US3488283A - Preparation of two different lube oil fractions by single solvent extraction - Google Patents

Preparation of two different lube oil fractions by single solvent extraction Download PDF

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Publication number
US3488283A
US3488283A US716974A US3488283DA US3488283A US 3488283 A US3488283 A US 3488283A US 716974 A US716974 A US 716974A US 3488283D A US3488283D A US 3488283DA US 3488283 A US3488283 A US 3488283A
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solvent
oil
extractor
extraction
phase
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US716974A
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Harold O Button
Theodor A Petry
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ExxonMobil Oil Corp
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Mobil Oil Corp
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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
    • 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
    • C10G21/30—Controlling or regulating

Definitions

  • Solvent extraction is a well established process used in the refining of petroleum, thefirst application having been made in about 1911. Originally, upgrading of kerosine was a major use but the improvement obtained in solvent extracting lubricating oils .and others soon became an important application. Solvent extraction is used extensively in the petroleum refining industry to refine lubricating oils, kerosine andv specialty oils for medicinal and agricultural purposes. Solventextraction has'also been used for the upgrading of charge stocks for catalytic cracking operations as well as the separation of light aromatics from gasoline.
  • Solventextraction is a process that separates hydrocarbon mixtures into tWo phases; a rafiinate phase which contains substances of relatively high hydrogen to carbon ratiooften called parafiinic typema terials and an extract phase which contains substances of relatively low hydrogen to carbon ratio. often called aromatic type materials. Therefore, it maybe said that solvent extraction ispossiblebecausedifierentliquid compounds have different solution afiinities for each other and some combinations are completely'miscible while other combinations are almost immiscible.
  • selectivity Theability to distinguish between high carbon to hydrogenaromatic type and low carbon to hydrogen or paraffinic type materials is termed selectivity. The more finely this distinguishing can be done the higher the selectivity of the solvent.
  • lube oils are exceedingly complex hydrocarbon mixtures made up principally of paraffins, naphthenes, aromatics and asphalts and the chemical constitution of oils stable to oxidation can only be guessed. That is, it is known that the polynaphthenic type materials oxidize more readily to-degradation products such as acids and/or insoluble asphaltenes than do those of parafiinic type. The latter usually tolerate oxidation at moderate temperatures for extended periods before visible signs of change appear, but it is not clear or certain that soluble oxidation products are not accumulating during this period. In agreement with this is the fact that the oxidation of mixed naphthenic oils is retarded by solvent extraction which removes the polynaphthenes and polyaromatics.
  • oil is made up of compounds consisting of naphthenic and aromatic rings carrying side chains of varying number, length and structure.
  • Long side chains are characteristic of molecules of high paraffinicity and high viscosity index, while poly- 3,488,283 Patented Jan. 6, 1970 naphthenic and polyaromatic structures with fewer and shorter chains will show low viscosity index, high viscosity-gravity constant and relatively poor stability against oxidation.
  • the division between compounds of long and short side chains therefore, is necessarily not sharp and undoubtedly some constituents of good quality are lost in any extraction process.
  • Solvents which have been used in commercial operations include furfural, phenol, cresylic acid, nitrobenzene, dichloroethyl ether, sulfur dioxide and others. If desired, these solvents may be used in the presence of diluents such as benzene, carbon disulfide, ethers and carbon tetrachloride. Generally the diluents increase the solubility of all of the hydrocarbons. The use of diluents however can reduce solvent selectivity.
  • Furfural is typical of a suitable solvent extraction agent. Its miscibility characteristics and physical properties permit use with both highly aromatic and highly paraflinic oils of wide boiling range. Diesel fuels and light and heavy lubricating stocks are refined with furfural. For lubricating oils it has been used in the prior art at elevated temperatures in the range of 120 F. to 290 F. and with from 1 to 4 volumes of furfural to 1 volume of oil. Furfural exhibits good selectivity at elevated temperatures (US-250 F.); this characteristic results in the benefits of reduced viscosity and high temperature gradient and permits operation on waxy stocks. In a typical furfural solvent extraction plant for lubricating oils, the raw feed or distillate fraction, at a temperature of about 110 to about 250 F.
  • Furfural is fed into the top or upper portion of the tower at a temperature selected from within the range of about 150 F. to about 290 F.
  • Recycle extract may be introduced into the lower section of the tower as reflux.
  • internal reflux is effected in, the tower by the temperature gradient which is brought about by introducing the solvent at an elevated tempenature and by intermediate cooling systems.
  • Furfural solvent is recovered from the rafiinate and extract phase streams or layers in suit-able distillation and stripping equipment. The stripped and recovered solvent is then returned or recycled for use in the process as above described.
  • Finished lubricating base oils are generally divided into the following three broad grade classifications:
  • Lube crude oils are classified by the Bureau of-Mines into three categories according to .the predominant-composition of their 736-788 F. fraction'as paraffinic, intermediate and naphthenic.
  • Parafiinic crude such as Pennsylvania or High Pour Haitin crudes contain considerable amounts of wax, while some'naphthenic crudes such as coastal crudes contain no wax.
  • Intermediate crudes such as Mid-Continent, Kuwait or East Texas contain varying amounts of both wax.
  • traction equipment proper is relatively simple but the solvent recovery facilities are necessarily complex and therefore expensive and any means by which these costs or facilities can be simplified greatly contribute to-the commercial interests of the process.
  • the present invention is concerned with a method of recovering a high V.I. lube oil product from a lube oil crude to the exclusion of undesired constituents by a solvent extraction process in an environment which emphasizes the solvent selectivity arid-improves the yields of a lower V.I.' lube oil product recovered simultaneously therewith.
  • the present invention is particularlyconcerned with the method and combination of processing steps for producing lubricating oil prod.-
  • V.Ii levels having at least different V.Ii levels; one of which has" the equivalent-of---a'-light neutral--VJ. -level upon dewaxing of at least about 120 V.I. or the equivalent of a heavy neutral V.I. level upon dewaxing of at least 115 and the other has a lower, V. I. level; but above V.I.
  • a,. lube oil crude fraction of hydrocarbon feed stock boiling above about 550,F. is contacted countercurrentlynwith solvent,such as furfural, in a first extractio'ri column comprising a plurality of separate and sequentially arranged extracting'steps under conditions of temperature,andnisolvent.concentration to improve the solvent selectivityand permit recovering therefrom a primary lube'o'il raflinatefractio'mwhich will produce upon dewaxing :alube;QiL productof at least 90 V.I. and-preferably at least about .-V.I.' The. primary raffinate fraction thus separated". from.
  • the secondary extract fraction' is cooled, add an anti-solvent such as "water or both to a temperature whichis-suitableifor releasing fromthe solvent an oil rich phase of desired V.I upon dewaxing.
  • the oil phase may be-separatedby decanting soas to recover from this secondaryextra'ct the desired first'oil 'rich phase or fraction which issuitablefor use*or' blendingwith'at least a portion of the first rafiinate 'phase from a concentrated solvent "fractionorsolvent rich phase.
  • this decantedfirst oil'rich phase is of a composition which is 'suitable' fOnu's'e as is or it frnay be used for blending with the primary raffinate product obtained from the first extractor andused'toproduce the lube oil of lower V.I.
  • the decanted solvent rich phase obtained fromthejsecond' extract is recovered and *all or a portion thereof is passed directly; after adjusting its temperature,
  • the first extract phase will then be treated in a suitable solvent recovery system to recover a purified solvent rich phase from an aromatic rich oil phase.
  • a significant portion of the process above described is particularly concerned with and directed to improving the overall economics of the process by minimizing the volume of solvent required, the solvent recovery stages required and taking advantage of the improved selectivity of the solvent rich second extract phase to obtain not only the solvent requirement of the first extractor but also to recover from the second extract those oil constituents which are suitable for blending with an oil product recovered from the first raffinate phase.
  • the present invention permits the recovery of the unusually high V.I. contributing constituents of oil crude sources in a manner not heretofore realized as economically attractive.
  • furfural is introduced to the upper portion of the extractor for countercurrent flow therein with the distillate charge introduced to the lower portion of the extractor, under conditions to maintain a temperature therein selected from within the range of from about 125 'F. to
  • An extract phase is Withdrawn from the bottom of the tractor 4 by conduit 10.
  • a portion of the first or primary raffinate phase in conduit 10 is passed by conduit 12 to a dewaxing section 14.
  • the remainingportion of the primary rafiinateinconduit- 10 is passed to a second extrac-- tor 16 and comprising 7 extraction stages.
  • extractor 16 the solvent extraction conditions are maintained sufiiciently intense or severe by using a large excess of furfural to remove from the primary rafiinate product a sufiicient amount of the low V.I.
  • extractor 16 it .is contemplated employing a large excess and from about 800 to about 1500% furfural to effect the intensity of extraction desired at a temperature maintained as low as possible and within the range of 175 to about 250 F; A temperature above about 225 F. is regarded as an excessive temperature for treatcomposition suitable for combining with the oil in the ment of light neutrals.
  • the secondary extract phase obtained by extractor 16 is removed from the bottom thereof by conduit 28 for passage to a cooling zone 30 and conduit 32 to a separation zone 34.
  • Separation zone 34 is maintained at a temperature of about P; so as to recover a parafiin rich oil phase separated from an aromatic rich extract phase.
  • the parafiin rich oil or rafiinate phase thus separated is removed from separator 34 by conduit 36 and is passed to dewaxing zone 14 either alone or in combination with the portion of the primary raflinate in conduit 12 being passed to the dewaxing zone.
  • dewaxing zone 14 is maintained at a temperature of about 0 F. so as to recover wax from the oil product.
  • Example I I Raw and dewaxed High Pour shamen (HPL) 114 SSU v at F. distillates were furfural extracted at high fur- 3,488,283 7 8 dewaxing of 125 V1. Eifecting a similar solvent treatment extractor process hereinbefore described. It will be notedat 500% dosage produced a 113 V1. oil product, The from Table 2 that the raflinate from extractor No. 1 is yield obtained varied from 2.62.9% volume on crude used as charge to the extractor No. 2. It is also to be for the 125 V.I. oil to 4.1-4.6% for the 113 V.I. oil.
  • Example IV TABLE 1.- 125 v1" LIGHT NEUTRAL LUBES FROM a t 1 VARIOUS CRUDES BY DEEP FURFUBAL EXTRACTION. .Table 3 below presents the results obtalned when preparing a 1118 V.I. heavy neutral from a 453 SSU at 130 Crude Source F. Kuwalt dlstlllate by deep solvent extractlon withfur- High Beaummt fural. The data of the table is arranged similarly to thaterien Kuwait MOS I I P d v presented m Table 2 for purposes of compar1son.
  • a method for producing lubricating oils by solvent extraction which comprises:

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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)
US716974A 1968-03-28 1968-03-28 Preparation of two different lube oil fractions by single solvent extraction Expired - Lifetime US3488283A (en)

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US (1) US3488283A (xx)
BE (1) BE724358A (xx)
DE (1) DE1806460A1 (xx)
FR (1) FR1599052A (xx)
GB (1) GB1189087A (xx)
NL (1) NL6815335A (xx)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2038209A1 (xx) * 1969-04-03 1971-01-08 Sun Oil Co
US3929626A (en) * 1974-07-31 1975-12-30 Mobil Oil Corp Production of lubricating oils blending stocks
US3989616A (en) * 1974-08-30 1976-11-02 Mobil Oil Corporation Production of lubricating oils blending stocks and selected components for asphalt production
EP0020094A1 (en) * 1979-05-30 1980-12-10 Mobil Oil Corporation An improved solvent extraction process for providing lubricating oil fractions
US5922193A (en) * 1995-09-01 1999-07-13 Mobil Oil Corporation Addition of ethers or aldehydes to furfural for aromatic extractions
RU2501936C1 (ru) * 2012-04-06 2013-12-20 Ильмар Раисович Айсматуллин Устройство теплообменника для удаления парафина и смол из нефти перед ее транспортировкой
CN111925860A (zh) * 2020-07-20 2020-11-13 安徽国孚凤凰科技有限公司 一种废润滑油馏分油二段抽提再生工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2054433A (en) * 1932-03-09 1936-09-15 Texas Co Manufacture of lubricating oil
US2161567A (en) * 1937-03-27 1939-06-06 Texas Co Solvent refining of oil
US2165638A (en) * 1937-02-19 1939-07-11 Texas Co Refining hydrocarbon oil
US2952610A (en) * 1956-05-17 1960-09-13 Sun Oil Co Manufacture of lubricating oils
US2953501A (en) * 1957-07-18 1960-09-20 R O M Societa Azionaria Raffin Apparatus for extraction by the double solvent method
US3205167A (en) * 1961-04-24 1965-09-07 British Petroleum Co Solvent extraction of hydrocarbon mixtures

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2054433A (en) * 1932-03-09 1936-09-15 Texas Co Manufacture of lubricating oil
US2165638A (en) * 1937-02-19 1939-07-11 Texas Co Refining hydrocarbon oil
US2161567A (en) * 1937-03-27 1939-06-06 Texas Co Solvent refining of oil
US2952610A (en) * 1956-05-17 1960-09-13 Sun Oil Co Manufacture of lubricating oils
US2953501A (en) * 1957-07-18 1960-09-20 R O M Societa Azionaria Raffin Apparatus for extraction by the double solvent method
US3205167A (en) * 1961-04-24 1965-09-07 British Petroleum Co Solvent extraction of hydrocarbon mixtures

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2038209A1 (xx) * 1969-04-03 1971-01-08 Sun Oil Co
US3929626A (en) * 1974-07-31 1975-12-30 Mobil Oil Corp Production of lubricating oils blending stocks
US3989616A (en) * 1974-08-30 1976-11-02 Mobil Oil Corporation Production of lubricating oils blending stocks and selected components for asphalt production
EP0020094A1 (en) * 1979-05-30 1980-12-10 Mobil Oil Corporation An improved solvent extraction process for providing lubricating oil fractions
US5922193A (en) * 1995-09-01 1999-07-13 Mobil Oil Corporation Addition of ethers or aldehydes to furfural for aromatic extractions
RU2501936C1 (ru) * 2012-04-06 2013-12-20 Ильмар Раисович Айсматуллин Устройство теплообменника для удаления парафина и смол из нефти перед ее транспортировкой
CN111925860A (zh) * 2020-07-20 2020-11-13 安徽国孚凤凰科技有限公司 一种废润滑油馏分油二段抽提再生工艺

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BE724358A (xx) 1969-05-22
GB1189087A (en) 1970-04-22
DE1806460A1 (de) 1969-10-16
FR1599052A (xx) 1970-07-15
NL6815335A (xx) 1969-09-30

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