US2847353A - Treatment of residual asphaltic oils with light hydrocarbons - Google Patents

Treatment of residual asphaltic oils with light hydrocarbons Download PDF

Info

Publication number
US2847353A
US2847353A US556495A US55649555A US2847353A US 2847353 A US2847353 A US 2847353A US 556495 A US556495 A US 556495A US 55649555 A US55649555 A US 55649555A US 2847353 A US2847353 A US 2847353A
Authority
US
United States
Prior art keywords
solvent
fraction
oil
deasphalting
line
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US556495A
Inventor
David K Beavon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Texaco Inc
Original Assignee
Texaco Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Texaco Inc filed Critical Texaco Inc
Priority to US556495A priority Critical patent/US2847353A/en
Application granted granted Critical
Publication of US2847353A publication Critical patent/US2847353A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10G21/00Refining of hydrocarbon oils in the absence of hydrogen, by extraction with selective solvents
    • 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
    • C10G21/00Refining of hydrocarbon oils in the absence of hydrogen, by extraction with selective solvents
    • C10G21/003Solvent de-asphalting

Description

TREATMENT F RESIDUAL ASPHALTIC OILS WITH LIGHT HY DROCARBONS David K. Beav'on, Westport, Conn., assigner to The Texas Company, New York, N. Y., a corporation of Delaware Application December 30, 1955, Serial No. 556,495

20 Claims. (Cl. 196-14.`11)

This invention is related to the treatment of residual, asphaltic oils with light hydrocarbons for the separation of asphaltic constituents therefrom. More particularly, this invention is concerned with the treatment of asphaltic, residual hydrocarbon oils for the recovery of the asphaltic constituents therefrom and for the production of a deasphalted oil suitable for use as a catalytic cracking feed stock. In accordance with one embodiment, this invention relates to a process for deasphalting residual hydrocarbon oils for the production of an asphalt fraction and a deasphalted oil fraction which is subsequently treated in accordance with the practice of this invention for the production of a catalytic cracking feed stock characterized by a relatively low metals content.

It is an object of this invention to provide an improved process for the treatment of residual, asphaltic hydrocarbon oils.

It is another object of this invention to provide a process for the treatment of residual asphaltic hydrocarbon oils with liquid, low molecular weight hydrocarbons, such as liqueed normally gaseous hydrocarbons, for the production of an asphalt fraction and a deasphalted oil fraction particularly suitable as catalytic cracking feed stock.

It is still another object of this invention to provide a -process for the treatment of residual asphaltic hydrocarbon oils wherein there is recovered a deasphalted oil fraction having a relatively reduced metals content and which is particularly suitable for use as a catalytic cracking charge stock.

How these and other objects of this invention are accomplished will become apparent with reference to the accompanying disclosure and drawing wherein there is schematically illustrated an embodiment of the practice of this invention.

Referring now in detail to the drawing a reduced crude, such as a mixture of reduced California crudcs, having an initial boiling point greater than about 650 F., usually having a boiling point higher than about 809 F., amounting to about 35-75% by volume of the original crude, is supplied via line 11 to vis-breaking zone l2 where it is subjected to temperature, pressure and throughput conditions so as to mildly lower the viscosity of the reduced crude. A temperature in the range 800- 1000 F., and a pressure in the range 50-800 p. s. i. g., are usually sufficient to eect mild vis-breaking of the reduced crude.

Vis-breaking of the reduced crude serves to reform or otherwise alter some of the high molecular weight or high boiling constituents of the reduced crude into relatively low molecular weight or low boiling constituents. The Vis-breaking operation tends to produce lower boiling, more aromatic constituents which are generally more refractory in a catalytic cracking operation than lower boiling, more parainic hydrocarbons which are also produced. The vis-breaking operation complements and otherwise cooperates with a subsequent combination of deasphalting and solvent refining operations in accordnited States "Patent ice ance with this invention and described hereinafter. The vis-breaking operation increases the yield of naphtha recoverable from the reduced -crude in that the relatively more aromatic hydrocarbons produced during the visbreaking operations are separated in subsequent combination fractionation and deasphalting solvent-refining steps with the resulting production of a more parainic catalytic cracking charge stock suitable for the production of a catalytic cracked naphtha.

The mildly vis-broken reduced crude from vis-breaking zone 12 is introduced via line 14 into fractionator or atmospheric iasher l5 from which there is recovered overhead via line 16 a gas fraction comprising normally gaseous hydrocarbons, such as propane and the butanes, a naphtha fraction via line 18, such as a 430 F. end point naphtha, and a gas oil fraction via line 119. There is also recovered from flasher l5 a bottoms fraction via line Ztl. The ilasher bottoms fraction is then introduced via line 2@ into a vacuum still or distillation zone 2l where it undergoes further fractionation for the production of a light gas oil fraction recovered via line 22 and a heavy gas oil fraction recovered Via line 24. a vacuum bottoms fraction is recovered from vacuum still 2i via line 25.

The vacuum bottoms fraction recovered from vacuum still 2l via line 25, usually having a gravity A. P. i. in the range 3-12 and a Conradson carbon residue in the range l5-40%, more o-r less., is introduced via line 25 into the `upper part of solvent deasphalting tower or zone 26. The solvent deasphalting operation may be a batch operation, a multiple vessel operation or a substantially continuous liquid-liquid countercurrent treating operation, as indicated in the drawing, wherein the vacuum bottoms to be deasphalted is introduced via line 25 into the top of deasphalting tower 26 and owed therein in countercurrent liquid-liquid contact with a suitable deasphalting solvent, such as a liqueed normally gaseous hydrocarbon, e. g., propane, n-butane, isobutane. The deasphalting solvent is introduced via line 29 into the bottom portion of deasphalting tower 26 from deasphalting solvent storage tank 28.

A suitable deasphalting solvent in accordance with the practice of this invention is a liquefied normally gaseous hydrocarbon such as ethane, ethylene, propane, propylene, normal butano, isobutane, n-butylene, isobutylene, pentane, isopentane and mixtures thereof, either alone 0r in the presence of a minor amount of additive materials to improve the deasphalting operation or otherwise increase the yield and quality of the deasphalted oil and/0r the recovered asphalt. The deasphalting operation is carried out at any suitable deasphalting temperature and pressure, the temperature and pressure being adjusted so as to maintain the deasphalting solvent in the liquid phase during the deasphalting operation. A deasphalting temperature inthe range 15G-325 F., usually not more than degrees Fahrenheit lower than the critical temperature of the deasphalting solvent, and a pressure inthe range 20G-SGO p. s. i. g., are employed depending upon the composition of the deasphalting solvent and the composition of the vacuum bottoms undergoing deasphalting. Generally, a deasphalting solvent to vacuum bottoms volume charge ratio in the range 2-10 is employed Within deasphalting tower 26. Deasphalting tower 26 may be operated isothermally or under a temperature gradient, top tower temperature greater than bottoms tower temperature by not more than about 40 degrees Fahrenheit; Also deasphalting tower 26 may be ered from deasphalting tower 26 a solvent deasphalted oil mix via line 31 and a solvent asphalt mix via line 30. The deasphalted oil in the mix in line 31 may have a gravity A. P. I. in the range 10-25 and a Conradson carbon residue in the range l-l% and a viscosity in the range 20G-600 SUS 210 F., more or less. The solvent deasphalted oil mix is introduced via line 31 into solvent recovery unit 32 wherein at least a portion or substantially all of the deasphalting solvent is removed from the deasphalted oil and returned to deasphalting solvent storage tank 2.8 via line 34.

Referring now to the gas oil fraction recovered from atmospheric flasher via line 19, this gas oil fraction is introduced into topping still 36 where there is produced overhead via line 3S a fraction having an end point of about 500 F., this overhead fraction being particularly suitable as a catalytic cracking charge stock. The bottoms fraction recovered from topping still 36 via line 39 is combined therein with the gas oil fractions recovered from vacuum fraetionator 21 via lines 22 and 24.

The deasphalted oil recovered from solvent recovery unit 32 via line 3S is introduced into pretreater 37 wherein it is contacted with a liquid selective solvent for aromatic hydrocarbons, such as furfural. Pretreater 37 may be any suitable device for effecting liquid-liquid contact between the liquid selective solvent employed and the deasphalted oil being pretreated. Preferably pretreater 37 is an apparatus suitable for effecting continuous countercurrent liquid-liquid contacting, such as a packed tower, a centrifugal contactor or a Rotating Disc Contactor. The deasphalted oil introduced into pretreater 37 is contacted with a solvent extract mix comprising selective solvent, such as furfural, together with dissolved hydrocarbons therein which is recovered from solvent refiningl unit 40, described hereinafter, and introduced into pretreater 37 via line 47. The resulting deasphalted oil raffinate from pretreater 37 is recovered therefrom via line 5S and introduced into line 39 for admixture With the bottoms fraction recovered from topping still 36 via line 39 and the gas oil fractions recovered from vacuum fractionator 21 via lines 22, 24 and 23. The resulting extract effluent from pretreater 37 is recovered via line 60 and introduced into selective solvent recovery Zone 61 wherein the selective solvent, e. g., furfural, is recovered and recycled to solvent refining unit 40 via line 62. The resulting separated extract is recovered from selective solvent recovery zone 61 via line 55. Various selective solvents may be employed in solvent refining unit 40, these include furfural, phenols (Selecto), nitrobenzene, sulfur dioxide, ALS,/3dichloroethyl ether (Chlorex), dimethyl formamide and other known selective solvents for aromatic hydrocarbons.

The resulting admixture in line 39 comprising the bottoms fraction from topping Still 36, the gas oil fractions from vacuum still 21 and the selective solvent pretreated deasphalted oil from pretreater 37 is introduced into solvent refining unit 40 wherein it flows in liquid-liquid counter-current contact with a liquid selective solvent, such as furfural, which selectively dissolves the more aromatic hydrocarbons therefrom. As previously indicated, the resulting extract mix from solvent refining unit 40 comprising selective solvent and extracted hydrocarbons is recovered via line 47 and introduced into pretreater 37.

The aromatic type hydrocarbons contained in the extract mix introduced into pretreater 37 via line 47 and employed to contact or pretreat the deasphalted oil should increase the solvent power of the selective solvent for the metal-containing components in the deasphalted oil A being thus pretreated and thus assist in their removal from the deasphalted oil. Furthermore, since the concentration of the metal-containing components would be greater in the deasphalted oil than in the admixture in line 39 introduced into the selective solvent refining unit a greater overall degree of metals removal is achieved. A1- so, the selective solvent contained in the deasphalted oil raffinate recovered from the pretreater 37 via line 33 serves to predilute the deasphalted oil raffinate introduced in admixture with `the gas oils' and bottoms fraction via line 39 into selective solvent refining unit 40. This predilution of the feed to the selective solvent refining unit 40 increases the efficiency vof the solvent refining operation therein. Still further, the deasphalted oil introduced into pretreater 37 via line 35 removes from the extract mix the lower molecular weight more paraffinic hydrocarbons therein which may have been taken into solution in the extract mix during the refining of the combined feed admixture supplied to the selective solvent refining unit 40 via line 39. These more parafiinic materials are returned continuously to the selective solvent refining unit 40 and thus the overall yield of the raffinate recovered from solvent refining unit 40 via line 41 is increased. The contacting or scrubbing of the extract mix Within pretreater 37 should result in a reduction in the quantity of the more parafinic materials withdrawn from pretreater 37 as lsolvent efliuent via line 60 and eventually removed from the system as extract suitable as cutter stock via line 55.

The resulting rafnate from selective solvent refining unit 40 having a reduced metals content, e. g., vanadium, nickel, copper and iron, in the range 0.2-5 p. p. m., after 'having been freed of its selective solvent content, is combined via line 41 with the 500 F. end point overhead fraction recovered from topping still 36 via line 33 and introduced as feed stock to tiuid catalytic cracking unit 42 where it is contacted with fluidized cracking catalyst. These cracking catalysts are usually oxides of metals of groups ll, HI, IV and V of the periodic table.

A suitable cracking catalyst comprises a silica-alumina catalyst containing about 5-30% by weight alumina. The average particle size of the cracking catalyst particles is usually below about 200 microns, a size suflicient to produce a dense iiuidized bed of cracking catalyst. The resulting catalytic cracked efliuent from fluid catalytic cracking unit 42 is introduced via line 44 into fractionator 4S wherein it is fractionated into a catalytic cracked naphtha recovered via line 46, a catalytic cracked light gas oil recovered via line 48 and a relatively heavy cycle gas oil recovered via line 49.

The solvent asphalt mix recovered from deasphalter 26 via line 30 is introduced into asphalt solvent recovery zone 50 wherein the deasphalting solvent is recovered via line 51 for return to deasphalting solvent storage tank 28. To the substantially solvent-free asphalt recovered from asphalt solvent recovery zone 50 via line S2, which asphalt may have a ring and ball softening point in the range -325 F., is added at least a portion of the gas oil fractions recovered from catalytic cracking fractionator 45 via lines 48, 49 and at least a portion of the selective solvent-free extract recovered from solvent recovery zone 61 via line 55, the resulting stream of combined catalytic cracked gas oils and selective solvent extract being added via line 54 as cutter stock to the substantially solventfree asphalt.

In accordance with one feature of this invention at least a portion of the light gas oil recovered via line i8 and/ or the heavy gas oil or FCCU decanted oil recovered via line 49 are passed via lines 54 and 57 to solvent refining unit 40 for the recovery of the more paraffinic constituents therefrom as raffinate via line 41 to provide additional catalytic cracking charge stock and for the recovery of the more aromatic constituents therefrom as extract via line 55 as cutter stock. If desired, particularly when the gas oil recovered from fractionator 45, such as the FCCU decanted oil, possesses a relatively high metals content, e. g., more than about 30 p. p. m., heavy metals the gas oils are introduced via lines S7 and 63 together with the deasphalted oil as feed to pretreater 37 to reduce its metals content.

Pretreater 37 is operated at any suitable temperature and pressure for effecting liquid-liquid contacting for the removal of the more aromatic components contained in the feed thereto. The operating conditions and solvent dosages employed within pretreater 37 are influenced to some extent by the composition of the feed thereto and the type of selective solvent employed therein. In the Portions of the above-identified vacuum still bottoms were solvent deasphalted, with liquid isobutane as the deasphalting solvent, employing a solvent:oil volume ratio of 5:1 at various temperatures in the range 20D-275 F. and at a pressure in the range 230-335 p. s. i. g. The results of these operations are set forth in accompanying Table No. I.

instance where furfural is employed as the selective solvent preti-eater 37 is operated at a solvent dosage in the range 75-250%, e. g., 125%, basis oil charge Whereas selective solvent rening unit 40, employing the same solvent (furfural) might beoperated at a relatively lower solvent dosage in the range -100%, e. g., about 25%, basis oil charge thereto. By operating in accordance with this feature of the invention the yield of recoverable catalytic cracked naphtha is further increased.

Desirably, especially when a particularly heavy crude, such as San Ardo California crude, is the source of the reduced crude introduced into the above-described operations via line 11, the asphalt in line 52, prior to the addition of cutter stock thereto via line 54,A is subjected to vis-breaking, -as indicated by vis-breaking zone 56 in the drawing, and the cutter stock added to the resulting visbroken asphalt via line 54a. Desirably, also, a portion of the combined stream employed as cutter stock is admixed via line 59 with the solvent asphalt mix recovered from deasphalter 26 via line 30 prior to introducing the same into asphalt solvent recovery unit 50 for the recovery of the deasphalting solvent therefrom. This addition of cutter stock to the solvent asphalt mix prior to introduction into the asphalt solvent recovery unit is desirable in order to alleviate coke deposition and reduce cracking which might occur Within the furnace heating tubes and upon the heated surfaces within the asphalt solvent recovery system.

The following is illustrative of the practice of this invention. A mixture comprising California crudes was atmospherically distilled to about 50-55% volume reduced crude based on the original crude mixture and charged through a heater operated under mild Viscositybreaking conditions at an outlet temperature of 850 F. The resulting mildly viscosity-broken reduced crude was introduced into an atmospheric asher from which was recovered overhead approximately 46% total volume yield of gas, naphtha and atmospheric viscosity-broken gas oil, basis reduced crude, in the following amounts: gas 1% volume; 430 F. end point naphtha 3.5% volume; gas oil 41.5% volume, the atmospheric flasher being operated at a maximum temperature of about 790-800 F. The remaining atmospheric flasher bottoms having a gravity of about 12 A. P. I. and a Conradson carbon residue of about 15 was introduced into a vacuum still operated at about mm. Hg and at a temperature of 665 F. There was recovered overhead from the vacuum still gas oil fractions amounting to about 42% by volume of the vacuum still charge and a heavy bottoms fraction amounting to about 16% by volume basis original crude mixture or about 33.8% by volume basis reduced crude. The vacuum still bottoms has a gravity of about 3.6 A. P. I., a penetration (100 gm./5 sec./77 F. cm. 102) in the range 27-29 and a Conradson carbon residue in the range 26-33.

The resulting deasphalted oils had a gravity in the range 15.346,8 A. P. I., a viscosity SUS 210 F. in the range 23S-281 and a K factor about 11.7. There was recovered from the aforesaid deasphalting operations an asphalt having a ring and ball softening point in the range 20G-30Wa F.

A high boiling petroleum fraction comparable to the deasphalted oil recovered from the aforesaid deasphalting operation is subjected to liquid-liquid contact with furrfural solvent extract mix at a solvent dosage in the range 1GO-200%, e. g., 125%, basis oil charge, the furfural solvent extract mix having been derived from the furfural solvent refining of the resulting deasphalted oil rafnate in admixture with VPS gas oil, said subsequent furfural rening being carried out at a solvent dosage in the range 15-75%, basis oil charge. The raiiinate resulting from the subsequent furfural refining operation possesses ay signicantly lower metals content, substantially below 30 p. p. m., in range 20-5 p. p. m. and lower.

In accordance with another feature of this invention the subsequent solvent reiining operation and/or the solvent pretreatment is carried out in the presence of a substantial amount of a light liquid hydrocarbon,such as the deasphalting solvent in an amount in the range 10-200 vol. percent, more or less, based on the deasphalted oil undergoing treatment either in pretreater 37 or in solvent refining unit 40. By so operating the metals content of the resulting refined deasphalted oil is further reduced,

e. g., below about 5 p. p. m. The advantages of carrying out a solvent reiining operation in the presence of liquid low molecular weight hydrocarbons, e. g., deasphalting solvent present due to the incomplete removal of deasphalting solvent from the deasphalted oil issuing from deasphalting unit 26 via line 31, is more completely set forth in my copending patent application Serial No. 547,638, led November 18, 1955, the disclosures of which are herein incorporated and made a part of this disclosure.

As will be apparent to those skilled in the art in the light of the foregoing, many substitutions, changes and alterations are possible in the practice -of this invention Without departing from the spirit or scope thereof.

I claim:

1. A process for treating a residual oil containing asphaltic constituents which comprises heating said oil to an elevated temperature under vis-breaking conditions, fractionating the resulting vis-broken oil to yield a first gas oil fraction and a rst bottoms fraction, fractionating said first bottoms fraction to produce a second gas oil fraction and a second bottoms fraction, fractionating said iirst gas oil fraction to separate therefrom constituents having a boiling point not greater than about 500 F. and to yield a third bottoms fraction, subjecting said second bottoms fraction to Contact with a liquid deasphalting solvent under deasphalting conditions to separate said asphaltic constituents from said second botaliases toms fraction and to yield a deasphalted oil fraction, contacting said deasphalted oil fraction with a lirst Solvent extract mix to yield a deasphalted oil raffinate and a second solvent extract mix, combining said third bottoms fraction, said second gas oil fraction and said deasphalted oil reafnate, subjecting the resulting combined stream to solvent refining in contact with a liquid solvent at least partially immiscible therewith under the conditions of contacting and which is a selective solvent for relatively more aromatic hydrocarbons, recovering from the aforesaid solvent reiining operation said rst extract mix and a finished raiiinate having a reduced amount of relatively more aromatic hydrocarbons relative to said combined stream, recovering from said second extract mix an extract having an increased amount of relatively more aromatic hydrocarbons relative to said combined stream, combining said finished raffinate with said constituents having a boiling point not greater than about 500 F., and subjecting the resulting combined stream to catalytic cracking.

2. A process in accordance with claim 1 wherein said elevated temperature is in the range 750-1000 F. and wherein said deasphalting solvent comprises a hydrocarbon selected from the group consisting of ethane, pro pane, normal butane, isobutane, normal pentane, isopentane and mixtures thereof.

3. A process in accordance with claim 1 wherein said solvent refining operation is carried out in the presence of said deasphalting solvent.

4. A process in accordance with claim l wherein said deasphalted oil fraction is contacted with said first solvent extract mix in the presence of a light liquid hydrocarbon.

5. A process in accordance with claim l wherein said deasphalting solvent comprises isobutane.

6. A process in accordance with claim l wherein said deasphalting solvent comprises isobutane and wherein said selectivesolvent is furfural.

7. A process in accordance with claim l wherein said deasphalting solvent comprises isobutane, and wherein said selective solvent is furfural and wherein said deas phalting is carried out at a temperature not more than 75 F. below the critical temperature of the deasphalting solvent.

8. A process for treating an asphaltic residual oil which comprises heating said oil to an elevated temperature under vis-breaking conditions, fractionating the resulting visbroken oil to yield a first gas oil fraction and a rst bottoms fraction, fractionating said irst bottoms rc to produce a second gas oil fraction and a second bottoms fraction, fractioning said first gas oil fraction to separate therefrom hydrocarbons having a boiling point not greater than about 500 F. and to yield a third bottoms fraction, subjecting said sec-ond bottoms fraction to contact with a liquelied normally gaseous hydrocarbon under deasphalting conditions to separate asphaltic constituents from said second bottoms fraction and to yield a deasphalted oil fraction, contacting said deasphalted oil fraction with a first solvent extract mix to yield a deasphalted oil rainate and a second solvent extract mix, combining said third bottoms fraction, said second gas oil fraction and said deasphalted oil raffinate, subjecting the `resulting combined stream to liquid-liquid solvent refining in Contact with a liquid selv tivo solvent immiscible with said resulting combined fractions and which is a selective solvent for relatively rnore aromatic hydrocarbons, recovering from the aforesaid solvent reining operation said first extract mix and a finished raiiinate having a reduced amount of more aromatic hydrocarbons and a lowered metals content relative to said combined stream, recovering from said second extract mix an extract having an increased amount of r :ratio hydrocarbons reiative to said resulting combined stream, combining said finished raflinate with said hydrocarbons l 'wing a boiling point not greater than about 500 F., ubjecting the resulting combined stream to catalytic cracking, separating from the resulting catalytic r1 uCLiOH A cracked eiuent a cracked gas oil fraction and admixing said extract and said cracked gas oil fraction with the asphaltic constituents separated from the aforesaid deasphalting operation. v

9. A process in accordance with claim 8 wherein said elevated temperature is in the range 750-1000" F., wherein said liquefied normally gaseous hydrocarbon is a C4 hydrocarbon, wherein said selective solvent is furfural and wherein the deasphalting conditions are such that the volume ratio of said liquefied normally gaseous hydrocarbon to said second bottoms fraction is about 5:1.v

l0. A process in accordance with claim 8 wherein said asphaltic constituents separated from said deasphalting operation are subjected to an elevated temperature under visbreaking conditions prior to being admixed with said extract and said cracked gas oil fraction.

ll. A process for treating a residual oil containing as` phaltic constituents which comprises heating said oil to an elevated temperature in the range 750-l000 F. under mild vis-breaking conditions, fractionating the resulting vis-broken o-i1 to yield a rst gas oil fraction and a iirst bottoms fraction, fractionating said rst botto-ms fraction to produce a second gas oil fraction and a second bottoms fraction, fractionating said first gas oil fraction to separate therefrom hydrocarbons having a boiling point not greater than 500 F. `and to yield a third bottoms fraction, subjecting said second bottoms fraction to liquidliquid contact with a liquid deasphalting solvent comprised of a major amount of a C4 paraiiinic hydrocarbon under deasphalting conditions to separate Iasphaltic constituents from said second bottoms fraction and to yield a deasphalted oil fraction, contacting said deasphalted oil fraction with a iirst solvent extract mix to yield a deasphalted oil raiiinate and a second solvent extract mix, combining said third bottoms fraction, said second gas oil fraction and said deasphalted oil raflinate, subjecting the resulting combined stream to liquid-liquid solvent rening in contact with furfural in the presence of a light paralnic hydrocarbon suitable for use as a deasphalting solvent, recovering from the aforesaid furfural solvent refining operation said first extact mix and a finished raffinate substantially free of furfural and having a reduced lamount of more aromatic hydrocarbons and a lowered metals content relative to said combined stream, recovering from said second extract mix an extract having an increased amount of relatively more aromatic hydrocarbons relative to said resulting combine-d fractions and said raiiinate, combining said finished raiiinate and said hydrocarbons having Ia boiling point not greater than about 500 F., subjecting the resulting combined stream to catalytic cracking, separating from the resulting catalytic cracked eiiiuent a cracked gas oil fraction, recovering said asphaltic constituents separated during said deasphalting operation, adding a portion of said extract and said cracked gas oil fraction to said recovered asphaltic constituents, fractionating the resulting admixture ycontaining said asphaltic constituents to separate therefrom said C4 parafiinic hydrocarbons deasphalting solvent 'and admixing additional `said extract Iand said cracked gas oil fraction with the resulting asphaltic constituents now substantially free of deasphalting solvent.

l2. A process in accordance with claim ll wherein said deasphalted oil raiinate in said combined stream subjected to furfural solvent refining contains adrnixed therewith C., paranic hydrocarbon deasphalting solvent.

13. A process in accordance with claim 1l wherein said deasphalting operation is carried out at a deasphalting solvent to second bottoms volume ratio of about 5:1 at a temperature in the range ZOO-300 F. and under sufficient pressure to maintain the deasphalting solvent in the liquid phase.

14. A process for treating an oil containing asphaltic constituents which comprises fractionating said oil toyield a gas oil fraction and a bottoms fraction containing said asphaltic constituents, subjecting said bottoms fraction to contact with a liquid deasphalting solvent under deasphalting conditions to separate said asphaltic constituents from said bottoms fraction and to yield a deasphalted oil, recovering said deasphalted oil, contacting said deasphalted oil with a lirst solvent extract mix to yield a deasphalted o il rafnate and a second solvent extract mix, combining said gas oil fraction and said deasphalted oil rainate, subjecting the resulting combined stream to solvent refining in contact with a liquid selective solvent which is at least partially immiscible therewith under the conditions of contacting and which is a selective solvent for relatively more aromatic hydrocarbons, and recovering from the aforesaid solvent rening operation said rst extract mix and a finished rainnate having a reduced amount of relatively more aromatic hydrocarbons relative to said combined stream.

15. A process in accordance with claim 14 wherein said selective solvent is furfural.

16. A process in accordance with claim 14 wherein said deasphalting solvent is isobutane.

17. A process in accordance with claim 14 wherein said deasphalted oil subjected to contact with said irst solvent extract mix and said deasphalted oil rainate subjected to contact with said selective solvent contain deasphalting solvent admixed therewith.

18. A process for treating a residual oil containing asphaltic constituents which comprises heating said oil to an elevated temperature under vis-breaking conditions, fractionating the resulting vis-broken oil to yield a gas oil fraction and a bottoms fraction containing said asphaltic constituents, deasphalting said bottoms fraction by contact with a liquid deasphalting solvent to precipitate said asphaltic constituents and to yield a deasphalted oil fraction, separating said deasphalted oil fraction, contacting said deasphalted oil fraction with a first solvent extract mix to yield a deasphalted oil raiinate, combining said deasphalted oil raffinate and said gas oil fraction, subjecting the resulting combined stream to solvent relining in contact with a liquid selective solvent, and recovering from the aforesaid solvent refining operation said tirst extract mix and a nished rainate having a reduced amount of aromatic hydrocarbons relative to said combined stream.

19. A process in accordance with claim 18 wherein said deasphalting solvent is isobutane, wherein said selective solvent is furfural and wherein said deasphalted oil fraction contains a substantial amount of deasphalting solvent admixed therewith.

20. A process in accordance with claim 18 wherein said finished raffinate is subjected to catalytic cracking to produce a catalytic cracked eiuent, separating from said catalytic cracked effluent a cracked gas oil fraction, recovering the aforesaid precipitated asphaltic constituents, combining said cracked gas oil fraction and said recovered asphaltic constituents and subjecting the resulting admixture to an elevated temperature under vis-breaking conditions.

References Cited in the le of this patent UNITED STATES PATENTS 2,202,389 Lewis et al. Mar. 28, 1940 2,396,302 Cummings et al Mar. 12, 1946 2,696,458 Strickland Dec. 7, 1954 2,702,782 Little Feb. 22, 1955 2,727,847 Hunn Dec. 20, 1955

Claims (1)

1. A PROCESS FOR TREATING A RESIDUAL OIL CONTAINING ASPHALTIC CONSTITUTENTS WHICH COMPRISES HEATING SAID OIL TO AN ELEVATED TEMPERATURE UNDER VIS-BREAKING CONDITIONS, FRACTIONATING THE RESULTING VIS-BROKEN OIL TO YIELD A FIRST GAS OIL FRACTION AND A FIRST BOTTOMS FRACTION, FRACTIONATING SAID FIRST BOTTOMS FRACTION TO PRODUCE A SECOND GAS OIL FRACTION AND A SECOND BOTTOMS FRACTION, FRACTIONATING SAID FIRST GAS OIL FRACTION TO SEPARATE THEREFROM CONSUTUENTS, HAVING A BOILING POINT NOT GREATER THAN ABOUT 500*F. AND TO YIELD A THRID BOTTONS FRACTION, SUBJECTING SAID SECOND BOTTOMS FRACTION TO CONTACT WITH A LIQUID DEASPHALTING SOLVENT UNDER DEAPHALTING CONDITIONS TO SEPARATE SAID ASHPHALTIC CONSTITUENTS FROM SAID SECOND BOTTOMS FRACTION AND TO YEILD AS DESPHATLTED OIL FRACTION, CONTACTING SAID DEASPHALTED OIL FRACTION WITH A FIRST SOLVENT EXTRACT MIX TO YIELD A DESPHALTED OL RAFFINATE AND A SECOND SOLVENT EXTRACT MIX, COMBINING SAID THIRD BOTTOMS FRACTION, SAID SECOND GAS OIL FRCTION AND SAID DEASPHALTED OIL REAFFINATE, SUBJECTING THE RESULTING COMBINED STREAM TO SOLVENT REFINING IN CONTACT WITH A LIQUID SOLVENT AT LEAST PARTIALLY IMMISCIBLE THEREWITH UNDER THE CONDITIONS OF CONTACTING AND WHICH IS A SELECTIVE SOLVENT FROM RELATIVELY MORE ATOMATIC HYDROCARBONS, RECOVERING FROM THE AFORESAID SOLVENT REFINING OPERATION SAID FIRST EXTRACT MIX AND A FINISHED RAFFINATE HAVING A REDUCED AMOUNT OF RELATIVELY MORE AROMATIC HYDROCARBONS RELATIVE TO SAID COMBINED STREAM, RECOVERING FROM SAID SECOND EXTRACT MIX AN EXTRACT HAVING AN INCREASED AMOUNT OF RELATIVELY MORE AROMATIC HYDROCABONS RELATIVE TO SAID COMBIED STREAM, COMBINING SAID FINISHED RAFFINATE WITH SAID CONSTITUENTS HAVING A BOILING POINT NOT GREATER THAN ABOUT 500*F., AND SUBJECTING THE RESULTING COMBINED STREAM TO CATALYTIC CRACKING.
US556495A 1955-12-30 1955-12-30 Treatment of residual asphaltic oils with light hydrocarbons Expired - Lifetime US2847353A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US556495A US2847353A (en) 1955-12-30 1955-12-30 Treatment of residual asphaltic oils with light hydrocarbons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US556495A US2847353A (en) 1955-12-30 1955-12-30 Treatment of residual asphaltic oils with light hydrocarbons

Publications (1)

Publication Number Publication Date
US2847353A true US2847353A (en) 1958-08-12

Family

ID=24221570

Family Applications (1)

Application Number Title Priority Date Filing Date
US556495A Expired - Lifetime US2847353A (en) 1955-12-30 1955-12-30 Treatment of residual asphaltic oils with light hydrocarbons

Country Status (1)

Country Link
US (1) US2847353A (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472760A (en) * 1967-12-04 1969-10-14 Chevron Res Process for converting asphaltenic oils and olefinic gasolines to high-value petroleum products
US3968023A (en) * 1975-01-30 1976-07-06 Mobil Oil Corporation Production of lubricating oils
FR2504936A1 (en) * 1981-04-29 1982-11-05 Raffinage Cie Francaise Process for obtaining synthetic raw oil
US4395330A (en) * 1980-11-28 1983-07-26 Institut Francais Du Petrole Process for solvent deasphalting of residual hydrocarbon oils
US4396493A (en) * 1982-06-24 1983-08-02 Shell Oil Company Process for reducing ramsbottom test of short residues
US4396494A (en) * 1981-09-21 1983-08-02 Shell Oil Company Process for reducing ramsbottom carbon test of asphalt
US4397733A (en) * 1981-07-17 1983-08-09 Shell Oil Company Process for reducing the Ramsbottom carbon test of asphalt
US4397734A (en) * 1981-06-25 1983-08-09 Shell Oil Company Process for reducing ramsbottom carbon test of short residues
US4469587A (en) * 1983-09-02 1984-09-04 Intevep, S.A. Process for the conversion of asphaltenes and resins in the presence of steam, ammonia and hydrogen
US4478705A (en) * 1983-02-22 1984-10-23 Hri, Inc. Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractions
US4514287A (en) * 1982-01-08 1985-04-30 Nippon Oil Co., Ltd. Process for the solvent deasphalting of asphaltene-containing hydrocarbons
US4522710A (en) * 1983-12-09 1985-06-11 Exxon Research & Engineering Co. Method for increasing deasphalted oil production
US4615795A (en) * 1984-10-09 1986-10-07 Stone & Webster Engineering Corporation Integrated heavy oil pyrolysis process
EP0202772A2 (en) * 1985-05-13 1986-11-26 Mobil Oil Corporation Oil upgrading by thermal processing
US4643821A (en) * 1985-07-15 1987-02-17 Exxon Research And Engineering Co. Integrated method for extracting nickel and vanadium compounds from oils
US4846957A (en) * 1986-04-11 1989-07-11 The British Petroleum Company P.L.C. Precipitation of asphaltene
US4883581A (en) * 1986-10-03 1989-11-28 Exxon Chemical Patents Inc. Pretreatment for reducing oxidative reactivity of baseoils
US5089114A (en) * 1988-11-22 1992-02-18 Instituto Mexicano Del Petroleo Method for processing heavy crude oils
US20050150816A1 (en) * 2004-01-09 2005-07-14 Les Gaston Bituminous froth inline steam injection processing
US20090301931A1 (en) * 2006-10-20 2009-12-10 Omer Refa Koseoglu Asphalt production from solvent deasphalting bottoms
EP2647691A1 (en) * 2011-05-31 2013-10-09 China University of Petroleum-Beijing Combined process for processing heavy oil
US20160177202A1 (en) * 2014-12-18 2016-06-23 Axens Process for the intense conversion of residues, maximizing the gas oil yield
US20160304793A1 (en) * 2013-12-03 2016-10-20 IFP Energies Nouvelles Process for refining a heavy hydrocarbon-containing feedstock implementing a selective cascade deasphalting

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2202389A (en) * 1934-09-07 1940-05-28 Standard Oil Dev Co Extraction of hydrocarbon material with light hydrocarbons
US2396302A (en) * 1940-12-07 1946-03-12 Standard Oil Dev Co Refining of mineral oils
US2696458A (en) * 1952-02-27 1954-12-07 Standard Oil Dev Co Deasphalting operation
US2702782A (en) * 1949-12-05 1955-02-22 Phillips Petroleum Co Hydrocarbon conversion
US2727847A (en) * 1952-05-16 1955-12-20 Sinclair Refining Co Process for recovering resins from petroleum fractions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2202389A (en) * 1934-09-07 1940-05-28 Standard Oil Dev Co Extraction of hydrocarbon material with light hydrocarbons
US2396302A (en) * 1940-12-07 1946-03-12 Standard Oil Dev Co Refining of mineral oils
US2702782A (en) * 1949-12-05 1955-02-22 Phillips Petroleum Co Hydrocarbon conversion
US2696458A (en) * 1952-02-27 1954-12-07 Standard Oil Dev Co Deasphalting operation
US2727847A (en) * 1952-05-16 1955-12-20 Sinclair Refining Co Process for recovering resins from petroleum fractions

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472760A (en) * 1967-12-04 1969-10-14 Chevron Res Process for converting asphaltenic oils and olefinic gasolines to high-value petroleum products
US3968023A (en) * 1975-01-30 1976-07-06 Mobil Oil Corporation Production of lubricating oils
US4395330A (en) * 1980-11-28 1983-07-26 Institut Francais Du Petrole Process for solvent deasphalting of residual hydrocarbon oils
FR2504936A1 (en) * 1981-04-29 1982-11-05 Raffinage Cie Francaise Process for obtaining synthetic raw oil
EP0064447A1 (en) * 1981-04-29 1982-11-10 COMPAGNIE FRANCAISE DE RAFFINAGE Société anonyme dite: Process for producing synthetic crude oil
US4397734A (en) * 1981-06-25 1983-08-09 Shell Oil Company Process for reducing ramsbottom carbon test of short residues
US4397733A (en) * 1981-07-17 1983-08-09 Shell Oil Company Process for reducing the Ramsbottom carbon test of asphalt
US4396494A (en) * 1981-09-21 1983-08-02 Shell Oil Company Process for reducing ramsbottom carbon test of asphalt
US4514287A (en) * 1982-01-08 1985-04-30 Nippon Oil Co., Ltd. Process for the solvent deasphalting of asphaltene-containing hydrocarbons
US4396493A (en) * 1982-06-24 1983-08-02 Shell Oil Company Process for reducing ramsbottom test of short residues
US4478705A (en) * 1983-02-22 1984-10-23 Hri, Inc. Hydroconversion process for hydrocarbon liquids using supercritical vapor extraction of liquid fractions
US4469587A (en) * 1983-09-02 1984-09-04 Intevep, S.A. Process for the conversion of asphaltenes and resins in the presence of steam, ammonia and hydrogen
US4522710A (en) * 1983-12-09 1985-06-11 Exxon Research & Engineering Co. Method for increasing deasphalted oil production
US4615795A (en) * 1984-10-09 1986-10-07 Stone & Webster Engineering Corporation Integrated heavy oil pyrolysis process
EP0202772A2 (en) * 1985-05-13 1986-11-26 Mobil Oil Corporation Oil upgrading by thermal processing
EP0202772A3 (en) * 1985-05-13 1988-07-27 Mobil Oil Corporation Oil upgrading by thermal processing
US4643821A (en) * 1985-07-15 1987-02-17 Exxon Research And Engineering Co. Integrated method for extracting nickel and vanadium compounds from oils
US4846957A (en) * 1986-04-11 1989-07-11 The British Petroleum Company P.L.C. Precipitation of asphaltene
US4883581A (en) * 1986-10-03 1989-11-28 Exxon Chemical Patents Inc. Pretreatment for reducing oxidative reactivity of baseoils
US5089114A (en) * 1988-11-22 1992-02-18 Instituto Mexicano Del Petroleo Method for processing heavy crude oils
US7914670B2 (en) 2004-01-09 2011-03-29 Suncor Energy Inc. Bituminous froth inline steam injection processing
US20050150816A1 (en) * 2004-01-09 2005-07-14 Les Gaston Bituminous froth inline steam injection processing
US7556715B2 (en) 2004-01-09 2009-07-07 Suncor Energy, Inc. Bituminous froth inline steam injection processing
US20100006474A1 (en) * 2004-01-09 2010-01-14 Suncor Energy Inc. Bituminous froth inline steam injection processing
US8685210B2 (en) 2004-01-09 2014-04-01 Suncor Energy Inc. Bituminous froth inline steam injection processing
US20090301931A1 (en) * 2006-10-20 2009-12-10 Omer Refa Koseoglu Asphalt production from solvent deasphalting bottoms
US9315733B2 (en) * 2006-10-20 2016-04-19 Saudi Arabian Oil Company Asphalt production from solvent deasphalting bottoms
EP2647691A1 (en) * 2011-05-31 2013-10-09 China University of Petroleum-Beijing Combined process for processing heavy oil
EP2647691A4 (en) * 2011-05-31 2014-06-18 Univ China Petroleum Combined process for processing heavy oil
US9290706B2 (en) 2011-05-31 2016-03-22 China University Of Petroleum-Beijing Integrated process for upgrading heavy oil
US20160304793A1 (en) * 2013-12-03 2016-10-20 IFP Energies Nouvelles Process for refining a heavy hydrocarbon-containing feedstock implementing a selective cascade deasphalting
US10160924B2 (en) * 2013-12-03 2018-12-25 IFP Energies Nouvelles Process for refining a heavy hydrocarbon-containing feedstock implementing a selective cascade deasphalting
US20160177202A1 (en) * 2014-12-18 2016-06-23 Axens Process for the intense conversion of residues, maximizing the gas oil yield
US10501695B2 (en) * 2014-12-18 2019-12-10 Axens Process for the intense conversion of residues, maximizing the gas oil yield

Similar Documents

Publication Publication Date Title
JP6427180B2 (en) How to upgrade refined heavy residual oil to petrochemical products
EP2084244B1 (en) Enhanced solvent deasphalting process for heavy hydrocarbon feedstocks utilizing solid adsorbent
US9505678B2 (en) Process to produce aromatics from crude oil
CA2439038C (en) Method of and apparatus for upgrading and gasifying heavy hydrocarbon feeds
EP3017021B1 (en) Method of producing aromatics and light olefins from a hydrocarbon feedstock
EP0246956B1 (en) Process for the elimination of asphaltenes from a hydrocarbon feedstock
US2409695A (en) Method for improving aviation fuels
US4454023A (en) Process for upgrading a heavy viscous hydrocarbon
CA2326259C (en) Anode grade coke production
US2727853A (en) Process for refining of petroleum, shale oil, and the like
US4239616A (en) Solvent deasphalting
US3227645A (en) Combined process for metal removal and hydrocracking of high boiling oils
US4450067A (en) Distillation-induced extraction process
US2380279A (en) Production of aromatics
US4302323A (en) Catalytic hydroconversion of residual stocks
US3617493A (en) Process for steam cracking crude oil
US3287254A (en) Residual oil conversion process
US2953513A (en) Hydrogen donor diluent cracking process
US2697684A (en) Reforming of naphthas
US2767124A (en) Catalytic reforming process
US2917448A (en) Hydrogenation and distillation of lubricating oils
US5024750A (en) Process for converting heavy hydrocarbon oil
US4592832A (en) Process for increasing Bright Stock raffinate oil production
JP2020007321A (en) Process and installation for conversion of crude oil to petrochemicals having improved ethylene yield
US3414506A (en) Lubricating oil by hydrotreating pentane-alcohol-deasphalted short residue