US3532619A - Hydrocatalytic treatment wherein temperatures are modified when changing feedstocks - Google Patents

Hydrocatalytic treatment wherein temperatures are modified when changing feedstocks Download PDF

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US3532619A
US3532619A US565585A US3532619DA US3532619A US 3532619 A US3532619 A US 3532619A US 565585 A US565585 A US 565585A US 3532619D A US3532619D A US 3532619DA US 3532619 A US3532619 A US 3532619A
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feedstock
treated
wax
colour
oil
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US565585A
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Howard Rees
Brian Linwood Wright
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BP PLC
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BP PLC
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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

  • the problem occurs when changing from microcrystalline to crystalline wax or from solvent treated to nonsolvent treated lub oils.
  • the temperature is raised to 750 F. maximum for 5-50 hours in the presence of a bufier feedstock (e.g., vacuum gas oil) or the new wax or lube oil feedstock.
  • the pressure may be lowered simultanously with the temperature increase.
  • This invention relates to the mild hydrocatalytic treatment of waxes and lubricating oils to improve colour, colour stability and odour, a treatment commonly referred to as hydrofinishing.
  • hydrofinishing of waxes is coming more into use on a commercial scale, replacing the older method of finishing waxes by treatment with acid and/or a solid adsorbent such a clay.
  • a hydrofinishing process has not only to be able to treat all grades of wax but also to allow changes in the grade of wax being treated on the run (i.e., without taking the plant off-stream).
  • the Waxes can be conveniently divided into two classes.
  • the crystalline waxes are usually obtained from distillate petroleum fractions and consist largely of n-parafiins: the microcrystalline waxes are usually obtained from petroleum residues and contain isoparaffins.
  • the microcrystalline Waxes normally need a higher hydrofinishing temperaturethan the crystalline waxes to give the required improvement in colour.
  • lubricating oils may be divided into two main grades, the nonsolvent treated grades, which are usually the lighter spindle oils and the higher boiling solvent treated grades.
  • the nonsolvent treated grades usually required slightly lower hydrofinishing operating temperatures than the solvent treated grades.
  • Solvent treatment means a preliminary treatment with acid or a 3,532,619 Patented Oct. 6, 1970 selective solvent to reduce the aromatic content of the lubricating oils. The nonsolvent treated grades thus have a higher aromatic content.
  • the present invention is thus concerned with facilitating the change over of feedstocks in hydrofinishing.
  • a process for the hydrocatalytic refining of waxes or lubricating oils at elevated pressure in the presence of hydrogen and a hydrogenation catalyst in which the feedstock is changed from a microcrystalline to a crystalline wax or from a solventtreated to a nonsolvent treated grade of lubricating oil is characterised in that the changeover is effected by discontinuing the passage of the existing feedstock while continuing the passage of hydrogen, substituting a petroleum hydrocarbon feedstock other than the existing feedstock raising the temperature to above that used for the first mentioned feedstock up to a maximum of 750 F. for a period of from 5 to 50 hours and then lowering the temperature and commencing processing of a crystalline wax or nonsolvent treated grade of lubricating oil.
  • the invention thus essentially makes use of a period of high temperature operation at the feedstock changeover during which, it is believed, the desorption of colour-forming bodies from the catalyst is accelerated.
  • the material processed during this high temperature period will contain these colour bodies and hence it is desirable, if possible, to use as the other petroleum hydrocarbon feedstock a material of lower quality and cost than lubricating oil or wax which will not be adversely affected by the presence of colour-forming bodies or which is to be subsequently processed in another unit such as a hydrofiner.
  • This type of other feedstock will hereinafter be referred to as a buffer feedstock and an example of a suitable buffer feedstock is gas oil, particularly a gas oil having a boiling range of 250 to 400 C.
  • a buifer feedstock is particularly conveniently used when hydrofinishing lubricating oils.
  • the other feedstock may be a nonsolvent treated grade of lubricating oil particularly if there is oil of this type available surplus to requirements.
  • the other feedstock is desirably crystalline Wax, particularly the crystalline wax to be subsequently processed.
  • crystalline Wax will be produced with this technique but the raised temperature greatly reduces the off-specification period to one of less than 50 hours and there is still a substantial gain in operating efficiency.
  • hydrofinishing process conditions for wax and lubricating oil may be chosen from the following broad ranges:
  • the ratio by weight of molybdenum oxide to cobalt oxide should be at least 1.5:1 and is preferably at least 3:1 and the amount of iron oxide is desirably in excess of the amount of molybdenum oxide.
  • the support is preferably a refractory oxide selected from Groups II to V of the Periodic Table, particularly one which has a low activity in itself under the hydrogenation conditions used.
  • the preferred support is alumina.
  • the alumina is preferably calcined before the addition of the molybdenum and nickel oxides at a temperature of from 500 to 900 C., particularly from 700 to 900 C.
  • the invention is illustrated by the following comparative examples.
  • Preferred range Particularly preferred range Particularly preferred temperatures are:
  • the hydrogen flow rate and feedstock space velocity may be Wlthm the same ranges as those used for proc' 35 A hydrocatalytic process for the refining of waxes used essing.
  • the pressure may also be within the processing range, but it is preferred, paticularly when treating waxes, to lower the pressure to below the actual processing pressure used, for example to a pressure within the range 0450 p.s.i.g. (127 ats.), particularly 0-250 p.s.i.g. (l-16 ats.).
  • the catalyst may consist of one or more hydrogenating metals on a support, preferably chosen from the metals of Group VIa or VIII of the Periodic Table, or rhenium.
  • the metals, particularly the Group VIa metals, the iron group metals or rhenium may be used in the form of their oxides or sulphides.
  • the amounts of each metal may be within the following ranges:
  • Group VIa metals3-25% wt. calculated as the oxide M003, Cl'203 01' W207.
  • Nickel or cobalt-l% wt. calculated as NiO or C00.
  • Rheniurn125% wt. calculated as R6 0
  • One particularly preferred catalyst especially suitable for wax hydrofinishing, consists of the oxides of nickel and molybdenum on a support.
  • the amount of molybdenum oxide may be from 3 to wt. by weight of total catalyst calculated as M00 and the amount of nickel oxide may be from 3 to 15% wt. calculated as NiO.
  • Particularly preferred catalysts contain from 9 to 15 wt. of molybdenum oxide and from 3 to 5% wt. of nickel oxide.
  • Another particularly preferred catalyst, especially suitable for lubricating oil hydrofinishing consist of the oxides of iron and molybdenum, and preferably also cobalt, on a support.
  • the amounts of the oxides may be:
  • Iron oxide Fe O percent wt.-420 preferably 6-1.5
  • Hydrogen flow rate36 v./ volume of wax (200 s.c.f.b.).
  • a microcrystalline wax having a congealing point of 160 F. and penetration at 25 C. of 25 mm./ 10 as measured by ASTM Test Method D1321/ 57 was first passed over the catalyst at a temperature of 650 F. for a period of 55 hours.
  • the feedstock had a colour of 5.5 and the product a colour of Ll.0 as measured by ASTM Test Method D1500.
  • the feedstock was then changed to a crystalline .wax having a melting point of F. and the temperature lowered to 550 F.
  • the crystalline wax feedstock had a colour of 20.0Y using a Lovibond 18-inch cell. 16 hours after the change of feed the colour was 2.8Y and at 48 hours it was 1.1Y. The desired colour of 0.6Y was not achieved until hours after changeover.
  • the run was repeated again, starting with the microcrystalline wax feedstock using the same conditions.
  • the temperature was, however, raised to 700 F. and the reactor pressure lowered to 400 p.s.i.g. These conditions were held for 20 hours after which the temperature was lowered to 550 F, and the pressure raised to 800 p.s.i.g.
  • the desired colour of 0.6Y was achieved within 40 hours of the changeover of feedstock.
  • the feedstock was then changed to a nonsolvent treated spindle oil having a viscosity of 9.2 cs. at 140 F. and the temperature lowered to 525 F.
  • the spindle oil feedstock had a colour of 2.5 (ASTM D1500) but the colour of the product immediately after the changeover was 3.5 (i .e., worse than that of the feedstock).
  • the product colour gradually improved with time but the desired product colour of 1.0 ASTM was not achieved until 48 hours after changeover.
  • the process being characterized in that the changeover is effected by discontinuing the passage of the first feedstock while continuing the passage of hydrogen, substituting a gas oil or a non-solvent treated grade of lubricating oil when the first feedstock is a solvent-treated grade of lubricating oil, or substituting crystalline wax when the first feedstock is a microcrystalline wax, raising the processing temperature for the substituted feedstock to above that used for the first feedstock, up to a maximum of 750 F. for a period of from 5 to 50 hours, then lowering the processing temperature to the normal processing temperature, and thereafter commencing processing of the second feedstock.
  • thermoforming wax is from 575 to 675 F. and for crystalline wax from 475 to 575 F.
  • the catalyst comprises one or more hydrogenating metals from Groups VIa or VIII of the Periodic Table on a support.
  • a process as claimed in claim 9 wherein the catalyst comprises molybdenum oxide and one or more iron group metals supported on alumina.

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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)
  • Lubricants (AREA)
  • Catalysts (AREA)
US565585A 1965-07-30 1966-07-15 Hydrocatalytic treatment wherein temperatures are modified when changing feedstocks Expired - Lifetime US3532619A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB32646/65A GB1094976A (en) 1965-07-30 1965-07-30 Improvements relating to the hydrocatalytic treatment of waxes

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US3532619A true US3532619A (en) 1970-10-06

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US (1) US3532619A (en, 2012)
AT (1) AT268487B (en, 2012)
BE (1) BE684838A (en, 2012)
DE (1) DE1545247A1 (en, 2012)
DK (1) DK121248B (en, 2012)
ES (1) ES330085A1 (en, 2012)
GB (1) GB1094976A (en, 2012)
NL (1) NL145275B (en, 2012)
NO (1) NO115542B (en, 2012)
YU (1) YU32461B (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048094A (en) * 1974-11-27 1977-09-13 Standard Oil Company (Indiana) Reactivation of hydrotreating catalyst by operating at a temperature in excess of normal operating temperature
US4764265A (en) * 1985-07-26 1988-08-16 Shell Oil Company Process for the manufacture of lubricating base oils

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3089841A (en) * 1959-12-30 1963-05-14 Exxon Research Engineering Co Refining process for petroleum wax
US3094480A (en) * 1960-10-31 1963-06-18 Union Oil Co Hydrodenitrogenation with high molybdenum content catalyst
US3228875A (en) * 1961-03-29 1966-01-11 British Petroleum Co Refining of lubricating oils
US3288704A (en) * 1963-12-26 1966-11-29 Universal Oil Prod Co Auto-regeneration of hydrofining catalysts
US3365385A (en) * 1964-10-06 1968-01-23 Union Oil Co Hydrorefining of petroleum wax fractions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3089841A (en) * 1959-12-30 1963-05-14 Exxon Research Engineering Co Refining process for petroleum wax
US3094480A (en) * 1960-10-31 1963-06-18 Union Oil Co Hydrodenitrogenation with high molybdenum content catalyst
US3228875A (en) * 1961-03-29 1966-01-11 British Petroleum Co Refining of lubricating oils
US3288704A (en) * 1963-12-26 1966-11-29 Universal Oil Prod Co Auto-regeneration of hydrofining catalysts
US3365385A (en) * 1964-10-06 1968-01-23 Union Oil Co Hydrorefining of petroleum wax fractions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4048094A (en) * 1974-11-27 1977-09-13 Standard Oil Company (Indiana) Reactivation of hydrotreating catalyst by operating at a temperature in excess of normal operating temperature
US4764265A (en) * 1985-07-26 1988-08-16 Shell Oil Company Process for the manufacture of lubricating base oils

Also Published As

Publication number Publication date
GB1094976A (en) 1967-12-13
NO115542B (en, 2012) 1968-10-21
BE684838A (en, 2012) 1967-01-30
YU236169A (en) 1974-10-31
YU32461B (en) 1975-04-30
ES330085A1 (es) 1967-06-01
NL145275B (nl) 1975-03-17
DK121248B (da) 1971-09-27
DE1545247A1 (de) 1970-01-29
AT268487B (de) 1969-02-10
NL6610708A (en, 2012) 1967-01-31

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