US2734850A - brown - Google Patents

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US2734850A
US2734850A US2734850DA US2734850A US 2734850 A US2734850 A US 2734850A US 2734850D A US2734850D A US 2734850DA US 2734850 A US2734850 A US 2734850A
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zone
cracking
coking
catalyst
coke
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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 the art of treating hydrocarbons and, more particularly, to a Vcombination of coking and catalytically cracking heavy hydrocarbons in a three-stage fluid system wherein heat for the coking step is supplied by indirect heat exchange with freshly regenerated catalyst.
  • -It is the object of the present invention to improve on the aforementioned system and to increase the yield of recoverable coke product. Another object is to improve the heat balance of the process and to take better advantage of the heat produced in regenerating the catalyst. -A further object is to reduce the ⁇ number of steps and of major reaction vessels required to carry out the process. Other objects will appear from the following detailed description and claims. v
  • Fig. l of the accompanying drawing diagrammatically illustrates an apparatus for carrying out a preferred modication-of the invention, according to which both a coking zone containing a heat exchanger anda catalytic cracking zone superimposed on the coking zone are located -within a single vessel.
  • Fig. 2 of the drawing illustrates an alternative embodiment Vof the invention wherein the coking zone and the catalytic cracking zone are contained in separate vessels, thus permitting separation and recovery of light and heavy fractions from the coker products before .a selected cut of the latter is passed to the catalytic cracker.
  • a residual petroleum stock as Aforlinstance a residuum having a gravity of about API and an atmospheric boiling lrange in excess of about l100 F. is preheated to about 70.0 F. by conventional -means (not shown) and is then injected through line 1 and jets 2 into the lower coker portion 3 of the reactor.
  • The-latter may contain about 0.5 to lbs. of coke particles perlbJhr. of feed, the icoke particles ranging in size between about 40 and 150 microns.
  • Steam is injected through line 6 into the bottom of the coker 3 so as Vto produce a total upward vapor velocity of about 1.5 to 3 ft./sec.
  • the hydrocarbon vapors formed in the coking zone stay there for a period corresponding to a residence time of about 3 to 10 seconds, before passing overhead into the catalytic cracking zone as subsequently described.
  • a shell-and-tube heat exchanger 8 submerged in the lluid coke bed 4 maintains the latter at about 850 to 950 F., which is a temperature suited for obtaining the desired degree of thermal cracking and low temperature coking of theresiduum feed.
  • The-necessary heat is supplied by withdrawing hot catalyst at about 1250 F. from catalyst regenerator 30 through line 37 and circulating such hot catalyst in a fluidized state through the shell of heat exchanger 8.
  • the coke mixture of lluidized bed 4 in which the heat exchanger 8 is submerged is maintained in a fluid state within the tubes 11of the heat exchanger 8.
  • ft. F. can'he .obtained and thus the required coking heat can-be supplied .by circulating regenerated 1250 F. catalyst through the Vexchanger to maintain 1l50 F. catalyst in the exchanger. Under such conditions a tube metal temperature of only about 1000 F. prevails in the exchanger, allowing the'use ofregular carbon steel tubes. Catalyst particles at about 12150 F. arey withdrawn from the heat exchanger shell through line 14 and returned to regenerator 3,0 via standpipe 15 and transfer line 16.
  • Coke is formed in the process primarily from the relatively heavy components of the feed, which component-s are most Vreadily deposited togetherwith the ash constituents on the ⁇ luidized particles in the coker and have an especial-ly great coke-forming tendency as indicated by a high Conradson carbon value.
  • v Particles of the net coke product are withdrawn from coke bed 4 downwardly -to storage through line 17 while the aeration steam and hydrocarbon vapors liberated in coke bed 4 pass from coker 3 upward, preferably ⁇ through cyclones 29 or other entrainment separators such as inclined bailes, and through perforated distribution v 19 ofthe two-zone reactor.
  • the diameter of the cracking portion 19 is preferably larger than the diameter of the lower, cokng portion 3 of the reactor because the'total vapor ⁇ Volume is increased during catalytic conversion.
  • the gas Velocity in cracker -19 is again suiicient to maintain the hot catalyst particles above plate 19 in a dense lluid phase 20 having an upper level 21,*above which is a more ⁇ dilute ⁇ phase Z2.
  • the hydrocarbon vapors are cracked on contactwith the synthetic silica-alumina gel or othersuitable cracking catalyst in dense bed 2i) and the cracked vapors together with the steam ⁇ are withdrawn overhead through cyclone 23 and passed through line 25 to :a ⁇ conventional fractionation system for recovery.
  • contact time of the vapors in the cracking zone rangesfrom. about S10 lto '30 seconds.
  • Catalyst l fines ⁇ entrained with the vapors-.are separated in the cyclone and returned to dense bed 20 through Ldip ⁇ leg ⁇ 24 which extends below theilevel 21 ofthe crackingzo'ne.
  • Heat of reaction is supplied to the crackingzone 20' by means of'hot regenerated catalyst whichis circulated from regeneration zone 30 through line 26 a-t arate suif cient to maintain the temperature of the cracking zone grid 18 into the cracking portion 3 at about 1000 F. while pressure in the dilute phase of the cracking zone is maintained at about l p. s. i. g.
  • Spent catalyst is withdrawn from catalyst bed through standpipe 15 and recirculated to the regeneration zone through transfer line 16 with the aid of a lift gas such as air which is injected into line 16 at the bottom of the standpipe through line 27. Minor amounts of an aeration gas such as steam may also be injected into standpipe 15 through one or more lines 28 to assure a free flowing condition for the spent catalyst.
  • the mixture of spent cracking catalyst and air is passed through perforated distributor plate 31 into the regenerator 30 where the carbonaceous contaminants are burned oif the catalyst while the catalyst is maintained in the form of a fluid bed at a temperature of about i250" F. and at a pressure of about 1 p. s. i. g., low regenerator pressures being preferred so as to keep down air compression costs.
  • the flue gas produced in the regenerator is removed overhead through a cyclone 32 wherein entrained catalyst fines are separated and returned through dip leg 33 to a point below level 34 of the fluid regenerator bed 35.
  • a substantial portion of the heat produced in the regenerator 30 is utilized to supply the heat of coking to coking zone 4 by means of the indirect heat exchanger 8, while another portion of the heat produced in the regenerator is supplied to the catalytic cracking zone 19 by returning hot regenerated catalyst through line 26 and mixing it directly into fluid bed 20.
  • Excess heat may be removed from the regeneration zone by means of an indirect heat exchanger 36 through which a cooling medium such as water is circulated to generate steam for use in the process or elsewhere.
  • a cooling medium such as water
  • separately fueled heaters for the coker solids can be eliminated by using the excess regenerator heat for operating the coker and at the same time the excess contamination of the catalyst by carbonaceous deposit during cracking is reduced by fractionating the hydrocarbon vapors produced in the coker into a coke-forming, heavy liquid fraction which may amount to about l0 to 35% of the residual hydrocarbon fed to the coker and which is recycled to the coker, and a lighter fraction which alone is then passed to the catalytic cracker.
  • the catalytic cracking feed preferably consists of a heavy gas oil having a boiling range between about 650 to 950 F. and amounting to about 25 to 50% of the residual hydrocarbon fed to the coker.
  • a vacuum pitch having a boiling range in excess of about 1100 F. (atmospheric equivalent) and a gravity of about 5 API is preheated to about 700 F. and sprayed through line 101 into a coking vessel 102.
  • vessel 102 finely divided coke particles ranging in size between 40 and 150 microns are maintained at a temperature of about 900 to 1000 F., preferably at about 950 F., in the form of a dense fluidized bed 103 having an upper level 104 by passing steam through line 105 below perforated distributor plate 106 at a sufficient rate to produce in coker 102 a total superficial vapor velocity of about 1.5 to 3.0 feet per second.
  • the required heat of reaction is supplied to coking bed 103 at a rate suhicient to maintain the temperature of the bed at the desiredV level, the heat transfer being accomplished by circulating a part of the coke particles back and forth to regenerator 301 where they become heated by indirect heat exchange with the catalyst bed maintained at a temperature of about 1250 F. as later herein described.
  • the vapors produced in the coker and amounting to about 70 to 90 wt. percent of the feed are withdrawn over head from the dilute phase of the coker through a solids separator such as cyclone 107 wherein entrained'coke fines are separated and returned to fluid bed 103 through dip leg 108 while the vapors themselves are passed through line 109 to distillation tower 110 for separation Yinto de- ⁇ sired fractions.
  • the heavy bottoms fraction which hasY an atmospheric boiling point above about 950 F. is recycled from the distillation tower to the coker through lines 111 and 101.
  • the intermediate fraction which lis preferably a heavy gas oil having an atmospheric boiling range between about 650 and 950 F.
  • the hot catalyst thus serves in a known manner to vaporize the oil as well as to supply the heat of reaction required in the catalytic cracking step.
  • the mixture of catalyst and vaporized gas oil formed in the transfer line 113 is then introduced into cracking vessel 201 below a perforated distributor plate 202. In vessel 201 the mixture of oil vapor and catalyst is maintained at a temperature of about 800 F.
  • the catalyst is likewise maintained in the forrn of a dense uid bed 304 having an upper level 30S and a more dilute phase 306 thereabove, whence the resulting flue gases are withdrawn through cyclone 307 and line 308.
  • the carbonaceous catalyst deposit is burned oif in the regenerator at 1000 to 1500 F., preferably at about 1250 F. with the production of suicient heat to operate not only the catalytic cracking step but also to supply the heat requirements of the coking step.
  • the large amount of heat required for coking of the heavy feed is supplied to fluid bed 103 by circulating coke between coke bed 103 and shell-and-tube type heat exchanger 309 which is submerged in the hot regenerator bed 304.
  • This circulation of coke is accomplished by withdrawing the coke from coke bed 103 through standpipe 114, injecting steam into the withdrawn coke through line 115 at the foot of standpipe 114 and passing the resulting .dilute suspension of coke particles steam through transfer line 116 to the -shell lof heat exchanger 309 similar to exchanger 8 illustrated in Fig. '1.
  • the coke particles are maintained in the* heat exchanger shell as a densefluid bed for a vsuliicientlength of time to ralse their temperature to about 950-1050" F. by indirectheat transfer from the hot iiuidcatalystbed 30.4.which passes through the tubes of the heat exchanger 309. ⁇ The reheated coke is linally withdrawn from the heatexchanger through standpipe 310 and returned .to coke bed 103 after mixing with steam in transfer line 105 as previously described.
  • the heat exchanger may be located within coke bed 103, in which eventa proper amount of hot regenerated catalyst is-passed from regeneratorobed 304 to the shell of the exchanger located in the coker while the iiuid coke bed ⁇ passes through the tubes of the heat exchanger in the manner previously described -in-.connection with Fig. l.
  • the regenerated catalyst maintained fluid and partially cooled in the shell of the heat exchanger Vlocated in the coker, 'may be subsequently mixed with the coker gas .oil instead ⁇ of using hot catalyst withdrawn directly from the regenerator as shown in Fig.
  • location of the heat exchanger in the high temperature regenerator bed may be preferred since the periodic heating of the coke particles to the higher temperature of about l000 F. inherent in this modification tends to dry out the coke more completely and thus prevents any uidization diliiculties in the coker, and also results in a better coke product, all of which may outweigh the increased metal cost required in this design.
  • the invention is broadly applicable to the treatment of heavy residual crude stocks as well as cycle stocks having a boiling range above about 900 to ll50 F. (atmospheric equivalent) and a gravity between about to 20 API, and even to lighter stocks such as gas oils.
  • the invention is of particular value with stocks having high coke forming tendencies as indicated by Conradson carbon values between about and 35 weight percent such as crudes obtained by atmospheric or vacuum distillation and representing about 2 to 25 vol. percent of the whole crude distilled, or the invention may be applied to clarified oil from catalytic cracking, various pitches, tars from visbreaking operations and the like.
  • the heavy feed stocks Prior to feeding to the coker, the heavy feed stocks may be cut back with naphtha or other light products, and preferably preheated to temperatures ranging from 200 to 1000 F., or especially 600 to 800 F.
  • the hydrocarbon feed may also be diluted in the various reaction zones with steam, recycle gas or other inert gas in amounts up to about 500 to 5000 cubic feet (at coker conditions) per barrel, since such diluent increases gas velocity in the cker such fluidizing velocities may .range from about 0.5 to 5 or 10 feet per second toestablish apparent densities'in the dense solids phase of about 10-50 lbs. per cu. ft. and about 0.01 yto 5 lbs. per cu. ft. in the disperse phase asis well known per se.
  • the contact solids used in the coker are preferably coke particles ranging in size from about 0 to 200 or 500 microns, thoughv other inert solids such as sand, vspent claysand lthe like may similarly be used if a coke product of .high ash content can be tolerated.
  • the contact solids inthe. .catalyst cracking zone may beany tinely divided cracking catalyst such .as activated clays, activated alumina, synthetic composites of silica with alumina, magnesia ⁇ .and/or boria, .activated carbon or .other conventional cracking catalyst.
  • the Particle size of .thesolids inthe catalytic cracking zone as well-as inthe regeneration zone, :and also apparent densities and specified gas velocities prevailing therein are substantially within. the same limits as given .above with reference to thecoker solids.v y
  • Reaction conditions may include coking temperatures offabout .800 .to 1200F.preferably S50-to 950 F. catalytic -crack-ing temperaturesof about 800 to 1200 F., preferably l9-00 to'1000 F.; and catalyst regeneration temperatures of about 1000 .to1500 F., preferably 1100 to 13.00 Vl"".,lo1 1oe importantlim-itation being that the 'regencrat-iontemperature be at least F. above ⁇ the ,coker temperature so as to permit the required indirect yheat exchange Ybetween coker solids and regenerated catalystto be accomplished in an, efcient manner.
  • the ⁇ .regenera-tion temperature must notrbe high enough to cause serious deterioration of the catalyst, as is well known.
  • the weight ratio of oil to total ⁇ solids may be from about 0.1 to 5 w./hr./w. (weights per hour per weight); the ratio of catalyst to oil in the dilute catalyst suspension such as is fed to cracking zone 201 through transfer line 113 in Fig. 2 may be from about l to 20 parts by weight of catalyst for one part by weight of oil.
  • the physical arrangement of the illustrated apparatus may be modified in various ways.
  • the heat exchanger is shown entirely submerged in the coker bed in Fig. 1 illustrating a one-vessel converter and entirely submerged in the regenerator bed in Fig. 2 illustrating a two-vessel converter
  • the heat exchanger may be only partially submerged in the dense fluid bed and may be located in the reverse location in either case, requiring only minor modifications in the ow of the streams as described earlier herein.
  • the heat exchanger itself may be of any convenient design other than of the tube-and-shell type illustrated, provided that finely divided solids can be fluidized therein on either side of the heat transfer surface.
  • Fig. 1 illustrating a one-vessel converter
  • Fig. 2 illustrating a two-vessel converter
  • the heat exchanger may be only partially submerged in the dense fluid bed and may be located in the reverse location in either case, requiring only minor modifications in the ow of the streams as described earlier herein.
  • the heat exchanger itself may be of any convenient design other than of
  • the regenerated catalyst cooled in the heat exchanger is shown to be returned to the regenerator, it can be passed to the catalytic reactor bed instead, especially where coker and catalytic reactor are contained in two separate vessels as' in Fig. 2, and then particularly when the heat exchanger is submerged in the Coker bed so that the catalyst is on the shell side of the exchanger.
  • injection of the feed stock directly into the dense coker bed as shown in Fig. 1 or into the more disperse phase as shown in Fig. 2 is optional, as either procedure offers certain advantages not possessed by the other.
  • a process for converting a residual petroleum stock which comprises the following steps: contacting a residual stock with coke particles maintained as a fluid bed at a coking temperature in a coking zone to form additional amounts of coke and hydrocarbon vapors, withdrawing net coke product from said coking zone, passing said hydrocarbon vapors after removing entrained solids therefromV directly to the lower portion of a cracking zone, contacting said hydrocarbon vapors therein with a uid bed of particulate cracking catalyst at a cracking temperature, withdrawing cracked product vapors from said cracking zone, withdrawing and mixing a portion of said cracking catalyst with a free oxygen-containing gas in a combustion zone, forming a iluid bed of the withdrawn catalytic solids therein at a regeneration temperature at least 100 F.
  • a residual oil conversion process wherein a residual oil is converted to conversion products in a coking zone by contact with uidized inert solids maintained at a coking temperature, wherein said conversion products are then further converted in a cracking zone by contact with tiuidized catalytic solids maintained at a cracking temperature with deposition of coke on said catalytic solids, wherein coke-containing catalytic solids are withdrawn from said cracking zone and regenerated as a iluid bed by contact with a free oxygen-containing gas at a -8 combustion temperature 4in a regeneration zone, and Wherein regenerated catalytic solids are circulated from said regeneration zone to said cracking zone to maintain said cracking temperature, the improvement which comprises maintaining said combustion temperature at least 100 F.
  • a process according to claim 2 wherein said conversion products are withdrawn from said coking vzone and fractionally separated to obtain a gas oil fraction which is then passed to said cracking zone, the end boiling point of said gas oil fraction being regulated to control the amount of coke deposited on said uidized catalytic solids whereby a suiicient amount of coke is deposited on said uidized catalytic solids to meet the heat requirements of said coking and cracking zones when the coke on the catalyst is consumed in said regeneration zone.

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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)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2859168A (en) * 1955-05-26 1958-11-04 Exxon Research Engineering Co Fluid coking reactor
US2906695A (en) * 1956-08-07 1959-09-29 Exxon Research Engineering Co High temperature short time hydrocarbon conversion process
US3303017A (en) * 1963-11-14 1967-02-07 Exxon Research Engineering Co Metal treating process
US20050279671A1 (en) * 2003-10-27 2005-12-22 Envision Technologies Corp. Process for converting a liquid feed material into a vapor phase product

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1030949B (de) * 1954-09-03 1958-05-29 Exxon Research Engineering Co Verfahren zur Beseitigung metallhaltiger Verunreinigungen aus schweren Gasoelen

Citations (5)

* 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
US2388055A (en) * 1942-06-13 1945-10-30 Standard Oil Dev Co Petroleum conversion process
US2436486A (en) * 1942-02-27 1948-02-24 Standard Oil Co Multistage hydrocarbon cracking process
US2447505A (en) * 1944-04-13 1948-08-24 Standard Oil Co Hydrocarbon synthesis with fluidized catalyst regeneration
US2676668A (en) * 1949-06-13 1954-04-27 Fmc Corp Apparatus for contacting gaseous fluids and granular solids

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2431630A (en) * 1941-10-30 1947-11-25 Standard Oil Co Method and apparatus for regeneration of catalyst
US2534859A (en) * 1946-04-18 1950-12-19 Socony Vacuum Oil Co Inc Method and apparatus for hydrocarbon conversion
US2542917A (en) * 1947-01-02 1951-02-20 Armour Res Found Differential spool drive
US2543884A (en) * 1947-08-12 1951-03-06 Standard Oil Dev Co Process for cracking and coking heavy hydryocarbons

Patent Citations (5)

* 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
US2436486A (en) * 1942-02-27 1948-02-24 Standard Oil Co Multistage hydrocarbon cracking process
US2388055A (en) * 1942-06-13 1945-10-30 Standard Oil Dev Co Petroleum conversion process
US2447505A (en) * 1944-04-13 1948-08-24 Standard Oil Co Hydrocarbon synthesis with fluidized catalyst regeneration
US2676668A (en) * 1949-06-13 1954-04-27 Fmc Corp Apparatus for contacting gaseous fluids and granular solids

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2859168A (en) * 1955-05-26 1958-11-04 Exxon Research Engineering Co Fluid coking reactor
US2906695A (en) * 1956-08-07 1959-09-29 Exxon Research Engineering Co High temperature short time hydrocarbon conversion process
US3303017A (en) * 1963-11-14 1967-02-07 Exxon Research Engineering Co Metal treating process
US20050279671A1 (en) * 2003-10-27 2005-12-22 Envision Technologies Corp. Process for converting a liquid feed material into a vapor phase product

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GB710144A (en) 1954-06-09
NL81459C (xx)
DE937723C (de) 1956-01-12

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