AU610671B2 - Process for the hydroisomerization of fischer-tropsch wax to produce lubricating oil - Google Patents

Description

iii f 4 r COMMONWEALTH OF AUSTRALIA 6 1 6 7 1 PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Application Number: Lodged: Int. Class Complete Specification Lodged: Accepted: S* Published: Priority: amendmcri ts in !.wJ xtAI, j4-Y a-lnfd Is Gorlect 'r rir-f ")g 0 Related Art: t00 a fl NamL of Applicant: Adlress of Applicant: 'Actual Inventor: Addres for Service Address for Service: EXXON RESEARCH AND ENGINEERING COMPANY P.O. Box 390, Florham Park, New Jersey 07932.

United States of America.

GLEN PORTER HAMNER, HEATHER ALEXIS BOUCHER and WILLIAM AUGUSTINE WACHTER EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: PROCESS FOR THE HYDROISOMERIZATION OF TMSCHER-TROPSCH WAX TO PRODUCE LUBRICATING OIL.

The following statement is a full desription of this invention, including the best method of performing it known to U 1.

r DECLARED at F1Qrh Z5. day 19..9.1..

EXXON R~ESEARCH AND ENGINEE~RING Signatuxe.. COMPANY To: THE COMMISSIONER OF PATENTS. Assistant Secretary Anne Hershkowitz Jacobson WATERMARK PATENT TRADEMARK ATTORNEYS I~vZIDOF THE I UION~ 1. Fid of the Invention This invention relates to a process for Iproducing lubricating oil from a Fischer-Tropsch wax.

More particularly, it relates to a process utilizing a ItGroup VIII metal-on-alumina catalyst for hydroisomeri- II c G zing a hydrotreated Fischer-Tropsch wax to produce a G lubricating oil having a high viscosity index and a low a C V a tee* pour point.

II. De9cr.2tLon ofthe..PXr..A~ the Fisc1ker-Tropsch process a synthesis gas (CO H2) made, from natural gas, is convert- ::ed over a catalyst, a ruthenium, iron or cobalt catalyst, to form a wide range of products inclusive of gaseous and liquid hydrocarbons, and oxygenates, and a normally solid paraffin wax which does not contain the *6 sulfur, nitrogen or metals impurities normally found in crude oil. It is generally known to catalytically convert the -paraffin wax, or syncrude obtained from 01'0 such process to lower boiling paraffinic hydrocarbons *~,~0:falling within tegasoline admiddle distillate boiling ranges.

Paraffin waxes have been isomerized over various catalysts, Group VIB and VIII catalysts of the Periodic Table of the Elements H. Sargent& Co,, Copyright 1964 Dyna-Slide Co.) Certain of hwuch catalysts can be characterized as halogenated supported r ii 2metal catalysts, a hydrogen chloride or hydrogen fluoride treated platinum-on-alumina catalyst as disclosed, in U.S. 2,668,866 to G. M. Good et al.

In the Good et al. process a partially vaporized wax, such as one from a Fischer-Tropsch synthesis process, is mixed with hydrogen and contacted at 300"C to 500'C over a bed of supported platinum catalyst. Palladium or nickel may be substituted for platinum. The support Sr may be a number of conventional carrier materials, such a as alumina or bauxite. The carrier material may be EC treated with acid, such as HCl or HF, prior to incorpo- E t rating the platinum. In preparing the catalyst, C C t a t pellets of activated alumina may be soaked in a solution of chloroplatinic acid, dried and reduced in hydrogen at 475°C.

U.S. Patent No. 2,817,693 discloses the catalyst and process of U.S. Patent No. 2,668,866 with the recommendation that the catalyst be pretreated with hydrogen at a pressure substantially above that to be o.o. used in the process.

oo 0 U.S. Patent No. 3,268,439 relates to the conversion of waxy hydrocarbons to give products which o 0 are characterized by a higher isoparaffin content than the feedstock. Waxy hydrocarbons are converted at elevated temperature and in the presence of hydrogen by contacting the hydrocarbons with a catalyst comprising a platinum group metal, a halogenatable inorganic oxide support and at least one weight percent of fluorine, the catalyst having been prepared by contacting the support with a fluorine compound of the general formula: F X

Y-X-F

3 3 where X is carbon or sulphur and Y is fluorine or hydrogen.

c cc I c c c e o 0o o 0 o0 a 0 00 000 a 00 o o o a o 0 a 0000 0 0 U.S. Patent No. 3,308,052 describes a hydroisomerization process for producing lube oil and jet fuel from waxy petroleum fractions. According to this patent, product quality is dependent upon the type of charg stock, the amount of liquid hydrocarbon in the waxy charge stock and the degree of conversion to products boiling below 650°F. The greater the amount of charge stock converted to material boiling below 650"F per pass the higher the quality of jet fuel. The catalyst employed in the hydroisomerization zone is a platinum group metal catalyst comprising one or more platinum, palladium and nickel on a support, such as alumina, bentonite, barite, faujasite, etc., containing chlorine and/or fluorine.

In U.S. Patent No. 3,365,390 a heavy oil feed boiling at least partly above 900°F is hydrocracked and the oil effluent thereof is separated into fractions, including a distillate fuel and a higher boiling hydrocracked lube oil boiling range fraction. The hydrocracked lubricating oil boiling range fraction is dewaxed to obtain a hydrocracked wax fraction which is hydroisomerized in the presence of a reforming catalyst and the oil effluent thereof is separated into fractions, including a distillate fuel and an isomerized lube oil boiling range fraction.

In U.S. Patent No. 3,486,993 the pour point of a heavy oil is lowered by first substantially eliminating organic nitrogen compounds present in the oil and then contacting the nitrogeh-free oil with a reforming catalyst in a hydrocracking-hydroisomerization zone. Hydroisomerization is conducted at a temperature of 750*F-900'F over a naphtha reforming

~C~

catalyst containing no more than two weight percent halide.

U.S. Patent No. 3,487,005 discloses a process for the production of low pour point lubricating ols by hydrocracking a high pour point waxy oil feed boiling at least partly above 700°F in at least two stages. The first stage comprises a hydrocracking- K denitrofication stage, followed by a hydrocrackingisomerization stage employing a naphtha reforming catalyst containing a Group VI metal oxide or Group •cr C VIII metal on a porous refractory oxide, such as 0:40 alumina. The hydrocracking isomerization catalyst may 0. I be promoted with as much as two weight percent fluorine.

SU.S. Patent No. 3,709,817 describes a process it which comprises contacting a paraffin hydrocarbon containing at least six carbon atoms with hydirogen, a etc fluorided Group VIB or VIII metal alumina catalyst and t water. These catalysts are classified by the patentee as a well-known class of hydrocracking catalysts.

O0 06 0000 000 III. Summary of the Invention 80O000 i A process for producing a lubricating oil having a high viscosity index and a low pour point from a Fischer-Tropsch wax which process comprises: contacting the Fischer-Tropsch wax with a hydrotreating catalyst and hydrogen to reduce the S oxygenate and trace metal levels of the wax and to partially hydrocrack/isomerize the wax; contacting the hydrotreated Fischer- Tropsch wax from step with hydrogen in a hydro- Sisomerization zone in the presence of a fluorided Group VIII metal-on-alumina catalyst having a bulk fluoride concentration ranging from about 2 to weight percent, wherein the fluoride concentration is a 5 less t..an about 3.0 weight percent at the outer surface layer to a depth less than one one hundredth of an inch provided the surface fluoride concentration is less than the bulk fluoride concentration, (ii) an aluminum fluoride hydrate level greater than 60 where an aluminum fluoride hydrate level of 100 corresponds to the X-ray diffraction peak height of 5.66A for a Reference Standard; I e fractionating the effluent from step (b) Se c to produce a lubricating oil fraction boiling at atmospheric pressure above about 640°F, preferably S* above 700"F; and oo. dewaxing the lubricating oil fraction o"°o from step to produce a dewaxed lubricating oil having a viscosity index of at least 130 and a pour point less than about 0°F.

o oo 0 00 0 00 o 00 oo00o In preferred embodiments, the hydrotreating catalyst will be unsulfided, the catalyst employed in "o the hydroisomerization zor. will be a fluorided plati- °ae0v num-on-aluminum catalyst, and the isomerate is contact- 0 a o ed with hydrogen in the presence of a hydrogenation Coo catalyst to reduce unsaturation of the isomerate and thereby improve its daylight and oxidation stability.

IV. Brief Description of the Drawing The Figure schematically depicts a process of the invention for the production of a lubricating oil boiling substantially in the range of about 700°F to 1050*F from a Fischer-Tropsch wix.

V. Description of the Preferred Embodiments In accordance with the invention, a Fischer- Tropsch wax is hydrotreated under relatively high severity conditions to remove impurities and partially convert the 1050"F+ wax, followed by hydroisomerization of the hydrotreated wax, hydrofining of the isomerate I I -i i~ 6 to improve daylight stability, fractionation to recover a lubricating oil fraction, and dewaxing to produce a high viscosity, low pour point lubricating oil.

Fischer-Tropsch wax may be made as a by-product from the conversion of natural gas or gasification of coal under known conditions to a synthesis gas (CO+H2) which may then be converted by the Fischer- So. Tropsch process to form gaseous and liquid hydrocarbons 0.s and a normally solid paraffin wax known as Fischer- 0 00o0 Tropsch wax. This wax does not contain the sulfur, 0 0 s 0 o nitrogen or metal impurities normally found in crude 0 Do o 0 oil, but is known to contain water, trace metals and a o number of oxygenate compounds such as alcohols, ketones, aldehydes, etc. These oxygenate compounds have an adverse effect on the performance of the 0 o 00 hydroisomerization/hydrocracking catalyst of the So0 o invention and it is, therefore, advantageous to produce lube oil products by the process scheme outlined in the So00 Figure.

0 000000 0 0 Referring to the Figure, a Fischer-Tropsch 0 o0 wax is introduced into Hydrotreater R-l along with o000 eas hydrogen and contacted therein with a hydrotreating catalyst. Fischer-Tropsch wax is generally composed of about 99+% normal paraffins, with trace amounts of metals and oxygenates as impurities. It is all high melting wax, and requires considerable structural modification (normal paraffin wax is first converted to iso-paraffin wax before oil is produced). Hydrotreating serves a dual purpose, namely, removal of the impurities and conversion of some of the Fischer- Tropsch wax, particularly the fraction boiling above 1050*F. Hydrotreating at mild conditions removes impurities in the Fischer-Tropsch Vax, but more severe hydrotreating conditions are preferred in the process of the present invention in order to convert some of 7 the higher boiling Fischer-Tropsch wax. This is in contrast, for example, to a petroleum slack wax which normally contains some relatively low melting wax which needs only a slight reduction in pour point to become oil. In the case of petroleum slack waxes relatively mild hydrotreating conditions are employed to remove nitrogen and sulfur, while avoiding conversion of the naphthenes and isoparaffins present in the slack wax.

C It has been found advantageous, therefore, to employ relatively severe hydrotreating conditions in c Hydrotreater R-1 in order to remove impurities and soften the Fischer-Tropsch wax prior to hydroisomerization. These conditions include a temperature in the range of about 650°F to 775"F, preferably 700°F to 750°F, a hydrogen pressure between about 500 and 2500 psig (pounds per square inch gauge), preferably between 1000 and 1500 psig, a space velocity of between about 0.1 and 2.0 V/V/Hr (volume of feed/volume of catalyst C c per hour), preferably 0.2 and 0.5 V/V/Hr, and a hydrogen gas rate between about 500 and 5000 SCF/B (standard cubic feet of hydrogen per barrel of feed), preferably S. between 1000 and 2000 SCF/B. The hydrotreating cata- 050oo0 lyst includes the well known hydrotreating catalysts such as Co/Mo or Ni/Mo on alumina. Other hydrotreating catalysts include combination of Co and/or Ni and Mo and/or W on a silica/alumina base. Typically such hydrotreating catalysts are presulfided, but it is preferred to employ a non-sulfided hydrctreating catalyst in R-l.

The hydrotreated Fischer-Tropsch wax from R-1 is introduced into Hydroisomerization Reactor R-2 along with fresh hydrogen or dewatered recycle hydrogen and contacted therein under hydroisomerization conditions with a fluorided Group VIII metal-on alumina catalyst.

I!

6 -8 Hydroisomerization is carried out at temperatures ranging between about 500°F and 750*F, preferably from about 600*F to 725"F, at a feed space velocity of from about 0.2 to 2.0 V/V/Hr., preferably from about to 1.0 V/V/Hr. Pressure is maintained at from about 500 to 2500 psig, preferably from about 1000 to 1500 psig, and hydrogen is fed into the reactor at a rate of about 500 to 10,000 :CF/B, preferably from about 2000 to 6000 SCF/B. The conditions in hydro- .c isomerization reactor R-2 are preferably selected to t ,convert about 10 to 35 weight percent prefer- S* ably 15 to 30 wt% to distillate and lighter (650'F-), of the hydrotreated Fischer-Tropsch wax delivered to 0 0 R-2. It has been found that such conversion in the to 30 percent range maximizes the production of the desired lubricating oil product.

a 00 S0° 0 The catalyst employed in hydroisomerization reactor R-2 is a particulate fluorided Group VIII g ao metal-on-alumina catalyst composition where Group VIII °ooea0 refers to the Periodic Table of Elements H. Sargent o a Co., Copyright 1964 Dyna-Slide Platinum is the 0 o0 preferred Group VIII metal. Alumina is the catalyst 0000 base and for purposes of this invention alumina includes alumina-containing materials such as silica alumina and the like.

The fluorided Group VIII metal-on-alumina catalyst comprises about 0.1 to about 2 percent, preferably from about 0.3 to about 0.6 percent Group VIII metal and from about 2 percent to about 10 percent fluoride, preferably from about 5 percent to about 8 percent fluoride, based on the total weight of the catalyst composition (dry basis), such fluoride concentration being herein referred to as the bulk fluoride concentration.

9 9 The particulate catalyst of the invention will have a fluoride concentration less than about weight percent, preferably less than about 1.0 weight percent and most preferably less than 0.5 weight percent at its outer surface layer, provided the surface fluoride concentration is less than the bulk fluoride concentration. The outer surface layer is measured to a depth less than one one hundredth of an S inch. The surface fluoride was measured by scanning electron microscope. The remaining fluoride is dis- I C tributed with the Group VIII metal at a depth below the o, outer shell into and within the particle interior.

The fluoride content of the catalyst can be determined in a number of ways.

One technique analyzes the fluorided catalyst •o o. using oxygen combustion methodology which is well established in the literature. Approximately 8-10 mgs of sample is mixed with 0.1 g benzoic acid and 1.2 gms of mineral oil in a stainless steel combustion capsule which is mounted in a 300 mL. Parr oxygen combustion bomb. The "sample" is purged of air and subsequently combusted under 30 Atms of pure oxygen. Combustion products are collected in 5 mL. of deionized water.

Once the reaction has gone to completion (about minutes), the absorbing solution is quantitatively transferred and made to fixed volume.

Fluoride concentration of the sample is determined by ion chromatography analysis of the combustion prod t 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 w 0 i0 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.

Another procedure employs the use of fluoride distillation with a titrimetric finish. Fluorides are converted into fluorosilicic acid (H 2 SiF 6 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 0o e the use of super heated, dry (rather than wet) steam is crucial in obtaining accurate results. Using a wet o a steam generator yielded results 10-20% lower. The collected fluorosilicic acid is tritrated with standardized sodium hydroxide solution. A correction has o0o 6 to be made for the phosphoric acid which is also o transferred by the steam. Fluoride data are reported on an ignition-loss-free-basis after determination of 00 o, ignition loss on sample heated to 400 degree C for 1 a0ooo hour.

o B o The platinum contained on the alumina compo- 0 nent of the catalyst will preferably have an average crystallite size of up to 50A, more preferably below about The preferred catalyst of the invention will be relatively free of nitrogen and, accordingly, the catalyst will have a nitrogen/aluminum (N/A1) ratio less than about 0.005, preferably less than about 0.002, and most preferably less than about 0.0015.

The catalyst used in the hydroisomerization reactor R-2 will have high intensity peaks characteristic of aluminum fluoride hydroxide hydrate as well as the peaks normally associated with gamma alumina.

12 X-ray diffraction data (X-ray Diffractometer, Scintag show that the fluoride present in ths ;ferred catalyst will be substantially in the form of aluminum fluoride hydroxide hydrate. This catalyst is described in detail in co-pending application OP-3402 filed in the names of Glen P. Hamner and Willard H. Sawyer.

The relative X-ray diffraction peak height at 20 5.66A is taken as a measure of the aluminum 0c a.

e as fluoride hydroxide hydrate content of the catalyst.

"aa 8 The 5.66A peak for the Reference Standard is taken as a SoO0 o0 value of 100. For example, fluorided platinum-on-alu- S0o mina catalyst having a hydrate level of 60 would ao w therefore have a 5.66A peak height equal to 60% of the 5.66A peak height of the Reference Standard, with a value of 80 corresponding to a catalyst having a 5.66A 0 peak height equal to 80% of the 5.66A peak height of the Reference Standard etc. The catalyst used in 0 0o reactor R-2 will have a hydrate level of at least 0o preferably at least 80, and most preferably at least o oa about 100.

0,,000 0 0 o 0o The Reference Standard contains 0.6 wt% Pt 0 0 0 o and 7.2 wt% F on alumina having a surface area of about 150 m 2 The Reference Standard is prepared by treatment of a standard reforming grade platinum on alpha alumina material containing 0.6 wt% Pt on 150 m 2 /g surface area V alumina with platinum, followed by single contact with an aqueous solution containing a high concentration of hydrogen fluoride 10-15 wt% HF solution such as 11.6 wt% HF solution) with drying at, 300F in accordance with the following procedure.

The catalyst employed in R-2 may be prepared in the following manner. The Group VIII metal, preferably platinum, can be incorporated with the alumina in

V}

-12any suitable manner, such as by coprecipitation oco-gellation with the alumina support, or by ion exchange with the alumina support. In the case of a fluorided platinum-on-alumina catalyst, a preferred mathod for adding the platinum group metal to the alumina support involves the use of an aqueous solution of a water soluble compound, or salt of platinum to impregnate the alumina support. For example, platinum may be added to the support by co-mingling the uncalcined alumina with an aqueous solution of chloroplatinic acid, ammonium chloroplatinate, platinum chloride, or the like, to distribute the platinum substantially uniformly throughout the particle. Following the impregnation, the impregnated support can then be t0 dried and subjected to a high temperature calcination, generally at a temperature in the range from about 700"F to about 1500°F, preferably from about 850°F to about 1300°F, generally by heating for: a period of time ranging from about 1 hour to about 20 hours, preferably from about 1 hour to about 5 hours. The platinum component added to the alumina support, is calcined at o high temperature to fix the platinum thereupon prior to adsorption of a fluoride, suitably hydrogen fluoride or 00 0o 0 o hydrogen fluoride and ammonium fluoridei mixtures, into *the platinum-alumina composite. Alternatively the solution of a water soluble compound, or salt of S °ooo. platinum can be used to impregnate a pre-calcined alumina support, and the platinum-alumina composite again calcined at high temperature after incorporation of the platinum.

.I

Ai 1 13 The Croup VIII metal component is substantially uniformly distributed throughout a precalcined alumina support by impregnation. The rroup VIII metalalumina composite is then calcined at high temperature, and the fluoride, preferably hydrogen fluoride, is distributed onto the precalcined Croup VIII metalalumina composite in a manner that most of the fluoride will be substantially composited at a level below the outer surface of the particles.

Sd'% The catalyst having the fluoride substanstc tially in the form of aluminum fluoride hydroxide hydrate is preferably prepared in the following manner.

The platinum is distributed, generally substantially i :t ,uniformly throughout a particulate alumina support and the platinum-alumina composite is calcined. Distribution of the fluoride on the catalyst, preferably hydrogen fluoride, is achieved by a single contact of o 0the precalcined platinum-alumina composite with a soluoo tion which contains the fluoride in sufficiently high concentration. Preferably an aqueous solution contain- 01 0 °o ing the fluoride in high concentration is employed, a solution generally containing from about 10 percent to about 20 percent, preferably from about 10 percent to 0o about 15 percent hydrogen fluoride. Solutions contain- :ing hydrogen fluoride in these concentrations will be adsorbed to incorporate most of the hydrogen fluoride, S1 ~at an inner layer below the outer surface of the platinum-alumina particles.

*i 9- 14- The platinum-alumina composite, after adsorption thereupon of the fluoride component is heated during preparation to a temperature ranging up to but not exceeding about 650 0 F, preferably about S00F, and more preferably 300 0 F. Where a HF/NHF solution is used to incorporate the fluoride, the catalyst is dried at a temperature ranging up to but not exceeding about 8500F. A characteristic of the inner platinum-fluoride containing layer is that it contains a high concentration of aluminum fluoride hydroxide hydrate. It can be shown by X-ray diffrac- 9 tion data that a platinum-alumina catalyst formed in such manner displays high intensity peaks characteris, tic of both aluminum fluoride hydroxide hydrate and gamma alumina.

The isomerate from R-2 may be fractionated The isomerate from R-2 may be fractionated a 9 99 9 9: 9* 09 9 O? 9 o a 99 9L 9 9 and then dewaxed or it may first be introduced with hydrogen into hydrofinishing reactor R-3 containing a hydrogenation catalyst to hydrogenate the unsaturates present in the isomerate product and thereby improve its daylight stability. The reactor conditions are relatively mild and include, for example, a temperature in the range of about 340-450°P, preferably about 356o0 to 425oF, at pressures of about 300 to 1500 psi H 2 preferably 500 to 1000 psi H 2 a gas rate of about 500 to 10,000 SCF/B, preferably 1000 to 5000 SCF/B and a space velocity of about 0.25 to 20 V/V/Hr., preferably about 1-4 V/V/Rr.

I

i §f The catalyst employed in R-3 includes, for example, the hydroisomerization catalyst employed in R-3 or a noble Group VIII metal on a refractory metal oxide such as alumina, silica-alumina and the like.

The effluent from R-3 is fractionated in distillation tower F-1 to produce an overhead light end rroduct boiling below 6400o, a lubricating oil fraction boiling in the range of 640OF 1I000F, preferably in the range of 700 0 F 900OF and a residual fraction. The lubricating oil fraction is then introduced into the dewaxing zone D-l where unconverted wax is removed to cc. result in a lubricating oil having a viscosity index of at least 130, preferably a viscosity index greater than i 140, and a pour point no greater than 0 0 F and preferably a pour point below -6 0 F. The residual fraction from F-I will typically have an initial boiling point at atmospheric pressure above 1000 0 C and will be recycled with the wax from D-l to the hydroisoneriza- °oo tion reactor R-2.

O 00 Dewaxing in D-1 is accomplished by techni- °0 0 ques which permit the recovery of unconverted wax, siuce, as indicated, this unconverted wax is recycled to the hydroisomerization unit. Solvent dewaxing is a o°oo utilized in D-1 and employs typical dewaxing solvents.

Oa,,,00 Solvent dewaxing utilizes typical dewaxing solvents such as C 3

-C

6 ketones methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof), C 6 -Co aromatic hydrocarbons toluene) mixtures of ketones and aromatics MEK/toluene), autorefrigerative solvents such as liquified, normally gaseous C 3

-C

4 hydrocarbons such as propane, propylene, butane, butylene k|1 -16and mixtures thereof, etc. at filter temperature of -18 0 F to -22 0 F. The isomerate may be dewaxed under miscible conditions with a high yield of dewaxed oil at a high filter rate with a mixture of MEK/MIBK (20/80) used at a temperature in the range -18 0 F to -22 0 F. Pour points lower than -6 0 F can be achieved using lower filter temperatures and other ratios of paid solvent but a penalty may be paid due to operation under immiscible conditions, the penalty being lower filter rates.

The invention is further illustrated by the following examples.

c e 0 Example Eee Coot St A synthetic hydrocarbon wax (Fischer-Tropsch c source) feed was obtained as a 700 0 F+ fraction by the °distillation of a total Fischer-Tropsch synthesis product. The synthesis wax feed had the following properties: S" Melting Point, OF >220 o 0 o Oil Content, wt% nil Sulfur, ppm nil o Nitrogen, ppm nil Oxygen, wt% 0.34 Metals (Fe,Co) trace The wax feed was hydroisomerized over a platinum on fluorided alumina catalyst having the following composition:

I

Platinum concentration, wt% 0.58 Platinum Cystallite size 26 Fluorine, wt% 7.9 Aluminum Fluoride 250 Hydroxide Hydrate level intensity 566 (X-ray diffraction) NlitrOgen/A.l 2

O

3 Atomic Ratio 0 .005 s3urface area, m 2 /g 138 Pore volume, cc/g 0.42 The catalys was reduced with hydrogen co 0 50OF for two hours orior to introducing the 700 0 F+ wax feed with hydrogen.

0000 0 0 Process conditions for the hydroisornerization and the dewaxing operation with isomerate (700 0

F+)

000 so produced are given in Table I with the corresponding dewxedoilproperties.

C. '00 op 0 Good 9 9* 99 0 900 0 90*0 0 0000 0890 0 00 00 0 0 00 0 0 0000 00 0 0 00 0 80 0 00 00 0 0 00 0 00 00 0 0 09 00 0 0 00 0 00 0 0 .h 0~ Od 0 0 o 00 00 0 90 9 0 Tab-e8- Tabaele Dewaxed Oils from Fischer-Tropsch Hydro isomerization Isorerization Condi tions Temverature, 0 UF 708 716 V/V/Mr.

I.

Pressure, psi 1.000 Treat SCF H 2 /bbl. 2500 Conversion to 700 0 13 19 Isomnerate (700 0 Feed to Dewaxing Cloud Point, OF 208 187 Viscos ity, Cs@ 210*F 7.3 oewaxing Conditions Solvent: 40/60 MEK/Toluene Diluent-Qil Ratio 4 to 1 Filter Tem~perature OF 22 Dewaxed oil Properties Pour Point -15? 9 -4 Viscosity, cs@l000F 39 33.8 'a-210 OF 7.5 6.7 Viscosity Indiex 163 159 Wax Recovered, wt% 48 Theoretical Dewax Oil Yield wt% 52 cm i I 19 It is apparent that at low levels of wax conversion and when using typical dewaxing solvents under standard conditions (filter temperature a low yield of dewaxed oil having an unsatisfactory pour point is produced. Lower filtration temperatures would produce the desired pour point but would produce an even lower dewax oil yield. Hydroisomerization at a higher level of conversion 30% wax remaining in the isomerate 700'F+) facilitates the production of a lower pour point product within the conventional dewaxing parameters employed in dewaxing plants. A major portion of the unconverted wax is associated with the 1050*F+ isomerate and thus the recycle of this fraction to the isomerization zone would be the preferred method of reducing the wax load to the dewaxing operation, as well as increasing the overall yield of oil from wax.

00 000 0 090 0 000 0090 0o 0 00 0 0 O0 09 0 0 a 0 0 00 0 0 00 0 0 0 00 0 o 0 0 o 0 00 0 0 009o oo o 0 o

Claims (8)

1. A process of producing a lubricating oil having a high viscosity index and a low pour point from a Fischer-Tropsch wax, which process comprises: contacting the Fischer-Tropsch wax at temperature in the range of 6500F to 7750F, a hydrogen pressure between 500 and 2500 psig, a space velocity of 0.1 and 2.0 V/V/Hr and a hydrogen gas rate between 500 and 5000 SCF/B with a hydrotreating catalyst and hydrogen to reduce the oxygenate and trace metal levels of the wax and to partially hydrocrack and isomeri.e the wax; contacting the hydrotreated Fischer-Tropsch wax from step with hydrogen in a hydroisomerization zone in the presence of a fluorided Group VIII metal-on-alumina catalyst having a bulk fluoride concentration ranging from 2 to 10 weight percent, wherein the fluoride concentration is less than 3.0 weight percent at the outer surface layer to a depth less than one one hundredth of an inch, provided the surface fluoride concentration is less than the bulk fluoride concentration, (ii) an aluminum fluoride hydroxide hydrate level greater than 60 where an aluminum fluoride hydrate level of 100 corresponds to the X-ray diffraction peak height of 5.66A for a Reference Standard, and (iii) a N/A1 ratio less than 0.005; fractionating the effluent from step to produce a lubricating oil fraction boiling above 640 F at atmospheric pressure; and solvent dewaxing the lubricating oil fraction from step to produce a dewaxed lubricating oil having a viscosity index of at least 130 and a pour point less than 0 0 F.

2. The. process of claim 1 wherein the Group VIII metal on the catalyst employed in step is platinum. i 7, i i q I -21-

3. The process of claim 1 wherein said catalyst contains abeot 0.3 to about 0.6 weight percent platinum and about- 5 to-abeut- 8 weight percent fluo- ride.

4. The process of claim 3 wherein the hydrotreating catalyst employed in step is unsul- fided. The process of claim 2 wherein the F,ischer-Tropsch wax is subjected to severe hydrotreat- ing conditions in step including a temperature of Saut700°F 750'*F and a hydrogen pressure of -about- 0* 1000 1500 psig. 0900 0 0 0 00

6. The process of claim 5 wherein ab~ou- 10 0 A0 o:o 30 wt% of the Fischer-Tropsch wax introduced into the no° hydroisomerization zone is converted to distillate and lighter products. 0o 7. The process of claim 6 wherein the 0 lubricating oil fraction recovered from step has a 00 boiling point in the range of a4bot 700°F 1000*F. 00 a 0 00 o 00

8. The process of claim 7 wherein the 0 0 fluorided platinum-on-alumina catalyst has an aluminum 0 a ,4 fluoride hydroxide hydrate level of at least about 100. 0 o 0

9. The process of claim 8 wherein a residual fraction is recovered from step and said residual fraction is recycled to the hydroisomerization zone. The process of claim 9 wherein the effluent from the hydroisomerization zdne is contacted with hydrogen and a hydrogenation catalyst under mild hydrofinishing conditions including a temperature of d:V

22- about 340F 450F and a pressure abOt 300 psi 1500 psi. 11. The process of claim 10 wherein the hydrogenation catalyst is a fluorided Group VIII metal on an alumina-containing base catalyst. 12. The process of claim 11 wherein the dewaxed lubricating oil recovered has a viscosity index of at least 140 and a pour point less than abou -6'F. 13. The process of claim 12 wherein the S'b Group VIII metal present on the hydrogenation catalyst oo000 9 S0 o is platinum. o0 o0. 0 o f O i 14. A process -fr- producing a lubricating oil having a high viscosity index and a low pour point from a Fischer-Tropsch wax, which process comprises: a 0 contacting the Fischer-Tropsch wax with an unsulfided hydrotreating catalyst and hydrogen to 0 60 o, reduce the oxygenate and trace metal levels of the wax .O and to partially hydrocrack and isomerize the wax; contacting the hydrotreated Fischer- 00 with hydrogen in a hydro- *oo0 Tropsch wax from step with hydrogen in a hydro- isomerization zone in the presence of a fluorided platinum-on-alumina catalyst having a bulk fluoride 0 concentration ranging from a4t- 2 to -abut 10 weight percent, wherein the fluoride concentration is less than a~b t 3.0 weight percent at the outer surface layer to a depth less than one one hundredth of an inch, provided the surface fluoride concentration is less than the bulk fluoride concentration, (ii) an aluminum fluoride hydrate level greater than 60 where an aluminum fluoride hydrate level of 100 corresponds to the X-ray diffraction peak height of 5.66A for a Reference Standard, and (iii) a N/Al ratio less than -fbitt 0.005, Ir ~3 :V 23 contacting the isomerate from step (b) with hydrogen and the platinum-on-alumina catalyst defined in step in a hydrofinishing zone run at mild conditions to reduce unsaturation of the isomerate and thereby improve its dalight stability and oxida- tion stability, fractionating the effluent from step (c) to produce a lubricating oil fraction boiling above -abet-700'F at atmospheric pressure; and dewaxing the lubricating oil fraction from step to produce a dewaxed lubricating oil having a viscosity index of at least 140 and a pour point less than about -6"F. The process of claim 14 wherein abot 30 wt% of the Fischer-Tropsch wax introduced into the hydroisomerization zone is converted therein to distil- o y e late and lower boiling material. SDATED THIS 15th day of December, 1988 EXXON RESEARCH AND ENGINEERING COMPANY EDWD. WATERS SONS, SPATENT ATTORNEYS, QUEEN STREET, MELBOURNE. VIC. 3000. i Ile t I