US2763600A - Upgrading of heavy hydrocarbonaceous residues - Google Patents

Upgrading of heavy hydrocarbonaceous residues Download PDF

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Publication number
US2763600A
US2763600A US227236A US22723651A US2763600A US 2763600 A US2763600 A US 2763600A US 227236 A US227236 A US 227236A US 22723651 A US22723651 A US 22723651A US 2763600 A US2763600 A US 2763600A
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United States
Prior art keywords
catalyst
solids
zone
coking
vapors
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Expired - Lifetime
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US227236A
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English (en)
Inventor
Clark E Adams
Jr Charles N Kimberlin
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to US227236A priority Critical patent/US2763600A/en
Priority to GB10018/52A priority patent/GB724117A/en
Priority to FR1060056D priority patent/FR1060056A/fr
Priority to DEST4849A priority patent/DE939945C/de
Application granted granted Critical
Publication of US2763600A publication Critical patent/US2763600A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps

Definitions

  • the present invention relates to a process of treating hydrocarbons. More particularly, the invention pertains to a method of producing from relatively heavy or high boiling hydrocarbonaceous residues of the type of topped or reduced crude, pitch, asphalt or similar heavy residues increased quantities of motor fuel range fractions of improved quality as well as higher boiling distillate fractions suitable for further cracking. Briefly, the invention provides for coking heavy residues of the type specified in contact with a dense, turbulent, fluidized mass of subdivided inert solids to produce volatile coking products and coke and then subjecting the total volatile coking products immediately and without condensation to catalytic cracking for a relatively short time in the presence of large proportions of finely divided catalyst suspended in the vapors to be cracked.
  • dense phase fluid operation does not readily lend itself to short time low severity cracking which is conducive to higher yields of better quality gasoline when applied to the volatile coking products of dense phase inert solids fluid-type coking of residual oils.
  • the present invention eliminates these drawbacks.
  • lt is, therefore, the principal object of the invention to provide improved means for producing motor fuels by coking heavy residua in contact with lluidized inert solids followed by catalytic cracking of the total volatile coking product on subdivided suspended catalysts.
  • Other objects and advantages will appear from the description of the invention given below wherein reference will be made to the accompanying drawing, the single ligure of which is a semi-diagrammatical illustration of a system suitable to carry out a preferred embodiment of the invention.
  • heavy hydrocarbonaceous residues of the type specified above are contacted at coking conditions in a dense phase fluid-type reactor with a dense, turbulent, uidized mass of catalytically substantially inert solids to convert the feed into lower boiling volatile products and coke depositing on the inert solids and to remove contaminating ash constituents of the feed.
  • the total volatile eliiuent of this coking stage is mixed immediately and without any prior condensation with finely divided cracking catalyst in relatively high proportions and the mixture formed is passed at cracking conditions in the form of a dense suspension and at a relatively high velocity through a narrowly confined extended path for a time sulicient to produce optimum yields of high quality motor fuels.
  • the process is preferably so operated that the cracking catalyst is added to the volatile eiuent of the coking stage immediately after the removal therefrom of solids fines entrained from the fluid coking Zone, so that the time interval for which the vapors are subjected to coking temperatures in the absence of suspended solids 'is reduced to a minimum or practically eliminated.
  • the best place for introducing at least a part of the catalyst is the point at which the vapors enter -thevapor withdrawal line of the coking reactor.
  • Fluidization conditions in the coking zone may be maintained within conventional ranges.
  • the particle size of the inert solids depends, of course, to a certain extent on their density. Assuming a density of the order of that of coke, the particle size may be about lll-200 microns, preferably 50p-15() microns.
  • Linear superficial lluidizing velocities of the iiuidizing medium may vary from 0.35 ft. per second, preferably from about 0.5-1.5 ft. per second, to establish an apparent density of the iiuidized bed of about 20-50 lbs. per cu. ft. and a definite upper interface Within the coking zone.
  • the cracking catalysts may be used in substantially the same size ranges and should be added to the vaporous coking zone eifluent in amounts of about 30G-5000 lbs. per barrel of residuum feed.
  • the mixture of vapors and catalyst may be passed through the transfer line cracking zone at a vapor velocity of about 5-25 ft. per second, preferably about lil-20 ft. per second to establish apparent densities of the turbulent suspension of about l-ZO lbs. per cu. ft., depending partly on the slope of the cracking path which may vary from substantially horizontal to substantially vertical with upward iiow of the reactants.
  • Reaction conditions may include coking temperatures of about 850-1l00 F. and catalytic cracking temperatures of about 800-1000 F. Pressures ranging from atmospheric to about 100 p. s. i. g. may be employed throughout.
  • the solids hold-up in the coking zone may be chosen to permit vapor residence times of about -60 seconds. Substantially shorter vapor residence times of about 2-10 seconds, preferably about 4 8 seconds, are maintained in the catalytic cracking zone.
  • Heat required by the endothermic coking and catalytic cracking reactions may be supplied by indirect heating or by the circulation of reheated process solids in any manner known in the art.
  • the heat generated by a combustion-type of catalyst regeneration is used to maintain the desired temperatures in the coking and catalytic cracking zones. It has been found that the coke deposited on the catalyst in the course of the catalytic cracking reaction carried out in accordance with the invention is sufficient for this purpose.
  • this may be accomplished by separating used catalyst from the cracked vapors, burning coke olf the catalyst in a dense vphase fluidtype regeneration zone and circulating coker solids from the coker through a heat exchange coil immersed in the regenerator bed and back to the coker, while returning hot regenerated catalyst to the catalytic cracking zone.
  • the system illustrated therein essentially comprises a dense phase fluid-type coker l1, .a catalytic transfer line type reactor 23 and a dense phase fluid-type catalyst regenerator 37.
  • the functions and coaction of these elements will be forthwith described using the conversion of virgin crude distillation bottoms into motor fuels as an example. It should be understood, however, that the systems may be employed for the conversion of .other coke-forming feed stocks ⁇ into the same or different products in a substantially analogous manner.
  • Coker 11 contains a dense, turbulent, iiuidized mass M11 of inert solids, having an upper interface L11 and maintained at about 850-l050 F.
  • the oil feed rate to coker 11 may be about 0.5 barrel to about 25 barrels per hour per ton of solids hold-up in coking zone 11 at oil vapor residence times of about l0 to 60 seconds in mass M11.
  • the feed rate depends upon the temperature; at SSW-959 F.y the feed rate may be 0.5-4 bbl./hr./ton, at 950%1050" F. the rate may be about 2.5-10 bbl./hr./ton, above l050 F. the rate may be about 5-25 bbl./hr./ ton.
  • a iiuidizing gas such as steam, hydrocarbon gases or vapors is supplied through line 1S and grid i3 to establish a linear superficial gas velocity of about 0.3-3 ft./sec. and an apparent density of about 2li-50 lbs/cu. ft. in mass M11.
  • Any of the inert solids mentioned above may be used in coker 1l. However, coke having a particle size of about 50-150 microns is preferred.
  • the temperature in coker 11 is maintained at about 850-105G F. as will appear hereinafter. Atmospheric or a slightly elevated pressure is generally most desirable. At these conditions, the oil feed may be converted to yield about 88-90 wt. percent of volatile products and about 10-12 wt.
  • a standpipe 16 is provided through which coke may be Withdrawn from mass M11 as required. A portion of the coke Withdrawn may be recovered through line 18. The remainder may be ground in grinder 29 to a fluidizable size and returned via lines 22 and 15 to mass M11. Volatile products containing entrained coke fines pass overhead from level L11 into suitable gas-solids separation means such as cyclone separator 17 provided with solids return pipe 19.
  • the mixture of catalyst and reactants v may enter reactor 2.3 at a tempera- ⁇ ture of Vabout Gl000 F. Due to the endothermic heat of cracking the temperature will decrease as the mixture of voil and catalyst pass through the Vtransfer line. The amount of this drop in temperature will depend upon the conversion in the transfer line and upon the catalyst lto oil ratio, and may be as much as 50 F.
  • reactor 2.3 y is shown as a substantially horizontal pipe having a length/ diameter ratio of at least about 12/1 which should be designed for a velocity of about itl-20 ft./sec. and a vapor residence time of about 4-8 seconds at the feed rates involved.
  • the sus-pension in reactor 23 will have a density of about 2-15 lbs/cu. ft., no appreciable solids ⁇ settling or backmixing taking place.
  • Reactor 239 discharges into a suitable gas-solids separator such as cyclone 311 from which a mixture of cracked products and carrier gas, substantially free of catalyst, may be withdrawn through jline to be passed to conventional product recovery equipment (not shown).
  • catalyst separated in cyclone 31 is dropped through dip-pipe 35 into catalyst regenerator 37 which is supplied with air through line 39 and grid 41, sufiicient in amounts to restore catalyst activity by coke combustion.
  • the linear superfici-al velocity of the gases in regenerator 37 is maintained at about 0.3-1.5 ft./sec. conductive to the formation of a dense, turbulent fluidized catalyst mass M37 having a definite interface L37 and an apparent density of about 20-50 lbs/cu. ft. and exhibiting excellent heat transfer characteristics.
  • Flue gases are Withdrawn overhead from level L37 through cyclone separator 43 to be vented through line 45. Separated catalyst fines may be returned via dip-pipe 47 to mass M31 or discarded through line 49.
  • the direction of diluent injection as indicated by the inclination of taps t is such that coke from mass M11 circulates through line 53 to coil 5'1 and through line 55 back to mass M11.
  • ICoke circulation may be readily so controlled in this manner that, at a practical surface area of coil 51, the catalyst in mass M37 may be maintained at desirable temperatures of about 10001l50 F. and mass M11 at the coking temperatures specified above.
  • Suitable circulation rates may be about 1-3 tons of coke per barrel of residuum feed assuming an immersed surface area of coil S1 of about 0.5-2 sq. ft. per barrel of daily feed rate.
  • Regenerated catalyst 4 is withdrawn substantially at the temperature of mass M37 through line 57 and may be further cooled to ⁇ about 800-1050 F. in heat exchange with the feed residuum in heat exchanger 3 as described above.
  • rPhe cataly-st in line 57 may be stripped and aerated by means of steam or other inert gas injected through lines 59.
  • Make-up catalyst may be added through line 61 as required.
  • Line 57 discharges into line 29 which is supplied via line 63 with a suitable carrier diluent such yas steam or hydrocarbon gas in amounts and at a velocity adequate to convey the catalyst to lines 25 and/or 27 as described above.
  • the yields will vary somewhat with the severity of the operations in both the thermal and catalytic zones and also with the rate of catalyst replacement.
  • the following may be given as illustrative of the yields to be expected from a South Louisiana vacuum residuum of gravity of about 12 API and Conradson carbon of about 17%:

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US227236A 1951-05-19 1951-05-19 Upgrading of heavy hydrocarbonaceous residues Expired - Lifetime US2763600A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US227236A US2763600A (en) 1951-05-19 1951-05-19 Upgrading of heavy hydrocarbonaceous residues
GB10018/52A GB724117A (en) 1951-05-19 1952-04-21 Improvements in or relating to the cracking of heavy hydrocarbon residues
FR1060056D FR1060056A (fr) 1951-05-19 1952-05-08 Traitement d'hydrocarbures
DEST4849A DE939945C (de) 1951-05-19 1952-05-17 Verfahren zur Herstellung niedriger siedender Kohlenwasserstoffoele aus schweren Kohlenwasserstoffrueckstaenden

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US227236A US2763600A (en) 1951-05-19 1951-05-19 Upgrading of heavy hydrocarbonaceous residues

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DE (1) DE939945C (fr)
FR (1) FR1060056A (fr)
GB (1) GB724117A (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813916A (en) * 1953-11-20 1957-11-19 Exxon Research Engineering Co Production of hydrocarbons from heavy hydrocarbonaceous residues by two stage processwith the use of inert solids
US2852441A (en) * 1954-10-22 1958-09-16 Exxon Research Engineering Co Conversion of hydrocarbons
US2867676A (en) * 1956-01-04 1959-01-06 Sinclair Refining Co Process for conducting high temperature conversions using fluidized solids as heat exchange media
US2886507A (en) * 1954-07-07 1959-05-12 Socony Mobil Oil Co Inc Method of supplying endothermic heat of reaction
US2904499A (en) * 1954-02-17 1959-09-15 Exxon Research Engineering Co Process and apparatus for conversion of heavy oil with coke particles in two stages employing inert and catalytic coke solids
US2913401A (en) * 1957-04-19 1959-11-17 Exxon Research Engineering Co Hydrogen production and hydroforming
US2938852A (en) * 1956-09-20 1960-05-31 Standard Oil Co Coking process
US2963421A (en) * 1958-03-26 1960-12-06 Exxon Research Engineering Co Catalytic conversion and stripping system with heat exchange
US3328292A (en) * 1964-05-11 1967-06-27 Mobil Oil Corp Method for catalytic conversion of hydrocarbons

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2348009A (en) * 1941-09-12 1944-05-02 Standard Oil Co Catalytic conversion process
US2378531A (en) * 1941-09-30 1945-06-19 Standard Oil Co Catalytic conversion of residual hydrocarbon oils
US2382755A (en) * 1941-05-24 1945-08-14 Standard Oil Dev Co Catalytic conversion of hydrocarbon oils
US2388055A (en) * 1942-06-13 1945-10-30 Standard Oil Dev Co Petroleum conversion process
US2396109A (en) * 1941-11-06 1946-03-05 Standard Oil Dev Co Treating hydrocarbon fluids
US2445328A (en) * 1945-03-09 1948-07-20 Hydrocarbon Research Inc Conversion process for heavy hydrocarbons
US2471104A (en) * 1944-11-10 1949-05-24 Standard Oil Dev Co Production of unsaturated hydrocarbons and hydrogen
US2675294A (en) * 1949-08-16 1954-04-13 Kellogg M W Co Method of effecting chemical conversions

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2382755A (en) * 1941-05-24 1945-08-14 Standard Oil Dev Co Catalytic conversion of hydrocarbon oils
US2348009A (en) * 1941-09-12 1944-05-02 Standard Oil Co Catalytic conversion process
US2378531A (en) * 1941-09-30 1945-06-19 Standard Oil Co Catalytic conversion of residual hydrocarbon oils
US2396109A (en) * 1941-11-06 1946-03-05 Standard Oil Dev Co Treating hydrocarbon fluids
US2388055A (en) * 1942-06-13 1945-10-30 Standard Oil Dev Co Petroleum conversion process
US2471104A (en) * 1944-11-10 1949-05-24 Standard Oil Dev Co Production of unsaturated hydrocarbons and hydrogen
US2445328A (en) * 1945-03-09 1948-07-20 Hydrocarbon Research Inc Conversion process for heavy hydrocarbons
US2675294A (en) * 1949-08-16 1954-04-13 Kellogg M W Co Method of effecting chemical conversions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813916A (en) * 1953-11-20 1957-11-19 Exxon Research Engineering Co Production of hydrocarbons from heavy hydrocarbonaceous residues by two stage processwith the use of inert solids
US2904499A (en) * 1954-02-17 1959-09-15 Exxon Research Engineering Co Process and apparatus for conversion of heavy oil with coke particles in two stages employing inert and catalytic coke solids
US2886507A (en) * 1954-07-07 1959-05-12 Socony Mobil Oil Co Inc Method of supplying endothermic heat of reaction
US2852441A (en) * 1954-10-22 1958-09-16 Exxon Research Engineering Co Conversion of hydrocarbons
US2867676A (en) * 1956-01-04 1959-01-06 Sinclair Refining Co Process for conducting high temperature conversions using fluidized solids as heat exchange media
US2938852A (en) * 1956-09-20 1960-05-31 Standard Oil Co Coking process
US2913401A (en) * 1957-04-19 1959-11-17 Exxon Research Engineering Co Hydrogen production and hydroforming
US2963421A (en) * 1958-03-26 1960-12-06 Exxon Research Engineering Co Catalytic conversion and stripping system with heat exchange
US3328292A (en) * 1964-05-11 1967-06-27 Mobil Oil Corp Method for catalytic conversion of hydrocarbons

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DE939945C (de) 1956-03-08
GB724117A (en) 1955-02-16
FR1060056A (fr) 1954-03-30

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