EP0074425B1 - Katalytisches Kracken von mit Metall verunreinigten Mineralölfraktionen - Google Patents

Katalytisches Kracken von mit Metall verunreinigten Mineralölfraktionen Download PDF

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EP0074425B1
EP0074425B1 EP81107233A EP81107233A EP0074425B1 EP 0074425 B1 EP0074425 B1 EP 0074425B1 EP 81107233 A EP81107233 A EP 81107233A EP 81107233 A EP81107233 A EP 81107233A EP 0074425 B1 EP0074425 B1 EP 0074425B1
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catalyst
activity
cracking
charge
metals
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EP0074425A1 (de
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David B. Bartholic
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BASF Catalysts LLC
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Engelhard Corp
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Priority to AT81107233T priority patent/ATE16289T1/de
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique

Definitions

  • the invention is concerned with increasing the portion of heavy petroleum crudes which can be utilized as catalytic cracking feedstock to produce premium petroleum products, particularly motor gasoline of high octane number.
  • the heavy ends of many crudes are high in Conradson Carbon and metals which are undesirable in catalytic cracking feedstocks.
  • the present invention provides an economically attractive method for utilizing the residues of atmospheric and vacuum distillations, commonly called atmospheric and vacuum residue or "resids".
  • the undesirable CC (for Conradson Carbon) and metal bearing compounds present in the crude tend to be concentrated in the resids because most of them are of high boiling point.
  • the effect of higher Conradson Carbon is to increase the portion of the charge converted to "coke" deposited on the catalyst.
  • the active surface of the catalyst is masked and rendered inactive for the desired conversion. It has been conventional to burn off the inactivating coke with air to "regenerate" the active surfaces, after which the catalyst is returned in cyclic fashion to the reaction stage for contact with and conversion of additional charge.
  • the heat generated in the burning regeneration stage is recovered and used, at least in part, to supply heat of vaporization of the charge and endothermic heat of the cracking reaction.
  • the regeneration stage operates under a maximum temperature limitation to avoid heat damage of the catalyst.
  • Metal bearing fractions contain, inter alia, nickel and vanadium which are potent catalysts for production of coke and hydrogen. These metals, when present in the charge, are deposited on the catalyst as the molecules in which they occur are cracked and tend to build up to levels which become very troublesome. The adverse effects of increased coke are as reviewed above.
  • Hydrogen being incondensible in the "gas plant" occupies space as a gas in the compression and fractionation train and can easily overload the system when excessive amounts are produced by high metal content catalyst, causing reduction in charge rate to maintain the FCC unit and auxiliaries operative.
  • the resid charge undergoes conversion on the surface of the coke particles during a residence time on the order of two minutes, depositing additional coke on the surfaces of particles in the fluidized bed.
  • Coke particles are transferred to a bed fluidized by air to burn some of the coke at temperatures upwards of 593°C (1100°F), thus heating the residual coke which is then returned to the coking vessel for conversion of additional charge.
  • Catalytic charge stock may also be prepared from resids by "deasphalting" in which an asphalt precipitant such as liquid propane is mixed with the oil. Metals and Conradson Carbon are drastically reduced but at low yield of deasphalted oil.
  • Solvent extractions and various other techniques have been proposed for preparation of FCC charge stock from resids.
  • Solvent extraction in common with propane deasphalting, functions by selection on chemical type, rejecting from the charge stock the aromatic compounds which can crack to yield high octane components of cracked naphtha.
  • Low temperature, liquid phase sorption on catalytically inert silica gel is proposed by Shuman and Brace, Oil and Gas Journal, April 16, 1953, Page 113.
  • the one of greatest present interest is Fluid Catalytic Cracking (FCC).
  • FCC Fluid Catalytic Cracking
  • the installed plants of this type are characteristically large, and usually designed to process from about 795 to 21,463 m 3 /day (5,000 to 135,000 bbls/day) of fresh feed.
  • the catalyst section of the plant consists of a cracking section where a heavy chargestock is cracked in contact with fluidized cracking catalyst, and a regenerator section where fluidized catalyst coked in the cracking operation is regenerated by burning with air. All of the plants utilize a relatively large inventory of cracking catalyst which is continuously circulating between the cracking and regenerator sections.
  • the size of this circulating inventory in existing plants is within the range of 43.4 to 544x10 3 kg (50 to 600 tons), the newer plants being designed for short time riser cracking with smaller catalyst inventory than that in older plants.
  • fresh makeup catalyst usually amounting to about one to two percent of the circulating inventory, which corresponds to about 0.045 to 0.11 kg per 159 litres (0.1 to 0.25 Ibs per bbl.) of fresh feed, is added per day to maintain optimal catalyst activity, with daily withdrawal plus losses of about like amount of aged circulating inventory, commonly referred to as "equilibrium" catalyst.
  • oils fed to this process are principally the petroleum distillates commonly known as gas oils, which boil in the temperature range of about 343° to 537°C (650°F to 1000°F), supplemented at times by coker gas oil, vacuum tower overhead, etc.
  • gas oils which boil in the temperature range of about 343° to 537°C (650°F to 1000°F)
  • API gravity in the range of about 15 to 45 and are substantially free of metal contaminants.
  • the chargestock which term herein is used to refer to the total fresh feed made up of one or more oils, is cracked in the reactor section in a reaction zone maintained at a temperature of about 426° to 648°C (800°F to 1200°F), a pressure of about 0.987 to 4.94 bar (1 to 5 atmospheres), and with a usual residence time for the oil of from about one to ten seconds with a modern short contact time riser design.
  • the catalyst residence time is from about one to fifteen seconds.
  • the cracked products are separated from the coked catalyst and passed to a main distillation tower where separation of gases and recovery of gasoline, fuel oil, and recycle stock is effected.
  • Petroleum refiners usually pay close attention in the fluid catalytic cracking process (hereinafter referred to as the FCC process) to supplying feedstocks substantially free of metal contaminants.
  • the reason for this is that the metals present in the chargestock are deposited along with the coke on the cracking catalyst. Unlike the coke, however, they are not removed by regeneration and thus they accumulate on the circulating inventory.
  • the metals so deposited act as a catalyst poison and, depending on the concentration of metals on the catalyst, more or less adversely affect the efficiency of the process by decreasing the catalyst activity and increasing the production of coke, hydrogen and dry gas at the expense of gasoline and/or fuel oil. Excessive accumulation of metals can cause serious problems in the usual FCC operation.
  • the amount of gas produced may exceed the capacity of the downstream gas plant, or excessive coke loads may result in regenerator temperatures above the metallurgical limits. In such cases the refiner must resort to reducing the feed rate with attendant economic penalty.
  • a catalyst inventory that contains excessive deposits of metal is normally regarded as highly undesirable.
  • the principal metal contaminants in crude petroleum oils are nickel and vanadium, although iron and small amounts of copper also may be present. Additionally, trace amounts of zinc and sodium are sometimes found. It is known that almost all of the nickel and vanadium in crude oils is associated with very large nonvolatile hydrocarbon molecules, such as metal porphyrins and asphaltenes. Crude oils, of course, vary in metal content, but usually this content is substantial.
  • An Arab light whole crude for example, may assay 3.2 ppm (i.e. parts by weight of metal per million parts of crude) of nickel and 13 ppm of vanadium.
  • a typical Kuwait whole crude, generally considered of average metals content may assay 6.3 ppm of nickel and 22.5 ppm of vanadium. Regardless of the crude source, however, it is known that distillates produced from the crude are almost free of the metal contaminants which concentrate in the residual oil fractions.
  • a chargestock having a metals factor greater than 2.5 is considered indicative of one which will poison cracking catalyst to a significant degree.
  • This factor takes into account that the adverse effect of nickel is substantially more than that of vanadium and iron present in equal concentrations with the nickel.
  • ppm Nickel Equivalent Another way of expressing the metals content of a chargestock is as "ppm Nickel Equivalent”. which is defined as
  • Nickel Equivalent For the purpose of this specification, the value of ppm Nickel Equivalent will be used in discussing metals content of metal-contaminated oils, distillate stocks, and catalysts. As shown above, no mention is made of copper because this metal usually is not present to any significant extent. However, it is to be understood herein that if it is present in significant concentration, it is to be included in the computation of Nickel Equivalent and weighted as nickel.
  • the circulating inventory is maintained at about 300 ppm Nickel Equivalents of metal, which is considered tolerable, the usual range being at about 200 to 600 ppm, with preferred operation being at about 200 to 400 ppm. It is to be understood, of course, that the metals content of the chargestock may vary from day to day without serious disruption, provided that the weighted average of the metals content does not exceed about 0.25 ppm nickel equivalent of metal.
  • references to the metals content of an oil, or of a chargestock refer to the time-weighted average taken over a substantial period of time such as one month, for example. Because of the large inventory of catalyst relative to the total metals introduced into the system by the chargestock in one day, for example, the metals content of the catalyst changes little each day with fluctuations in the quality of the chargestock. However, a persistent increase in the metals content of the latter will in time result in a well-defined, calculatable increase in the metals content of the circulating inventory of catalyst, which determines the performance of the FCC unit. In fact, it is evident that the circulating inventory of catalyst, by its metals content, provides a time-average value of the metals content of the chargestock. It is in this context, then, that the phrase "metals content of the chargestock" is used herein.
  • chargestocks to the FCC process that contain up to about 0.40 ppm Nickel Equivalent of metal contaminants will be regarded as substantially free of metal contaminants.
  • Chargestocks that contain at least about 0.50 ppm Nickel Equivalents of metal will include those chargestocks referred to as metal-contaminated.
  • the residual fraction of single stage atmospheric distillation or two stage atmos- pheric/vacuum distillation also contains the bulk of the crude components which deposit as resinous or tar-like bodies on cracking catalysts without substantial conversion. These are frequently referred to as "Conradson Carbon” from the analytical technique of determining their concentration in petroleum fractions.
  • Conradson Carbon from the analytical technique of determining their concentration in petroleum fractions.
  • the Cimbalo article above cited classifies coke on spent catalyst in four groups: catalytic coke resulting from cracking of charge components; cat-to-oil, related to reactor stripper efficiency; carbon residue (Conradson) as just discussed; and contaminant coke derived from dehydrogenation reactions promoted by the heavy metalk poisons nickel, vanadium, etc.
  • Patent 3,944,482 proposes a cracking catalyst of active aluminosilicate zeolite dispersed in a matrix of large pore refractory inorganic oxide.
  • the patentee suggests that the tendency of the metals to deposit in large pore structures renders the matrix a sacrificial component which protects the active zeolite cracking surfaces of the zeolite from metal contamination.
  • the effectiveness of large pore structures in adsorbing and/or converting metal bearing components of crude is widely recognized.
  • Many hydrotreating catalysts are preferably prepared by deposit of a Group VI metal with nickel or cobalt on a large pore alumina or the like. See also Patent 3,947,347 on demetallizing petroleum fractions in admixture with hydrogen over a large pore catalyst without added hydrogenation metal catalysts and patents 2,472,723 and 4,006,077.
  • catalyst manufacturers stand prepared to deliver different grades of catalyst over a range of activities.
  • One way to accomplish this without conducting manufacturing operations in accordance with a large number of schemes is to manufacture one or a few different catalysts of differing activity.
  • Intermediate grades are conveniently achieved by blending substantially inert particles of like fluidization properties with an active fluid catalyst to thereby provide a total catalyst of lower activity than the active portions.
  • US-A-3092568 proposes-during the process for the cracking of a high-boiling metal-containing hydrocarbon feed-to contact the feed with a particle form solid catalyst and to remove a part of de-activated catalyst as well as to replace by fresh catalyst in such a way that the catalyst replacement was changed to a lower rate.
  • a finely-divided inert solid material in admixture with the catalyst.
  • US-A-2723223 relates to a process of converting heavy residual hydrocarbon oil to more volatile products, however this process falls in the category of fluid coking.
  • the heavy residues are coked by passing the feed upwardly through a fluidized mass consisting of relatively coarse inert solids and of relatively fine catalyst, which are both preheated. In the contacting zone said mass was maintained in fluidized condition and such velocity that the catalyst was substantially completely elutriated therefrom.
  • the liquid product is distilled and "conversion" is reported as 100 minus weight per cent based on feed of liquid product boiling above 216°C (421°F). Activity is then calculated as
  • the refiner who presently wishes to charge residual stocks is compelled to adjust his operations to the options available to him.
  • the catalyst make-up rate to his catalytic cracker is determined by the activity considerations spelled out in the Lee article.
  • the refiner hydrotreats the resid, sends it to a coker or deasphalter or lives with the problem of metal on cracking catalyst of whatever fresh activity he selects.
  • a technique for operation of catalytic cracking equipment is now provided which decouples maintenance of equilibrium activity from management of the metals problem. This is accomplished by a catalyst make-up policy for concurrent addition to the unit of two inventory components, namely an active cracking catalyst and a large pore inert solid for selective acceptance of the large molecules characteristic of metal and Conradson Carbon content of the charge.
  • the system of this invention is based on determination of a make-up rate which will maintain a desired metals level on total inventory including fresh catalyst, partially deactivated catalyst, completely deactivated catalyst (essentially inert porous solids of small pore size) and catalytically inert material of large pore size characteristic of practice of the invention.
  • the make-up rate so determined will be unconventionally high, say upwards of 10% of inventory per day.
  • the activity of catalyst required to maintain equilibrium activity is then calculated by the equation above.
  • the unit is then supplied with a quantity of active catalyst and a quantity of large pore inert solid such that blend of the two exhibits the desired activity and quantity of the two satisfies the make-up rate for metals level maintenance.
  • the process of this invention contemplates an embodiment in which an FCC Unit is operated at unconventionally high levels of metal on the circulating inventory of catalyst and inert material, hereinafter called "catalyst inventory" for simplicity despite the fact that it contains a high proportion of material not usually considered to be catalyst.
  • the metals content of the catalyst inventory may be held at levels more usual in the art.
  • the invention makes available to the refiner a broad scope of operation from metals levels in the neighborhood of 2 wt % on catalyst (20,000 ppm) or above down to any lower level desired.
  • Suitable hydrometallurgy may be treatment with sulfur dioxide and water leach followed by liquid- liquid ion exchange of the leach solution. It will be noted that the metal enriched catalyst is unusually well suited to hydrometallurgy since the metal values are on surfaces rather than combined with silica and the like in the body of the "ore" as is the case with many natural ores.
  • the operator of a catalytic cracker will maintain a stock of two different solid materials having physical characteristics (size, density, porosity, etc.) suited to operation of the type of unit.
  • One stock is constituted by cracking catalyst of any desired type, preferably a catalyst of high activity.
  • the catalyst is the more expensive component to be added as make-up and it now becomes feasible in practice of the present invention for the refiner to justify the higher cost of more active catalyst.
  • cracking catalysts of fresh MAT activity above 10 will be found useful and catalysts of fresh MAT activity as high as 20 or above will show economic advantage despite the high cost of such catalysts.
  • the invention can utilize the older amorphous silica-alumina catalysts, but preference is noted for the more active catalysts constituted by rare earth and/or hydrogen forms of crystalline zeolites such as those having the crystalline structure faujasite in a matrix of silica-alumina or the like.
  • Such catalysts are described in patents 3,140,249 and 3,140,253. Many techniques and compositions for high activity have been described. Although it is preferred to employ catalysts of high activity, the particular means adopted to achieve that high activity is not of particular significance and reference to knowledge in the art will suffice for the present purposes.
  • the large pore inert material to be added with active catalyst constitutes the real distinction from knowledge of catalyst components normally taken into account by those responsible for operation of catalytic cracking units.
  • dilution of cracking catalyst with inert solids is a convenient means by which a catalyst supplier can make several activity levels available with relatively fewer methods of catalyst manufacture.
  • Such blends are sold on the basis of overall activity, selectivity and physical properties such as hardness, tendency to erode equipment and the like. Dilution, if any, is a matter of little concern to the purchaser except as it results in reduced cost of the catalyst blend.
  • the large pore material is essentially inert in the sense that it induces minimal cracking of heavy hydrocarbons by the standard microactivity test. Conversion by that test will be less than 20, preferably about 10, representing essentially thermal cracking.
  • microspheres of calcined kaolin clay preferably used in the process of the invention are known in the art and are employed as a chemical reactant with a sodium hydroxide in the manufacture of fluid zeolitic cracking catalysts as described in U.S. 3,647,718 to Haden et al.
  • the microspheres of calcined kaolin clay are not used as a chemical reactant.
  • the chemical composition of the microspheres of calcined clay used in practice of this invention corresponds to that of a dehydrated kaolin clay.
  • the calcined microspheres analyze about 51 % to 53% (wt.) Si0 2 , 41 to 45% AI 2 0 3 , and from 0 to 1 % H 2 0, the balance being minor amounts of indigenous impurities, notably iron, titanium and alkaline earth metals.
  • iron content (expressed as Fe 2 0 3 ) is about 1/2% by weight and titanium (expressed as Ti0 2 ) is approximately 2%.
  • the microspheres are preferably produced by spray drying an aqueous suspension of kaolin clay.
  • kaolin clay as used herein embraces clays, the predominating mineral constituent of which is kaolinite, halloysite, nacrite, dickite, anauxite and mixtures thereof.
  • a fine particle size plastic hydrated clay i.e., a clay containing a substantial amount of submicron size particles, is used in order to produce microspheres having adequate mechanical strength.
  • the powdered hydrated clay is preferably dispersed in water in the presence of a deflocculating agent exemplified by sodium silicate or a sodium condensed phosphate salt such as tetrasodium pyrophosphate.
  • a deflocculating agent exemplified by sodium silicate or a sodium condensed phosphate salt such as tetrasodium pyrophosphate.
  • spray drying may be carried out at higher solids levels and harder products are usually obtained.
  • slurries containing about 55 to 60% solids may be prepared and these high solids slurries are preferred to the 40 to 50% slurries which do not contain a deflocculating agent.
  • One procedure is to dry blend the finely divided solids, add the water and then incorporate the deflocculating agent.
  • the components can be mechanically worked together or individually to produce slurries of desired viscosity characteristics.
  • Spray dryers with countercurrent, cocurrent or mixed countercurrent and cocurrent flow of slurry and hot air can be employed to produce the microspheres.
  • the air may be heated electrically or by other indirect means.
  • Combustion gases obtained by burning hydrocarbon fuel in air can be used.
  • air inlet temperatures to 648°C (1200°F) may be used when the clay feed is charged at a rate sufficient to produce an air outlet temperature within the range of 121° to 315°C (250 to 600°F).
  • free moisture is removed from the slurry without removing water of hydration (water of crystallization) from the raw clay ingredient.
  • Dehydration of some or all of the raw clay during spray drying is contemplated.
  • the spray dryer discharge may be fractionated to recover microspheres of desired particle size. Typically particles having a diameter in the range of 20 to 150 microns are preferably recovered for calcination.
  • the microspheres While it is preferable in some cases to calcine the microspheres at temperatures in the range of about 870° to 1148°C (1600 to 2100°F) in order to produce particles of maximum hardness, it is possible to dehydrate the microspheres by calcination at lower temperatures; for example, temperatures in the range of 537° to 870°C (1000 to 1600°F), thereby converting the clay into the material known as "metakaolin". After calcination the microspheres should be cooled and fractionated, if necessary, to recover the portion which is in desired size range.
  • Pore volume of the microspheres will vary slightly with the calcination temperature and duration of calcination. Pore size distribution analysis of a representative sample obtained with a Desorpta analyzer using nitrogen desorption indicates that most of the pores have diameters in the range of 150 to 600x10 -10 m (150 to 600 Angstrom units), primarily 300 to 600x10-'° m (300 to 600 A). In general, the inert materials used in accordance with the invention will have a majority of pores (determined as pores constituting more than half the total pore volume) of at least 100x10 -10 m (100 Angstrom units) diameter.
  • the surface area of the calcined microspheres is usually within the range of 10 to 15 m 2 /g as measured by the well-known B.E.T. method using nitrogen absorption. It is noted that the surface areas of commercial fluid zeolite catalysts is considerably higher, generally exceeding values of 100 m 2 /g as measured by the B.E.T. method.
  • solids of low catalytic activity and of like pore diameter and particle size may be employed.
  • solids of low cost are recommended since it is contemplated that the high make-up rate characteristic of the invention is offset by low net cost of the catalyst plus inert material to be added.
  • the invention is applied to a catalytic cracker for which a predetermined activity and metals level have been established. These may vary within rather wide ranges depending primarily on nature of the charge stock and the product slate dictated by market demand. Thus a cracker in a refinery serving a market which demands relatively large quantity of diesel fuel and distillate fuel oils will operate with a catalyst of relatively low activity as compared with one serving a market of high gasoline demand. Predetermined metals level on catalyst will normally be higher when practicing the present invention than would be the case with cracking catalysts of the prior art.
  • the average metal content of the inventory circulated in the unit is determined by analysis and is the predetermined value which is to be held constant.
  • the refiner derives a rate of metal deposition and thus maintains the metal level constant at about the predetermined value.
  • the rate of replacement will be a value in per cent of circulating inventory per day which is readily converted to tons of make-up per day having regard to the weight of inventory in the circulating catalyst.
  • the rate of make-up is simply obtained by dividing total metal input with charge by the predetermined metals level on inventory in weight percent.
  • the make-up rate S is so high compared with the constant K that the latter becomes relatively unimportant to the calculation.
  • the two components may be premixed in the required proportions and added to the unit intermittently or continuously at the rate S in tons per day. Concurrently, there will be an amount of equilibrium catalyst withdrawn from the unit to maintain a constant inventory, i.e.
  • the components of the make-up blend may be added separately to the unit for mixing as the inventory is circulated. This is particularly effective in FCC operations where any added material is very quickly and very thoroughly mixed with the inventory being circulated.
  • the invention is best utilized in units which provide short contact time of catalyst and charge stock in order that the two components of the make-up blend may act with maximum effectiveness.
  • the desired result is advantageously achieved at contact times less the 20 seconds, preferably 2 seconds or less.
  • the fresh catalyst should have high activity, A MAT of at least 1.5, preferably 4 or greater. These high activities of the active catalyst component of the blend make possible high proportions of large pore inert material, upwards of 50%, preferably more than 75%.
  • the combination of short contact time, high proportion of large pore inert material, and high activity of the active catalyst component of the blend provide further advantages in management of coke make in the reactor and control of temperature in the regenerator of an FCC unit.
  • the active catalyst component acquires coke which is primarily due to catalytic cracking. Coke due to dehydrogenation by contaminant metals is at a low-level for these short contact times. Most of the Conradson Carbon coke (additive coke) is deposited on the large pore inert component. Regenerator temperatures may be reduced in this system of operation.
  • the make-up rate according to the invention will be in excess of 3% of inventory per day and in excess of 0.14 kg/catalyst blend (0.3 Ib/catalyst blend) with inerts per barrel of feed, up to 20% of inventory per day, with recommended levels of about 10% of inventory per day for most operations in cracking of metal contaminated resids.
  • vapor pressure of hydrocarbons in the reactor is advantageously reduced by adding steam with the charge to the unit.
  • the steam is provided by vaporization of water present as the internal phase of a water and oil emulsion with charge hydrocarbons.
  • the emulsified water is vaporized with explosive violence to disperse the oil surrounding the water droplets in the emulsion and thus promote rapid effective contact of charge with catalyst for rapid vaporization of charge.

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Claims (10)

1. Verfahren zum katalytischen Cracken von metallhaltigen Kohlenwasserstoffchargen durch Behandeln der Chargen bei Cracktemperaturen mit einem festen teilchenförmigen Crackkatalysator, wobei Bestandteile der Charge in niedriger siedende Kohlenwasserstoffe umgewandelt werden unter gleichzeitigem Ablagern von Metallen der Charge und von einer inaktivierenden Kohlenstoffverunreinigung auf dem Katalysator, mit Wiederherstellung der katalytischen Crackaktivität des verunreinigten Katalysators durch Verbrennen der Kohlenstoffablagerungen bei Belassung der auf dem Katalysator abgelagerten Metalle und Inberührungbringen des so regenerierten Katalysators mit weiterer Charge, wobei der Katalysator zu Lasten der Crackreaktion Metalle ansammelt und in der Regenerieraktivität während der wiederholten Zyklen von Chargenbehandlungen nachläßt, sowie mit Rückgewinnung und Aufrechterhaltung der durchschnittlichen Aktivität und des Metallgehalts vom Katalysatorbestand bei im wesentlichen konstanten Gleichgewichtswerten, dadurch gekennzeichnet, daß ein Teil vom Katalysatorbestand durch frischen Katalysator mit einer Aktivität oberhalb und einem Metallgehalt unterhalb der besagten Gleichgewichtswerte ersetzt wird und dabei die Gleichgewichtswerte der Aktivität und des Metallgehaltes entkoppelt werden, indem im Zuge der Katalysatorzugabe eine Teilmenge vom Katalysator mit einer Aktivität oberhalb und einem Metallgehalt unterhalb der Gleichgewichtswerte sowie der Rest als poröse feste Teilchen mit einem Metallgehalt unter dem Gleichgewichtswert und mit physikalischen Eigenschaften ähnlich denen des Katalysators unter Variieren des Verhältnisses zwischen frischem Katalysator und inerten Teilchen zur separaten Einstellung des Gleichgewichtswerts in einer solchen Weise zugesetzt werden, daß die Gesamtmenge des frischen Katalysators und des inerten Festkörpers in der Zeiteinheit im wesentlichen der Gesamtmetallzufuhr durch die Charge in der Zeiteinheit dividiert durch den Metallgleichgewichtswert entspricht.
2. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die festen Inertteilchen zu wenigstens 50% des Porenvolumens Poren von wenigstens 100x10-11 m aufweisen.
3. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die festen Inertteilchen zu wenigstens 50% des Porenvolumens Poren von 150 bis 600x10-'° m aufweisen.
4. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die festen Inertteilchen zu wenigstens 50% des Porenvolumens Poren von 300 bis 600x10-'o m aufweisen.
5. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die festen Inertteilchen den Hauptbestandteil der besagten Gesamtmenge bilden.
6. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß der frische Katalysator eine MAT-Aktivität größer als 4 hat.
7. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die Berührungszeit der Charge mit dem Crackkatalysator weniger als 10 Sekunden beträgt.
8. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die Berührungszeit der Charge mit dem Crackkatalysator weniger als 2 Sekunden beträgt.
9. Verfahren gemäß Patentanspruch 1, dadurch gekennzeichnet, daß die Gesamtmenge des frischen Katalysators und der festen Inertteilchen eine Crackaktivität AF aufweist entsprechend der Gleichung
Figure imgb0007
worin AE den Gleichgewichtswert der Aktivität, S den ersetzten Katalysatoranteil in Prozent vom Katalysatorbestand je Tag und K eine die Abnahmerate der katalytischen Aktivität wiedergebende Konstante bedeuten, und daß der Anteil F des frischen Katalysators in der Gesamtmenge in Übereinstimmung mit der Gleichung
Figure imgb0008
steht, in der AF die obige Bedeutung hat und Ac die Aktivität des frischen Katalysators ist.
10. Verfahren gemäß Patentanspruch 1, 4 oder 9, dadurch gekennzeichnet, daß die festen Inertteilchen aus calciniertem Kaolin mit einer Oberflächenentfaltung von etwa 10 bis 15 m2/g bestehen.
EP81107233A 1981-09-14 1981-09-14 Katalytisches Kracken von mit Metall verunreinigten Mineralölfraktionen Expired EP0074425B1 (de)

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EP81107233A EP0074425B1 (de) 1981-09-14 1981-09-14 Katalytisches Kracken von mit Metall verunreinigten Mineralölfraktionen
AT81107233T ATE16289T1 (de) 1981-09-14 1981-09-14 Katalytisches kracken von mit metall verunreinigten mineraloelfraktionen.
DE8181107233T DE3172778D1 (en) 1981-09-14 1981-09-14 Catalytic cracking of metal contaminated mineral oil fractions

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EP81107233A EP0074425B1 (de) 1981-09-14 1981-09-14 Katalytisches Kracken von mit Metall verunreinigten Mineralölfraktionen

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US2455915A (en) * 1944-07-06 1948-12-14 Kellogg M W Co Catalytic conversion of hydrocarbons
US2472723A (en) * 1947-06-05 1949-06-07 Standard Oil Dev Co Method for removal of metal compounds from oil feed to fluid catalyst cracking
US2723223A (en) * 1951-05-10 1955-11-08 Exxon Research Engineering Co Cracking of reduced crude with catalyst and inert particles
US3092568A (en) * 1960-01-07 1963-06-04 Kellogg M W Co Method for cracking high boiling hydrocarbons
US3816342A (en) * 1963-05-14 1974-06-11 Mobil Oil Corp Process for preparing a crystalline aluminosilicate zeolite
US3891541A (en) * 1973-08-29 1975-06-24 Mobil Oil Corp Process for demetalizing and desulfurizing residual oil with hydrogen and alumina-supported catalyst
US4116814A (en) * 1977-07-18 1978-09-26 Mobil Oil Corporation Method and system for effecting catalytic cracking of high boiling hydrocarbons with fluid conversion catalysts

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DE3172778D1 (en) 1985-12-05
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