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US2554282A - Lubricating oil manufacture - Google Patents

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Publication number
US2554282A
US2554282A US696604A US69660446A US2554282A US 2554282 A US2554282 A US 2554282A US 696604 A US696604 A US 696604A US 69660446 A US69660446 A US 69660446A US 2554282 A US2554282 A US 2554282A
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Prior art keywords
lubricating oil
stock
oil
catalyst
per
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US696604A
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Jr Alexis Voorhies
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Standard Oil Development Co
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Standard Oil Development Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44Hydrogenation of the aromatic hydrocarbons
    • C10G45/46Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10Lubricating oil

Definitions

  • My invention relates to improvements in the manufacture of lubricating oils and in particular it relates to correcting or improving the viscosity index of a lubricating oil and at the same time obtaining maximum yields.
  • lubricating oils have been subjected to treatment with phenol for the purpose of dissolving out of the lubricating oil constituents which are detrimental thereto.
  • the ordinary crude lubricating oil stock contains aromatic compounds which render the lubricating oil sensitive to temperature change, that is to say, heating the oil causes it to lower inordinately in viscosity.
  • this is highly undesirable because, for example, when the oil is to be used to lubricate an automobile engine, the high temperatures to which it is subjected on the bearings will cause the oil to become lower in viscosity to the extent that the oil film will be disrupted and to be of insufficient strength to prevent wear.
  • my catalysts are mixtures of metallic sulfides, that is to say, mixtures of sulfides of metals of the sixth and eighth group of the periodic system such as for example amixture. of nickel sulfide and tungsten sulfide.
  • the main object of my present invention therefore is to improve the property of a lubricating oil with respect to its viscosity index or its tend- Lubricating Oil Work-upz ency to decrease rapidly in viscosity as the temperature of the oil increases.
  • l represents a reaction zone containing a body of catalyst.
  • the oil to be treated enters the system through line 3 and is pumped by a pump 4 through a preheater 5 and then discharged into the bottom of I.
  • a hydrogen-containing gas enters the system through line It]
  • pump ll into line 3 where it mixes with the oil and passes with the latter through the preheater into the reaction zone I.
  • product is withdrawn through line [3, passed through a cooler l4 and then separated in a separator I5.
  • separator l5 unconsumed hydrogen is separated and withdrawn through line 20 and pumped by pump 2
  • the oil is withdrawn from separator l5 through line '25 and then discharged into a frac-' tional distillation column 26 where it is separated into four fractions, as follows:
  • Example 1 Catalyst Pressure, pounds per sq. in. gauge H Gas Rate, Cubic feet per barrel Feed.
  • I may use 0.5 to 50 mols NiS per' mol MOSz.
  • other mixtures may involve 0.5 to 50 mols A per mol B in the compound AS-BSz where A is an element of the eighth group of the periodic system and B an element of; the sixth group.
  • Such mixed sulfides have. been employed in the past for selective simple hydrogenation of comparatively low boiling hydrocarbons, but so far as I am aware have not been employed for lubricating oil improvement.
  • ha I c aim is:

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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)

Description

May 22, 1951 A. VOORHIES, JR
LUBRICATING OIL MANUFACTURE Filed Sept. 12, 1946 2 m 9 4 5 2 z a w 6 6 f ,M V 6 d N z 8 Z i a we 2 av w MP0 llll' Patented May 22, 1951 2,554,282 LUBRIGATING on. MANUFACTURE Alexis Voorhies, Jr.,
Baton Rouge, La., assignor to Standard Oil Development Company, a corporation of Delaware Application September 12, 1946, Serial No. 696,604
3 Claims.
My invention relates to improvements in the manufacture of lubricating oils and in particular it relates to correcting or improving the viscosity index of a lubricating oil and at the same time obtaining maximum yields.
Heretofore and prior to my present invention lubricating oils have been subjected to treatment with phenol for the purpose of dissolving out of the lubricating oil constituents which are detrimental thereto. For example, the ordinary crude lubricating oil stock contains aromatic compounds which render the lubricating oil sensitive to temperature change, that is to say, heating the oil causes it to lower inordinately in viscosity. Of course, this is highly undesirable because, for example, when the oil is to be used to lubricate an automobile engine, the high temperatures to which it is subjected on the bearings will cause the oil to become lower in viscosity to the extent that the oil film will be disrupted and to be of insufficient strength to prevent wear. By treating the oil with a phenolic body the oil becomes less sensitive to temperature increase. However, the treatment of a lubricating oil stock with phenol often results in rather poor yields especially if a high degree of improvement is sought, since the phenol treating process merely separates good molecules from bad molecules without efiecting any chemical change. In other words the phenol treating process cannot create any new molecules of improved characteristics.
I am aware that also prior to my present invention others have subjected lubricating oil stocks to hydrogenation in the presence of catalysts for the purpose of rendering the oil less sensitive to viscosity change during an increase in temperature. Improvement of lubricating oils by hydrogenation is a radically different process than phenol treating. Hydrogenation is essentially a chemical process; phenol extraction, a physical process. With hydrogenation, the inferior molecules can be actually upgraded in quality; so that there exists the potentialities, with a superior catalyst, of achieving higher yields at a given lubricating oil quality than obtainable by phenol extraction. The best catalyst heretofore used for improving a lubricating oil by hydrogenation is molybdenum sulfide. I,
have now discovered a new class of catalysts which improves the lubricating oil so as to render it less sensitive to a lowering in viscosity as the temperature increases, and at the same time, gives a higher yield of desired product. Stated briefly at first, my catalysts are mixtures of metallic sulfides, that is to say, mixtures of sulfides of metals of the sixth and eighth group of the periodic system such as for example amixture. of nickel sulfide and tungsten sulfide.
The main object of my present invention therefore is to improve the property of a lubricating oil with respect to its viscosity index or its tend- Lubricating Oil Work-upz ency to decrease rapidly in viscosity as the temperature of the oil increases.
In the accompanying drawing, 1 have shown diagrammatically an apparatus layout in which a modification of my invention may be carried into effect.
In the drawing, l represents a reaction zone containing a body of catalyst. The oil to be treated enters the system through line 3 and is pumped by a pump 4 through a preheater 5 and then discharged into the bottom of I. Meanwhile, a hydrogen-containing gas enters the system through line It], is pumped by pump ll into line 3 where it mixes with the oil and passes with the latter through the preheater into the reaction zone I. Under conditions which will be subsequently described by way of several specific examples, the desired conversion takes place in I, product is withdrawn through line [3, passed through a cooler l4 and then separated in a separator I5. From separator l5 unconsumed hydrogen is separated and withdrawn through line 20 and pumped by pump 2| into line 3 for furtheruse in the process. The oil is withdrawn from separator l5 through line '25 and then discharged into a frac-' tional distillation column 26 where it is separated into four fractions, as follows:
(1) A gas which is withdrawn through line 21,
(2) A naphtha-gas oil fraction, which is withdrawn through line 28,
(3) A light lubricating oil, which is withdrawn through line 29, and
(4) The main product, which is withdrawn through line 36.
Example 1 Catalyst Pressure, pounds per sq. in. gauge H Gas Rate, Cubic feet per barrel Feed.
Feed Rate, Volumes Feed per Volume Catalyst per hour Yield on Feed, Per cent by Volume. Gravity, API Viscosity at F. (Seconds Saybolt Universal) Viscosity at 210 F. (Seconds Saybolt Universal) Viscosity Index 1 Pour, F Flash, F
A. S. T. M.D507-41 vide Ind. and Eng. Chem, vol. 32, pp. 102 107, 1940.
l A. S. T. M.D50T4l vide Ind. and Eng. Chem., vol. 32, pp. 102- 107, 1940.
Example 3 Catalyst MoSz ZNiS-WS:
Pressure, pounds per sq. in. gauge 2, 500 Hi Gas Rate, Cubicieet per barrel Feed 10, 000 Feed Rate, Volume Feed per Volume 2-) Catalyst per Hour 0.6 Max. Temperature, F 720 750 Feed Product Lubricating Oil Work-up:
Yield on Feed, Per cent by Volume. 100 77 Gravity, API 26.0 34. 4 33.0 no Viscosity at 100 F. (Seconds Saybolt Universal) 520 225 230 Viscosity at 210 F. (Seconds Saybolt Universal) 04. 3 50. 9 51.1 Viscosity Index 96 125 123 Pour, "F 120 115 120 Flash, F 480 475 450 3 a LA. S. T. M.D50741 vide Ind. and Eng. Chem., Vol.32, pp. 102- 107, 1,940.
Example 4 Catalyst MOS; ZNiS-WS:
Pressure, pounds per sq. in. gauge z, 500 H Gas Rate, Cubic feet pcrbarrcl Feed. 10, 000 Feed Rate, Volume Feed per Volume Catalyst per Hour 0.6 Max. Temperature, F 750 775 Product Lubricating Oil Work'up:
Yield on Feed, Per cent by Volume. 100 48 Gravity, API 26. 0 36. 1 36. O Viscosity at 100 F. (Seconds Say:
bolt Universal) 520 168 15 9 Viscosity at 210 F. (Seconds Saybolt Univcrsal) G4. 3 47. 0 46. 4 Viscosity Index 133 135 Four, F 120 110 95 Flash, "F 480 440 400 1 A. S. T. M.D50741 vide Ind. and Eng. Ohcin, Vol.32, pp. 102- 107,1940.
It can be seen from the foregoing specific examples that for the same quality of lubricating oil I am enabled by my process employing my catalysts to obtain a much higher yield of desired product. For example, in Example 1 the yield is increased from 48 volume per cent to 63 volume per cent for the same quality oil. In other words, a yield increase of nearly one third. Obviously this is very important from the standpoint of economics. It is not intended herein to limit the catalyst composition to the single formula shown above, but rather to embrace the range of mixed sulfide catalysts commonly employed for effecting saturation of aromatic rings without concomitant excessive destructive hydrogenation. For example I may employ various mixtures of NiS and WS2, such as 0.5 to 50 mols of N18 per mol of W32. Also I may use 0.5 to 50 mols NiS per' mol MOSz. Similarly other mixtures may involve 0.5 to 50 mols A per mol B in the compound AS-BSz where A is an element of the eighth group of the periodic system and B an element of; the sixth group. Such mixed sulfides have. been employed in the past for selective simple hydrogenation of comparatively low boiling hydrocarbons, but so far as I am aware have not been employed for lubricating oil improvement.
Numerous modifications of my invention may made by those who are familiar with this art without departing from the spirit thereof.
ha I c aim is:
1. The method of upgrading a lubricating oil stock which consistsessentially in subjecting said stock to: the influence of hydrogen and mild hydrogenation conditions of temperature and pressure, the presence-of a catalyst which consists essentially of a mixture of two mols of nickel sulfide; and one molof tungsten sulfide for a suflicient period of time to efiect the conversion of a major portion of said stock to a lubricating oil of improved viscosity index and thereafter recovering said-v improved lubricating oil.
2. The method of upgrading a lubricating oil stock which consists essentially in subjecting said stock; to. the influence of hydrogen and mild hydrogenation conditions including temperatures of, about TOW-750 F. in the presence of a catalyst consisting of a mixture of nickel sulfid and tungsten sulfide in the approximate molar ratio of 2:1- for a sufficient period of time to. efiect thecqnversion of a major portion of said stock to.- a lubricating oil of improved viscosity index and; thereafter recovering; said improved lubrie t ng; Oi
3. The; method ofclaim 2 in which said conditionsinclude pressures of about 2590 lbs. per 59;. in, anda lubricating oil stock feed rate of about 0.2-0.6 volumes of feed per volume of catalyst, per hour.
ALEXIS VOORI-IIEKS, JR.
REFERENCES CITED The following. references are of record in the file. of; this. patent:
UNITED STATES PATENTS Number Name Date 1,908,286 Dorrer May 9, 1933 1,932,186. Pier et al. Oct. 24, 1933 1,932,369, Guthke Oct. 24, 1933 1,954,972. Yotmg Apr. 17, 1934 1,963,385 Russell June 19, 1934 2,278,407. Anthes et al Apr. 7, 1942 2,406,200 Cole Aug. 20, 1946 2,409,382 Peck Oct. 15, 1946 FOREIGN PATENTS Number Country Date 333,511 Great Britain Aug. 5, 1930 48846.51. Great Britain July 7, 1938 OTHER. REFERENCES Ellis,- Hydrogenation of' Organic Substances,
3rdedi-tion; 1930; D. VanNostrand' Co., New York, pages 57 6-580".
-Hydrogenation of Petroleum by Haslam. et'
al., Ind: & Eng Chem. vol. 22; No. 10; pages 1030 to 1034, Oct, 1930.

Claims (1)

1. THE METHOD OF UPGRADING A LUBRICATING OIL STOCK WHICH CONSISTS ESSENTIALLY IN SUBJECTING SAID STOCK TO THE INFLUENCE OF HYDROGEN AND MILD HYDROGENATION CONDITIONS OF TEMPERATURE AND PRESSURE IN THE PRESENCE OF A CATALYST WHICH CONSISTS ESSENTIALY OF A MIXTURE OF TWO MOLS OF NICKEL SULFIDE AND ONE MOL OF TUNGSTEN SULFIDE FOR A SUFFICIENT PERIOD OF TIME OF EFFECT THE CONVERSION OF A MAJOR PORTION OF SAID STOCK TO A LUBRICATING OIL OF IMPROVED VISCOSITY INDEX AND THEREAFTER RECOVERING SAID IMPROVED LUBRICATING OIL.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2654696A (en) * 1950-06-02 1953-10-06 Sun Oil Co Treatment of lubricating oil
DE943187C (en) * 1953-05-16 1956-05-17 Standard Oil Dev Co Process for the production of lubricating oils
US2787582A (en) * 1955-04-12 1957-04-02 Universal Oil Prod Co Production of lubricating oils
US2904505A (en) * 1955-06-16 1959-09-15 Texaco Inc Mild hydrogenation process for lubricating oils
US2934492A (en) * 1956-12-03 1960-04-26 Exxon Research Engineering Co Hydrogenation of heavy oils
US2960458A (en) * 1957-08-02 1960-11-15 Gulf Research Development Co Process for preparing a multi-grade lubricating oil and product
US3080313A (en) * 1959-11-24 1963-03-05 Gulf Research Development Co Method of producing a medicinal mineral oil
US3177159A (en) * 1961-12-27 1965-04-06 Shell Oil Co Hydroisomerization of olefin
US3192153A (en) * 1962-11-06 1965-06-29 Socony Mobil Oil Co Inc Preparation of transformer oils
US20040235653A1 (en) * 2003-02-24 2004-11-25 Laszlo Domokos Catalyst composition, its preparation and use
WO2005005582A1 (en) * 2003-07-08 2005-01-20 Shell Internationale Research Maatschappij B.V. Process to prepare a base oil
US20060207917A1 (en) * 2004-09-08 2006-09-21 Laszlo Domokos Hydrocracking catalyst composition

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB333511A (en) * 1929-04-02 1930-08-05 Ig Farbenindustrie Ag Improvements in the manufacture and production of hydrocarbons which are saturated with hydrogen
US1908286A (en) * 1928-12-03 1933-05-09 Ig Farbenindustrie Ag Production of hydrocarbons
US1932369A (en) * 1927-06-24 1933-10-24 Ig Farbenindustrie Ag Removal of sulphur compounds from crude hydrocarbons
US1932186A (en) * 1927-11-19 1933-10-24 Standard Ig Co Production of refined hydrocarbon oils
US1954972A (en) * 1929-07-22 1934-04-17 Standard Ig Co Hydrogenation of oils
US1963385A (en) * 1930-01-08 1934-06-19 Standard Ig Co Process for producing lubricants by hydrogenation of hydrocarbon oils
GB488651A (en) * 1936-12-07 1938-07-07 Ig Farbenindustrie Ag Improvements in or relating to the production of hydrocarbon products of low boilingpoint by the treatment of carbonaceous materials of elevated temperatures
US2278407A (en) * 1940-04-05 1942-04-07 Ig Farbenindustrie Ag Thermal treatment of carbonaceous materials
US2406200A (en) * 1944-11-27 1946-08-20 Shell Dev Catalytic treatment of hydrocarbon oils
US2409382A (en) * 1942-03-11 1946-10-15 Standard Catalytic Co Aviation gasoline production

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1932369A (en) * 1927-06-24 1933-10-24 Ig Farbenindustrie Ag Removal of sulphur compounds from crude hydrocarbons
US1932186A (en) * 1927-11-19 1933-10-24 Standard Ig Co Production of refined hydrocarbon oils
US1908286A (en) * 1928-12-03 1933-05-09 Ig Farbenindustrie Ag Production of hydrocarbons
GB333511A (en) * 1929-04-02 1930-08-05 Ig Farbenindustrie Ag Improvements in the manufacture and production of hydrocarbons which are saturated with hydrogen
US1954972A (en) * 1929-07-22 1934-04-17 Standard Ig Co Hydrogenation of oils
US1963385A (en) * 1930-01-08 1934-06-19 Standard Ig Co Process for producing lubricants by hydrogenation of hydrocarbon oils
GB488651A (en) * 1936-12-07 1938-07-07 Ig Farbenindustrie Ag Improvements in or relating to the production of hydrocarbon products of low boilingpoint by the treatment of carbonaceous materials of elevated temperatures
US2278407A (en) * 1940-04-05 1942-04-07 Ig Farbenindustrie Ag Thermal treatment of carbonaceous materials
US2409382A (en) * 1942-03-11 1946-10-15 Standard Catalytic Co Aviation gasoline production
US2406200A (en) * 1944-11-27 1946-08-20 Shell Dev Catalytic treatment of hydrocarbon oils

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2654696A (en) * 1950-06-02 1953-10-06 Sun Oil Co Treatment of lubricating oil
DE943187C (en) * 1953-05-16 1956-05-17 Standard Oil Dev Co Process for the production of lubricating oils
US2787582A (en) * 1955-04-12 1957-04-02 Universal Oil Prod Co Production of lubricating oils
US2904505A (en) * 1955-06-16 1959-09-15 Texaco Inc Mild hydrogenation process for lubricating oils
US2934492A (en) * 1956-12-03 1960-04-26 Exxon Research Engineering Co Hydrogenation of heavy oils
US2960458A (en) * 1957-08-02 1960-11-15 Gulf Research Development Co Process for preparing a multi-grade lubricating oil and product
US3080313A (en) * 1959-11-24 1963-03-05 Gulf Research Development Co Method of producing a medicinal mineral oil
US3177159A (en) * 1961-12-27 1965-04-06 Shell Oil Co Hydroisomerization of olefin
US3192153A (en) * 1962-11-06 1965-06-29 Socony Mobil Oil Co Inc Preparation of transformer oils
US20040235653A1 (en) * 2003-02-24 2004-11-25 Laszlo Domokos Catalyst composition, its preparation and use
US7557062B2 (en) 2003-02-24 2009-07-07 Shell Oil Company Catalyst composition, its preparation and use
US20090239743A1 (en) * 2003-02-24 2009-09-24 Laszlo Domokos Catalyst composition, its preparation and use
US7749937B2 (en) 2003-02-24 2010-07-06 Shell Oil Company Catalyst composition, its preparation and use
WO2005005582A1 (en) * 2003-07-08 2005-01-20 Shell Internationale Research Maatschappij B.V. Process to prepare a base oil
US20060207917A1 (en) * 2004-09-08 2006-09-21 Laszlo Domokos Hydrocracking catalyst composition
US7648939B2 (en) 2004-09-08 2010-01-19 Shell Oil Company Hydrocracking catalyst composition

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