Classifications

• • 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
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents
• • 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
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
• • 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
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
• • 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

• naphthenic lubricating oils are their-high grease yields, i.e., a high ratio of oil to soap for a given consistency.
• naphtheniclubricating oils yield soft carbon deposits in diesel engines, particularly in railroad diesels, and consequently cause less wear on moving parts.
• Naththenic lubricating oils are highly compatible with the various additives u sedin cutting oil compositions and for thisreason are preferred for such service.
• cc c v Due to the specific properties possessed by 'naphthenic lubricating oils the demand 'for them is very great.
• the pi'ocess of our invention comprises subjecting a mixed base lubricating oil distillate fraction to .solvent extraction by a solvent selective for aromatics in a manner to yield a particular. fraction,.dewaxing this particular fraction and hydrogenating the dewaxed fraction.
• the dewaxing step can precede the solvent extraction.
• the particular fraction is derived by. particular treatment of the extract phase of a conventional solvent extraction, rather. than from the normally desirable rafiinate phase.
• Such extract phases have few known uses and are unsuitable for use as lubricating oils.
• our invention also provides a process for obtaining naphthenic type lubricating oils from a normally undesirable extract phase.
• This fraction is obtained by separating the. extract phase,.from the conventional solvent extraction of a mixed base lubricating oil distillate fraction, into a second extract phase which is similar to the first extract phase in that it has a high aromatic and low paraflin content and a second raffinate phase from which most of the paraflins and aromatics have been excluded. It is this second r affinate or heart-cut fraction which is treated 'byihydrogenation in accordance with the process of our invention.
• the separation can be carried out by cooling the first extract phase, or by injectingan anti-solvent into the Lfirst extractrphase-orfbya combination of cooling andinjectiontofan anti-solvent to produce a second extract and rafiinate phase which can then be separated in a settler with the upper (rafiinate) phase being the desired or heart-cutflfraction.
• the vseparation can alsobe carried out by subjecting the first extract. phase to re-extraction by means of.
• a mixed baselubricating oil distillate fraction is-subjected toa conventionalsolvent extraction-process to produce an extract phase.
• the amount of solvent can vary from to IOOO volume percent solvent based upon the lubricating oil fraction.
• the temperature employed in this extraction process can vary somewhat according-to the particular solvent used,-e.g., phen0l-155to2l0 R; furfural-lSO to 250 Fgliqu-id sulfur dioxide-less than 150 F.
• phen0l-155to2l0 R furfural-lSO to 250 Fgliqu-id sulfur dioxide-less than 150 F.
• toseparate this extracttphase into second extractand, raflinate phases. using the. cooling or antisolvent method described above it is not necessary to remove the solvent prior to further processing of the first extract.
• the extract removed from a conventional solvent extraction process will usually be at a temperature about 180 F., it is necessary only to cool the extract to a temperature of about 100 to F. to
• phase separation While phasetse paration can be accomplished by the injection of a sufficient quantity of anti-solvent, it is desirable tolimit theinjection of an antisolven-nsuch as water to about 5 to 25 percent by volume. When employing water in this quantity it is preferred to cool the extract to a temperature in the range from about 105 to To obtain the second extract andraffinatephases using the re-extraction method described above the quantity of solvent employedin the second extraction step is usually somewhat less than in the first extraction step. Normally itis satisfactory to employ from '50 to 700 volume percent solvent based upon the first extract.
• the temperature employed in the reextraction is usually lower than employed in the first extraction, e.g., phen'ol90 to F.;fu1ifural-9O to 200 F.
• phen'ol90 to F.;fu1ifural-9O to 200 F e.g., phen'ol90 to F.;fu1ifural-9O to 200 F.
• the extraction steps are operated so that the first extract preferably represents from about 20 to about 70 volumepercent of the raw lubricating oil distillate and the second raffinate (the heart-cut) preferably "represents from about 20 to .70 volume percent of the first extract.
• suitable solvents that can be employed include phenol, furfural, liquid sulfur dioxide, nitrobenzene, 'nitro paraflins and other solvents selective f0r-aromatics.
• Such processes and solvents are well known. For example, when employing phenol, a particularly advantageous solvent, the
• extraction comprises passing a feed stock through a phen01 treating tower, removing a raffinate oil from the top of the tower and removing an extract oil from the bottom and removing the phenol from the raffinate oil and extract oil by distillation.
• a suitable anti-solvent for use in our process is water.
• the dewaxing step of the process of our invention can be carried out by employing a conventional lubricating oil dewaxing process such as solvent dewaxing, e.g., with a methyl ethyl ketone and toluene solvent blend, or urea dewaxing through the formation of adducts of urea and straight chain parafiins.
• a conventional lubricating oil dewaxing process such as solvent dewaxing, e.g., with a methyl ethyl ketone and toluene solvent blend, or urea dewaxing through the formation of adducts of urea and straight chain parafiins.
• the dewaxing can precede the solvent extraction but for the proper control of pour point it is preferred to extract first and then dewax.
• the extracted and dewaxed fraction is then subjected to catalytic hydrogenation.
• the hydrogenation step of our process is conducted at a pressure from about 1000 to about 3500 p.s.i.g., a temperature from about 600 to about 750 F. and at a weight hourly space velocity from about 0.25 to about 3.0 pounds of oil per pound of catalyst per hour.
• Any of the well known hydrogenation catalysts such as molybdenum, chromium, tungsten, vanadium, platinum, zinc, tin, nickel, copper, iron and cobalt or their oxides or sulfides either unsupported or supported on a suitable catalyst carrier such as alumina or silica can be employed in this step of our process.
• catalysts are the iron transition metals (iron, cobalt and nickel) and the Group VI B metals (chromium, molybdenum and tungsten) especially combinations of metals from each of these groups, for instance, cobalt and molybdenum, nickel and tungsten, and nickel and molybdenum supported on alumina.
• iron transition metals iron, cobalt and nickel
• Group VI B metals chromium, molybdenum and tungsten
• cobalt and molybdenum, nickel and tungsten, and nickel and molybdenum supported on alumina we prefer to employ a cobaltmolybdate on alumina catalyst such as that described in US. Patent No. 2,898,308.
• the hydrogenated product of our process can be fractionated in order to yield certain narrower fractions particularly suited to certain end uses.
• specific dispersion can be used to control the various steps.
• the first solvent extraction preferably should yield an extract having a minimum specific dispersion of 160 and the heartcut fraction preferably should have a specific dispersion between 135 and 185.
• the heart-cut fraction should have a gravity of about to 30 API and a viscosity of about 35 to 200 SUS at 210 F.
• the specific dispersion of the heart-cut feed should be reduced about 10 to 70, preferably about to 30.
• the final hydrogenated product should have a specific dispersion between 105 and 140 depending upon the properties required for end use.
• the mixed base lubricating oil distillate fraction is derived from mixed base crude oils which have a composition intermediate that of the paraffinic, e.g., Pennsylvania, and naphthenic types of crude oil.
• mixed base crude oil is found in the Mid-Continent area. For example, such crudes include Oklahoma City and East Texas.
• the composition of mixed base crude oils is intermediate that of paraflinic and naphthenic crudes the physical properties of a mixed base crude are usually intermediate those of paraflinic and naphthenic crudes.
• the fraction of a mixed base crude boiling between 428 F. and 527 F. at atmospheric pressure will have an API gravity between about 33 and 40 API while the fraction boiling between 527 F. and 572 F. at 40 mm.
• mixed base crude oils can be chemically classified as parafiinic-naphthenic crude oils according to the system set forth in The Science of Petroleum, volume V, part I, pages 75-77, Oxford University Press, New York, 1953, and A. N. Sachanen, The Chemical Constituents of Petroleum, pages 4l9427, Reinhold Publishing Corporation, New York, 1945.
• Such crude oils are an Oklahoma City crude with the approximate composition, by weight, of 36% paraffins, 45% naphthenes, 14% aromatics and 5% resins and asphaltenes and a ring analysis showing 65% paratfin side chains, 25% naphthenic rings and 10% aromatic rings and an East Texas crude with the approximate composition of 33% paraflins, 41% naphthenes, 17% aromatics and 9% resins and asphaltenes and a ring analysis showing 60% paraffin side chains, 26% naphthenic rings and 14% aromatic rings.
• Usually Mid-Continent mixed base crude oils will contain from 60 to 70 percent by weight parafilnic side chains and at least 20 percent by weight naphthenic rings.
• Example A mixed base East Texas crude oil was fractionated by atmospheric and vacuum distillation to yield gas, gasoline, kerosene, lube distillate, gas oil and asphalt fractions.
• the lube distillate fraction had the analysis shown in Table I.
• This lube distillate was solvent extracted with phenol on a counter-current extraction tower using a solvent dosage of volume percent, a top tower temperature of 191 F., a bottom tower temperature of 178 F., and 3.2 volume percent of water based on solvent injected at the tower bottom. This produced 65.9 volume percent yield of rafiinate (Ratfinate A) and 34.1 volume percent of extract (Extract B).
• Raffinate A was dewaxed using a 50/50 blend of MEK and toluene and a filter temperature of -10 F. to obtain 68.4 volume percent of dewaxed Mid-Continent lubricating oil (Lube C).
• Extract B tested 17.3 API gravity, 43.6 SSU at 210 F. viscosity, +60 F. pour, and 194.5 specific dispersion. In order to compare compositions, a portion of Extract B was dewaxed in a manner similar to Rafiinate A to yield 93.0 volume percent of a finished aromatic oil (Lube D).
• Extract B was batch solvent extracted with phenol containing 20.0 volume percent water using a solvent dosage of 665 volume percent and a temperature of 105 F. This produced 64.3 volume percent of raffinate (Raffinate E) and 35.7 volume percent of extract (Extract F). Raflinate E was dewaxed in the same manner as Ratlinate A to yield 90.2 volume percent of dewaxed lubricating oil (Lube G).
• Lube G was hydrogenated at 1500 p.s.i.g., 700 F., and 1.0 WHSV over a cobalt-molybdenum supported on alumina, catalyst to yield 98.4 volume percent of finished naphthenic type lubricating oil (Lube H).
• Lube H represents the product from the process of this invention.
• Two lubricating oil stocks were prepared by the conventional manner from a blend of equal parts of Gulf Coast Pickett Ridge, Damon and Thompson crude oils.
• the crude was fractionated by atmospheric and vacuum distillation to yield gas, gasoline, light and medium lubrieating oil distillates, gas oil and asphalt. Distillation was over caustic to remove naphthenic acids.
• the lube distillates were treated with 14 and 25 pounds per barrel of 98% sulfuric acid, respectively, neutralized with caustic and contacted at 180 F. with 3 pounds of fullers earth per barrel of oil.
• Overall yield from the light lubricating oil distillate (Lube J) was 87.3 volume percent and from the medium lubricating oil distillate (Lube K) 83.5 volume percent. These two lubricating oils are typical of those produced from naphthenic base crude oils.
• Table I lists the properties of the various lubricating oils produced in this example.
• the procedure employed is described in the article, Properties of High-Boiling Petroleum Products, L. T. Eby, Analytical Chemistry, vol. 25, page 1057, July 1953.
• the mass spectrometer methods employed are described in Mass spectrometric Analysis of High Molecular Weight Saturated Hydrocarbons, R. J. Clerc, Archie Hood and M. J. ONeal, Jr., Analytical Chemistry, vol. 27, page 868, June 1955, and Composition of an East Texas Lube Oil Distillate, B. A. Drkin, J. G. Bendoraitis, R. Brown and R. H. Williams, Symposium on Composition of Petroleum Oils, Determination and Evaluation, sponsored by Research Division IV of ASTM Committee D-2, February 8, 9, 1957, New La.
• Lube C which is a typical Mid- Continent solvent refined oil, difiers considerably in composition from Lubes J and K, typical naphthenic lubricating oils from South Texas Gulf Coast crude oils. Specifically, Lube C has a considerably higher saturates content and is particularly rich in paraflin.
• Lube D the aromatic extract
• Lubes J and K the aromatic extract
• Lube G the heart-cut fraction, is more related to Lubes J and K but is still high in aromatic content and low in cycloalkanes.
• Lube H hydrogenated Lube G
• Lube H closely approximates the composition of Lubes J and K and has similar properties, with the exception of pour point.
• dewaxing conditions for Lube H can be adjusted, for example by reducing the filtering temperature to F., to yield an oil having pour properties more related to Lubes J and K. More severe dewaxing will also reduce the paraffin content of Lube H.
• the process of our invention produces a lubricating oil having a composition and properties similar to those of typical naphthenic lubricating oils and is obtained by the treatment of a mixed base lubricating oil fraction.
• a process for producing naphthenic type lubricating oils having a specific dispersion between about and about from a mixed base lubricating oil distillate fraction which comprises subjecting the mixed base distillate fraction to a solvent extraction treatment including the steps of extracting the distillate fraction with a solvent selective for aromatics to yield a first extract phase comprising about 20 to about 70 volume percent of the mixed base distillate fraction and having a specific dispersion of at least about and separating the first extract phase into a second extract phase and a second raffinate phase from which second raifinate phase most paraffinic and most aromatic components have been excluded by said solvent extraction treatment and said separating and having a specific dispersion of from about 135 to about and comprising about 20 to about 70 volume percent of the first extract phase, subjecting said second raffinate phase -to a dewaxing treatment, and hydrogenating the dewaxed second rafiinate phase while in contact with a hydrogenation catalyst at a temperature from about 600 F. to about 750 F., a pressure
• a process for producing naphthenic type lubricating oils having a specific dispersion between about 105 and about 140 from a mixed base lubricating oil distillate fraction which comprises solvent extracting the mixed base distillate fraction with a solvent selective for aromatics to yield a first extract phase comprising about 20 to about 70 volume percent of said mixed base distillate fraction and having a specific dispersion of at least about 160,'subjecting the first extract phase to re-extraction with a solvent selective for aromatics and containing an antisolvent at a temperature lower than that at which the first solvent extraction is conducted to yield a second rafiinate phase from which most paraffinic and most aromatic components have been excluded by said solvent extraction treatment and said separating and having a specific dispersion of from about 135 to about 185, a gravity from about 15 to about 30 API and a viscosity from about 35 to about 200 SUS at 210 F.

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• Oil, Petroleum & Natural Gas (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Lubricants (AREA)

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• 0
  • NL NL133635D patent/NL133635C/xx active
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• 1961
  • 1961-12-21 US US161283A patent/US3232863A/en not_active Expired - Lifetime
• 1962
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  • 1962-12-20 DE DE19621470639 patent/DE1470639A1/de active Pending

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