US3579437A - Preparation of high v.i. lube oils - Google Patents

Preparation of high v.i. lube oils Download PDF

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Publication number
US3579437A
US3579437A US813255A US3579437DA US3579437A US 3579437 A US3579437 A US 3579437A US 813255 A US813255 A US 813255A US 3579437D A US3579437D A US 3579437DA US 3579437 A US3579437 A US 3579437A
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solvent
extraction
oil
employed
product
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US813255A
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William W Wentzheimer
Ronald W Reynolds
William Chalpin
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Sunoco Inc
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Sun Oil Co
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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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • ABSTRACT OF THE DISCLOSURE A process for producing high quality and highly stable lubricating oils with a high viscosity index wherein a lubricating oil fraction is first solvent extracted with a solvent having preferential solubility for aromatics to reduce the polycyclic aromatic content thereof and wherein raffinate from said extraction is hydrocracked under conditions to increase the viscosity index thereof and wherein hydrocracked lubricating oil product is subjected to a second extraction with a solvent having preferential solubility for aromatics, and including the improvement herein comprising separating the solvent and extract from the lubricating oil rafifinate product of said second extraction and employing said solvent with product extract therein for the extraction of hydrocracker charge stock in said first extraction.
  • This invention broadly relates to the production of high V.I. lube oils and, more particularly, to improvements in a process scheme for producing high V.I. lube oils which are stable and of high quality.
  • the improvements involve solvent extracting at least part of the lube oil fraction to be hydrocracked with a solvent having preferential solubility for aromatics so as to selectively remove the more aromatic compounds (i.e., polycyclics containing multiple rings) which are more re- 3,579,437 Patented May 18, 1971 fractory under hydrocracking conditions and have a poor V.I.
  • the highly aromatic extract is a good rubber oil stock, and the rafi inate can be hydrocracked at milder conditions to avoid overcracking of some of the lube oil material and to achive substantial economies in such a hydrocracking operation.
  • Each of the solvent extractions involved can be carried out in a fashion substantially identical to that wherein an entirely fresh solvent is employed for each of the extractions; i.e., the extraction of the hydrocracker feed charge and the post-hydrocracking stabilizing extraction.
  • the hydrocracking step can likewise be carried out by any one of several known suitable techniques. We prefer to carry out the hydrocracking and prehydrocracking solvent extraction in substantially the same fashion as described in commonly assigned and copending application Ser. No. 743,915 referred to above. The important features of that step will be discussed briefly. Reference can be made to that application for any further information desired on that step.
  • Illustrative but nonlimiting examples of the solvents that can be employed in both extractions of the present invention are furfural, acetophenone, phenol, acetonitrile, nitrobenzene, aniline, 2,2-dichlorodiethyl ether, and dimethyl sulfoxide and mixtures thereof.
  • the particular solvent selected is often dependent upon several considerations, not the least of which is economics; but, generally speaking, furfural and phenol are the more preferred solvents. With the exxception of those lubes or fractions which are of sufficiently low asphalt and metals content, the hydrocracker feed material is to be deasphalted before the first extraction.
  • the temperature of all the prehydrocracking extractions must be below the temperature of miscibility of the oil and the solvent in order to have any extractive separation, and usually well below the temperature of miscibility for a highly efficient operation with good yields of oil as hydrocracker charge.
  • the lower limit of temperature is controlled in part by the pour point of the charge when it has been dewaxed. If the charge has not been dewaxed, then the minimum temperature of the extraction is controlled by the point at which solids appear.
  • the extraction temperature is too low, the extraction will be too selective and require application of compensating features such as additional amounts of solvent and extraction stages; otherwise, the benefits accruing may be too limited.
  • the temperature range encompassing all of the suitable operating temperatures for all of the solvents is, generally speaking, about to 350 F. In the case of furfural, however, a temperature in the more restricted range of about 125 to 325 F. is preferably employed. In the case of phenol, a temperature in the range of about 150 to 255 F. is usually preferred.
  • a Lagomedio crude fraction boiling in the range of about 850 to 950 F. is preferably solvent extracted at a temperature of about 200 to 250 F. and a solvent dosage in the range of about 1:2 parts by volume of furfural per volume of treated oil.
  • the fraction boiling above 950 F. from the same crude which has been deasphalted with propane is preferably solvent extracted at a temperature of about 225 to 275 F. and a solvent dosage of about 2:3 volumes of furfural per volume of treated oil.
  • the fractions boiling below about 850 F. are generally not extracted because the benefits thereof are small relative to the cost. Fractions from other crudes, of course, would require some modification of the foregoing.
  • the equipment that may be employed is not critical as any conventional solvent extraction equipment can be employed.
  • rotating disc contactors, Podbielniak contactors, and countercurrent packed bed extraction columns may be named as illustrative.
  • the extraction can be carried out in either a batch-Wise operation or a continuouswise one, although the latter is generally found more convenient, economic, and preferred.
  • the preferred hydrocracking procedure comprises hydrocracking the solvent extracted material at about 650 to 825 F., but preferably between 700 and 800 F., at a pressure above about 1,500 p.s.i., but more usually and preferably above about 2,000 p.s.i., and at a liquid hourly space velocity between about 0.2 and 4.0, but more usually between about 0.4 and 1.5.
  • the hydrocracking treatment is, of course, carried out in the presence of hydrogen over a hydrocrackin-g catalyst, i.e., a catalyst having both aromatic saturation and ringscission activity.
  • a sulfactive catalyst is employed.
  • Sulfactive catalysts broadly comprse a sulfide of any metal of Group VI, left-hand column, of the periodic system of a sulfide of an iron group metal but preferably a sulfide of the Group VI metals mixed with a sulfide of an iron group metal; for example, a nickel sulfide and tungsten sulfide catalyst in about a 1:1 to 4:1 metal ratio respectively is excellent on an alumina, silica, or-aluminasilica base.
  • Hydrocracking catalysts of free metals such as palladium on a mole-sieve base, etc., can be used but are less preferred.
  • ratio of solvent to oil that can be employed in the extraction is not particularly critical, and ratios varying over a wide range can be employed; however, advantages obtain in using certain ratios.
  • a ratio in excess of 2:1 of a solvent to oil is not employed because such increases the economic cost of the process due to the large volume of the solvent to be handled and reduces the yield of lubricating oil product.
  • ratios lower than about 0.25:1 require a compensating increase in the number of stages to achieve the desired effect.
  • Ratios of solvent to oil on the order of 0.5 to 1.25:1 are preferably employed.
  • the temperature will, of course, vary with the particular solvent employed in a given case. Generally, however, a temperature within the range of above about 0 to 300 F., is employed with any of those solvents taught herein. Of course, in order to obtain high selectivity, a narrower temperature within that range is to be employed with each of the suitable solvents. In the case of furfural, which is the most preferred solvent, a temperature in the range of above about 0 to about 150 F. can be advantageously employed; however, a temperature on the order of about 80 to 130 F. is preferred.
  • the next preferred solvent is phenol or Selecto (phenol and a mixture of cresols), and the preferred temperature is above the melting point of phenol, i.e., about 106 to about 140 F, although the preferred temperature will vary on occasion.
  • solvents that can be employed in this process are, of course, the same solvents or mixtures that are suitable for extracting the hydrocracker feed since using the same solvent in both extractions without an interim purification is an important feature of this invention.
  • the apparatus which can be employed to conduct the process is not special, and any of the conventional solvent extraction equipment may be employed for same.
  • Illustrative but nonlimiting examples are rotating disc contactors, Podbielniak contactors, and countercurrent extraction columns, and the like. It is thus apparent that the same type of equipment is suitable in both of the extractions of this invention.
  • rotary disc contactors or columns are preferably employed in carrying out the invention. It will be appreciated that the extraction can be carried out in either a batch-wise or continuous-wise operation, although the latter is more convenient and is generally preferred.
  • the equipment need not be adapted for special pressure conditions because atmospheric pressure is usually preferred.
  • the solvent-extract mixture from the product purification stage in the feed preparation extraction some additional fresh furfural or other solvent will generally be added because large amounts of solvent are required there and also to compensate in some cases for the reduced extraction capacity due to the extract contained therein.
  • the combined extracts from the two extraction operations can be cracked to gasoline.
  • the combined extracts can be used as a rubber oil, but because of the presence of UV unstable compounds, a stabilizing treatment may be desirable in some cases.
  • Boiling range Light vacuum distillate About 775 to 855 F. Heavy vacuum distillate About 855 to 955 F. Deasphalted oil About 955 F. and above.
  • the heavy vacuum distillate and deasphalted oil are then separately extracted with the adulterated solvent from a post-hydrocracking extraction.
  • a makeup amount of fresh or cleaned-up solvent is combined with the adulterated solvent from the post extraction containing the unstable materials removed from the hydrocracked product. This extraction is carried out as follows:
  • Heavy vacuum distillate 50. 4 21. 9 33 29 Deasphalted oil- 23 1. s-l. 9s 4s 26
  • the foregoing materials are blended to prepare feeds for hydrocracking as follows:
  • Pressed oil from the dewaxer above is then charged to a rotating disc contactor about 3 inches in diameter which contains about 66 discs and is extracted at a temperature of approximately 120 F. using approximately 100 volume percent of furfural to produce a raffinate comprising approximately 97% of the charge to the extractor.
  • the raffinate is then distilled to produce three distillate fractions: N0. 1 (100 Neutral), No. 2 (200 Neutral), No. 4 (500 Neutral), and a bright stock.
  • N0. 1 100 Neutral
  • No. 2 200 Neutral
  • No. 4 500 Neutral
  • a bright stock a bright stock.
  • Total lube yield (based on vol. percent of charge to hydrocracker) 58.6 V.I. range 105-115
  • the color of the lube fractions separated into blending stocks consisting of a 100 Neutral, 200 Neutral, 500 Neutral, and a bright stock typically varies from about 0.25 to about 3.0 using ASTM color test D-1500.
  • DIAGRAMMATIC F LOW SCHEME An illustrative, diagrammatic representation of an overall flow scheme will be found beneficial and will now be set forth (with dewaxing omitted for simplicity). Such discussion is to be viewed in reference to the figure.
  • the deasphalted residuum is charged via line 1 to a first hydrocracker feed or prehydrocracking extraction zone 2 wherein the residuum is extracted to remove a portion of the more aromatic materials according to the procedure described hereinabove.
  • the rafiinate with a small amount of solvent entrained therein is charged via line 3 to a feed separation stage 4 wherein the solvent is removed, for example, by distillation.
  • the lube oil raflinate recovered in 4 is charged to the hydrocracker 5 and is hydrocracked therein according to the procedure found hereinabove.
  • the hydrocracked pro duct is charged through line 6 to the second extraction stage 7 and is solvent extracted with a fresh or purified solvent charge to achieve the degree of stability desired according to the procedure found hereinabove for such extractions.
  • the raffinate from the second or product extraction stage 7 is charged via line 8 to a product separation stage (e.g., a distillation column) 9 wherein the finished lube oil product is separated from the entrained solvent and each is separately recovered.
  • the solvent plus extract from the second extraction stage 7 is drawn oil through line 10 and is charged directly to the first extraction stage with a makeup amount of solvent, for example, via line 11.
  • the solvent phase plus the aromatic extract is drawn oil from 2 through line 12 and is charged to a solvent recovery stage 13 where the solvent is purified, recovered, and is again used by charging to line 14 and/or line 15.
  • a process for preparing high viscosity index lube 5 oils comprising:
  • the solvent employed in the extractions is selected from the group consisting of furfural, phenol, acetophenone, acetonitn'le, nitrobenzene, aniline, 2,2-dichlorodiethyl ether, and dimethyl sulfoxide.

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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)
US813255A 1969-04-03 1969-04-03 Preparation of high v.i. lube oils Expired - Lifetime US3579437A (en)

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US (1) US3579437A (enrdf_load_stackoverflow)
JP (1) JPS4949009B1 (enrdf_load_stackoverflow)
BE (1) BE748345A (enrdf_load_stackoverflow)
DE (1) DE2015805C3 (enrdf_load_stackoverflow)
FR (1) FR2038209B1 (enrdf_load_stackoverflow)
GB (1) GB1286383A (enrdf_load_stackoverflow)
NL (1) NL162687C (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923636A (en) * 1974-06-03 1975-12-02 Texaco Inc Production of lubricating oils
US4170544A (en) * 1978-06-12 1979-10-09 Chevron Research Company Hydrocracking process including upgrading of bottoms fraction of the product
US5232577A (en) * 1990-08-14 1993-08-03 Chevron Research And Technology Company Hydrocracking process with polycyclic aromatic dimer removal
US20180187102A1 (en) * 2016-12-29 2018-07-05 Exxonmobil Research And Engineering Company Block processing with bulk catalysts for base stock production from deasphalted oil

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8425837D0 (en) * 1984-10-12 1984-11-21 Shell Int Research Manufacture of lubricating base oils
RU2382812C1 (ru) * 2008-08-25 2010-02-27 Открытое акционерное общество "Воронежский синтетический каучук" Способ получения нефтяных масел и экологически безопасных ароматических наполнителей и пластификаторов каучука и резины
RU2388793C1 (ru) * 2009-04-07 2010-05-10 Общество с ограниченной ответственностью "ИМПА Инжиниринг" Способ получения нефтяных масел и экологически безопасных ароматических наполнителей и пластификаторов каучука и резины и нефтяной экологически безопасный ароматический наполнитель и пластификатор каучука и резины
US10711208B2 (en) 2017-06-20 2020-07-14 Saudi Arabian Oil Company Process scheme for the production of optimal quality distillate for olefin production

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB938769A (enrdf_load_stackoverflow) * 1961-04-24
US3488283A (en) * 1968-03-28 1970-01-06 Mobil Oil Corp Preparation of two different lube oil fractions by single solvent extraction

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3923636A (en) * 1974-06-03 1975-12-02 Texaco Inc Production of lubricating oils
US4170544A (en) * 1978-06-12 1979-10-09 Chevron Research Company Hydrocracking process including upgrading of bottoms fraction of the product
US5232577A (en) * 1990-08-14 1993-08-03 Chevron Research And Technology Company Hydrocracking process with polycyclic aromatic dimer removal
US20180187102A1 (en) * 2016-12-29 2018-07-05 Exxonmobil Research And Engineering Company Block processing with bulk catalysts for base stock production from deasphalted oil
US20180187092A1 (en) * 2016-12-29 2018-07-05 Exxonmobil Research And Engineering Company Block processing for base stock production from deasphalted oil
CN110121545A (zh) * 2016-12-29 2019-08-13 埃克森美孚研究工程公司 基础油料和含有该基础油料的润滑油组合物

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Publication number Publication date
FR2038209B1 (enrdf_load_stackoverflow) 1974-07-12
GB1286383A (en) 1972-08-23
NL7004064A (enrdf_load_stackoverflow) 1970-10-06
BE748345A (fr) 1970-10-02
DE2015805C3 (de) 1978-05-18
NL162687C (nl) 1980-06-16
DE2015805A1 (de) 1970-12-03
DE2015805B2 (de) 1977-09-29
JPS4949009B1 (enrdf_load_stackoverflow) 1974-12-25
NL162687B (nl) 1980-01-15
FR2038209A1 (enrdf_load_stackoverflow) 1971-01-08

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