EP0066387B1 - Procédé de combinaison pour l'amélioration d'huiles résiduelles - Google Patents

Procédé de combinaison pour l'amélioration d'huiles résiduelles Download PDF

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Publication number
EP0066387B1
EP0066387B1 EP82302428A EP82302428A EP0066387B1 EP 0066387 B1 EP0066387 B1 EP 0066387B1 EP 82302428 A EP82302428 A EP 82302428A EP 82302428 A EP82302428 A EP 82302428A EP 0066387 B1 EP0066387 B1 EP 0066387B1
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Prior art keywords
zone
stream
catalyst
conduit
gas
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German (de)
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EP0066387A1 (fr
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Lloyd E. Busch
Paul W. Walters
Oliver J. Zandona
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Ashland LLC
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Ashland Oil Inc
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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

Definitions

  • Crude oil from which desired gaseous and liquid fuels are made contain a diverse mixture of hydrocarbons and other compounds which vary widely in molecular weight and therefore boil over a wide range.
  • crude oils are known in which 30 to 60% or more of the total volume of oil is composed of compounds boiling at temperatures above 650°F (343°C).
  • crudes in which about 10% to about 30% or more of the total volume consists of compounds so heavy in molecular weight that they boil above 1025°F (552°C) or at least will not boil below 1025°F (552°C) at atmospheric pressure.
  • Crude oils in the natural state contain a variety of materials which tend to have quite troublesome effects on FCC processes, and only a portion of these troublesome materials can be economically removed from the crude oil.
  • these troublesome materials are coke precursors (such as asphaltenes, polynuclear aromatics, etc.), heavy metals (such as nickel, vanadium, iron, copper etc.), lighter metals (such as sodium, potassium, etc.), sulfur, nitrogen and others. Certain of these, such as the lighter metals, can be economically removed by desalting operations, which are part of the normal procedure for pretreating crude oil for fluid catalytic cracking.
  • vanadium tends to form fluxes with certain components of commonly used FCC catalysts, lowering the melting point of portions of the catalyst particles sufficiently so that they begin to sinter and become ineffective cracking catalysts. Accumulations of vanadium and other heavy materials, especially nickel, also "poison" the catalyst. They tend in varying degrees to promote excessive dehydrogenation and aromatic condensation, resulting in excessive production of carbon and gases with consequent impairment of liquid fuel yield.
  • An oil such as a crude or crude fraction or other oil that is particularly abundant in nickel and/or other metals exhibiting similar behavior, while containing relatively large quantities of coke precursors, is referred to herein as a carbo-metallic oil, and represents a particular challenge to the petroleum refiner.
  • VGO vacuum gas oil
  • a gas oil of atmospheric distillation in combination with vacuum gas oil is used as feedstock for conventional FCC processing.
  • the heavier fractions of the crude oil are normally employed for a variety of other purposes, such as for instance production of asphalt, residual fuel oil, #6 fuel oil, or marine Bunker C fuel oil, which represents a great waste of the potential value of this portion of the crude oil, especially in the light of the great effort and expense which the art has been willing to expend in the attempt to produce generally similar materials from coal and shale oils.
  • the present invention is aimed at the cracking of gas oils and heavier fractions of crude oils containing substantial quantities of both coke precursors, heavy metals, and other troublesome components either alone or in conjunction with the lighter oils, thereby increasing the overall yield of gasoline and other desired liquid fuels from a given crude oil. It is believed that the process of this invention is uniquely advantageous for dealing with the problem of treating high boiling carbo-metallic oils in an economically and technically sound manner.
  • the coke-forming tendency or coke precursor content of an oil can be ascertained by determining the weight percent of carbon remaining after a sample of that oil has been pyrolized.
  • the industry accepts this value as a measure of the extent to which a given oil tends to form non-catalytic coke when employed as feedstock in a catalytic cracker.
  • Two established tests are recognized, the Conradson Carbon and Ramsbottom Crbon tests, the latter being described in ASTM Test No. D524-76.
  • Ramsbottom carbon values on the order of about 0.1 to about 1.0 are regarded as indicative of acceptable feed.
  • the present invention is concerned with the use of hydrocarbon feedstocks which have higher Ramsbottom carbon values and thus exhibit substantially greater potential for coke formation than the usual feeds.
  • the heavy metals content of an oil can be expressed by the following formula (patterned after that of W. L. Nelson in Oil and Gas Journa/, page 143, October 23, 1961) in which the content of each metal present is expressed in parts per million of such metal, as metal, on a weight basis, based on the weight of feed:
  • the heavy metal content of feedstock for FCC processing is controlled at a relatively low level, e.g. about 0.25 ppm Nickel Equivalents or less.
  • the present invention is concerned with the processing of feedstocks containing metals substantially in excess of this value, and which therefore have a significantly greater potential for accumulating on and poisoning catalyst.
  • the above formula can also be employed as a measure of the accumulation of heavy metals on cracking catalyst, except that the quantity of metal employed in the formula is based on the weight of catalyst (moisture free basis) instead of the weight of feed.
  • the metal content of the catalyst is maintained at a level which may for example be in the range of about 200 to about 600 ppm Nickel Equivalents.
  • the process of the present invention is concerned with the use of catalyst having a substantially larger metals content, and which therefore has a much greater than normal tendency to promote dehydrogenation, aromatic condensation, gas production or coke formation. Therefore, such higher metals accumulation is normally regarded as quite undesirable in FCC processing.
  • the present invention is concerned with the conversion of the higher boiling portions of crude oils known as residual oils and/or resids recovered from as the bottoms product of atmospheric and/or vacuum distillation and containing substantial quantities of coke precursors and heavy metal contaminants, sulfur and nitrogen compounds.
  • Sodium found in crude oil is also a troublesome component in deactivating a cracking catalyst.
  • the combination process of this invention is a unique sequence of operations designed to dispose of and/or handle the undesirable components of reduced crudes in a manner permitting conversion of high boiling hydrocarbon components in association therewith to more desirable gaseous and liquid fuel products.
  • the process of the present invention comprises upgrading metal-contaminated topped crude oils having boiling points above 600°F (315°C), metal contents in excess of 100 ppm Ni and V, and Ramsbottom carbon values in excess of 1.0 by a combination of thermal visbreaking and catalytic cracking and involving the steps of
  • This combination of steps represents a highly productive approach to the conversion and recovery of product of conversion of high boiling crude oil feedstocks comprising carbo-metallic feed components such as found in topped crudes, residual oils, reduced crudes and resids.
  • hydrocarbon feeds which may be processed in the combination operation of this invention are specifically identified in Table 1 below.
  • Figure IV is an arrangement of apparatus identified as the (MRS) metals removal system unit considered in one aspect as a thermal visbreaker relying on hot fluidizable inert solids for effecting initial contact of a reduced crude containing feed as herein identified with a solid sorbent material to effect removal of metal contaminants and thermal degradation of high boiling carbon forming materials in the feed.
  • MRS metals removal system unit
  • the integrated operation of this invention briefly outlined above is a coalescence of novel operating contributions specifically discussed below which synergistically contribute one to the other to form a novel combination of steps for efficiently processing distress hydrocarbon stocks to more desirable gaseous and liquid products in an economically satisfactory manner.
  • the distress stocks which may be processed by the combination operation of this invention include fractions of atmospheric and vacuum distillation such as topped crudes, residual oil, resids, reduced crudes and other heavy hydrocarbon materials obtained from coal, oil, shale, tar sands and a combination of such materials.
  • the oil feeds will all boil above about 600°F (315°C) and comprise high molecular weight hydrocarbon components vaporizable upto about 1025°F (552°C).
  • the initial boiling point of the charge to the MRS unit may be within the range of 700°F up to 1000°F (371° to 538°C).
  • the combination operation of this invention is a thermally attractive energy efficient method for selectively removing and utilizing undesirable high boiling components of crude oils and metal contaminants in the production of more desirable premium fuel.
  • the present invention particularly concentrates on upgrading the "bottom of the barrel" of a crude oil to useful products.
  • FIG. 1 a simplified block flow arrangement of the combination process of this invention.
  • a high boiling hydrocarbon feed such as a reduced crude
  • a residual oil feed boiling above about 650°F (343°C) and comprising reduced crude components such as porphyrins, asphaltenes and polycyclic compounds are charged by conduit 2 to a MRS metals removal thermal contacting system 4 wherein the feed is contacted with solid sorbent particulate material having little if any cracking activity under conditions to thermally visbreak and reduce metal contaminants to a more acceptable lower level in conjunction with reducing the feed Conradson carbon value.
  • a wet gas product is formed and recovered by conduit 6 a Cg+ naphtha product recovered by conduit 8 and a 430°F+ (221°C) product material recovered by conduit 10.
  • the C s plus product material in conduit 8 and the 430°F (221°C) plus product material in conduit 10 are charged to an RCC (reduced crude cracking) unit 12 more fully discussed below with respect to Figures V and VII.
  • a wet gas product stream is formed and recovered by conduit 14
  • a main column overhead liquid is recovered by conduit 16
  • a 430 to 630°F (221° to 332°C) product fraction is recovered by conduit 18
  • a 630°F (332°C) plus unconverted material stream is recovered by conduit 20.
  • the RCC conversion products recovered by conduits 18 and 20 may be used in fuel oil blending operations not shown.
  • the 630°F (332°C) plus product may be further converted by catalytic cracking either in a separate FCC unit not shown or as recycle to the RCC unit 12.
  • the 430°F-630°F (221° to 332°C) product in conduit 18 may also be further refined as desired to meet fuel demands as by cracking, hydrogeneration and other processing steps suitable for the purpose.
  • the RCC main column overhead liquid in conduit 16 is passed to a gas concentration unit 22 discussed below. So also is the wet gas in conduits 6 and 14 blended and passed by conduit 6 to unit 22. A detailed discussion of the gas concentration unit operation is provided below with respect to Figure III.
  • the operation of the gas concentration unit provides a fuel gas stream withdrawn by conduit 24, which material is then passed to an MEA absorber 26 before being recovered by conduit 28.
  • a gasoline product boiling in the range of C 5 hydrocarbons up to about 400 or 430°F (204° and 221°C respectively) is recovered from unit 22 by conduit 30 and passed to a gasoline treating unit 32 before being recovered by conduit 34.
  • gasoline treating unit 32 it is contemplated treating the gasoline with a caustic wash and an electrostatic precipitator to remove undesired impurities in a manner known in the industry.
  • a C 3 /C 4 product fraction is recovered from unit 22 by conduit 36 and passed to a C 3 /C 4 treating unit 38.
  • the C 3 /C 4 fraction is treated to remove sulfur impurities and then caustic washed.
  • the product of treating unit 38 is passed by conduit 40 to a hydrogeneration unit 42 designed to particularly accomplish hydrogenation of diolefins before being recovered by conduit 44.
  • FIG. IV by way of example there is shown one arrangement of apparatus for effecting thermal contact of the residual oil or reduced crude containing feed with a solid sorbent material to accomplish metals removal and reduce the Conradson carbon producing components of the feed.
  • the contact system of Figure IV is referred to herein as the MRS system (metals removal system) by thermal visbreaking comprising a riser contact zone for selectively thermally contacting the heavy residual oil feed comprising metal contaminants with a solid sorbent particulate material such as a kaolin solid particulate material of little or no catalytic cracking activity at a temperature within the range of 900 to 1050°F (482° to 565°C) under space velocity conditions and hydrocarbon feed partial pressure selected to accomplish substantial metals removal in the absence of excessive thermal cracking for the production of thermal naphtha boiling range products.
  • MRS system metal removal system
  • atomizing water is added by conduit 1 to a reduced crude containing feed introduced by conduit 3 to a riser reactor 5 and above the bottom portion thereof.
  • Steam in conduit 7 and/or admixed with water in conduit 9 obtained from the main column overhead drum discussed below with respect to Figure 7 is admixed with circulated hot solid particulate at a temperature in the range of 1300 to 1500°F (704° to 816°C) in the bottom portion of the riser in amounts and under conditions selected to adjust the temperature of the hot solids obtained from regeneration thereof and before contacting the oil feed particularly selected for charge to the riser.
  • the "wet gas" recycled from the RCC or MRS unit or other lift gas e.g.
  • diluents can be employed to convey the particulate through the riser reactor 5.
  • the particular combination of diluents admixed with solids permits establishing a vertical velocity component to the solids before contact with dispersed hydrocarbon feed material in the riser under selected temperature and pressure conditions.
  • a suspension of solid sorbent particulate and atomized feed of low partial pressure in the presence of steam diluent at a temperature below about 1025°F (552°C) is recovered from the riser 5 at a velocity providing a hydrocarbon residence time less than 5 seconds and preferably within the range of 0.5 to 4 seconds.
  • the riser 5 is provided with a plurality of vertically spaced apart feed inlet means to accomplish the above change in hydrocarbon residence time.
  • the suspension passed through riser 5 is discharged from the top or open end of the riser and separated so that vaporous hydrocarbons of thermal visbreaking and gasiform diluent material are caused to flow through a plurality of parallel arranged cyclone separators 11 and 13 - positioned about the upper open end of the riser contact zone. Hydrocarbon vapours separated from entrained solids by the cyclone separators are collected in a plenum chamber 15 before withdrawal or recovery by conduit 17 at a temperature of about 970°F (521°C).
  • the vaporous material in conduit 17 is quenched in one specific embodiment to a temperature well below its dewpoint by admixture with a portion of the main column bottoms product in conduit 17 of the MRS (metals removal system) product recovery section of Figure IV more fully discussed below.
  • Solid particulate material comprising kaolin particulate in this specific embodiment comprising accumulated metal deposits and carbonaceous .
  • material of thermal degradation are collected in a bottom portion of vessel 21 comprising a stripping section 23 to which stripping gas is charged by conduit 25 at a temperature of at least about 400°F (204°C). Higher stripping temperatures up to 1050°F (565°C) are also contemplated.
  • Stripped solid absorbent particulate material is passed by standpipe 27 providing with a flow control valve to fluid bed of particulate in a bottom portion of a regeneration zone 29.
  • Regeneration gas or combustion supporting gas such as oxygen modified gas or air is charged to a bottom portion of the regeneration zone by conduit 31 through a plenum distribution chamber 33 supporting a plurality of radiating gas distributor pipes 35.
  • Regeneration of the sorbent particulate by burning deposited carbonaceous material is accomplished at a temperature up to about 1500°F (816°C) preferably in an oxygen lean or restricted oxygen containing gas restricted atmosphere promoting the formation of a (CO) carbon monoxide rich regeneration flue gas.
  • Combustion product gases and catalyst pass from an upper level 37 of a fluid bed of particulate through a restricted passageway 39 as a suspended mass of particulate in flue gases to an upper enlarged portion of the regeneration vessel where a separation is made between solid particulate and product flue gasses by the combination of hindered settling and cyclone seperator means.
  • the separated particulate is collected as a fluid bed of material 41 in an annular zone about restricted passageway 39.
  • Flue gas separated from solids pass through a plurality of cyclones 43 positioned about the open upper end of passageway 39 for removal of entrained fines.
  • the CO rich flue gases then pass to plenum chamber 45 for withdrawal therefrom by conduit 47.
  • Regenerated solid sorbent particulate at an elevated temperature within the range of 1000 to 1500°F (538° to 816°C) is passed by standpipe 49 to the bottom portion of riser 5 for use as herein proposed.
  • a portion of the hot regenerated sorbent is withdrawn by conduit 51 for passage to a heat exchanger 53 wherein 450 psig (3.1 MPa) steam is particularly generated by indirect heat exchange with charged boiler feed water introduced by conduit 55 and steam recovered by conduit 57.
  • the thus partially cooled solid particulate is withdrawn by conduit 59 for passage to a bottom portion of the fluid bed of particulate in a bottom portion of regeneration zone 29 for temperature control of the metals contaminated particulate being regenerated.
  • Figure VI is concerned particularly with the product recovery section of the MRS unit for the recovery of different valuable fractions and heat exchange utilization contributing to the overall efficiency of the combination operation.
  • the demetallized vapors recovered by conduit 17 following addition of quench fluid substantially immediately upon recovery from plenum 15 is charged to a product fractionating or main column 61 maintained at a bottom temperature of about 590°F (310°C) and a top temperature of about 285°F (141°C).
  • a gaseous material is withdrawn at a temperature of about 285°F (141°C) from the column by conduit 63 for passage through air cooler 65, cooler 67 and thence to drum 69 wherein a separation is made at a temperature sufficiently reduced to recover a gasiform stream by conduit 71 passed to compressor 73 and then by conduit 75 to the gas concentration system of Figure III.
  • a naphtha fraction is recovered from drum 69 by conduit 77, a portion of which is recovered by conduit 79 for recycle to the riser reactor 5 with the remaining portion thereof being recycled as reflux to column 61 by conduit 81 to an upper portion of the MRS main column 61.
  • a sour water stream is recovered from drum 69 by conduit 83, a portion of which is passed to a sour water stripper not shown with the remaining portion being recycled to the MRS riser reactor as quench fluid introduced by conduit 9.
  • An intermediate boiling range product fraction boiling above naphtha boiling material is withdrawn by conduit 85, a portion of which is recycled to the column as pump around conduit 87, with another portion thereof being passed through a plurality of heat exchangers 89 to develop low pressure 150 psig (1 MPa) stream before being recycled to the main column by conduit 91.
  • Another portion of the material withdrawn by conduit 85 is passed by conduit 93 to heat exchanger 95 and received therefrom by conduit 97 for use as a portion of the demetallized charge to the RCC unit discussed below with respect to Figure V.
  • all or a portion of the material in conduit 97 may be passed by conduit 99 to heat exchanger 101 and air cooler 103 before being passed to storage as a demetallized liquid product thereafter available for further treatment or use as desired.
  • a bottom fraction withdrawn from column 61 by conduit 105 at a temperature of about 590°F (310°C) is passed in parallel flow arrangement partially through a high pressure stream generating heat exchanger 107 and partially through a crude oil feed heat exchanger 109 before being combined again as a single temperature reduced stream for passage through heat exchanger 111 provided for generating 150 psig (1 MPa) steam indirectly.
  • a portion of the bottoms fraction thus cooled is passed by conduit 113 directly to the main column 61.
  • a portion of this material is diverted by conduit 19 for use as quench fluid of the MRS vapors as discussed above.
  • Still another portion of the cooled material withdrawn from exchanger 111 is pased by conduit 115 to a slurry settler drum 117.
  • slurry settler drum 117 a separation is made which permits withdrawal of a demetallized material by conduit 119 which is further cooled in heat exchanger 121 before admixture with material in conduit 93 charged to heat exchanger 95.
  • Heat exchanger 121 is relied upon to produce 150 psig (1 MPa) steam with heat exchanger 95 providing preheat to boiler feed water for producing 450 psig (3.1 MPa) steam.
  • the high boiling hydrocarbon charge recovered from drum 123 by conduit 127 is passed directly to the MRS riser reactor for demetallization as above described or it may be diverted at least in part through the slurry settler 117 and withdrawn from the bottom thereof by conduit 131 before being charged as feed to the MRS riser reactor with solid particulate recovered from slurry settler 117.
  • FIG. V there is shown an arrangement of vessels with interconnecting conduits comprising an RCC riser reactor-regenerator system relied upon to process the demetallized feed materials obtained from the MRS thermal demetallizing unit.
  • the residual metals in the RCC feed on the basis of (Ni+V) nickel plus vanadium charged to the RCC riser reactor will be considerably reduced by the MRS solid contacting unit and usually will be less than about 100 ppm Ni+V.
  • the operation of the RCC system is similar in many respect to an (RCC) fluid catalyst cracking system but is more critically and selectively controlled with respect to catalyst regeneration and catalyst use in order to process thermal converted high boiling residual oils or reduced crudes which have been partially demetallized and decoked as herein provided.
  • Operation of the RCC unit is critical with respect to heat balance and feed conversion selectivity since relatively substantial amounts of carbonaceous deposits are laid down on the catalyst depending on feed charged, metal deposits accumulated on the circulated catalyst and over cracking of charged feed is potentially eminent so that product selectivity may be undesirable, altered when the balance of the operation is permitted to vary from a relatively restricted range of operating conditions into less than an efficient and economic operation.
  • the catalyst regeneration operation is considered unique in generating CO rich flue gas subsequently used to advantage in the process to generate high pressure steam in conjunction with providing a mass of active zeolite containing catalyst particles of restricted temperature and residual coke on the catalyst particles. More importantly however is the identification of operating conditions utilized in the hydrocarbon conversion riser reactor which permits one to process thermally treated heavy crudes partially demetallized and decoked as herein identified under conditions particularly increasing the yield of desired liquid fuel products comprising gasoline and gasiform materials readily converted to useful fuel products including gasoline boiling range product materials such as by alkylation, isomerization, polymerization or a combination thereof.
  • the hydrocarbon conversion riser operations of the MRS and the RCC system are relatively high velocity operations as herein provided.
  • the temperature of the conversion product vapors is restricted to within the range of 950°F to about 1050°F (510° to 566°C) and more particularly restricted not to exceed about 1000°F (538°C) when charging the demetallized feed of MRS processing herein described to the riser at a temperature of about 400°F (204°C).
  • the use of water injection and steam dispersion is relied upon in substantial measure for temperature control, feed atmoized dispersion and in achieving a high velocity suspension of catalyst particles and hydrocarbon feed in the riser cracking reaction time frame of hydrocarbons in contact with catalyst particles in the riser less than about 4 seconds and more usually less than about 3 seconds.
  • the riser reactor is designed to achieve high velocity (about 180 ft/second; 54.9 m/second) mixing of hot catalyst particles with fluidizing gaseous material and with charged partially demetallized high boiling feed material in a lower restricted diameter portion of the riser reactor section and thereafter decreasing the velocity of the suspension to a discharge velocity of about 85 or 86 ft/second (25.9 and 26.2 m/second, respectively) adjacent the upper discharge end of the riser.
  • This combination and alteration of the suspension velocity is accomplished particularly by gradually increasing the diameter of the riser in an upper transition section thereof.
  • the initially formed suspension is at a velocity of about 180 ft/second (54.9 m/second) and the velocity of the suspension discharged from the open upper end of the riser reactor is about 86 ft/second (26.2 m/second) after passing through an expanding transition section and the discharge temperature is maintained below about 1025°F (552°C) but above about 975°F (524°C) in a specific embodiment.
  • the riser reactor of Figure V is about 198 ft.
  • Figure V shows introducing a mixture of the demetallized feed obtained from the MRS unit MRS naphtha and water obtained from the main column overhead drum to a bottom or upper portion of riser reactor 50 as desired. Steam may be charged separately to the bottom of the riser and with demetallized feed as charged to assist with atomized and vaporized dispersion of the heavy oil feed in contact with the regenerated hot catalyst particles charged to the bottom portion of the riser by conduit 52.
  • the suspension is discharged from the top open end of the riser and rapidly separated by passing gasiform product material comprising hydrocarbon vapors with some entrained catalyst particles through a plurality of parallel arranged cyclone separators 54 generally comprising one stage of cyclone separator positioned about the upper end of the riser.
  • cyclone separators 54 generally comprising one stage of cyclone separator positioned about the upper end of the riser.
  • at least two cyclone separators in series may also be employed.
  • Separated product vapors or gasiform material comprising hydrocarbon conversion products are collected in plenum chamber 56 and withdrawn therefrom by conduit 58 communicating with a RCC product recovery section represented by Figure VII and discussed below.
  • Catalyst particles separated from vaporous products of hydrocarbon conversion are collected and passed downwardly through a stripping zone 60 counter-current to stripping gas such as steam introduced by conduit 62.
  • the temperature of the RCC stripping operation is generally maintained within the range of 900°F to 1050°F (482° to 566°C).
  • the stripped catalyst is passed by a standpipe or conduit 64 to a bed of catalyst is passed by a standpipe or conduit 64 to a bed of catalyst 66 in the first stage of catalyst regeneration affected in the upper portion of a two stage catalyst regeneration vessel 68.
  • Regeneration vessel 68 is unique in that the upper portion thereof is of larger diameter than a bottom portion and separated from one another by a centrally located air distributor plenum chamber 70 supported by an annular baffle 72 provided with flue gas flow through passageway 74.
  • a plurality of radiating arm means 76 are provided with plenum 70 for introducing additional regeneration gas to a lower portion of catalyst bed 66.
  • Regenerator air in a specific embodiment amounting to about 75% of that required to achieve desired carbonaceous material removal by burning and regeneration of the catalyst is introduced to plenum chamber 70 by conduit 78.
  • the regeneration gas such as air may be preheated by means not shown to a desired elevated temperature of about 300°F (149°C).
  • the catalyst introduced to bed 66 by conduit 64 comprises carbonaceous deposits of the riser hydrocarbon conversion operation and contain some hydrogen.
  • the regeneration temperature is kept to a low value in the range of about 1200°F (649°C) up to about 1300°F (704°C) under combustion supporting conditions of carbonaceous deposits sufficient to effect partial removal of carbonaceous deposits and produce a CO rich flue gas.
  • CO rich flue gases comprising CO 2 , sulfur oxides, nitrogen and water vapor pass through a combination of parallel arranged cyclone separators and which may comprise two on series and represented by cyclones 80 wherein entrained catalyst particles are separated from flue gas and returned by the cyclone dipleg to the catalyst bed 66.
  • Flue gas separated from catalyst particles is passed to a plenum chamber 82 for withdrawal therefrom by conduit 84 as a CO rich flue gas for use as discussed below.
  • the partially regenerated catalyst of bed 66 is passed to a second stage of catalyst regeneration below the first stage through an external standpipe 86 provided with a catalyst cooler 88 wherein high pressure 450 psig (3.1 MPa) steam is generated.
  • the catalyst partially cooled in steam boiler 88 and only partially regenerated is then passed by conduit 90 to a fluid bed of catalyst 92 in the lower portion of the regeneration vessel 68 and comprising the second stage of catalyst regeneration.
  • Standpipe 94 is also provided as a secondary external standpipe for transfer of catalyst from bed 66 to bed 92.
  • standpipe 86 is the primary route of catalyst transfer from bed 66 to bed 92.
  • transfer standpipes The use of these transfer standpipes is to transfer partially regenerated catalyst and maintain temperature control in the lower regeneration stage for residual carbon burn below at a temperature within the range of 1325°F (718°C) to about 1500°F (816°C).
  • Regeneration of catalyst in bed 92 is effected at a temperature generally higher than that of bed 66 and more usually is maintained at a temperature within the range of 1350°F (732°C) up to about 1400°F (760°C) and in the presence of an oxygen containing gas sufficient to achieve substantial burning of residual coke on the partially regenerated catalyst obtained from bed 66.
  • the amount of air or oxygen modified gas employed in the second stage of catalyst regeneration introduced by conduit 96 beneath a distribution grid 98 is only about 25% of that required to accomplish desired catalyst regeneration and produce a CO rich flue gas for passage to and recovery or at least in part from the first stage of regeneration. That is, all of the flue gas from the second stage of regeneration pass through openings 74 in baffle member 72 separating the upper regenerator from the lower regenerator.
  • the hotter flue gases of the second stage operation comprising CO, C0 2 and any unreacted oxygen containing gas pass into the bottom portion of bed 66 thereby contributing heat to catalyst bed 66 whereby initiation of the combustion of carbonaceous deposits is implemented.
  • Regenerated catalyst of relatively low residual coke below about 0.25 weight percent and at a temperature within the range of 1300° to 1500°F (704° to 816°C) is withdrawn from catalyst bed 92 for passage by conduit (standpipe) 52 to a lower bottom portion of riser 50 and reuse as herein before discussed.
  • FIG. VII The product recovery section of the RCC unit is shown in Figure VII.
  • vaporous hydrocarbon products and diluent materials of the RCC reactor withdrawn by conduit 58 Figure V
  • a vaporous or gasiform material comprising hydrocarbon vapors and diluent is withdrawn from the top of column 100 by conduit 102 for passage through air cooler 104, and heat exchanger 106 to drum 108.
  • drum 108 maintained at a temperature sufficient to recover 400°F (204°C) material by conduit 110, a separation is made which permits the recovery of equilibrium hydrocarbon vapors comprising 400°F (204°C) minus material by conduit 110, a gasoline boiling range product material is also recovered by conduit 112, a portion of which is recycled as reflux to column 100 by conduit 114 and the remaining portion being passed by conduit 116 to a primary absorber column of the RCC gas concentration section of Figure III discussed below.
  • Sour water comprising sulfur compounds is recovered from drum 108 by conduit 118 for distribution to a sour water stripper not shown or as recycled by conduit 118 to the RCC riser reactor as discussed above with respect to Figure V.
  • a light cycle oil (LCO) recovered in the system of Figure III is charged by conduit 120 to an upper portion of column 100 below about tray 12, but above a grid packing section shown.
  • a light cycle oil is withdrawn from column 100 above tray 13 by conduit 122. A portion of this withdrawn LCO may be recycled directly to the column with the major portion thereof being passed directly to the system of Figure III discussed below.
  • a portion of the LCO withdrawn by conduit 122 is passed by conduit 124 to a LCO stripper 126. Material stripped from the light cycle oil with steam in zone 126 is returned to the main column by conduit 128.
  • Stripped LCO is withdrawn from stripper 126 by conduit 130 for passage through heat exchanger 132, air cooler 134 and cooler 136 before passage to storage. A portion of this material may be used as flushing fluid in pumps, instruments and othe process equipment of the combination process.
  • a heavy cycle oil is recovered from column 100 by conduit 138 for passage to a heat exchanger 140 in the system of Figure III whereby cooling of the HCO is accomplished before recycle thereof to an upper portion of the main column by conduit 142.
  • a bottoms fraction is recovered from the main column by conduit 144 for passage to heat exchange means 146 associated with the debutanizer tower of Figure III disclosed below. This material following cooling thereof by heat exchange means 146 is recycled to the main column of Figure VII by conduit 148. Provision is also made for passing a portion of the high boiling material in conduit 144 through a steam boiler 150 by conduit 152 and heat exchange cooler 154.
  • the high boiling material thus cooled is combined with slurry material in conduit 148 for recycle to the main column below about tray 20 to maintain the temperature in a bottom portion of the column about 650°F (343°C)
  • a portion of the high boiling material in conduit 144 may also be passed by conduit 156 to slurry settler 158 from which a clarified oil is recovered by conduit 160 and cooled by heat exchanger 162 and 164 before being passed to storage for other use as desired.
  • the clarified oil thus recovered is suitable for use in heavy fuel oil blending operations or it may be recycled to the RCC riser for further conversion thereof.
  • the reduced crude containing feed demetallized by the MRS system of Figures IV and VI and recovered by conduit 97 is passed to charge drum 168 wherein depending on temperature conditions maintained, a separation may or may not be made before passing the RCC charge material all or in part thereof to the slurry settler 158 by conduit 170. A portion of the RCC charge material may also be passed through exchanger 154 before being combined with the slurry settler bottoms and passage as feed to the RCC riser reactor by conduit 172. Low boiling component material in the charge passed to drum 168 may be separated and passed overhead by conduit 174 to the main column 100. On the other hand it is contemplated recovering a heavy cycle oil (HCO) type material from the main column for admixture in drum 168 by conduit 174 with the charge material introduced by conduit 97.
  • HCO heavy cycle oil
  • the vaporous material is further compressed in compressor 192 and recovered therefrom at an elevated pressure by conduit 194 for passage to drum 200 downstream thereof at a pressure in the range of about 210-215 psig (1.4 to 1.5 MPa) and a temperature of about 60°F (16°C).
  • the compressed vaporous material in conduit 194 is mixed with liquid in conduit 188 provided with a pump not shown for passage to air cooler 196 and heat exchanger 198 before entering drum 200 briefly referred to above.
  • Vaporous material from the MRS wet gas compressor in conduit 75 is added to vaporous material in conduit 194 before passing up to air cooler 196.
  • an equilibrium separation is made at a temperature of about 60°F (16°C) and a pressure of about 215 psig (1.5 MPa) to recover a hydrocarbon vaporous material boiling below 400°F (204°C) withdrawn by conduit 202 from a liquid hydrocarbon product recovered by conduit 204 and water recovered by conduit 206.
  • the vaporous material in conduit 202 is passed to the lower bottom portions of a primary absorber column 208.
  • Liquid material recovered from the main column 100 overhead drum 108 by conduit 116 ( Figure VII) is charged to an upper portion of absorber column 208.
  • a primary function of absorber column 208 maintained at a top temperature of 114°F (46°C) and a bottom temperature of 111°F (44°C) is to effect a separation of C 3 + material from lower boiling gaseous material comprising ethane withdrawn by conduit 226.
  • a first pump around stream is withdrawn from an upper portion of the absorber column above tray 13 by conduit 210, cooled in cooler or heat exchanger 212 and returned to the column by conduit 214.
  • a second pump around stream is withdrawn about tray 27 by conduit 216, cooled in cooler or heat exchanger 218 and returned by conduit 220 to the column above tray 27.
  • absorber column 208 The efficiency of absorber column 208 is further improved by charging gasoline product material recovered as herein after discussed by conduit 222 to an upper top portion of the tower 208. This method of operating the primary absorber has been found to considerably improve the separation and recovery of C 2 and lower boiling materials from more desirable higher boiling material produced and separated in the process.
  • the absorber bottoms is recovered by conduit 224 and passed to air cooler 196 along with material in conduit 194 and that withdrawn from the top of stripper 242.
  • the gaseous overhead material of column 208 is withdrawn by conduit 226 for passage to a sponge oil absorber tower 228.
  • a light cycle oil (LCO) product recovered from the main column fractionator Figure VII by conduit 122 and cooled as hereinafter discussed is employed as sponge oil in column 228 to effect recovery of C 3 + constituents from C 2 components in the gaseous stream of conduit 226 comprising ethane and hydrogen.
  • the C 2 product is withdrawn by conduit 230.
  • the sponge oil (LCO) in conduit 112 is passed through cooler 232 heat exchanger 234 and cooler 236 before discharge in an upper portion of column 228.
  • the sponge oil enriched with C 3 + components is withdrawn by conduit 238 for passage through heat exchanger 234 and recovery therefrom by conduit 240 and return to the main column by conduit 120.
  • the liquid hydrocarbon product recovered by conduit 204 from drum 200 is pumped for discharge in the upper top portion of a stripper column 242.
  • a 400°F (204°C) minus material charged to stripper 242 is withdrawn from the bottom of stripper 242 by conduit 248 for passage to a debutanizer tower 250.
  • Debutanizer tower 250 is maintained at a top temperature of 143°F (62°C) and a bottom temperature of 394°F (201°C) and pressure conditions promoting the separation of C 3 + material charged by conduit 248 to be separated into a C 3 -C 4 rich fraction removed from the top of the tower by conduit 252 and passage through air cooler 254, cooler 256 to drum 258.
  • Separated C3-C4 product material is recovered from drum 258 for further treating as desired such as alkylation, polymerization and isomerization with a portion thereof recycled to an upper portion of tower 250, as reflux.
  • a C 5 + gasoline fraction is recovered from the bottom of tower 250 by conduit 260.
  • a portion of this C 5 + gasoline fraction i. passed to heat exchanger 246, then to air cooler 262, heat exchanger 264 and recovery therefrom by conduit 266.
  • a portion of this recovered gasoline fraction is recycled by conduit 222 to tower 208 as discussed above to improve separation and recovery between ethane and lower boiling material from higher boiling C 3 + hydrocarbons.
  • Another portion of the C 5 + gasoline recovered by conduit 260 is separated into parallel streams for passage through exchangers 140 and 146 to raise the temperature thereof before recycle to a lower portion of column 250.
  • FIG II is particularly directed to an arrangement and utilization of CO rich flue gas obtained from the regenerator vessel of the MRS unit and the RCC unit discussed in more detail above.
  • a further significant aspect of the operation is concerned with the recovery of sulfur oxides found in the regeneration flue gas so that cooled flue gas may be vented directly to the atmosphere without harmful effect.
  • CO rich flue gas from the RCC regenerator of Figure V withdrawn by conduit 84 is charged in part to CO boiler 270 and by conduit 272 to CO boiler 274.
  • Regeneration flue gas recovered from the MRS regenerator by conduit 47 is charged in part to CO boiler 274 and by conduit 276 to CO boiler 270.
  • This parallel flow arrangement of CO rich flue gas to the parallel arranged CO boilers in admixture with added combustion supporting gas permits operating one without the other during shut down for any particular reason.
  • the CO boilers contemplated for use comprise directly contacting limestone particulate with combustion flue gas following combustion of CO with added air and in indirect heat exchange with boiler feed water charged to a given CO boiler arrangement for generation of high pressure 450 psig (3.1 MPa) steam recovered therefrom by means provided.
  • Combustion product gases of CO boiler 274 are passed by conduit 290 to bag house 292 for removal of entrained fines before passage by conduit 294 to stack 288 either separately or admixed with gases in conduit 286.
  • High pressure steam is recovered from zone 270 by conduit 296 and from zone 274 by conduit 298.
  • An important aspect of the combination operation of this invention is concerned with the utilization of generated steam by the process and heat exchange arrangement provided to accomplish transfer, utilization and recovery of heat energy by the combination operation. That is the high pressure steam generated by CO boiler arrangement is relied upon to drive turbines for the air blowers for the MRS and RCC regenerators above discussed, there being two such air blower arrangements for the MRS regenerator because of the regeneration air requirements thereof. This generated high pressure steam is also utilized to drive air blower providing combustion air to the CO boilers, as well as to drive turbines forthe RCC wet gas compressors 180 and 192 and the MRS wet gas compressor 73.
  • the RCC slurry steam generator 150 provides 450 psig (3.1 MPa) steam as does the MRS steam drum 107.
  • This generated high pressure steam is utilized to drive turbines for the MRS charge pump (not shown), the RCC charge pump (not shown), the RCC slurry pumps (not shown) and a boiler feed water pump (not shown).
  • the RCC slurry steam generator 154 is relied upon to generate 150 psig (1 MPa) steam as does the MRS steam drum 111. This 150 psig (1 MPa) steam is supplemented by the recovery of 150 psig (1 MPa) steam from the 450 psig (3.1 MPa) blow down of steam generators.
  • the 150 psig (1 MPa) steam thus generated is used to drive the lube oil pumps (not shown) and is also used as RCC reactor stripping steam, LCO stripper steam above discussed and for condensor vacuum jets required in the process but not discussed. Condensate recovered from the above briefly discussed steam utilization is charged as boiler feed water to the various heat exchangers identified in the drawing above specifically discussed.
  • Another important aspect of the combination operation of this invention above discussed is concerned with the severity of thermal conversion relied upon in the MRS operation employing relatively inert fluidizable solids to provide a suitable feed material to be converted with a crystalline zeolite containing catalyst in the downstream RCC catalytic conversion operation.
  • the operating techniques of this combination of operations are concerned with effecting the catalytic conversion of a thermally prepared feed material comprising a relatively high level of metal contaminants up to about 100 ppm Ni+V with cracking catalyst comprising catalytically active crystalline zeolite of relatively large pore dimensions as provided by faujasite type crystalline zeolites in admixture with a sorbent matrix material and said catalyst comprising a higher contaminating metals loading than previously thought usable in similar cracking operations.
  • tailoring of the operating conditions employed in the MRS thermal visbreaking operation and feed preparation unit are made to provide a thermally processed high boiling portion of crude oil as feed for a downstream catalytic conversion step and comprising up to about 100 ppm Ni+V.
  • This interrelated tailoring of operating conditions for feed preparation and utilization thereof are adjusted dependent upon the composition of the high boiling feed to be processed, its initial boiling point and the level of metal contaminants and Conradson carbon producing components upon pyrolysis.
  • thermal preparation of the feed will be accomplished under conditions permitting up to 100 ppm Ni+V remaining in the feed to be charged to the RCC catalytic cracking operation. It is also desirable within this processing arrangement to limit the production of thermally produced naphtha even though such thermal naphtha can be and is intended to be upgraded in the zeolite cracking operation along with thermally demetallized high boiling feed charged thereto as above discussed.
  • the thermal conversion or visbreaking operation effected in the absence of added molecular hydrogen provides a variety of operating parameters in that the inert solid sorbent particulate material may comprise a high loading of metal contaminants to provide a residual oil feed or high boiling portions thereof comprising up to 100 ppm Ni+V for processing in a downstream zeolite catalyst cracking operation.
  • the downstream zeolite cracking operation may circulate a catalyst composition comprising at least 3000 ppm Ni+V metal contaminants.
  • the efficiency of the separate operations are of a high order of magnitude and synergistically related by the recovery of high pressure steam from the combined flue gases of each regeneration operation and utilization thereof to some considerable advantage in providing energy requirements of the combination operation. More importantly is the economic efficiency attached to the recovery section of Figure III referred to as the gas concentration section for processing the wet gas streams recovered from each cracking operation in conjunction with separating the main column overhead accumulated liquid of the RCC product recovery section of Figure VII.
  • the thermal visbreaking of metals containing feed material is accomplished in a riser conversion zone provided with a plurality of vertically spaced apart feed inlet means to achieve a hydrocarbon residence time within the riser of either one of 0.5 seconds, 1.2 seconds and 1.5 seconds when passing a suspension of solids in gasflow material through the riser at a velocity of 100 ft/second (30.5 m/second).
  • the riser reactor provided for the zeolite catalyst conversion operation wherein the circulated catalyst comprises a lever of metal contaminants in excess of 3000 ppm Ni+V, greater than 5000 ppm Ni+V may even comprise as high as 10,000 ppm Ni+V equivalent, relies upon a high velocity contact system of riser reactor permitting the use of suspension velocities up to as high as 180 or 200 feet/second (55 and 61 m/second respectively) which velocity is thereafter reduced in an expanded upper section of the riser to permit a suspension discharge velocity of not more than about 85 or 86 feet/second (25.9 and 26.2 m/ second respectively).
  • the hydrocarbon residence time in the presence of substantial amounts of diluent such as steam is restricted not to exceed about 4 seconds and more usually is retained within the range of 0.5 to 2 or 3 seconds.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Claims (10)

1. Un procédé d'amélioration de pétroles bruts étêtés souillés par des métaux et ayant des points d'ébullition supérieurs à 600°F (315°C), des teneurs en métaux supérieures à 100 ppm (parties par million) de Ni et V et des valeurs de carbone Ramsbottom supérieures à 1,0, par une combinaison d'abaissement thermique de la viscosité et de craquage catalytique, caractérisé par les opérations consistant:
i) à mettre en contact la matière d'alimentation formée de pétroles bruts souillés par des métaux, avec de la vapeur d'eau dans une zone adsorbant-contact à une température élevée, et contenant une matière à base de solides en particules fluidisées qui est pratiquement inerte dans les conditions de réaction existant dans la zone adsorbant-contact;
ii) à récupérer de la zone adsorbant-contact a) un courant gazeux, b) un courant de naphte et c) un courant d'hydrocarbure à point d'ébullition élevé, démétallisé, ayant un point d'ébullition supérieur à 430°F (221°C) et une teneur en métaux ramenée à moins de 100 ppm de Ni+V;
iii) à faire passer le courant de naphte venant de la zone adsorbant-contact et le courant d'hydrocarbure à point d'ébullition élevé démétallisé à travers une zone de craquage catalytique contenant un catalyseur de craquage fluidisé du type zéolite cristalline contenant des impuretés métalliques déposées à raison de plus de 3 000 ppm de Ni+V, avec un temps de contact de moins de 4 secondes et à une température réglée de façon telle que les vapeurs sortant de la zone de craquage soient à une température de l'intervalle de 950° à 1 200°F (510° à 649°C);
iv) à séparer de la zone adsorbant-contact un courant latéral de matière solide en particules, à amener le courant latéral de solides en particules à une zone de régénération, à régénérer les solides dans ladite zone en brûlant des dépôts carbonés en présence d'un gaz entretenant la combustion qui contient une quantié restreinte d'oxygène, de manière à former un gaz de combustion qui est riche en CO, à recycler les particules régénérées chaudes depuis la zone de régénération vers la zone adsorbant-contact;
v) à séparer de la zone de craquage un courant latéral de particules de catalyseur, à amener le courant latéral de particules de catalyseur vers une zone de régénération de catalyseur, à régénérer les particules de catalyseur dans ladite zone de régénération en brûlant des dépôts carbonés sur le catalyseur en présence d'un gaz entretenant la combustion qui contient une quantité restreinte d'oxygène, de manière à former un deuxième gaz de combustion qui est riche en CO, à recycler les particules de catalyseur régénérées chaudes depuis la zone de régénération de catalyseur vers la zone de craquage;
vi) à utiliser les gaz de combustion riches en CO venant des deux zones de régénération pour alimenter en combustible une chaudière produisant de la vapeur d'eau;
vii) à séparer le produit à l'état de vapeur venant de la zone de craquage en un courant gazeux, un courant de produit à base d'essence et un courant d'hydrocarbures lourds ayant un point d'ébullition supérieur à celui du courant de produit à base d'essence;
viii) à amener les courants gazeux venant de la zone adsorbant-contact et de la zone de craquage et le courant de produit à base d'essence récupéré de la zone de craquage vers une unité de concentration de gaz; et
ix) à récupérer séparément, de l'unite de concentration de gaz, un courant gazeux hydrocarboné comprenant de l'hydrocarbure en C2 et de l'hydrogène, un courant d'hydrocarbures en C3/C4 et un courant d'essence.
2. Un procédé selon la revendication 1, dans lequel on met en contact la matière d'alimentation formée de pétroles bruts souillés par des métaux avec la matière en particules dans une zone adsorbant-contact à colonne montante, à une température de l'intervalle de 900° à 1 050°F (482° à 566°C) et avec un temps de séjour des hydrocarbures inférieur à 5 secondes.
3. Un procédé selon la revendication 2, dans lequel après passage à travers la zone adsorbant-contact à colonne montante, on sépare le produit à l'état de vapeur de la matière en particules entraînées, on le refroidit et on le fractionne pour donner le courant gazeux, le courant de naphte et le courant d'hydrocarbures à point d'ébullition élevé démétallisé, la matière en particules séparée étant envoyée à la zone de régénération pour y être régénérée et être recyclée au bas de la zone d'abaissement de viscosité à colonne montante, à une température de recyclage de l'intervalle de 1 000° à 1 500°F (538° à 816°C) une partie des particules régénérées étant retirée, refroidie par échange indirect de chaleur avec de l'eau, ce qui produit de la vapeur d'eau pour utilisation dans le procédé et de la matière en particules régénérée refroidie que l'on recycle vers la zone de régénération pour régler la température de la zone de régénération.
4. Un procédé selon l'une quelconque des revendications 1-3, caractérisé en ce que l'on met en contact le courant de naphte venant de la zone adsorbant-contact et le courant d'hydrocarbures à point d'ébullition élevé démétallisés avec le catalyseur de craquage dans une colonne montante à grande vitesse, avec un temps de contact total de moins de 4 secondes, ladite colonne ayant une première section de diamètre restreint à travers laquelle les particules de catalyseur et le gaz de fluidisation se déplacent à une vitesse d'environ 180 ft/seconde (55 m/seconde), et une section supérieure de plus grand diamètre, à travers laquelle les particules de catalyseur et le gaz de fluidisation se déplacent à une vitesse d'environ 86 ft/seconde (26 m/seconde) et depuis laquelle le gaz craqué est évacué à une température de sortie de l'intervalle de 975° à 1 205°F (524° à 552°C).
5. Un procédé selon l'une quelconque des revendications 1-4, caractérisé en ce que l'on régénère le catalyseur de craquage du type zéolite en deux stades, en amenant le catalyseur usé récupéré depuis la zone de craquage vers la couche supérieure de deux couches fluidisées séparées de particules de catalyseur usé situées l'une au-dessus de l'autre dans un récipient de régénération de catalyseur, en mettant en contact les particules de catalyseur dans chacune des deux couches avec un gaz de régénération de catalyseur, le courant de gaz de fluidisation amené à la couche supérieure des deux couches comprenant aussi le gaz de combustion venant de la couche inférieure des deux couches, en amenant les particules de catalyseur partiellement régénéré depuis la couche supérieure vers la couche inférieure des deux couches, et en récupérant les particules de catalyseur complètement régénéré depuis la couche inférieure des deux couches pour le recyclage vers la zone de craquage.
6. Un procédé selon la revendication 5, caractérisé en ce que l'on fait passer au moins une portion des particules de catalyseur partiellement régénéré depuis la couche fluidisée supérieure vers la couche fluidisée inférieure, en passant par un tuyau montant comprenant un échangeur de chaleur refroidi par eau, dans lequel les particules de catalyseur partiellement régénéré sont refroidies avant d'être amenées à la couche inférieure avec formation concomitante d'un autre courant de vapeur d'eau pour utilisation dans le procédé.
7. Un procédé selon la revendication 6, caractérisé en ce que l'on amène la majeure proportion du catalyseur partiellement régénéré, en passant par ledit tuyau montant et l'échangeur de chaleur, vers la couche fluidisée inférieure, tandis que l'on amène une moindre proportion, en passant par un deuxième tuyau montant, directement depuis la première vers la deuxième couche fluidisée sans refroidissement intermédiaire.
8. Un procédé selon la revendication 5, 6 ou 7, caractérisé en ce que l'on amène le gaz de régénération en courants séparés vers les deux couches fluidisées, environ 75% du gaz de régénération total étant amenés vers la couche supérieure et environ 25% étant amenés vers la couche inférieure.
9. Un procédé selon l'une quelconque des revendications 5-8, caractérisé en ce que l'on maintient la couche fluidisée supérieure, dans le récipient de régénération de catalyseur, à une température de l'intervalle de 1 200° à 1 300°F (649° à 704°C) et en ce que l'on maintient la couche fluidisée inférieure à une température de l'intervalle de 1 350° à 1 400°F (732° à 760°C).
10. Un procédé selon l'une quelconque des revendications 1-9, caractérisé en ce que l'on récupère en outre de la zone de craquage un courant séparé d'hydrocarbures à base de produit à point d'ébullition élevé, à point d'ébullition de 430° à 630°F (221° à 332°C), pour l'utiliser comme mazout.
EP82302428A 1981-05-13 1982-05-12 Procédé de combinaison pour l'amélioration d'huiles résiduelles Expired EP0066387B1 (fr)

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PCT/US1981/000648 WO1982004062A1 (fr) 1981-05-13 1981-05-13 Procede de combinaison pour l'affinage d'huiles residuelles

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US4569753A (en) * 1981-09-01 1986-02-11 Ashland Oil, Inc. Oil upgrading by thermal and catalytic cracking
RU2518481C1 (ru) * 2013-05-21 2014-06-10 Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (ОАО "ВНИИ НП") Способ получения высокооктанового базового бензина
CN112604718B (zh) * 2020-12-24 2022-06-24 新疆大全新能源股份有限公司 一种高沸裂解反应中残液的回收工艺

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US2526881A (en) * 1948-05-17 1950-10-24 Shell Dev Catalytic conversion of hydrocarbons to produce alkyl naphthalenes
US2688401A (en) * 1949-09-29 1954-09-07 Standard Oil Co Flotation of active catalyst from spent catalyst
US2766184A (en) * 1952-02-01 1956-10-09 Exxon Research Engineering Co Combination oil refining process
FR1363813A (fr) * 1963-07-22 1964-06-12 Shell Int Research Procédé et appareil pour la récupération de l'énergie des gaz usés d'une unité de craquage catalytique
US3303123A (en) * 1964-10-16 1967-02-07 Phillips Petroleum Co Catalytic cracking of residuum oils containing metal contaminants in several stages
US3767566A (en) * 1970-01-26 1973-10-23 Standard Oil Co Catalytic petroleum conversion process
US3763034A (en) * 1972-02-03 1973-10-02 Exxon Research Engineering Co Process for the preparation of high octane gasoline fractions
CA1093050A (fr) * 1975-12-19 1981-01-06 Iacovos A. Vasalos Craquage catalytique avec emission reduite de gaz nocifs
US4200520A (en) * 1978-01-30 1980-04-29 Exxon Research & Engineering Co. Catalytic cracking process
US4263128A (en) * 1978-02-06 1981-04-21 Engelhard Minerals & Chemicals Corporation Upgrading petroleum and residual fractions thereof
CA1127581A (fr) * 1978-02-06 1982-07-13 David B. Bartholic Obtention de charges de craquage catalytique fluide a partir de fractions residuelles
US4243514A (en) * 1979-05-14 1981-01-06 Engelhard Minerals & Chemicals Corporation Preparation of FCC charge from residual fractions
US4274942A (en) * 1979-04-04 1981-06-23 Engelhard Minerals & Chemicals Corporation Control of emissions in FCC regenerator flue gas
US4260475A (en) * 1979-11-01 1981-04-07 Chevron Research Company Hydrocarbon cracking process
US4276150A (en) * 1979-11-05 1981-06-30 Standard Oil Company (Indiana) Fluid catalytic cracking of heavy petroleum fractions

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AU568964B2 (en) 1988-01-14
ES8401122A1 (es) 1983-11-16
DE3267379D1 (en) 1985-12-19
ES512277A0 (es) 1983-11-16
AU5137485A (en) 1986-04-17
AU549952B2 (en) 1986-02-20
EP0066387A1 (fr) 1982-12-08
AU7412181A (en) 1982-12-07
IL67653A0 (en) 1983-05-15
EP0078797A1 (fr) 1983-05-18
CA1185914A (fr) 1985-04-23
WO1982004062A1 (fr) 1982-11-25
MX160803A (es) 1990-05-25
IL67653A (en) 1986-07-31

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