US3793191A - Process for manufacturing lubricating oil - Google Patents

Process for manufacturing lubricating oil Download PDF

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Publication number
US3793191A
US3793191A US00241690A US3793191DA US3793191A US 3793191 A US3793191 A US 3793191A US 00241690 A US00241690 A US 00241690A US 3793191D A US3793191D A US 3793191DA US 3793191 A US3793191 A US 3793191A
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United States
Prior art keywords
percent
weight
process according
lubricating oil
reactor
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Expired - Lifetime
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US00241690A
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English (en)
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A Billon
M Derrien
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INST PETROLE CARBURANTS LUBRIF
INST PETROLE CARBURANTS LUBRIFIANTS FR
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INST PETROLE CARBURANTS LUBRIF
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
    • 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

  • ABSTRACT A process for manufacturing a lubricating oil comprising a first step of passing a deasphalted crude oil distillation residue containing by weight at least 85 percent of constituents boiling above 500C and at least percent of consituents boiling above 525C, with hydrogen over a hydrogenating catalyst with a cracking carrier at 330-450C, at a hydrogen partial pressure of -240 kg/cm at such a flow rate that the hydrocarbons in the resulting product boiling below 525C amount to 70-95 percent of the initial weight of such hydrocarbons, separating the products boiling below 525C, and recovering a first lubricating oil fraction of high V.l.
  • oils exhibiting high viscosimetric properties and a satisfactory content of hetero-atoms (particularly sulphur and nitrogenlwith moderate manufacturing costs and a relatively narrow distillation range.
  • This process consists in performing a hydrotreatment in two stages, under the conditions stated below, of a charge consisting essentially of a deasphalted vacuum distillation residue.
  • the process for manufacturing the lubricating oil is remarkable in that it comprises passing a deasphalted distillation residue of crude oil containing at least 85 percent by weight of constituents boiling above 500C and at least 75 percent by weight of constituents boiling above 525C, together with additional hydrogen,
  • the treatment of the second step can be performed only on heavy products having an initial boiling point substantially higher than 525C, for example 570C or more.
  • the hydrocarbons boiling below 525C will amount to from 85 to 92 percent by weight of the initial hydrocarbons. It is essential, according to the invention, to comply with the limits of 70 to 95 percent, for the proportion of products boiling below 525C at the end of the first step. As a matter of fact, higher values will result in a quick deactivation of the catalyst; for lower values, the resultin oil will have a low viscosity index.
  • Through line 1 is fed a charge formed of a preliminarily deasphalted vacuum distillation residue of a raw petroleum or of a mixture of such a residue with a vacuum distillate.
  • the deasphalting may be achieved according to any known technique for example, by treatment with of lower paraffinic hydrocarbons, such as propane, butane or a mixture of propane and butane.
  • lower paraffinic hydrocarbons such as propane, butane or a mixture of propane and butane.
  • a viscosity at 989 C in the range of from 5 to cst, preferably from 5 to 50 est;
  • the operating conditions of reactor 4 are preferably as follows:
  • the distillation residue is conveyed through line 20 and after passage through a second oven sent .to a second distillation column 22 operated under reduced pressure.
  • the products issuing from the second distillation column have a content of sulphur impuritieslower than 0.1 percent by weight and generally lower than 0.02 percent.
  • Nitrogen amounts to less than 30 ppm by weight (parts per million of parts of oil).
  • the Conradson carbon amounts to less than 0.10 percent by weight and generally less than 0.05 percent.
  • the hydrotreatment to which the charge is subjected in the reactor 4 is equivalent to a hydrogenation combined with a cracking; this operation is accompanied with a formation of hydrogen sulphide H S, ammonia NH; and very light hydrocarbons, more particularly methane.
  • the catalyst may for example contain:
  • the outflow from the hydrotreatment reactor is directed, through line 6, to a first gas-liquid separator or flash 8, also called high pressure separator (HP).
  • a first gas-liquid separator or flash 8 also called high pressure separator (HP).
  • the temperature of the mixture flowing through duct 6 has been previously lowered by passage of the mixture through the cooler 7.
  • separator 8 there is recovered, at one end, a liquid phase conveyed through line 9 to a second separator l0, called'low pressure separator (LP) and, at the other end, a gaseous mixture rich of hydrogen and flowing through duct 11.
  • LP low pressure separator
  • a portion of said gaseous stream is removed, the other being recycled, through line 5, to the hydrotreatment reactor 4.
  • the gas removed from the system may be used for other purposes, for example as combustible gas.
  • the operation of the separator 10 is similar to that of the first separator except that the pressure is considerably lower (a few kg/cm instead of several tens or even hundreds of kg/cm).
  • a gaseous mixture removed through line 12 and a liquid phase ammonia and partially the hydrogen sultide and the very light hydrocarbons. This is achieved by known means.
  • the vacuum distillation residue containing at least 50 percent by weight of constituents boiling above 525C, withdrawn through duct 27, mayeither be considered as a base oil and used as such, or may be recycled into the reactor 4.
  • the distillate withdrawn from lines 24, 25 and 26 must have relatively constant characteristics.
  • the operating conditions of reactor 30 are preferably as follows:
  • L.H.S.V. of from 0.1 to 2 liters of liquid charge per liter of catalyst and per hour.
  • Ratio of the flow rate of pure gaseous hydrogen to the flowrate of liquid charge from 500 to 5,000 liters per liter.
  • the operating conditions in the second reactor 30 are not so severe as those in the first reactor 4, i.e. the L.H.S.V. is higher (1.2 to 2 times higher than the L.H.S.V. in reactor 4), and the temperature lower (for example from 10 to 100C lower than the temperature in reactor 4); the hydrogen partial pressures being the same in reactors 4 and 30.
  • Reactor 30 comprises, as well as reactor 4, at least one catalyst bed.
  • the catalyst may, for example, contain:
  • Alumina may be amorphous or crystallized; in the latter case, suitably exchanged zeolites may be incorporated thereto (zeolites with a sodium, calcium or lanthanum base by way of example).
  • the zeolitic portion amounts for example to 3 to 15 percent by weight of the total catalyst.
  • catalysts for use in the first or second stage of the process may contain at least one noble metal from group VIII, for example platinum, and at least one carrier such as alumina-silica, chlorinated alumina or fluorinated alumina. Molybdenum or tungsten may also be used, with or without nickel or cobalt, on a halogenated alumina carrier. Other equivalent catalysts, known in the art, may also be used.
  • the effluent from the hydrotreatment reactor is conveyed through lines 31 and 33 to the first gas-liquid separator 8.
  • the temperature of the mixture flowing through duct 6 has been previously lowered by passage of the mixture through the cooler 32.
  • the recycling according to the invention by passage of the distillation residue to a second reactor, avoids the above mentioned inconveniences. Moreover, this treatment gives a very high flexibility to the process of manufacturing lubricating oils. Particularly, it provides for the possibility, at the desired V.I. level, of maximizing the yields of oily distillates withdrawn from lines 24, 25 and 26 and of changing the distribution of these fractions according to the demand on the markets.
  • the different oil fractions obtained from the second distillation are generally subjected to a dewaxing treatment not illustrated on the FIGURE (for example by a mixture methylethylketone-toluene) before being used as base oils to which various additives are generally incorporated.
  • FIGURE is only a simplified diagram on which the pumps, compressors, and the like are not shown.
  • EXAMPLE 1 Manufacture of Bases for Multigrade Oils EXAMPLE 1
  • the charge is a deasphalted residue having the following composition:
  • This base oil distilled under reduced pressure, gives the following fractions: 100 Neutral: 25% i.e. 12.5% by weight of the initial charge 180 Neutral: 30% i.e. l5 by weight of the initial charge 400 Neutral: 25 i.e. 12.5 by weight of the initial charge
  • the distillation is discontinued when the temperature (corrected at the atmospheric pressure) reaches 525C.
  • the remaining distillation residue thus amounts to 20 percent of the base oil, i.e. 10 percent by weight of the initial charge.
  • the catalyst used in the first reactor had the following composition:
  • the catalyst of the second reactor has the following composition:
  • V.I. The viscosity index
  • the total yield by weight is as follows:
  • a process for manufacturing a lubricating oil comprising passing a deasphalted distillation residue of crude oil containing at least 85 percent by weight of constituents boiling above 500 C. and at least 75 percent by weight of constituents boiling above 525 C. with hydrogen through a first catalytic zone containing a hydrogenating element and a cracking carrier consisting essentially of, by weight, 2 10 percent cobalt or nickel, l 30 percent molybdenum or tungsten, 40 percent silica and 22 83 percent alumina, with a weight ratio of A1 0 to SiO of 1.5 6, at a temperature of from 330 to 450 C.
  • a second catalytic zone containing a hydrogenating element and a cracking carrier consisting essentially of, by weight, 2 10% cobalt or nickel, 10 30 percent molybdenum or tungsten, 25 percent silica and 2 75 percent alumina, with a ratio by weight of A1 0 to SiO of 0.1 1, at a temperature of from 330 to 450 C. and a hydrogen partial pressure of from to 240 kg/cm at such a flow rate that at least the major part of said relatively heavy products of said first zone is converted to products boiling below 525C, and distilling the resulting products to separate a second lubricating oil fraction.
  • a cracking carrier consisting essentially of, by weight, 2 10% cobalt or nickel, 10 30 percent molybdenum or tungsten, 25 percent silica and 2 75 percent alumina, with a ratio by weight of A1 0 to SiO of 0.1 1, at a temperature of from 330 to 450 C. and a hydrogen partial pressure of from to 240 kg/c
  • a process according to claim 1, wherein the deasphalted residue has an initial boiling point higher than 300C, and contains at least percent by weight constituents having a boiling point higher than 500C.
  • a process according to claim 4, wherein the deasphalted residue has a viscosity of from 5 to 50 centistokes at 989 C., a viscosity index of from 0 to 100, a maximum content of asphaltenes of 0.3 percent by weight, a nitrogen content lower than 0.3 percent by weight and a maximum Conradson carbon of 5 percent by weight.

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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)
US00241690A 1971-04-07 1972-04-06 Process for manufacturing lubricating oil Expired - Lifetime US3793191A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7112416A FR2132540B1 (enrdf_load_stackoverflow) 1971-04-07 1971-04-07

Publications (1)

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US3793191A true US3793191A (en) 1974-02-19

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US00241690A Expired - Lifetime US3793191A (en) 1971-04-07 1972-04-06 Process for manufacturing lubricating oil

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US (1) US3793191A (enrdf_load_stackoverflow)
JP (1) JPS5515516B1 (enrdf_load_stackoverflow)
DE (1) DE2216462A1 (enrdf_load_stackoverflow)
ES (1) ES401454A1 (enrdf_load_stackoverflow)
FR (1) FR2132540B1 (enrdf_load_stackoverflow)
GB (1) GB1336822A (enrdf_load_stackoverflow)
IT (1) IT951191B (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB508118I5 (enrdf_load_stackoverflow) * 1974-09-23 1976-02-17
US4758544A (en) * 1985-07-17 1988-07-19 Chevron Research Company Catalyst composition and hydroprocessing of oils using same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242068A (en) * 1962-12-24 1966-03-22 Chevron Res Production of lubricating oil
US3365390A (en) * 1966-08-23 1968-01-23 Chevron Res Lubricating oil production
US3463724A (en) * 1967-12-22 1969-08-26 Chevron Res Process for stabilizing lubricating oil
US3493493A (en) * 1968-10-01 1970-02-03 Gulf Research Development Co Process for enhancing lubricating oils and a catalyst for use in the process
US3494854A (en) * 1968-04-01 1970-02-10 Sinclair Research Inc Two-stage catalytic hydrogen processing of a lube oil
US3560370A (en) * 1967-06-30 1971-02-02 Inst Francais Du Petrole Manufacture of lubricating oil with the use of new catalysts
US3684695A (en) * 1970-03-09 1972-08-15 Emmanuel E A Neel Hydrocracking process for high viscosity index lubricating oils

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1472728A (fr) * 1965-03-31 1967-03-10 Shell Int Research Procédé de craquage hydrogénant d'une huile d'hydrocarbures
FR1582758A (enrdf_load_stackoverflow) * 1967-10-04 1969-10-10

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242068A (en) * 1962-12-24 1966-03-22 Chevron Res Production of lubricating oil
US3365390A (en) * 1966-08-23 1968-01-23 Chevron Res Lubricating oil production
US3560370A (en) * 1967-06-30 1971-02-02 Inst Francais Du Petrole Manufacture of lubricating oil with the use of new catalysts
US3463724A (en) * 1967-12-22 1969-08-26 Chevron Res Process for stabilizing lubricating oil
US3494854A (en) * 1968-04-01 1970-02-10 Sinclair Research Inc Two-stage catalytic hydrogen processing of a lube oil
US3493493A (en) * 1968-10-01 1970-02-03 Gulf Research Development Co Process for enhancing lubricating oils and a catalyst for use in the process
US3684695A (en) * 1970-03-09 1972-08-15 Emmanuel E A Neel Hydrocracking process for high viscosity index lubricating oils

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB508118I5 (enrdf_load_stackoverflow) * 1974-09-23 1976-02-17
US3992283A (en) * 1974-09-23 1976-11-16 Universal Oil Products Company Hydrocracking process for the maximization of an improved viscosity lube oil
US4758544A (en) * 1985-07-17 1988-07-19 Chevron Research Company Catalyst composition and hydroprocessing of oils using same

Also Published As

Publication number Publication date
GB1336822A (en) 1973-11-14
FR2132540B1 (enrdf_load_stackoverflow) 1973-12-28
ES401454A1 (es) 1975-09-01
JPS5515516B1 (enrdf_load_stackoverflow) 1980-04-24
FR2132540A1 (enrdf_load_stackoverflow) 1972-11-24
DE2216462A1 (de) 1972-10-26
IT951191B (it) 1973-06-30

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