EP0065626B1 - Immobilisierung von Vanadin, das bei der Behandlung von Koksvorläufer und Schwermetalle enthaltenden Ölen auf Adsorbenzien abgelagert worden ist - Google Patents

Immobilisierung von Vanadin, das bei der Behandlung von Koksvorläufer und Schwermetalle enthaltenden Ölen auf Adsorbenzien abgelagert worden ist Download PDF

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EP0065626B1
EP0065626B1 EP82101769A EP82101769A EP0065626B1 EP 0065626 B1 EP0065626 B1 EP 0065626B1 EP 82101769 A EP82101769 A EP 82101769A EP 82101769 A EP82101769 A EP 82101769A EP 0065626 B1 EP0065626 B1 EP 0065626B1
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Prior art keywords
sorbent
vanadium
feed
coke
regenerated
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French (fr)
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EP0065626A2 (de
EP0065626A3 (en
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William P. Hettinger, Jr.
James D. Carruthers
William D. Watkins
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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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
    • C10G25/09—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents

Definitions

  • This invention relates to processes for producing a high grade of oil feed having lowered metals and Conradson carbon values for use as feedstocks for reduced crude conversion processes and/or for typical FCC processes from a poor grade of carbo-metallic oil having extremely high metals and Conradson carbon values. More particularly, this invention is related to a method of immobilizing vanadium compounds deposited on the sorbent during pretreatment of the oil feed.
  • VGO vacuum gas oils
  • the catalysts employed in early homogenous fluid dense beds were of an amorphous siliceous material, prepared synthetically or from naturally occurring materials activated by acid leaching.
  • Tremendous strides were made in the 1950's in FCC technology in the areas of metallurgy, processing equipment, regeneration and new more-active and more stable amorphous catalysts.
  • increasing demand with respect to quantity of gasoline and increased octane number requirements to satisfy the new high horsepower-high compression engines being promoted by the auto industry put extreme pressure on the petroleum industry to increase FCC capacity and severity of operation.
  • the new catalyst developments revolved around the development of various zeolites such as synthetic types X and Y and naturally occurring faujasites; increased thermal-steam (hydrothermal) stability of zeolites through the inclusion of rare earth ions or ammonium ions via ionexchange techniques; and the development of more attrition resistant matrices for supporting the zeolites.
  • these heavier crude oils also contained more of the heavier fractions and yielded less or lower volume of the high quality FCC charge stocks which normally boil below about 551,6°C and are usually processed so as to contain total metal levels below 1 ppm, preferably below 0.1 ppm, and Conradson carbon values substantially below 1.0.
  • the effect of increased Conradson carbon is to increase that portion of the feedstock converted to coke deposited on the catalyst.
  • the amount of coke deposited on the catalyst averages about 4-6 wt% of the feed.
  • This coke production has been attributed to four different coking mechanisms, namely, contaminant coke from adverse reactions caused by metal deposits, catalytic coke caused by acid site cracking, entrained hydrocarbons resulting from pore structure adsorption and/or poor stripping, and Conradson carbon resulting from pyrolytic distillation of hydrocarbons in the conversion zone.
  • the coked catalyst is brought back to equilibrium activity by burning off the deactivating coke in the regeneration zone in the presence of air, and the regenerated catalyst is recycled back to the reaction zone.
  • the heat generated during regeneration is removed by the catalyst and carried to the reaction zone for vaporization of the feed and to provide heat for the endothermic cracking reaction.
  • the temperature in the regenerator is normally limited because of metallurgical limitations and the hydrothermal stability of the catalyst.
  • the hydrothermal stability of the zeolite-containing catalyst is determined by the temperature and steam partial pressure at which the zeolite begins to rapidly lose its crystalline structure to yield a low activity amorphous material.
  • the presence of steam is highly critical and is generated by the burning of adsorbed and absorbed (sorbed) carbonaceous material which has a significant hydrogen content (hydrogen to carbon atomic ratios generally greater then about 0.5).
  • This carbonaceous material is principally the high boiling sorbed hydrocarbons with boiling points as high as 815,6-926,7°C or above that have a modest hydrogen content and the high boiling nitrogen containing hydrocarbons, as well as related porphyrins and asphaltenes.
  • the high molecular weight nitrogen compounds usually boil above 551,6°C and may be either basic or adidic in nature.
  • the basic nitrogen compounds may neutralize acid sites while those that are more acidic may be attracted to metal sites on the catalyst.
  • the porphyrins and asphaltenes also generally boil above 551,6°C and may contain elements other than carbon_and hydrogen.
  • the term "heavy hydrocarbons" includes all carbon and_ hydrogen containing compounds that do not boil below about 551,6°C regardless of whether other elements are also present in the compound.
  • the heavy metals in the feed are generally present as porphyrins and/or asphaltenes.
  • cartain of these metals, particularly iron and copper, may be present as the free metal or as inorganic compounds resulting from either corrosion of process equipment or contaminants from other refining processes.
  • the metal containing fractions of reduced crudes contain Ni-V-Fe-Cu in the form of porphyrins and asphaltenes. These metal containing hydrocarbons are deposited on the catalyst during processing and are cracked in the riser to deposit the metal or are carried over by the coked catalyst as the metallo-porphyrin or asphaltene and converted to cause non-selective or degradative cracking and dehydrogenation to produce increased amounts of coke and light gases such as hydrogen, methane and ethane. These mechanisms adversely affect selectivity, resulting in poor yields and quality of gasoline and light cycle oil. The increased production of light gases, while impairing the yield and selectivity of the processes, also puts an increased demand on the gas compressor capacity. The increase in coke production, in addition to its negative impact on yield, also adversely affects catalyst activity - selectivity, greatly increases regenerator air demand and compressor capacity, and may result in uncontrollable and/or dangerous regenerator temperatures.
  • 4,243,514 is an inert solid initially composed of kaolin, which has been spray dried to yield microspherical particles having a surface area below 100 m 2 /g and a catalytic cracking micro-activity (MAT) value of less than 20 and subsequently calcined at high temperature so as to achieve better attrition resistance.
  • MAT catalytic cracking micro-activity
  • the rate of vanadium buildup on the sorbent and the equilibrium or steady state of vanadium on the sorbent is a function of vanadium content of the feed and especially the sorbent addition and withdrawal rates which are equal at equilibrium conditions.
  • the following table presents a typical case for a 47.600 hi/day unit in which the vanadium content of the feed is varied from 1 ppm (treatment of an FCC feed comprised of VGO and 5 to 20 percent of a heavy hydrocarbon fraction) up to 25 to 400 ppm (treatment of a reduced crude for RCC operations).
  • the sorbent addition rate can be varied to yield equilibrated vanadium values of from 5000 to 30,000 ppm.
  • a process for treating a hydrocarbon oil feed having a significant content of vanadium and Conradson carbon to provide a product substantially lower in vanadium and Conradson carbon.
  • the hydrocarbon oil feed is contacted with a sorbent whereby coke and vanadium are deposited on said sorbent, the sorbent is separated from the remaining feed, and is regenerated in the presence of an oxygen- containing gas under conditions whereby the vanadium is retained in an oxidation state lower than +5.
  • the regenerated sorbent is recycled to contact fresh feed.
  • Vanadium in an oxidation state of +5 melts at a temperature within the range at which the regeneration is carried out; however, vanadium in the +3 or +4 oxidation state melts at-temperatures significantly greater than those encountered in the regenerator, and therefore does not present the problem resulting from coalescence of particles as does vanadium in the +5 oxidation state.
  • the invention provides a method of producing a high grade of reduced crude conversion (RCC) feedstocks having lowered metals and Conradson carbon values relative to a poor grade of reduced crude or other carbo-metallic oil having extremely high metals and Conradson carbon values.
  • the invention may further be used for processing crude oils or crude oil fractions with significant levels of metals and/or Conradson carbon to provide an improved feed-stock for typical fluid catalytic (FCC) cracking processes.
  • FCC fluid catalytic
  • the invention thus provides an improved method for treating petroleum oil feeds containing significant levels of vanadium (at least about 1.0 ppm). More particularly, this invention reduces particle coalescence and loss of fluidization caused by the vanadium contaminants in oil feeds of all types utilized in FCC and/or RCC operations. The invention is particularly useful in the pretreatment of carbo-metallic oil feeds to be utilized in RCC units.
  • Figs. 1 and 2 are schematic designs of sorbent regeneration and associated cracking apparatus which may be used in carrying out this invention.
  • the invention may be carried out by controlling the regeneration of the spent, vanadium - containing sorbent using several methods, alone or in combination.
  • the objective of these methods is to retain vanadium in a low oxidation state, either by not exposing the vanadium to oxidizing conditions, or by exposing vanadium to oxidizing conditions for too short a time to oxidize a significant amount of vanadium to the +5 state.
  • the concentration of vanadium on the sorbent particles increases as the catalyst is recycled, and the vanadium on the sorbent introduced into the reactor becomes coated with coke formed in the reactor.
  • the regenerator conditions are selected to ensure that at least enough coke is retained on the sorbent to keep vanadia in a reduced state. This coke may serve either to ensure a reducing environment for the vanadium, or to provide a barrier to the movement of oxidizing gas to underlying vanadium.
  • the concentration of coke on the sorbent particles is preferably at least about 0.05 percent and a more .preferred coke concentration is at least about 0.15 percent.
  • the regeneration is carried out in an environment which is non-oxidizing for the vanadium in an oxidation state less than +5. This may be accomplished by adding reducing gases such as, for example, CO or ammonia to the regenerator, or by regenerating under oxygen-deficient conditions. Oxygen-deficient regeneration increases the ratio of CO to C0 9 and in this method of providing a non-oxidizing atmosphere the CO/CO 2 ratio is at least about 0.25, preferably is at least about 0.3, and most preferably is at least about 0.4.
  • reducing gases such as, for example, CO or ammonia
  • the CO/CO 2 ratio may be controlled by controlling the extent of oxygen ' deficiency within the regenerator.
  • the CO/CO 2 ratio may also be increased by providing chlorine to the regenerator oxidizing atmosphere, preferably in concentrations of about 100 to about 400 ppm.
  • Regeneration in a reducing atmosphere is especially useful in combusting coke in zones where the coke level approaches or is reduced below about 0.05 percent, and it is preferred to have a CO/C0 2 ratio of at least about 0.25 in zones where the coke loading is less than about 0.05 percent by weight.
  • a reducing atmosphere will be employed in zones within the regenerator wherein the sorbent particles are in a relatively dense bed, such as in a dense fluidized or settled bed. It is especially useful to keep the vanadium in a reduced state under such conditions wherein the particles are in contact or in relatively frequent contact with each other, and are thus more likely to coalesce.
  • a reducing gas such as for example CO, methane, or ammonia may be added to a zone having a dense catalyst phase, such as for example a bed having a density of about 400 to about 800 kg per cubic meters.
  • the sorbent is regenerated in one or more stages, in one stage of which, preferably the final regeneration state, the sorbent particles are in contact with an oxidizing atmosphere for a short period of time, such as for example, less than 2 seconds, and more preferably less than one second.
  • the sorbent particles are in a dispersed rather than a dense phase.
  • a riser regenerator is used as the stage in a multi-state regenerator to contact the catalyst with an oxidizing atmosphere for a short period of time, such as for example less than about two seconds and preferably less than about one second.
  • the riser stage of the regenerator has the advantage in reducing the carbon concentration to a level less than about 0.15 percent or less than about 0.05 percent, that vanadium, which is no longer protected by a coating of carbon, may not be in an oxidizing atmosphere for a long enough time to form molten +5 vanadium.
  • the low density of the particles in the riser - regenerator minimizes coalescence of those particles which may have liquid pentavalent vanadia on their surfaces.
  • the particles are contacted with a reducing atmosphere, such as one containing CO or other reducing gas, after leaving the riser and before accumulating in a dense bed of regenerated particles.
  • a reducing atmosphere such as one containing CO or other reducing gas
  • the preferred riser regenerator is similar to the vented riser reactor as is disclosed in U.S. Patents 4,066,533 and 4,070,159 to Myers et al which achieves ballistic separation of gaseous products from catalyst.
  • This apparatus has the advantages of achieving virtually instantaneous separation of the regenerated catalyst, now containing some vanadia to which any oxygen present would have access, from the oxidizing atmosphere.
  • the catalyst is contacted with a reducing atmosphere, preferably immediately after its separation from the oxidizing atmosphere and most preferably also in collection zones for the regenerated catalyst.
  • This invention may be used in processing any hydrocarbon feed containing a significant concentration of vanadium. It is, however, especially useful in processing reduced crudes having high metal and high Conradson carbon values, and the invention will be described in detail with respect to its use in processing an RCC feed.
  • RCC feed having a high metal and Conradson carbon values is preferably contacted in a riser with an inert solid sorbent of low surface area at temperatures above about 482,2°C Residence time of the oil in the riser is below 5 seconds, preferably 0.5-2 seconds.
  • the preferred sorbent is a spray-dried composition in the form of microspherical particles generally in the size range of 10 to 200 micrometers, preferably 20 to 150 micrometers, and more preferably between 40 and 80 micrometers, to ensure adequate fluidization properties.
  • the sorbents useful in this invention include solids of low catalytic activity, such as spent catalyst, clays, bentonite, kaolin, montmorillonite, smectites, and other 2-layered lamellar silicates, mullite, pumice, silica, laterite, and combinations of one or more of these or like materials.
  • the surface area of these sorbents are preferably below 25 m 2 /g, have a pore volume of approximately 0.2 cc/g or greater and a micro-activity value as measured by the ASTM Test Method No. D3907-80 of below 20.
  • the RCC feed is introduced at the bottom of the riser and contacts the sorbent at a temperature of 621,1-760°C to yield a temperature at the exit of the riser in the sorbent disengagement vessel of approximately 482,2-593,3°C.
  • water, steam, naphtha, flue gas, or other vapors or gases may be introduced to aid in vaporization and act as a lift gas to control residence time.
  • Coked sorbent is rapidly separated from the hydrocarbon vapors at the exit of the riser by employing the vented riser concept developed by Ashland Oil, Inc., and described in U.S. Patent Nos. 4,066,533 and 4,070,159 to Myers, et al., which patents are incorporated herein by reference.
  • the metal and Conradson carbon compounds are deposited on the sorbent.
  • the coked sorbent is deposited as a dense but fluffed bed at the bottom of the disengagement vessel, transferred to a stripper and then to the regeneration zone.
  • the coked sorbent is then contacted with an oxygen - containing gas to remove the carbonaceous material through combustion to carbon oxides to yield a regenerated sorbent in accordance with this invention.
  • the regenerated sorbent is then recycled to the bottom of the riser where it again joins high metal and Conradson carbon containing feed to repeat the cycle.
  • This vanadia immobilization method is preferably employed to provide an RCC feedstock for the processes for carbo-metallic oil conversion described in U.S. Patents 4,299,687; 4,332,673; 4,341,624; 4,347,122 and 4,354,923.
  • the preferred feeds capable of being cracked by these RCC methods and apparatuses are comprised of 100% of less of 343,3°C material of which at least 5 wt%, preferably at least 10 wt%, does not boil below about 551,6°C.
  • high molecular weight and/or “heavy” hydrocarbons refer to those hydro-carbon fractions having a normal boiling point of at least 551,6°C and include non-boiling hydrocarbons, i.e., those materials which may not boil under any conditions.
  • the feedstocks for which the invention is particularly useful will have a heavy metal content of at least about 5 ppm of nickel equivalents, a vanadium content of at least 2.0 ppm, and a Conradson residue of at least about 2.0. The greater the heavy metal content and the greater the proportion of vanadium in that heavy metal content, the more advantageous the processes of this invention become.
  • a particularly preferred feedstock for treatment by the process of the invention includes a reduced crude comprising 70% or more of a 343,3°C material having a fraction greater than 20%' boiling about 551,6°C at atmospheric pressure, a metals content of greater than 5.5 ppm nickel equivalents of which at least 5 ppm is vanadium, a vanadium to nickel atomic ratio of at least 1.0, and a Conradson carbon residue greater than 4.0.
  • This feed may also have a hydrogen to carbon ratio of less than about 1.8 and coke precursors in an amount sufficient to yield about 4 to 14% coke by weight based on fresh feed.
  • Sodium vanadates have low melting points and may also flow and cause particle coalescence in the same manner as vanadium pentoxide. Thus, it is desirable to maintain low sodium levels in the feed in order to minimize coalescence as well as to avoid sodium vanadates on the sorbent.
  • such metals may accumulate on the sorbent to levels in the range of from about 3000 to 70,000 ppm of total metals, preferably 10,000 to 30,000 ppm, of which 5 to 100%, preferably 20 to 80% is vanadium.
  • the treating process according to the methods of the invention will produce coke in amounts of 1 to 14 percent by weight based on weight of fresh feed.
  • This coke is laid down on the sorbent in amounts in the range of about 0.3 to 3 percent by weight of sorbent, depending upon the sorbent to oil ratio (weight of sorbent to weight of feedstock) in the riser.
  • the severity of the process should be sufficiently low so that conversion of the feed to gasoline and lighter products is below 20 volume percent, preferably below 10 volume percent. Even at these low levels of severity, the treatment process is effective to reduce Conradson carbon values by at least 20 percent, preferably in the range of 40 to 70 percent, and heavy metals content by at least 50 percent, preferably in the range of 75 to 90 percent.
  • the feed, with or without pretreatment, is introduced as shown in Fig. 1 into the bottom of the riser along with a suspension of hot sorbent.
  • Steam, naphtha, water, flue gas and/or some other diluent is preferably introduced into the riser along with feed.
  • These diluents may be from a fresh source or may be recycled from a process stream in the refinery. Where recycle diluent streams are used, they may contain hydrogen sulfide and other sulfur compounds which may help passivate adverse catalytic activity by heavy metals accumulating. on the catalyst. It is to be understood that water diluents may be introduced either as a liquid or as steam.
  • Water is added primarily as a source of vapor for dispersing the feed and accelerating the feed and sorbent to achieve the vapor velocity and residence time desired.
  • Other diluents as such need not be added but where used, the total amount of diluent specified includes the amount of water used. Extra diluent would further increase the vapor velocity and further lower the feed partial pressure in the riser.
  • the feed As the feed travels up the riser, it forms basically four products known in the industry as dry gas, wet gas, naphtha, and RCC or FCC feedstock.
  • the sorbent particles are ballistically separated from product vapors as previously described.
  • the sorbent which then contains the coke formed in the riser is sent to the regenerator to burn off the coke and the separated product vapors are sent to a fractionator for further separation and treatment to provide the four basic products indicated.
  • the regenerating gas may be any gas which can provide oxygen to convert carbon to carbon oxides.
  • Air is highly suitable for this purpose in view of its ready availability. The amount of air required per pound of coke for combustion depends upon the desired carbon dioxide to carbon monoxide ratio in the effluent gases, and upon the amount of other combustible materials present in the coke, such as hydrogen, sulfur, nitrogen and other elements capable of forming gaseous oxides at regenerator conditions.
  • the regenerator is operated at temperatures in the range of about 482,2 to 815,6°C preferably 621 to 760°C most preferably 648,9 to 704,4°C to achieve adequate combustion while keeping sorbent temperatures below those at which significant sorbent degradation can occur.
  • it is necessary to control the rate of burning which, in turn, can be controlled at least in part by the relative amounts of oxidizing gas and carbon introduced into the regeneration zone per unit time.
  • the feedstock is partially catalytically cracked in passing up riser 2 and the product vapors are separated from coke-coated sorbent in vessel 8.
  • the sorbent particles move upwardly from riser 2 into the space within vessel 8 and fall downwardly into dense bed 16.
  • the cracking products together with some sorbent fines pass through horizontal line 4 into cyclone 5.
  • the gases are separated from the sorbent and pass out through line 6.
  • the sorbent fines drop into bed 16 through dipleg 19.
  • the spent sorbent is fluidized with a mixture of air, CO and C0 2 passing through porous plate 21 from lower zone 20, is partially regenerated in bed 18 and is passed into the lower portion of vented riser 13 through line 11.
  • Air is introduced into riser 13 through line 12 where it is mixed with the partially regenerated sorbent which is forced rapidly upwards through the riser and falls into dense settled bed 17.
  • Line 14 provides a source of reducing gas such as CO for bed 17 to keep the regenerated sorbent in a reducing atmosphere and thus keep vanadium present in a reduced oxidation state.
  • Regenerated sorbent is returned to the riser reactor 2 through line 3, which is provided with a source of a reducing gas such as CO through line 22.
  • Fig. 2 spent sorbent coated with coke and vanadium in a reduced state flow into dense fluidized bed 32 of regenerator 31 through inlet line 33. Air to combust the coke and fluidize the sorbent is introduced through line 34 and porous plate 35 which distributes the air. Coke is burned and the partially regenerated sorbent passes upwardly into riser regenerator 36. The partially regenerated sorbent which reaches the riser 36 is contacted with air from line 17 which completes the regeneration and helps move the sorbent rapidly up the riser. The regenerated sorbent passes upwardly from the top of the riser 36 and falls down into dense settled bed 37.
  • Dense bed 37 and the zone above 37 through which the regenerated sorbent falls are supplied with a reducing gas such as CO through lines 40 and 41.
  • the regenerated sorbent is returned to the reactor through line 38, and the CO-rich flue gases leave the regenerator through Line 39.
  • a carbo-metallic feed at a temperature of about 204,4°C is fed at a rate of about 906 kg per hour into the bottom of a vented riser reactor where it is mixed with sorbent at a temperature of about 690,5°C and a sorbent to oil ratio by weight of about 11.
  • the carbo-metallic feed has a heavy metal content of about 200 ppm Nickel Equivalents of heavy metals including 100 ppm vanadium, and has a Conradson carbon content of about 12 percent. About 85 percent of the feed boils above 343,3°C and about 20 percent of the feed boils above 551,6°C.
  • the temperature within the reactor is about 537,8°C and the pressure is about 1,89 kg/cm 2 .
  • About 20 percent of the feed is converted to fractions boiling at a temperature less than 221,1°C and about 10 percent of the feed is converted to gasoline. During the reactions, about 11 percent of the feed is converted to coke.
  • the sorbent containing about one percent by weight of coke contains about 20,000 ppm Nickel Equivalents including about 12,000 ppm vanadium.
  • the sorbent is stripped with steam at a temperature of about 537,8°C to remove volatiles and the stripped sorbent is introduced into the upper zone of the regenerator as shown in Fig. 1 at a rate of about 10419 kg per hour, and is partially regenerated to a coke concentration of about 0.2 percent by a mixture of air, CO and C0 2 .
  • the CO/C0 2 ratio in the fluidized bed in the upper zone is about 0.3.
  • the partially regenerated sorbent is passed to the bottom of a riser reactor where it is contacted with air in an amount sufficient to force the sorbent up the riser with a residence time of about 1 second.
  • the regenerated catalyst having a coke loading of about 0.05 percent exits from the top of the riser and falls into a dense bed having a reducing atmosphere comprising CO.
  • the regenerated catalyst is recycled to the riser reactor for contact with additional feed.
  • the invention is useful in the treatment of both FCC and RCC feeds as described above.
  • the present invention is particularly useful in the treatment of high boiling carbo-metallic feedstock of extremely high metals-Conradson carbon values to provide products of lowered metals-Conradson carbon values suitable for use as feedstocks for FCC and/or RCC units.
  • these oils are reduced crudes and other crude oils or crude oil fractions containing metals and/or residua as above defined.
  • This invention is particularly useful in processing feedstocks containing vanadium in a concentration of over about 100 ppm or over about 200 ppm and having Conradson carbon values greater than about 8%.
  • Feedstocks for which the invention is particularly useful are those in which the vanadium content is at least about 50 percent of the heavy metal content.
  • this invention has applicability in treating other feedstocks containing significant levels of vanadium and is applicable, for example, for treating a gas oil having a vanadium concentration greater than about 0.1 ppm and having a Conradson carbon value of less than about 1.
  • the treating process is preferably conducted in a riser reactor of the vented type, other types of risers and other types of reactors with either upward or downward flow may be employed.
  • the treating operation may be conducted with a moving bed of sorbent which moves in counter-current relation to liquid (unvaporized) feedstock under suitable contact conditions of pressure, temperature and weight hourly space velocity.
  • the process .conditions, sorbent and feed flows and schematic flow of a moving bed operation are described in the literature, such as those disclosed, for example, in articles entitled "T.C. Reforming", Pet. Engr., April (1954); and “Hyperforming" Pet. Engr., April (1954); which articles are incorporated herein by reference.

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Claims (10)

1. Verfahren zur Behandlung von Kohlenwasserstoff - Ölbeschickungen mit erheblichem Gehalt an Vanadium und Conradson - Kohlenstoff unter Ausbilden eines Produktes mit wesentlich geringerem Gehalt an Vanadium und Conradson - Kohlenstoff, vermittels Inberührungbringen der Beschickung mit einem in wesentlichen inerten, festen Sorptionsmaterial, wodurch Vanadium und andere Metallbestandteile und Koks auf den Sorptionsmitteln niedergeschlagen werden sowie abtrennen des Sorptionsmaterials von der behandelten Beschickung und inberührungbringen der Sorptionsmaterialien mit einer Sauerstoffquelle zwecks entfernen der Niederschläge aus dem Conradson - Kohlenstoff und zurückführen des regenerierten Sorptionsmaterials in ein Reaktionsgefäß für das Inberührungbringen mit zusätzlicher frischer Beschickung, gekennzeichnet durch a) regenerieren de verbrauchten Sorptionsmaterialien vermittels inberührungbringen mit einem sauerstoffhaltigen Gas unter derartigen Bedingungen, daß der Koks auf den Sorptionsmaterialien verbrannt wird, gasförmige Produktein Form von CO und CO2 gebildet werden, die Regenerierung unter derartigen Bedingungen ausgeführt wird, daß Vanadium in einem Oxidationszustand von kleiner als +5 gehalten wird und b) die regenerierten Sorptionsmaterialien durch Inberührungbringen mit frischer Beschickung zurückgeführt werden.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Ölbeschickung ein reduziertes Rohöl oder Rohöl ist, das 100 ppm oder mehr Metalle bestehend aus Nickel, Vanadium, Eisen und Kupfer enthält und einen Conradson - Kohlenstoffwert von 8 Gew.% oder mehr aufweist.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Ölbeschickung ein reduziertes Rohöl oder Rohöl ist, das 75 ppm oder weniger Vanadium enthält und einen Conradson - Kohlenstoffwert von 8 Gew.% oder weniger aufweist.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Sorptionsmaterial in Kugelform vorliegt und eine Größe von 10-200 Mikrometer für die Anwendung in einer fluidisierten Überführungszone des Reaktionsgefäßes besitzt.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Sorptionsmaterial in wenigstens zweit Stufen regeneriert wird, wobei inder ersten Stufe das verbrauchte Sorptionsmaterial in einem dichten fluidisierten Bett mit einem Gas in Berührung gebracht wird, das weniger als eine stöchiometrische Menge an Sauerstoff enthält unter umwandeln des Wasserstoffs in dem Koks in H20 unddes Kohlenstoffs in dem Koks in CO und CO2, und in der abschließenden Stufe teilweise regeneriertes Sorptionsmaterial mit wenigstens einer stöchiometrischen Menge an Sauerstoff eine Zeitspanne von weniger als etwa 2 Sekunden lang in Berührung gebracht wird.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß das teilweise regenerierte Sorptionsmaterial mit einem stöchiometrischen überschuß an Sauerstoff in einem Regenerator in Berührung gebracht wird, wobei sich die Verweilzeit des Sorptionsmaterial in dem Regenerator auf weniger als etwa 2 Sekunden beläuft und das regenerierte Sorptionsmaterial von den gasförmigen Produkten abgetrennt wird.
7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das abgetrennte, regenerierte Sorptionsmaterial sofort mit einem reduzierenden Gas in Berührung gebracht und sodann in einem dichten Bett gesammelt wird, das unter einer reduzierenden Atmosphäre gehalten wird.
8. Verfahren nach Anspruch 6, dadurch gekennzeichnet, daß das regenerierte Sorptionsmaterial von den gasförmigen Produkten dadurch abgetrennt wird, daß dasselbe in einer durch den Regenerator vorgegebenen Richtung oder einer Verlängerung desselben geführt wird, während die gasförmigen Produkte veranlaßt werden, eine plötzliche Richtungsänderung durchzuführen, wodurch sich eine plötzliche, praktisch sofortige ballistische Trennung der gasförmigen Produkte von dem regenerierten Sorptionsmaterial ergibt.
9. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Beschickung mehr als 100 ppm Vanadium enthält.
10. Verfahren nach Anspruch 1, dadurch' gekennzeichnet, daß die Konzentration des Vanadium auf dem Sorptionsmaterial größer als 5 Gew.% des Sorptionsmaterials ist.
EP82101769A 1981-04-20 1982-03-06 Immobilisierung von Vanadin, das bei der Behandlung von Koksvorläufer und Schwermetalle enthaltenden Ölen auf Adsorbenzien abgelagert worden ist Expired EP0065626B1 (de)

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AT82101769T ATE20903T1 (de) 1981-04-20 1982-03-06 Immobilisierung von vanadin, das bei der behandlung von koksvorlaeufer und schwermetalle enthaltenden oelen auf adsorbenzien abgelagert worden ist.

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US25593181A 1981-04-20 1981-04-20
US255931 1981-04-20

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JP (1) JPS57182387A (de)
AT (1) ATE20903T1 (de)
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US4162213A (en) * 1976-04-29 1979-07-24 Mobil Oil Corporation Catalytic cracking of metal-contaminated oils
CA1127581A (en) * 1978-02-06 1982-07-13 David B. Bartholic Preparation of fcc charge from residual fractions
US4243514A (en) * 1979-05-14 1981-01-06 Engelhard Minerals & Chemicals Corporation Preparation of FCC charge from residual fractions
US4311580A (en) * 1979-11-01 1982-01-19 Engelhard Minerals & Chemicals Corporation Selective vaporization process and dynamic control thereof
US4280895A (en) * 1979-12-31 1981-07-28 Exxon Research & Engineering Co. Passivation of cracking catalysts

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BR8202229A (pt) 1983-03-29
EP0065626A2 (de) 1982-12-01
ATE20903T1 (de) 1986-08-15
CA1175375A (en) 1984-10-02
JPS57182387A (en) 1982-11-10
AU8131182A (en) 1982-10-28
JPS6253038B2 (de) 1987-11-09
EP0065626A3 (en) 1983-03-23
DE3272069D1 (en) 1986-08-28
AU534630B2 (en) 1984-02-09

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