US2655464A - Residuum coking and cracking - Google Patents

Residuum coking and cracking Download PDF

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Publication number
US2655464A
US2655464A US230746A US23074651A US2655464A US 2655464 A US2655464 A US 2655464A US 230746 A US230746 A US 230746A US 23074651 A US23074651 A US 23074651A US 2655464 A US2655464 A US 2655464A
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United States
Prior art keywords
zone
coke
catalyst
cracking
coking
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Expired - Lifetime
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US230746A
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English (en)
Inventor
James W Brown
Charles E Jahnig
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Standard Oil Development Co
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Standard Oil Development Co
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Publication date
Priority to BE508568D priority Critical patent/BE508568A/xx
Priority to NL83484D priority patent/NL83484C/xx
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US230746A priority patent/US2655464A/en
Priority to FR1050493D priority patent/FR1050493A/fr
Application granted granted Critical
Publication of US2655464A publication Critical patent/US2655464A/en
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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
    • 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
    • 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
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/18—Modifying the properties of the distillation gases in the oven

Definitions

  • a characteristic feature a heavy hydrocarbon feed is contacted with hot the coking zone as well as the catalytic cracking bed, followed by a cracking step wherein the zone are supplied by direct mixing of hot reresulting hydrocarbon vapors are contacted with generated catalyst with the inert solids 1n a mixa dense fluid bed of a cracking catalyst having ing zone, whereupon catalyst and reheatedinerts a particle size distribution substantially differ-
  • such processes have not been ⁇ cornmeroff while in a dense iluid phase, a heat exchange cially attractive in view of the great heat restep wherein the hot regenerated catalyst is quirements involved, especially since it has been mixed with coke particles withdrawn from the a feed cut which had to be revaporlzed in the ation or the like into its two principal compofeeding of a'heat carrying medium such as coke 35 ing of the seed coke withdrawn from the coking similarly Valuable extraneous fuels such as fuel 40 illustrated by severalspeciiic examples wherein
  • Fig. 1 is a semi-diagrammatic illustration of to mixing with hot regenerated catalyst in a separate mixing and elutriation zone whence reheated coke particles are returned to the cokng Zones and regenerated catalyst is returned to the catalytic cracking zone;
  • Fig. 2 illustrates an alternative modification of the invention, according to which the catalytic cracking zone is superimposed on the coking zone in the same vessel which also contains the mixing-and-elutriation Zone in direct communication with the coking zone; and finally Fig. 3 illustrates a third alternative according to which low temperature coking oi the hydrocarbon feed is essentially completed in a transfer line wherein the feed is mixed with hot coke particles prior to admission to the catalytic cracking acne wherefrom relatively fine catalyst is entrai ed overhead with the product vapors eventual recycling to the cracking zone whereas the relatively coarse coke is withdrawn at the bottom and mixed with further amounts of hydrocarbon feed.
  • reduced crude such as an 8% bottoms fraction of about lil-30 Conradson carbon, oi about 5 AP gravity and obtained from the vacuum distillation of a West Texas crude 'or a similar heavy residue is sup-plied to coking Zone 2 through line i as a liquid at a temperature of about 300 to 800 F., or preferably at about 700 lneit solids, preferably petroleum coke particles having a particle size in the range between about 100 and 500 microns are maintained in the cokf 35 coking zone, e. g. at 1000 F., but a substantial ing Zone at a temperature of about 850 F. to 950 F.
  • the vapors produced in the hot coking Zone 5 2. are passed therefrom through perforated plate 5 into the superimposed catalytic cracking Zone 5 maintained at about 900 F. to 1000D F. and containing a dense, turbulent, fluidized bed 1 of a cracking catalyst such as one of the known synthetic silica-alumina composites.
  • a cracking catalyst such as one of the known synthetic silica-alumina composites.
  • the physical characteristics of catalyst bed 1 are essentially similar to those of the coke bed 3 described above, except that the catalyst particle size is within the range of about 50 to 150 microns and is preferably at least to 50 microns smaller than the smallest particles constituting a substantial portion of the coke in bed 3, so as to assure an efficient separation of the two solids in the subsequent elutriation.
  • the catalyst particles are preferably in the range between 20 and 50 or 80 microns, but when the coke particles of the process range in size between about 365 200 and 300 microns, catalyst particles in the range up to about 150 microns may be used.
  • the cracked. hydrocarbon vapors are withdrawn from cracking zone Ei through cyclone 8 or other gas- I solid separator means and passed through line 0 to a conventional finishing system for recovery of naphtha, gas oil and other desired hydrocarbon fractions.
  • Spent catalyst is withdrawn from bed 1 through standpipe l0, which may have taps ll 7 for admitting a small amount ci an aeration gas, and the withdrawn catalyst is finally mixed with air admitted through line l2 and passed to regenerator I3 where carbonaceous deposits are 5 burned off the catalyst in fluid phase at a temperature of about 1100* F. to l250 F. in a manner well known per se.
  • Excess heat may be removed from the system by means of heat exchanger l4 and hot regenerated catalyst is use l0 to supply the heat requirements of the coking zones as well as the catalytic cracking zones in the manner described later herein.
  • exchanger Hi is intended for preheating feed and thus supplying a portion l5 of the regeneration heat directly to the coker, it
  • regenerator temperature may be necessary to locate the exchanger in a separate vessel through which hot catalyst is circulated. This allows greater flexibility and control over regeneration temperature without 20 causing undue coking of feed within the heat exchanger, as might otherwise be the case if regenerator temperature permitted only a low feed circulation rate through the exchanger when immersed directly in the regenerator bed as shown in Fig. l.
  • Coke from bed 3 of the coking zone is withdrawn through downcomer l5 to another stage It where the coke is again maintained as a dense, turbulent, fluidized bed ll and where any unconverted, oily residuum which may be adhering to some of the coke particles is cracked and converted into vapors and dry coke.
  • the second and any further consecutive stages are preierably at a higher temperature than the main advantage is obtained even when all stages are at the same temperature 'as the main coking Zone 2, since the main purpose of such staging is the prevention of oil soaked, incompletely 40 coked particles leaving the coker bed in the coke portion withdrawn to the mixer as later described, which portion is a fairly representative sample of the particle mixture present in the particular bed.
  • Net coke product may be withdrawn from the last bed l1 through pipe I8, it being particularly desirable to remove those coke particles which have grown too large for good iiuidiaation in the system.
  • Control of the coke particle size in the system can be achieved by screening out the largest coke particles while recycling the smaller ones, or the withdrawn particles may even be ground before being returned to the system.
  • a side stream of the coke from the dry coke bed l1 is withdrawn through line I8 to mixer- '5 elutriator 20 where the coke particles are mixed rwith hot catalyst particles withdrawn from remildest cracking conditions.
  • the hydrocarbon vapors such as steam is introduced into the bottom of liberated in the coking steps pass overhead from they exhange heat so that the catalyst is cooled below the cracking section
  • the relatively fine catalyst is stripped flow up through the dense, turbulent. iuidized bed from the Iiuidized mixture in vessel 20 and enof cracking catalyst
  • Spent catalyst is stripped with steam in zone
  • Air is bloivn into the regenerator of the hot mixing vessel V and standpipe 24 30 opening
  • Fig 2 the modification illustrated .Wall Opening
  • the heavy hydrowhile the coke particles are uidized but are not carbon feed preheated to about 700 F. is
  • the transfer line, colii'ng of the feed is completed ⁇ this can be done by locating a cyclone
  • the cufculty can be overcome by mixing the coke as it leaves the coking bed. with hot recycle coke and then providing sufficient holding time to dry the coke in an intermediate zone before it contacts the hot catalyst in the heat transfer zone and stripping steam can be added to assist the operation.
  • the pressure drop across the grid be such as to cause the desired upward flow of catalyst from the mixer-elutriator iii to the catalyst bed
  • the required pressure drop will usually range between about 1 and 5 or 10 pounds per square inch and must be at least enough to offset the differential between the hydrostatic pressure exerted by the relatively dense upward stream of catalyst fines suspended in steam in the upper portion of the mixer-elutriator section of the reactor vessel the apparent density of this phase being between about 10 and i0 lbs. per cu.
  • the velocity through the openings in grid l l0 should be maintained in the proper range to give the required pressure drop so as to coinpensate for the lower density in the dilute phase above level
  • the temperature at the coke-catalyst mix point is regulated to give the desired heat balance.
  • the coke circulation rate is controlled by the valve in line
  • Fig. 3 illustrates still another embodiment of the invention.
  • a liquid residuum of the type previously described, preheated to about 300 to 800 F. may be supplied through line
  • Hot inert solids, specifically coke having a particle size of about 100 to 500 microns may be added from standpipe his at a temperature of about 900 to 1100 F. in an amount of about 700 to '7,000 lbs/barrel.
  • the temperature of the feed may be raised to about 800 to 1000 F. whereby the more volatile components of the feed are more or less completely vaporlzed without, however, being converted to naphtha and lighter products in any substantial degree.
  • the resulting dispersion of coke in hydrocarbons may enter reactor
  • About r100 to 5,000 lbs. of hot regenerated catalyst per barrel of feed may be supplied f from standpipe
  • this catalyst has a particle distribution range below the range of the above-described coke particles, for instance, the catalyst may have a particle size up to about microns and must be readily entrainable at the fluidization conditions of reactor
  • Mass M146 is maintained at a temperature of about 900 to 1l00 F. conducive to the desired catalytic cracking operation and may be composed of a highly active silica-alumina composite or other known cracking catalyst.
  • 46 may be provided with an elutriation well
  • the elutriation well is a small-diameter vertical section which extends downwardly from a point just below dense bed level Lus so as to be in open communication with dense, fluidized bed M146 and is preferably lled with a packing of bodies of non-fluidizable size, such as Raschig rings or the like, having interstices which permit percolation of the fluidized solids within the packing.
  • the elutriation gas may be supplied via line
  • the catalyst which may contain up to about 3 wt. per cent of coke is readily entrained by the product vapors and elutriation gas and carried in the form of a dilute suspension overhead from mass Mms through line
  • Separated catalyst, preferably stripped of hydrocarbons by injection of an inert gas such as steam through one or more taps t to a stripping zone may be supplied via line
  • 08 Simultaneously, air is blown into regenerator
  • Flue gases and entrained catalyst may pass into cyclone
  • Make-up catalyst may be added aanmet- Q Having described specific embodiments of the ble to the treatment of heavy residual crude reactor temperatures, as otherwise the Wet coke be reduced -crudesobtamed hy atmospheric or andai-'1ct coke ⁇ particles are mixed therein in a.
  • Reaction conditions may include coking ternabout 800 to 1200 F., catalytic cracking temperatures of about 800 to 1000 F. and catalyst regeneration temperatures of about 1000 to 1200 or 1300 F., depending on the nature of the catalyst used.
  • the regenerator temperature and the rate of circulation of catalyst and coke to the inert solids are reheated to the temperature by direct heat exchange lyst before separation and recyclingI version zones, are so adjusted as to tended temperature conditions both in the zones and the catalytic cracking zones.
  • a process for convertng a residual petroleum feed stock boiling predominantly above 900 F. into ts and coke which lighter produc comprises introducing the residual stock into a primary coking zone to the congive the incoking wherein coke particles of a size between 100 and 500 microns are maintained at a temperature between about 800 and 1100 F. as a dense fluidized bed with a less dense phase thereabove, and wherein the petroleum stock is vaporized and partially coked substantial conversion to naphtha and lighter products, passing the resulting petroleum vapors upwardly through a cracking zone maintained at about 900 to 1100 F.
  • a process for converting a residual hydrocarbon feed characterized by a Conradson carbon value in excess of 5 which comprises preheating the feed to a temperature between 600 and 800 F., mixing the feed with coke particles ranging in size between about and 300 microns and heated to a temperature between about 800 and 1200 F. to form a dilute suspension of coke in hydrocarbon vapors, passing the resulting suspension at a temperature oi about 800 to 1100 F.
  • a process for converting heavy hydrocarbons which comprises mixing a heavy hydrocarbon feed with coke particles ranging in size between about 100 and 300 microns and heated to about 900 to 1200 F. to form a dilute suspension of oilcoated coke particles in hydrocarbon vapors, passing the resulting suspension through a constricted elongated coking zone at a temperature between 800 and 1100 F.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US230746A 1951-06-09 1951-06-09 Residuum coking and cracking Expired - Lifetime US2655464A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE508568D BE508568A (it) 1951-06-09
NL83484D NL83484C (it) 1951-06-09
US230746A US2655464A (en) 1951-06-09 1951-06-09 Residuum coking and cracking
FR1050493D FR1050493A (fr) 1951-06-09 1951-12-15 Procédé de cokéfaction et de cracking de résidus

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US230746A US2655464A (en) 1951-06-09 1951-06-09 Residuum coking and cracking

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2731395A (en) * 1951-06-19 1956-01-17 Exxon Research Engineering Co Conversion of hydrocarbons in two stages with inert and catalyst particles
US2737475A (en) * 1953-05-13 1956-03-06 Exxon Research Engineering Co Conversion of hydrocarbons
US2765261A (en) * 1952-07-02 1956-10-02 Exxon Research Engineering Co Hydroforming process and apparatus
US2773017A (en) * 1952-08-05 1956-12-04 Exxon Research Engineering Co Integrated refining of crude oil
US2789082A (en) * 1954-09-29 1957-04-16 Exxon Research Engineering Co Dual bed process for coking and catalytic cracking of hydrocarbons
US2843529A (en) * 1954-08-17 1958-07-15 Exxon Research Engineering Co Upgrading of petroleum oils
US2858253A (en) * 1954-12-01 1958-10-28 Texas Co Fluid contact coking of hydrocarbon oils, fines recirculation improvement
US2861943A (en) * 1952-07-16 1958-11-25 Hydrocarbon Research Inc Hydrocracking process with the use of fluidized inert particles
US2862871A (en) * 1953-10-30 1958-12-02 Exxon Research Engineering Co Fluid coking process and apparatus
US2868715A (en) * 1953-08-25 1959-01-13 Exxon Research Engineering Co Process and apparatus for conversion of hydrocarbon oils
US2871182A (en) * 1956-08-17 1959-01-27 Socony Mobil Oil Co Inc Hydrogenation and coking of heavy petroleum fractions
US2889267A (en) * 1953-12-31 1959-06-02 Exxon Research Engineering Co Process for cracking oil
US2892773A (en) * 1953-12-29 1959-06-30 Gulf Research Development Co Fluidized process and apparatus for the transfer of solids in a fluidized system
US2893946A (en) * 1954-04-08 1959-07-07 Exxon Research Engineering Co Fluid coking process
US2905618A (en) * 1952-04-04 1959-09-22 Gulf Research Development Co Fluid catalytic hydrocracking of high boiling hydrocarbon oils in several stages
US3071538A (en) * 1955-07-25 1963-01-01 Phillips Petroleum Co Catalytic conversion
US3169916A (en) * 1953-05-19 1965-02-16 Standard Oil Co Multistage hydrocarbon reforming with fluidized platinum catalyst
US4306995A (en) * 1978-11-20 1981-12-22 Atlantic Richfield Company Method for separation of conversion catalysts from vapor-catalyst mixtures
US20050279671A1 (en) * 2003-10-27 2005-12-22 Envision Technologies Corp. Process for converting a liquid feed material into a vapor phase product
WO2012005861A1 (en) * 2010-07-09 2012-01-12 Exxonmobil Chemical Patents Inc. Integrated process for steam cracking
US8399729B2 (en) 2010-07-09 2013-03-19 Exxonmobil Chemical Patents Inc. Integrated process for steam cracking

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2388055A (en) * 1942-06-13 1945-10-30 Standard Oil Dev Co Petroleum conversion process
US2393636A (en) * 1941-08-27 1946-01-29 Standard Oil Co Conversion of hydrocarbons with suspended catalysts
US2416730A (en) * 1942-02-27 1947-03-04 Standard Oil Co Multistage hydrocarbon conversion system
US2573559A (en) * 1948-06-21 1951-10-30 Phillips Petroleum Co Method for replacing deactivated hydrocarbon synthesis catalyst with fresh catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2393636A (en) * 1941-08-27 1946-01-29 Standard Oil Co Conversion of hydrocarbons with suspended catalysts
US2416730A (en) * 1942-02-27 1947-03-04 Standard Oil Co Multistage hydrocarbon conversion system
US2388055A (en) * 1942-06-13 1945-10-30 Standard Oil Dev Co Petroleum conversion process
US2573559A (en) * 1948-06-21 1951-10-30 Phillips Petroleum Co Method for replacing deactivated hydrocarbon synthesis catalyst with fresh catalyst

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2731395A (en) * 1951-06-19 1956-01-17 Exxon Research Engineering Co Conversion of hydrocarbons in two stages with inert and catalyst particles
US2905618A (en) * 1952-04-04 1959-09-22 Gulf Research Development Co Fluid catalytic hydrocracking of high boiling hydrocarbon oils in several stages
US2765261A (en) * 1952-07-02 1956-10-02 Exxon Research Engineering Co Hydroforming process and apparatus
US2861943A (en) * 1952-07-16 1958-11-25 Hydrocarbon Research Inc Hydrocracking process with the use of fluidized inert particles
US2773017A (en) * 1952-08-05 1956-12-04 Exxon Research Engineering Co Integrated refining of crude oil
US2737475A (en) * 1953-05-13 1956-03-06 Exxon Research Engineering Co Conversion of hydrocarbons
US3169916A (en) * 1953-05-19 1965-02-16 Standard Oil Co Multistage hydrocarbon reforming with fluidized platinum catalyst
US2868715A (en) * 1953-08-25 1959-01-13 Exxon Research Engineering Co Process and apparatus for conversion of hydrocarbon oils
US2862871A (en) * 1953-10-30 1958-12-02 Exxon Research Engineering Co Fluid coking process and apparatus
US2892773A (en) * 1953-12-29 1959-06-30 Gulf Research Development Co Fluidized process and apparatus for the transfer of solids in a fluidized system
US2889267A (en) * 1953-12-31 1959-06-02 Exxon Research Engineering Co Process for cracking oil
US2893946A (en) * 1954-04-08 1959-07-07 Exxon Research Engineering Co Fluid coking process
US2843529A (en) * 1954-08-17 1958-07-15 Exxon Research Engineering Co Upgrading of petroleum oils
US2789082A (en) * 1954-09-29 1957-04-16 Exxon Research Engineering Co Dual bed process for coking and catalytic cracking of hydrocarbons
US2858253A (en) * 1954-12-01 1958-10-28 Texas Co Fluid contact coking of hydrocarbon oils, fines recirculation improvement
US3071538A (en) * 1955-07-25 1963-01-01 Phillips Petroleum Co Catalytic conversion
US2871182A (en) * 1956-08-17 1959-01-27 Socony Mobil Oil Co Inc Hydrogenation and coking of heavy petroleum fractions
US4306995A (en) * 1978-11-20 1981-12-22 Atlantic Richfield Company Method for separation of conversion catalysts from vapor-catalyst mixtures
US20050279671A1 (en) * 2003-10-27 2005-12-22 Envision Technologies Corp. Process for converting a liquid feed material into a vapor phase product
US9327260B2 (en) 2010-01-22 2016-05-03 Exxonmobil Chemical Patents Inc. Integrated process for steam cracking
WO2012005861A1 (en) * 2010-07-09 2012-01-12 Exxonmobil Chemical Patents Inc. Integrated process for steam cracking
US8399729B2 (en) 2010-07-09 2013-03-19 Exxonmobil Chemical Patents Inc. Integrated process for steam cracking
CN103154203A (zh) * 2010-07-09 2013-06-12 埃克森美孚化学专利公司 蒸汽裂化的整合方法
CN103154203B (zh) * 2010-07-09 2015-11-25 埃克森美孚化学专利公司 蒸汽裂化的整合方法

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NL83484C (it)
FR1050493A (fr) 1954-01-07

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