ 24 hours It is seen that none of these dewaxed isomerate base oil products exhibit acceptable daylight stability since conventional lube base oils normally have day­light stability in excess of 10 days.
  • Base oils 3 and 4 were hydrofinished over sulfided KF-840 (Ni-Mo/Al2O3) at 300°C at 500 psi, 500 SCF H2/bbl and 1 v/v/hr. These hydrofinished base oils were evaluated for daylight stability and found to exhibit the following somewhat improved but still unacceptable daylight stabilities: TABLE 4 KF-840 Hydrofined Dewaxed Base Oil Daylight Stability 3 Haze/sludge, 50 hours 4 Haze/sludge, 100 hours
  • Dewaxed base oils 3, 4 and 5 were hydro­finished over Pt/F-Al2O3 Catalyst B under a number of conditions (recited in Table 4).
  • the hydrofinished base oils were evaluated for daylight stability and found to exhibit the following: TABLE 5 Dewaxed Base Oil Feed 3 4* 5 Catalyst B B B Hydrofinishing Conditions Temperature °C 160 180 200 200 225 200 Pressure, psi H2 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 Space Vel
  • the hydro­finished material was fractionated to obtain the 370°C+ fraction for subsequent dewaxing to -21°C pour using 100% MIBK solvent at a 4/1 solvent to oil dilution ratio and -26°C filter temperature. This dewaxed oil fraction was evaluated for daylight stability.
  • the 600N slack wax isomerate (TLP), feed D and Bright Stock slack wax isomerate (TLP) feed B were hydrofinished over Pt/alumina, catalyst E (previously described), under the conditions recited below.
  • the hydrofinished materials were fractioned into 370°C+ fraction and dewaxed to -20°C pour as recited in Example 4.
  • the dewaxed fraction were evaluated for daylight stability (Table 7).
  • the hydrofinished isomerate was functioned to obtain the 370°C+ fraction for solvent dewaxing to -21°C pour using 100% MIBK solvent at 4/1 solvent to oil dilution ratio and -26° filter temperatures to dewax as recited in Example 4.
  • the dewaxed fraction was evaluated for daylight stability (Table 8).
  • the hydrofinished isomerate was fractioned to obtain the 370°C+ fraction for segment dewaxing to -21°C pour using 100% MIBK solvent at 4/1 solvent to oil dilution ratio and -26°C filter tempera­ture to dewax as recited in Example 4.
  • the dewaxed fraction was evaluated for daylight stability (Table 9).
  • Bright Stock slack wax isomerate (TLP), feed (a) was hydrofinished over Pt/F-Al2O3, Catalyst B, conditions recited below.
  • the unhydrofinished TLP and the hydrofinished materials were vacuum distilled to product 460 to 550°C fractions, then dewaxed. These fractions were dewaxed with 5% toluene/95% MIBK at a solvent oil ratio of 4:1 and a filter temperature of -27°C. Each dewaxed fraction was then evaluated for daylight stability.
  • the hydrofinished materials were vacuum distilled to produce heart-cut fractions boiling in the 370°C to 580°C range. These fractions were dewaxed with 100% MIBK using a solvent:oil ratio of 4:1 and a filter temperature of -30°C.
  • the dewaxed heart-cut fractions were then further fractionated into light (4.5 cSt) and heavy (8.4 cSt) dewaxed oil frac­tions as shown in Table 11 and evaluated for daylight stability.
  • hydrofinishing the total liquid products coming from the isomerization unit using the Group VIII metal on refractory metal oxide or Group VIII metal on haloge­nated refractory metal oxide catalyst produced dewaxed base oils which exhibit superior daylight stability as compared to the unhydrofinished dewaxed base oils and dewaxed base oil hydrofinished using conventional hydrofinishing catalyst.
  • the examples shows that hydro­finishing must be performed within a narrow window of temperature conditions, i.e. about 170-270°C, preferively 180-220°C when operating under consistent mild pressure, treat gas rate and flow velocity conditions.
  • a hydrocracked lube basestock was prepared as follows:
  • the lube distillate was solvent dewaxed using a 40/60 mixture of MEK/MIBK, solvent to oil ratio of 2/1, and a filter temperature of -22°C.
  • the resulting dewaxed oil had the following properties: Viscosity at 40°C cSt 13.44 Viscosity Index 109 Saturates, Wt.% 96.0
  • This basestock has excellent viscometric properties.
  • a sample of this basestock was hydro­finished over a conventional sulphided Ni/Mo on Al2O3 catalyst (KF-840) at 300°C, 2.0 LHSV, 350 psi H2, 500 SCF/B, H2, treat gas rate.
  • a similar sample of frac­tionated hydrocrackate was hydrofinished according to the invention over a Pt/F/Al2O3 catalyst (Catalyst B) at 200°C, 1.0 LHSV, 1000 psi H2 and 5000 SCF/bbl treat gas rate.
  • a 5 ml vial was three-quarters filled with sample, loosely plugged with cotton wool, exposed to daylight in a north-facing window, and checked daily when pos­sible for appearance.
  • oil samples (again in a 5 ml vial plugged with cotton wool) were exposed continuously in a light box apparatus in which the lamp used Excella fluorescent tube from Sunburst Electric) simulates the intensity and frequency range of actual radiation. Samples were rated daily in terms of time to haze, floc and sludge.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)
EP19880311988 1987-12-18 1988-12-16 Verfahren zur Stabilisierung von Hydroisomeraten Expired EP0323724B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13514987A 1987-12-18 1987-12-18
US135149 1987-12-18

Publications (3)

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EP0323724A2 true EP0323724A2 (de) 1989-07-12
EP0323724A3 EP0323724A3 (en) 1990-03-28
EP0323724B1 EP0323724B1 (de) 1992-09-09

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EP (1) EP0323724B1 (de)
JP (1) JP2711120B2 (de)
AU (1) AU609553B2 (de)
CA (1) CA1328635C (de)
DE (1) DE3874510T2 (de)
ES (1) ES2034274T3 (de)
MX (1) MX169942B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0471524A1 (de) * 1990-08-14 1992-02-19 Exxon Research And Engineering Company Verfahren zur hydrierenden Behandlung von schwerem Bodenprodukt einer Hydroisomerisatfraktionierung zur Herstellung eines leichten Öls hoher Qualität nach einer darauffolgenden Fraktionierung
US5453176A (en) * 1993-10-13 1995-09-26 Narloch; Bruce A. Process for preparing white oil containing a high proportion of isoparaffins
EP0710710A3 (de) * 1994-11-01 1996-07-03 Exxon Research Engineering Co Katalysatorkombination für Isomerisation von Wachs
EP0743351A3 (de) * 1995-05-19 1997-01-22 Shell Int Research Verfahren zur Herstellung von Basisschmierölen
EP0744452A3 (de) * 1995-04-28 1997-01-22 Shell Internationale Researchmaatschappij B.V. Verfahren zur Herstellung von Basisschmierölen
CN1102641C (zh) * 1995-04-28 2003-03-05 国际壳牌研究有限公司 生产润滑基础油的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7132042B2 (en) * 2002-10-08 2006-11-07 Exxonmobil Research And Engineering Company Production of fuels and lube oils from fischer-tropsch wax
US20150060328A1 (en) * 2012-03-30 2015-03-05 Jx Nippon Oil & Energy Corporation Lubricant base oil and method for producing same
US20150060327A1 (en) * 2012-03-30 2015-03-05 Jx Nippon Oil & Energy Corporation Lubricant base oil and method for producing same
SG11202101661SA (en) * 2018-09-07 2021-03-30 Eneos Corp Method for producing wax, wax, and method for producing lubricant base oil

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1069452A (en) * 1974-04-11 1980-01-08 Atlantic Richfield Company Production of white oils by two stages of hydrogenation
US3979279A (en) * 1974-06-17 1976-09-07 Mobil Oil Corporation Treatment of lube stock for improvement of oxidative stability
FR2320775A1 (fr) * 1975-08-13 1977-03-11 Raffinage Cie Francaise Catalyseurs d'isomerisation d'hydrocarbures, procede de preparation et application desdits catalyseurs
JPS5242506A (en) * 1975-10-02 1977-04-02 Toa Nenryo Kogyo Kk Hydrotreating process of petroleum wax
JPS5397006A (en) * 1977-02-04 1978-08-24 Labofina Sa Production of heavy paraffins free from aromatic components

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0471524A1 (de) * 1990-08-14 1992-02-19 Exxon Research And Engineering Company Verfahren zur hydrierenden Behandlung von schwerem Bodenprodukt einer Hydroisomerisatfraktionierung zur Herstellung eines leichten Öls hoher Qualität nach einer darauffolgenden Fraktionierung
US5453176A (en) * 1993-10-13 1995-09-26 Narloch; Bruce A. Process for preparing white oil containing a high proportion of isoparaffins
EP0710710A3 (de) * 1994-11-01 1996-07-03 Exxon Research Engineering Co Katalysatorkombination für Isomerisation von Wachs
EP0744452A3 (de) * 1995-04-28 1997-01-22 Shell Internationale Researchmaatschappij B.V. Verfahren zur Herstellung von Basisschmierölen
CN1102641C (zh) * 1995-04-28 2003-03-05 国际壳牌研究有限公司 生产润滑基础油的方法
EP0743351A3 (de) * 1995-05-19 1997-01-22 Shell Int Research Verfahren zur Herstellung von Basisschmierölen

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DE3874510T2 (de) 1993-03-18
ES2034274T3 (es) 1993-04-01
CA1328635C (en) 1994-04-19
MX169942B (es) 1993-08-02
AU2694188A (en) 1989-06-22
JP2711120B2 (ja) 1998-02-10
DE3874510D1 (de) 1992-10-15
EP0323724B1 (de) 1992-09-09
EP0323724A3 (en) 1990-03-28
AU609553B2 (en) 1991-05-02
JPH02263896A (ja) 1990-10-26

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