US2756183A - Hydrotreating lubricating oil to improve color and neutralization number using a platinum catalyst on alumina - Google Patents

Hydrotreating lubricating oil to improve color and neutralization number using a platinum catalyst on alumina Download PDF

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Publication number
US2756183A
US2756183A US287523A US28752352A US2756183A US 2756183 A US2756183 A US 2756183A US 287523 A US287523 A US 287523A US 28752352 A US28752352 A US 28752352A US 2756183 A US2756183 A US 2756183A
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United States
Prior art keywords
lubricating oil
neutralization number
alumina
hydrogen
catalyst
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US287523A
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English (en)
Inventor
Jr William T Knox
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Publication date
Priority to NL94402D priority Critical patent/NL94402C/xx
Priority to NLAANVRAGE7809547,C priority patent/NL177372B/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US287523A priority patent/US2756183A/en
Priority to GB5551/53A priority patent/GB737020A/en
Priority to FR1079926D priority patent/FR1079926A/fr
Priority to DEST6376A priority patent/DE961479C/de
Application granted granted Critical
Publication of US2756183A publication Critical patent/US2756183A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • 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 present invention is concerned with a process for the hydrofining of hydrocarbons boiling in the lubricating oil boiling range.
  • the invention is more particularly concerned with the use of a platinum catalyst utilizing .mild hydrofining conditions.
  • improved lubricating oil products are secured by mildly hydrofining hydrocarbons boiling in the lubricating oil boiling range utilizing a platinum catalyst.
  • the hydrogen consumption is maintained below about 150 cu. .ft. per ban rel at standard conditions, preferably below about 75 cu. ft. per barrel.
  • the neutralization number is an indication of the quantity of acidic materials present, usually naphthenic acids and related compounds.
  • the naphthenic acids are very undesirable in a lubricating oil since under operating conditions of high temperatures and pressures they tend to cause excessive corrosion and sludging in the engine.
  • Manufacturing experience has shown that a high viscosity index is not required in many lubricating oils if other properties are provided. For instance, when solvent extracting lube distillate fractions secured from coastal crudes boiling in the lubricating oil boiling range with phenol to a viscosity index of 60, the neutralization number is reduced to only about .2. This is not a satisfactory lubricating oil product as regards neutralization number and viscosity index is higher than required.
  • the lubricat ing feed oils from these sources have initial neutralization numbers of about .7 and above.
  • present invention is particularly adapted for the processing of lubricating oil feed fractions which have neutralization numbers above about 0.5, particularly above about 0.7.
  • a .feed oil comprising lubricating oil constituents is introduced into distillation zone 1 by means of feed line 2. Temperature and pressure conditions are adjusted in zone 1 to remove overhead by means of line 3, normally gaseous hydrocarbons. Hydrocarbons boiling in the motor fuel boiling range are removed by means of line 4 while gas oil constituentsare removed by means of line 5 and passed to a cracking zone. A residuum fraction is removed by means of line 6 while a hydrocarbon fraction boiling in the lubricating .oil boiling range (about 700 F. to 1l00 F. at 760 mm. pressure) is removed by means of line 7. In accordance with the present invention, this lubricating oil fraction is passed into zone 8 wherein temperature and pressure and other operating conditions are adjusted to secure a mild hydrofining operation, which will be hereinafter described.
  • the hydrofined product is withdrawn from zone '8 by means of line 9, passed through a cooling zone 10 and then introduced into a hydrogen separation zone 11. Hydrogen is removed overhead from separation zone 11 by means of line 12, recompressed in compressor zone 13 and then preferably recycled to Zone 8 by means of line 14 with the fresh hydrogen feed which is introduced into zone 8 by means of line 15. Y
  • the refined product free of hydrogen is removed from the bottom of zone 11 by means of line 16 and introduced into .a separation zone 17. Temperature and pressureconditions in zone 17 are adapted to remove overhead by means of line 18 hydrogen sulfide and any light or .low boiling hydrocarbons. Steam may be introduced into zone 17 by means of line 19. A hydrofined lubricating oil product of a low neutralization number, below about 0.1 and having a satisfactory color, is withdrawn from zone 17 by means of line 20.
  • the present invention is broadly concerned with the mild hydrofining of hydrocarbon oil fractions boiling in the lubricating oil boiling range.
  • oils are normally virgin distillates having viscosities at 100 F. in the range from about 100 to 1000 Saybolt seconds, viscosity indexes in the range from about 50 to 50 and boil above about 700 F. at 760 mm. pressure.
  • these oils boil in the range from about 700 F. to 1100 F. at 760 .mm. pressure.
  • the catalyst comprises a platinum catalyst supported on a solid carrier.
  • the carrier preferably comprises alumina or silica gel.
  • the amount of catalyst by weight based upon the carrier such as alumina is in the range from about .05 to 1.0%.
  • One method of preparing the catalyst is to activate a carrier such as alumina by calcining the same.
  • the alumina is then impregnated with an aqueous solution of chlor platinic acid to secure a paste.
  • the impregnated alumina is then dried at a temperature in the range from about room temperature to 250 F.
  • the dried material is then calcined very slowly wherein the temperature is raised from about 50 to per hour ing oil fraction is mildly hydrofined.
  • the hydrofined lubricating oil after removal from the hydrofining zone may be further treated to remove small traces of dissolved hydrogen sulfide.
  • the hydrofined lube oil may be caustic-washed.
  • the hydrofining operation conducted on the lubricating oil be a mild hydrofining operation utilizing a platinum catalyst preferably supported on alumina.
  • Such hydrofining operations previously employed have utilized pressures in the range from about 200 to 500 lbs. p. s. i. at feed rates of .5 to 2.0 volumes of feed per volume of catalyst per hour.
  • Relatively high rates of hydrogen recycle have been employed, as for example, 2,000 to 4,000 standard cu. ft. per barrel in order to prevent carbonization of the catalyst.
  • very active catalysts have been used which are effective for desulfurization.
  • the catalyst heretofore employed has been a cobalt molybdate supported on a carrier, as for example alumina.
  • the mild hydrofining conditions of the present invention may be secured by lowering the temperature, increasing the feed rate per volume of catalyst or by using a less active catalyst.
  • the temperatures used are in the range from about 400 to 700 F., preferably in the range from about 600 F. to 700 F.
  • Pressures employed are in the range from about 50 to 250 lbs. per sq. in., preferably in the range from about 100 to 200 lbs. per sq. in.
  • the feed rates, in accordance with the present process are in the range from about .5 to 5 volumes of liquid per volume of catalyst per hour. Preferred feed rates are in the range from 1 to 2 v./v. hr.
  • the hydrogen in the gas to the hydrofining unit may vary from 50 to 100%. This means that, for example, dilute hydrogen from a hydroformer can be used in the hydrofining process.
  • the mild hydrofining conditions of the present invention are secured by the interadjustment of the above enumerated operating conditions. For instance, if a relatively high liquid feed rate is used as compared to the amount of catalyst present, the higher temperature range may be employed.
  • the mild hydrofining conditions of the present invention are measured by the amount of hydrogen consumption per barrel of oil feed.
  • conventional hydrofining operations utilized for the desulfurization of certain stocks are conducted under conditions whereby the hydrogen consumption ranges from 200 to 600 standard cu. ft. of hydrogen per barrel of oil. These operations used heretofore in the art secured a substantial sulfur reduction (50 to 90%). In accordance with the present.
  • operating conditions are adjusted so that the hydrogen consumption in standard cu. ft. per barrel does not exceed 150 and is preferably less than 75 cu. ft. per barrel.
  • the extent of the sulfur reduction when utilizing the mild hydrofining conditions of the present invention does not exceed about 35% and preferably does not exceed about 25%.
  • Another indication of the extent to which hydrofining conditions are adjusted to secure a mild hydrofining operation is that the viscosity index of the oil is not increased above about 25 and is preferably increased to an extent less than about 20 points.
  • Example A lubricating 011 having the following inspections:
  • the process of producing high quality lubricating oil of improved color and low neutralization number which comprises: treating a lubricating oil having a neutralization number above about 0.5 with hydrogen in contact with a catalyst consisting of about 0.05 to 1.0% of platinum supported on active alumina at controlled hydrogenation conditions selected from the range of 400-700 F., 50-250 p. s. i., and 0.5-5 volumes of liquid feed per volume of catalyst per hour, characterized by a hydrogen consumption of less than about standard cubic feet per barrel, a sulfur reduction which does not exceed about 37%, and an increase in viscosity index which does not exceed about 25.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
US287523A 1952-05-13 1952-05-13 Hydrotreating lubricating oil to improve color and neutralization number using a platinum catalyst on alumina Expired - Lifetime US2756183A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL94402D NL94402C (en)) 1952-05-13
NLAANVRAGE7809547,C NL177372B (nl) 1952-05-13 Bijzondere abonneelijn met een vierdraadssectie.
US287523A US2756183A (en) 1952-05-13 1952-05-13 Hydrotreating lubricating oil to improve color and neutralization number using a platinum catalyst on alumina
GB5551/53A GB737020A (en) 1952-05-13 1953-02-27 Improvements in or relating to hydrotreating lubricating oils
FR1079926D FR1079926A (fr) 1952-05-13 1953-04-03 Procédé d'hydroraffinage d'huiles lubrifiantes
DEST6376A DE961479C (de) 1952-05-13 1953-05-09 Verfahren zur Herstellung hochwertiger Schmieroele

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US287523A US2756183A (en) 1952-05-13 1952-05-13 Hydrotreating lubricating oil to improve color and neutralization number using a platinum catalyst on alumina

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US2756183A true US2756183A (en) 1956-07-24

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DE (1) DE961479C (en))
FR (1) FR1079926A (en))
GB (1) GB737020A (en))
NL (2) NL177372B (en))

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900332A (en) * 1955-04-06 1959-08-18 British Petroleum Co Hydrocatalytic desulfurization of gas oil
US2944014A (en) * 1956-12-10 1960-07-05 Sun Oil Co Obtaining neutral distillates from petroleum
US2967816A (en) * 1957-07-23 1961-01-10 Sinclair Refining Co Process for decolorizing petroleum resins and products obtained by adding the decolorized resins to fuel oil
US3658692A (en) * 1969-10-28 1972-04-25 Exxon Research Engineering Co Preparation of white oils with aluminum-alkyl activated iron group metal catalysts
US3979279A (en) * 1974-06-17 1976-09-07 Mobil Oil Corporation Treatment of lube stock for improvement of oxidative stability
US5158671A (en) * 1987-12-18 1992-10-27 Exxon Research And Engineering Company Method for stabilizing hydroisomerates
US6274029B1 (en) 1995-10-17 2001-08-14 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US6309432B1 (en) 1997-02-07 2001-10-30 Exxon Research And Engineering Company Synthetic jet fuel and process for its production
US6822131B1 (en) 1995-10-17 2004-11-23 Exxonmobil Reasearch And Engineering Company Synthetic diesel fuel and process for its production

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1134468B (de) * 1956-05-28 1962-08-09 British Petroleum Co Verfahren zur Verbesserung der Farbe und Oxydationsstabilitaet von Schmieroelen
DE1174007B (de) * 1959-05-16 1964-07-16 Universal Oil Prod Co Verfahren zur Herstellung von Schmieroel

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542471A (en) * 1946-06-15 1951-02-20 Standard Oil Dev Co Removal of peroxides from cracked gasoline by catalytic hydrogenation
US2574331A (en) * 1947-10-29 1951-11-06 Standard Oil Dev Co Hydrogenation of unstable petroleum wax

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR376496A (fr) * 1906-06-14 1907-08-10 Albin Haller Procédé d'épuration et de désodorisation des huiles de pétrole, essences, éthers, benzine, huiles de schistes, de résines et produits similaires

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542471A (en) * 1946-06-15 1951-02-20 Standard Oil Dev Co Removal of peroxides from cracked gasoline by catalytic hydrogenation
US2574331A (en) * 1947-10-29 1951-11-06 Standard Oil Dev Co Hydrogenation of unstable petroleum wax

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900332A (en) * 1955-04-06 1959-08-18 British Petroleum Co Hydrocatalytic desulfurization of gas oil
US2944014A (en) * 1956-12-10 1960-07-05 Sun Oil Co Obtaining neutral distillates from petroleum
US2967816A (en) * 1957-07-23 1961-01-10 Sinclair Refining Co Process for decolorizing petroleum resins and products obtained by adding the decolorized resins to fuel oil
US3658692A (en) * 1969-10-28 1972-04-25 Exxon Research Engineering Co Preparation of white oils with aluminum-alkyl activated iron group metal catalysts
US3979279A (en) * 1974-06-17 1976-09-07 Mobil Oil Corporation Treatment of lube stock for improvement of oxidative stability
US5158671A (en) * 1987-12-18 1992-10-27 Exxon Research And Engineering Company Method for stabilizing hydroisomerates
US6274029B1 (en) 1995-10-17 2001-08-14 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US6296757B1 (en) 1995-10-17 2001-10-02 Exxon Research And Engineering Company Synthetic diesel fuel and process for its production
US6607568B2 (en) 1995-10-17 2003-08-19 Exxonmobil Research And Engineering Company Synthetic diesel fuel and process for its production (law3 1 1)
US6822131B1 (en) 1995-10-17 2004-11-23 Exxonmobil Reasearch And Engineering Company Synthetic diesel fuel and process for its production
US6309432B1 (en) 1997-02-07 2001-10-30 Exxon Research And Engineering Company Synthetic jet fuel and process for its production
US6669743B2 (en) 1997-02-07 2003-12-30 Exxonmobil Research And Engineering Company Synthetic jet fuel and process for its production (law724)

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Publication number Publication date
GB737020A (en) 1955-09-21
FR1079926A (fr) 1954-12-03
NL94402C (en))
DE961479C (de) 1957-04-04
NL177372B (nl)

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