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US3579435A - Hydrocracking process - Google Patents

Hydrocracking process Download PDF

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Publication number
US3579435A
US3579435A US738432A US3579435DA US3579435A US 3579435 A US3579435 A US 3579435A US 738432 A US738432 A US 738432A US 3579435D A US3579435D A US 3579435DA US 3579435 A US3579435 A US 3579435A
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hydrocracking
fractions
fraction
boiling
range
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US738432A
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Albert T Olenzak
Sheldon L Thompson
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Sunoco Inc
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Sun Oil 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions

Definitions

  • the charge stock is fractionated into three fractions, the first fraction boiling in the range of about 650 to 850 F., the second fraction boiling in the range of about 850 to 1000 F., and the third fraction containing all the material boiling above about 1000 P. which has been deasphalted; and each of the foregoing fractions is separately hydrocracked for at least a portion of the total time it is hydrocracked, preferably over a hydrocracking catalyst comprised of a sulfide of a Group VI metal, left-hand column, and/ or an iron group metal, and most preferably a mixture of nickel sulfide and tungsten sulfide in a 1/ 1 to 4/1 metal ion ratio, at a temperature in the range of about 735 to 825 F. and a hydrogen partial pressure of about 2500 to about 4000 p.s.i.
  • the present invention relates to the art of petroleum refining or processing and, more particularly, to the production of lubricating oils of high viscosity index. Still more particularly, the present invention is directed to a process for treating a lube oil hydrocracker charge whereby the high viscosity index oils produced have a high quality and are produced in greater yields than heretofore by subjecting separate fractions of a lube oil hydrocracker charge stock to hydrocracking conditions for a time and temperature commensurate with the polyfused-ring aromatics present in the respective separate fraction.
  • a particularly desired lubricating oil product is one which possesses a multiple viscosity characteristic or alternatively described as a high viscosity index (V.I.) oil in order that the oil will perform at a high degree of efficacy at varying degrees of temperature to which it is subjected in use.
  • V.I. viscosity index
  • lube oil hydrocracking processes use a relatively heavy charge stock containing a large amount of cyclic compounds such as the naphthenes, aromatics, and in most cases polycyclic fused-ring compounds.
  • Typical charge stocks are unpressed vacuum distillates, deasphalted reduced crudes, pressed and unpressed deasphalted residuums, all usually boiling above about 650 F. While not wishing to be bound by any theories set forth herein, it is believed that those theories advanced heretofore by others are correct as to the mechanism involved in hydrocracking enhancement of the V.I. of such lube oil fractions. These theories postulate that the V.I.
  • the hydrocracker feed stock is invariably a complex mixture of compounds as indeed any petroleum fraction is, and the heavier frac tions invariably comprise a mixture of polyfused-ring compounds of various types. Certain of these polyfusedring compounds are easier to break than others.
  • Hydrocracking operating conditions are quite naturally adjusted to the particular feed and based on the results obtained therewith. The greater the amount of hydrocracking refractory materials present, the more operating conditions tend to be adjusted upward, the temperature in particular. In making such adjustments in operating conditions, certainly more of the refractory materials are caused to break and open up into aliphatic substituents on a remaining ring(s).
  • a hydrocracking reactor constructed to provide for a plurality of separate feed conduits at various intermediate points of the catalyst bed(s) of a plurality of serial arranged beds or manifold means for charging separate feeds to different intermediate points of the length of the catalyst bed(s).
  • Feed fractions containing an intermediate amount of more refractory materials are to be passed over an intermediate length of the catalyst bed(s) and thereby are exposed to hydrocracking conditions for an intermediate amount of time commensurate with its refractory content.
  • the fraction boiling above about 1000 F. is deasphalted, and after deasphalting it no longer contains as much polycyclics as the preceding fraction and treatment is varied accordingly.
  • the fractions containing larger amounts of polycyclics may be treated at higher temperatures to bring about suflicient cracking of the more refractory materials.
  • the lub stock is separated into three fractions: the first fraction boiling in the range of about 650 to 875 F., but preferably about 700 to 850 F.; the second fraction boiling in the range of about 850 to l000 F and the third fraction containing all of the material which has been deasphalted boiling at about 1000 F. and above. It is to be fully appreciated in stating the foregoing temperature limits of the fractions that they are capable of some variation depending on several factors; however, the 100 F. cut point for the deasphalter is especially subject to variation by a substantial number of degrees.
  • the minimum boiling material charged to a deasphalter is about 1000 F., but the precise cut point is determined by economic considerations based on the fact that dcasphalting is an expense which is, if it can, to be avoided. On the other hand, the particular crudes character and especially the efiiciency or efiicacy of the vacuum tower are perhaps even more important.
  • Deasphalting as those skilled in the art are well aware, is carried out to remove metals, asphaltens, resins, and other undesired materials before further processing them under conditions in which they exert an adverse effect. Accordingly, the approximate 1000 F. limitation on the deasphalted fraction and the preceding fraction is to be viewed in light of this wellknow technology.
  • the catalyst composition may be the same or different in the several beds or zones of a single bed with the composition selected dependent on the charge stock to be passed over same and the known characteristics of the particular catalyst composition.
  • Any lube oil hydrocracking catalyst suitable for the manufacture of high V.I. lubes can be employed; however, generally preferred catalysts are sulfides of a Group VI metal, lefthancl column, of the periodic system, mixed with an iron group metal. Most preferably, the catalyst is a mixture of nickel sulfide and tungsten sulfide in a l/1 to 4/1 metal ion ratio.
  • the temperatures employed can be the same throughout the bed(s) or different but, in general, will be in the range of about 650 to 875 F., more usually and preferably in the range of about 735 to 925 F.
  • the partial pressure of hydrogen should be at least about 1500 psi. and more usually above about 2500 psi. to about 4000 psi, although hydrogen partial pressures as high as about 10,000 psi can be employed. If adequate provisions are taken in constructing the equipment, the pressure can be varied in the various catalyst beds. Operating with different pressures in the different catalyst beds is more easily accomplished in either a blockedout operation or by using a plurality of parallel reactors wherein the various feed fractions are separately charged and the products separately recovered.
  • reaction variables are interdependent, and particularly temperature and resi deuce time, or as it is more frequently stated, the flow rates. This has particular significance in a blocked-out or other operation Where completely separate reactors are employed. Because of the possibilities presented by a blocked-out operation, parallel reactors, or other means of processing fractions completely separately, such embodiments are not to be regarded as full equivalents although certainly there is some functional equivalence.
  • temperature and residence time vary inversely on a particular oil charge if substantially equivalent results are to be obtained.
  • the residence time is to be decreased by increasing the flow rates if substantially equivalent results are to be obtained.
  • temperature accelerates cracking rates exponentially so that as the temperature is increased to the higher ranges a greater incremental change is required in the residence time to offset its effect than in the lower ranges.
  • a product of higher aromaticity is sometimes produced with all other properties being substantially the same. This is because of an apparent hydrogenation-dehydrogenation equilibrium which is reached in the higher ranges of temperature. It is with the foregoing qualifications understood that the discussions above and below have equated temperature and residence time on an inverse effect basis.
  • reaction temperature and residence time has considerably more commercial importance when properly applied to two diflFerent charge fractions in a blocked-out or parallel reactor embodiment if the product streams of the different fractions are not mixed as they are in the case of serially arranged reactors. This is because the heavier fractions which contain more refractory materials are subjected to more vigorous conditions, which invariably results in more cracking of heavier molecules to lower molecular weight compounds. This is true whether the more vigorous conditions consist of an increased temperature or longer reaction time or a combination of the two.
  • the low V.I. in between that of the low V.I. cleavage product and that of the high V.I. product from the lighter charge fraction.
  • the composite V.I. of the blend may be so low as to require rerunning the blend to upgrade the V.I., and in any event the blend has a substantially lowered V.I. as compared to the high V.I. product from the lighter charge.
  • these materials can be recovered separately and the low V.I. material from cleavage-cracking of the heavier fraction alone can, if desired, be rerun to increase its V.I.
  • any fraction present in excess can be reduced in amount by adjusting process conditions or rerunning it in a fashion commensurate with its refractory character to reduce its yield by cleavage-cracking and thereby produce a corresponding amount of lower molecular weight product with a relatively low V.I.
  • the lower molecular weight product then can be upgraded to a higher V.I. by rerunning at conditions which are more favorable to upgrading than cleavage-cracking. Any rerunning can be conveniently carried out by recycle of material in a continuous operation.
  • a suitable hydrocracking charge residuum boiling above about 650 F. is split into three fractions and placed in separate reservoirs.
  • In Rerservoir No. 1 is placed the material boiling in the range of about 650 to 850 F.
  • In Reservoir No. 2 is placed the material boiling in the range of about 850 to 1000 F.
  • In Reservoir No. 3 is placed the ma- 6 terial boiling at about 1000 F. and above including asphaltenes, and the like, normally present in such heavy fractions.
  • the material from Reservoir No. 3 is first charged via line 3 to deasphalter 4, and the deasphalted product is charged via line 5 to connecting conduit 9 and into Hydrocracker No. 2 which is the middle reactor of three serially arranged hydrocracking reactors.
  • This reactor (and all the other hydrocracking reactors described hereinafter) contains a catalyst bed comprising a nickel sulfide-tungsten sulfide mixture (in a metals ratio of about 4/1 respectively) on alumina carrier.
  • the temperature is maintained at about 770 F. and a hydrogen partial pressure is maintained at about 2500 p.s.i. (g.), the latter being maintained by hydrogen additions through line 7.
  • the material from Reservoir No. 2 is charged via line 2. to the first hydrocracker, Hydrocracker No. 33, wherein the temperature is maintained at about 770 F. and the partial pressure of hydrogen is maintained at about 2500 p.s.i.(g.) by the addition of hydrogen via line 7.
  • the feed fraction charged is passed over a catalyst similar to that in Hydrocracker No. 2 at the foregoing conditions; and the reactor effluent is charged via connecting conduit 9 to Hydrocracker No. 2, admixed with deasphalted oil from Reservoir No. 3, and processed therewith.
  • the material from Reservoir No. 1 is charged via line 1 to connecting conduit 10, admixed therein with the effluent from Hydrocracker No. 2, and passed over a nickel sulfide-tungsten sulfide catalyst at a temperature of about 750 F and a partial pressure of hydrogen of about 2500 p.s.i. (g.) maintained by the addition of hydrogen through line 6.
  • the effluent from Hydrocracker No. 1 is passed via line 11 to a fractionating tower 12 where the gases and other very light materials are separated and the hydrocracked oil is fractionated into Neutral, 200 Neutral, 500 Neutral, and Bright stock fractions of typical respective viscosities but of high V.I.s on the order of to 116.
  • Example II a suitable hydrocracking charge residuum boiling above about 650 F. is spit into three fractions and placed in separate reservoirs.
  • Reservoir No. 1 is placed the material boiling in the range of about 650 to 850 F.
  • Reservoir No. 2 is placed the material boiling in the range of about 850 to 1000 F.
  • Reservoir No. 3 is placed the material boiling at about 1000 F. and above including asphaltenes, and the like, normally present in such heavy fractions.
  • the material from Reservoir No. 3- is first charged via line 3 to deasphalter 4, and the deasphalted product is charged via line 5 to Hydrocracker No. L2 which is one of three separate hydrocrackers.
  • This reactor contains a catalyst bed comprising a nickel sulfidetungsten sulfide mixture (in a metals ratio of about 4/1 respectively) on alumina carrier.
  • the temperature is maintained at about 755 F. and hydrogen partial pressure is maintained at about 2500 p.s.i.g., the latter being maintained by hydrogen additions through line 6.
  • the efiluent from Hydrocracker No. 2 is charged to Fractionator No.
  • the material from Reservoir No. 1 is charged via line 1 to separate Hydrocracker No. 1 and is admixed in line 1 with the separated light fraction of the eflluent from Hydrocracker No. 2 and is passed over a catalyst similar to that in Hydrocracker No. 2 at a temperature of about 748 F. and a partial pressure of hydrogen of about 2500 p.s.i.g. maintained by the addition of hydrogen through line 10.
  • the efiiuent from Hydrocracker No. 1 is passed via line 11 to Fractionator No.
  • the material from Reservoir No. 2 is charged via line 2 to separate Hydrocracker No. 3, wherein the temperature is maintained at about 755 F. and the partial pressure of hydrogen is maintained at about 2500 p.s.i.g. by the addition of hydrogen via line 13, and is passed over a catalyst similar to that in Hydrocracker No. 2.
  • the reactor effluent is charged via line 14 to Fractionator No. 3 where it is fractionated into a light fraction similar in boiling point and viscosity to the deasphalted residuum charged to Hydrocracker No. 2, and this material is charged via line 15 to feed line and then into Hydrocracker No. 2 for upgrading in V.I.
  • the effiuent from Hydrocracker No. 3 is also fractionated into a fraction which has typical boiling points and viscosities of a No. 2 and No. 4 distillate, both of which are highly suitable as high V.I. lube stocks.
  • the space velocity can vary considerably but usually will be in the range of about 0.1 to 4. In most cases, it is preferably to operate at space velocities in the range of about 0.25 to 1.5.
  • a process of hydrocracking lube oil stocks to high viscosity index oils comprising fractionating a lube oil charge stock boiling above about 650 F. into a plurality of fractions having different boiling ranges, subjecting a higher boiling fraction to hydrocracking conditions of from 650 to 875 F. under a hydrogen partial pressure of at least about 1500 p.s.i. in the presence of a hydrocracking catalyst and comibning this hydrocracked higher boiling fraction with a lower boiling fraction and subjecting the thus formed mixture to hydrocracking conditions of from 650 F. to 875 F. under a hydrogen partial pressure of at least 1500 p.s.i.
  • lube oil charge stock is an unpressed vacuum distillate, a deasphalted reduced crude, a pressed deasphalted residuum, an unpressed deasphalted residuum, or blend-s thereof.

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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)
US738432A 1968-06-20 1968-06-20 Hydrocracking process Expired - Lifetime US3579435A (en)

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US73843268A 1968-06-20 1968-06-20

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US (1) US3579435A (pt)
JP (1) JPS4816681B1 (pt)
BE (1) BE734950A (pt)
BR (1) BR6909927D0 (pt)
DE (1) DE1931441A1 (pt)
FR (1) FR2011293B1 (pt)
GB (1) GB1231157A (pt)
NL (1) NL6909452A (pt)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3730876A (en) * 1970-12-18 1973-05-01 A Sequeira Production of naphthenic oils
US3764518A (en) * 1971-10-20 1973-10-09 Gulf Research Development Co Procedure for the preparation of high viscosity - high vi lubricating oils
US3876522A (en) * 1972-06-15 1975-04-08 Ian D Campbell Process for the preparation of lubricating oils
US3902989A (en) * 1970-01-14 1975-09-02 Mobil Oil Corp Method for producing hydrocracked lube oil products
US3941680A (en) * 1971-10-20 1976-03-02 Gulf Research & Development Company Lube oil hydrotreating process
US4011154A (en) * 1973-03-26 1977-03-08 Chevron Research Company Production of lubricating oils
US4211635A (en) * 1979-04-23 1980-07-08 Mobil Oil Corporation Catalytic conversion of hydrocarbons
US5904835A (en) * 1996-12-23 1999-05-18 Uop Llc Dual feed reactor hydrocracking process
US6113775A (en) * 1997-12-05 2000-09-05 Uop Llc Split end hydrocracking process
US20050205462A1 (en) * 2004-03-17 2005-09-22 Conocophillips Company Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3902989A (en) * 1970-01-14 1975-09-02 Mobil Oil Corp Method for producing hydrocracked lube oil products
US3730876A (en) * 1970-12-18 1973-05-01 A Sequeira Production of naphthenic oils
US3764518A (en) * 1971-10-20 1973-10-09 Gulf Research Development Co Procedure for the preparation of high viscosity - high vi lubricating oils
US3941680A (en) * 1971-10-20 1976-03-02 Gulf Research & Development Company Lube oil hydrotreating process
US3876522A (en) * 1972-06-15 1975-04-08 Ian D Campbell Process for the preparation of lubricating oils
US4011154A (en) * 1973-03-26 1977-03-08 Chevron Research Company Production of lubricating oils
US4211635A (en) * 1979-04-23 1980-07-08 Mobil Oil Corporation Catalytic conversion of hydrocarbons
US5904835A (en) * 1996-12-23 1999-05-18 Uop Llc Dual feed reactor hydrocracking process
US6113775A (en) * 1997-12-05 2000-09-05 Uop Llc Split end hydrocracking process
US20050205462A1 (en) * 2004-03-17 2005-09-22 Conocophillips Company Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons
US7354507B2 (en) 2004-03-17 2008-04-08 Conocophillips Company Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons

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Publication number Publication date
BE734950A (pt) 1969-12-22
GB1231157A (pt) 1971-05-12
FR2011293A1 (pt) 1970-02-27
DE1931441A1 (de) 1970-01-02
BR6909927D0 (pt) 1973-03-13
FR2011293B1 (pt) 1973-11-16
JPS4816681B1 (pt) 1973-05-24
NL6909452A (pt) 1969-12-23

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