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US2973317A - Refining raw lube oil stock with a mild hydrogen treatment followed by sulfuric acid - Google Patents

Refining raw lube oil stock with a mild hydrogen treatment followed by sulfuric acid Download PDF

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Publication number
US2973317A
US2973317A US713539A US71353958A US2973317A US 2973317 A US2973317 A US 2973317A US 713539 A US713539 A US 713539A US 71353958 A US71353958 A US 71353958A US 2973317 A US2973317 A US 2973317A
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United States
Prior art keywords
oil
acid
sulfuric acid
lube oil
hydrogen treatment
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US713539A
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William B Watson
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Sinclair Refining Co
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Sinclair Refining 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
    • C10G17/00Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/02Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acids or acid-containing liquids, e.g. acid sludge
    • C10G17/04Liquid-liquid treatment forming two immiscible phases
    • C10G17/06Liquid-liquid treatment forming two immiscible phases using acids derived from sulfur or acid sludge thereof

Definitions

  • Sulfuric acid strength can vary, in general, from about 85 weight percent to Weight percent oleum, but 93 to 98 Weight percent sulfuric acid is most often employed.
  • the hydrogenation step of my process involves employing a hydrogenation catalyst.
  • a hydrogenation catalyst Various methods for manufacturing such catalysts have been described in the art, such as in Byrns Patent 2,325,033, and such catalysts generally consist of from about 2 to 5 percent by weight of cobalt oxide and 5 to 15 percent by weight of molybdic oxide, the balance being alumina.
  • Also useful are, for instance, nickel on porcelain, silica or alumina; molybdenum, tungsten, cobalt, nickel oxides and sulfides; and, platinum and palladium on alumina.
  • a preferred catalyst is cobalt molybdate supported'on :aluminapr'epared by the method .of Keith .et al. described in copending application .Ser. .No. 612,892, .filedSeptemb'er 28, 1956;
  • R .apressure of from 400 to 1500. p.s.i.g. and a weight hourly-spacevelocity (weightunits of .oilper weight unit of catalyst per hour) of .from 0.5 .to 5.0 .are used.
  • the oil is hydrogenated while itis in admixture with from 700 to 5000 standard cubic feet of hydrogen per'barrel o f oil;v
  • the first distillate portion was then hydrogenated With 1500 standard cubic feet of hydrogen per barrel 'of'dis; tillate at a temperature of 700 F. and a pressure of 500 p.s.i.g. by passing it into contact with a cobalt molybdate on alumina catalyst at a weight hourly space velocity of 3.0.
  • the catalyst used analyzed, on an ignited basis, 2.45 weight percent cobalt, 8.53 Weight percent molybdic oxide and the remainder alumina.
  • the steam-stripped, hydrogenated oil wassubjected to sulfuric acid treatment.
  • the strength of the acid employed was 98 Weight percent and the acid dosage was 16 pounds of acid per barrel of oil.
  • the acid oil mixture was mixed for 45 minutes at a temperature of from to F. It was then allowed to settle for 16 hours and sludge was drawn olf. The acid oil mixture was then subjected to an air blow for 2 hours and again allowed is not essential to the process.
  • acid treated, neutralized, contacted oil were as follows:
  • the second portion of the vacuum distilled Gulf Coast reduced crude oil was acid treated by the same procedure employed for the first portion, but without prior hydrogenation. In this instance, 32 pounds of 98 weight percent sulfuric acid per barrel of distillate were required and the yield of finished oil, i.e., after neutralization, was 86.0 percent by weight. Such finished oil had the follow- Thus, a comparison of the procedures used on and the products derived from the two portions of Gulf Coast The characteristics of the 4 v reduced crude vacuum distillate shows that, although the products are essentially equivalent in degree of refining in terms of viscosity indices, specific dispersions and aniline points, the product of my process of hydrogenating before acid treating and neutralizing required one-half of the acid used in the known process of acid treating and neutralizing. In addition, the yields, when employing my process, were 5.4 percent higher than that of when the old process was employed.
  • the steps consisting essentially of passing the lubricating oil and hydrogen into contact with a hydrogenation catalyst at a temperature within the range from 550 F. to 750 F. and at a pressure within the range 400 to 1500 p.s.i.g. to provide a hydrogenated oil and then treating the hydrogenated oil with sulfuric acid to provide an acid oil, said raw lubricating oil being derived from a naphthenic base crude selected from the group consisting of Gulf Coast and California crudes.

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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

REFINING RAW LUBE OIL STOCK WITH A .MILD
HYDROGEN TREATMENT'FOLLOWED BY SUL- FURICACID William B. Watson, Park Forest, IlL, assignor to Sinclair Refining Company, New York, N.Y., a corporation of Maine- No Drawing. Filed Feb. 6, 1958, Ser. No. 713,539
2 Claims. (Cl. 208-264) sultant sludge to 'producean acid oil layer, removing the sludge, neutralizing the sulfonic acids and unreacted sulfuric acid present in the'acid oil layer with a base material such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or sodium carbonate in Water solution, e.g., 20 percent solution, and water washing to remove excess base and toyielda neutral oil. The amount of acid required depends upon the strength of the acid employed, and the viscosity of the distillate being treated. Acid dosages can vary over a wider range, but, in general, vary from about 5 pounds per barrel of 50 SUS/ 100 F. (ASTM D 88) distillate to about 50 pounds per barrel of 6,000 SUS/ 100 F. distillate. Sulfuric acid strength can vary, in general, from about 85 weight percent to Weight percent oleum, but 93 to 98 Weight percent sulfuric acid is most often employed.
There are numerous modifications for sulfuric acidtreating oils and removing the sludge formed by the acid treatment. However, regardless of these modifications, this process has a major drawback in that a substantial quantity of, for instance, a raw lube fraction is converted to a sludge material of little or no value.
I have now found that, if the raw stock is hydrogenated prior to the sulfuric acid-treating step, higher yields of finished oil are obtained and, in addition, lesser amounts of acid are required in the acid-treating step. By increasing the yield on acid-treating and decreasing the amounts of acid required, the overall costs of my process are considerably less than those of a straight sulfuric acid-treating process.
My process has been found to be particularly eiiective in the preparation of lubricating oils from distillates'of naphthenic base crudes, e.g., Gulf Coast and California crudes. Such crude oils, if they contain wax, are, preferably, dewaxed prior to the hydrogenation step and the acid-treating step, although the dewaxing can follow the hydrogenation operation. This dewaxing can be carried out, for example, by solvent dewaxing using methyl ethyl ketone and toluene as the solvent to achieve oil of below F. pour point (ASTM D 97). The pour point after dewaxing is determined by that required in the finished oil.
The hydrogenation step of my process involves employing a hydrogenation catalyst. Various methods for manufacturing such catalysts have been described in the art, such as in Byrns Patent 2,325,033, and such catalysts generally consist of from about 2 to 5 percent by weight of cobalt oxide and 5 to 15 percent by weight of molybdic oxide, the balance being alumina. Also useful are, for instance, nickel on porcelain, silica or alumina; molybdenum, tungsten, cobalt, nickel oxides and sulfides; and, platinum and palladium on alumina. A preferred catalyst is cobalt molybdate supported'on :aluminapr'epared by the method .of Keith .et al. described in copending application .Ser. .No. 612,892, .filedSeptemb'er 28, 1956;
Further, inthe hydrogenation step of .my. process, a temperature of from 550 to 75.0". R, .apressure of from 400 to 1500. p.s.i.g. anda weight hourly-spacevelocity (weightunits of .oilper weight unit of catalyst per hour) of .from 0.5 .to 5.0 .are used. The oil is hydrogenated while itis in admixture with from 700 to 5000 standard cubic feet of hydrogen per'barrel o f oil;v
'A'specific example which 'illustrates-lriyprocess and compares it with the known process of acidtreating and then neutralizing .a charge stock without a .prior hydrogenation is as follows: a
Two portions of Gulf Coast reduced crude were vacuum distilled to yield distillate portions having'the following characteristics:
Gravity, API(ASTM D287) I 19.9 Flash, F.'(ASTM D '92 440 Viscosity, SUS/l'0'0" F. (ASTM 'D'88)' 159.4 Viscosity,'SUS/2l0 F. (ASTM'D'88) '8l.12 Viscosity index (ASTM D 567) 9.9 Pour, (ASTM'D '97) f5-'- ColorfNPA (ASTM D155) '8- Specific dispersion 5,141.9 Aniline point, 1C. 1(A-STM .D.-.6l 1:).
Reference: The Chemical Constituents of Petroleum, by A. N. Sachanen, page 109, published by. Reinhold Publishing Corporation in 1945. and'E lines of mercury were used in refractometer measurements and temperature was 20 C.
The first distillate portion was then hydrogenated With 1500 standard cubic feet of hydrogen per barrel 'of'dis; tillate at a temperature of 700 F. and a pressure of 500 p.s.i.g. by passing it into contact with a cobalt molybdate on alumina catalyst at a weight hourly space velocity of 3.0. The catalyst used analyzed, on an ignited basis, 2.45 weight percent cobalt, 8.53 Weight percent molybdic oxide and the remainder alumina.
The weight yield of hydrogenated distillate after being lightly steam stripped was 99.9 percent, and the resulting product had the following characteristics:
The steam-stripped, hydrogenated oil wassubjected to sulfuric acid treatment. The strength of the acid employed was 98 Weight percent and the acid dosage Was 16 pounds of acid per barrel of oil. The acid oil mixture was mixed for 45 minutes at a temperature of from to F. It was then allowed to settle for 16 hours and sludge was drawn olf. The acid oil mixture was then subjected to an air blow for 2 hours and again allowed is not essential to the process. acid treated, neutralized, contacted oil were as follows:
Gravity, API 21.3 Flash, F. 425 Viscosity, SUS/ 100 F. 1205 Viscosity, SUS/210 F. 74.47 Viscosity index 24.8 Pour, F. Color, NPA 2+ Specific dispersion 131.4 Aniline point, C. 91.4
The second portion of the vacuum distilled Gulf Coast reduced crude oil was acid treated by the same procedure employed for the first portion, but without prior hydrogenation. In this instance, 32 pounds of 98 weight percent sulfuric acid per barrel of distillate were required and the yield of finished oil, i.e., after neutralization, was 86.0 percent by weight. Such finished oil had the follow- Thus, a comparison of the procedures used on and the products derived from the two portions of Gulf Coast The characteristics of the 4 v reduced crude vacuum distillate shows that, although the products are essentially equivalent in degree of refining in terms of viscosity indices, specific dispersions and aniline points, the product of my process of hydrogenating before acid treating and neutralizing required one-half of the acid used in the known process of acid treating and neutralizing. In addition, the yields, when employing my process, were 5.4 percent higher than that of when the old process was employed.
I claim:
1. In the refining of a raw petroleum lubricating oil, the steps consisting essentially of passing the lubricating oil and hydrogen into contact with a hydrogenation catalyst at a temperature within the range from 550 F. to 750 F. and at a pressure within the range 400 to 1500 p.s.i.g. to provide a hydrogenated oil and then treating the hydrogenated oil with sulfuric acid to provide an acid oil, said raw lubricating oil being derived from a naphthenic base crude selected from the group consisting of Gulf Coast and California crudes.
2. The method of claim 1 wherein said catalyst is cobalt molybdate supported on alumina.
References Cited in the file of this patent UNITED STATES PATENTS 1,847,623 Ott Mar. 1, 1932 2,692,226 Smith Oct. 19, 1954 2,706,167 Harper et a1. Apr. 12, 1955 2,779,711 Goretta Ian. 29, 1957 2,779,713 Cole et al J an. 29, 1957

Claims (1)

1. IN THE REFINING OFD A RAW PETROLEUM LUBRICATING OIL, THE STEPS CONSISTING ESSENTIALLY OF PASSING THE LUBRICATING OIL AND HYDROGEN INTO CONTACT WITH A HYDROGENATION CATALYST AT A TEMPERATURE WITHIN THE RANGE FROM 550* F. TO 750* F. AND AT A PRESSURE WITHIN THE RANGE 400 TO 1500 P.S.I.G. TO PROVIDE A HYDROGENATED OIL AND THEN TREATING THE HYDROGENATED OIL WITH SULFURIC ACID TO PROVIDE AN ACID OIL, SAID RAW LUBRICATING OIL BEING DERIVED FROM A NAPHTHENIC BASE CRUDE SELECTED FROM THE GROUP CONSISTING OF GULF COAST AND CALIFORNIA CRUDES.
US713539A 1958-02-06 1958-02-06 Refining raw lube oil stock with a mild hydrogen treatment followed by sulfuric acid Expired - Lifetime US2973317A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085061A (en) * 1959-05-20 1963-04-09 Exxon Research Engineering Co Shale oil refining process
US3487012A (en) * 1968-02-23 1969-12-30 Marathon Oil Co Processes for the improvement of initial color and long-term color stability of aromatic concentrates
US3549520A (en) * 1968-07-19 1970-12-22 Texaco Inc Color improvement of sulfur-containing lubricating oils with a mordenite type zeolite
US4786405A (en) * 1986-03-04 1988-11-22 Al Sanea Chemical Products Method of desulfurizing and deodorizing sulfur bearing hydrocarbon feedstocks

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1847623A (en) * 1929-07-15 1932-03-01 Union Oil Co Method of treating oil
US2692226A (en) * 1950-10-07 1954-10-19 Standard Oil Dev Co Shale oil refining process
US2706167A (en) * 1950-06-16 1955-04-12 Sun Oil Co Process for hydrogenating hydrocarbon oils
US2779711A (en) * 1955-02-28 1957-01-29 Standard Oil Co Refining of lubricating oils
US2779713A (en) * 1955-10-10 1957-01-29 Texas Co Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1847623A (en) * 1929-07-15 1932-03-01 Union Oil Co Method of treating oil
US2706167A (en) * 1950-06-16 1955-04-12 Sun Oil Co Process for hydrogenating hydrocarbon oils
US2692226A (en) * 1950-10-07 1954-10-19 Standard Oil Dev Co Shale oil refining process
US2779711A (en) * 1955-02-28 1957-01-29 Standard Oil Co Refining of lubricating oils
US2779713A (en) * 1955-10-10 1957-01-29 Texas Co Process for improving lubricating oils by hydro-refining in a first stage and then hydrofinishing under milder conditions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3085061A (en) * 1959-05-20 1963-04-09 Exxon Research Engineering Co Shale oil refining process
US3487012A (en) * 1968-02-23 1969-12-30 Marathon Oil Co Processes for the improvement of initial color and long-term color stability of aromatic concentrates
US3549520A (en) * 1968-07-19 1970-12-22 Texaco Inc Color improvement of sulfur-containing lubricating oils with a mordenite type zeolite
US4786405A (en) * 1986-03-04 1988-11-22 Al Sanea Chemical Products Method of desulfurizing and deodorizing sulfur bearing hydrocarbon feedstocks

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