DE3043107C2 - - Google Patents

Description

In general, gasoline and other liquid hydrocarbon fuels boil in the range of 37.8 ° to 343.3 ° C. However, the crude oil contains from which These fuels are produced a different Mixture of hydrocarbons and other compounds that have a very different molecular weight and therefore over boil a wide range. They are, for example, crude oils known to be 30 to 60% or more of the total oil volume consist of compounds that are at temperatures above Boil at 343.3 ° C. There are some of these crude oils to 10% to 30% or more of their total volume consist of compounds of such high molecular weight that they boil above 551.7 ° C or at least not below Boil 551.7 ° C at atmospheric pressure.

Because these are relatively abundant, high boiling components of crude oil for inclusion in gasoline or other liquid hydrocarbon fuels unsuitable, has the petroleum refining industry Process for cracking or breaking up the molecules the high-molecular, high-boiling compounds into smaller ones Molecules that boil over a suitable boiling range, developed. The most commonly used cracking process for this purpose is known as Fluid Catalytic Cracking (FCC). Although the FCC process reaches a far advanced state has developed and numerous modified forms and variations is common to all of them that one is in the vapor state offset hydrocarbon feedstock at a elevated temperature in contact with a cracking catalyst, the is suspended in the starting material vapors, a cracking process is subjected. Once the desired level of molecular weight and boiling point reduction is achieved, becomes the catalyst separated from the desired products.

The crude oil contains a multitude in its natural state of materials that have a very disturbing effect on the FCC process and only a part of these disturbing materials can be economically removed from the crude oil.  Among these interfering materials are coke precursors (such as Asphaltenes, polynuclear aromatics, etc.), heavy metals (like nickel, vanadium, iron, copper, etc.), lighter Metals (such as sodium, potassium, etc.), sulfur, Nitrogen and other substances. Of these materials, certain, like the lighter metals, in an economical way Desalination be removed, which is part of the normal Process for pretreating crude oil for fluid catalytic cracking are. Other materials, such as coke precursors, asphaltenes and the like, are prone to degradation during coking Cracking process, which settles on the catalyst and thereby the contact between the hydrocarbon feedstock and the catalyst, and generally the same Reduced level of performance or activity. The heavy metals go almost quantitatively from the starting material on the catalyst surface over.

When the catalyst is used over and over again to treat reusable starting material, which is normally the case is, then the heavy metals can be on the catalyst accumulate to such an extent that they are unfavorable Way to change the composition of the catalyst and / or the nature of the catalyst action on the starting material. For example Vanadium tends to form fluxes or melts with certain constituents of commonly used FCC catalysts, wherein the melting point of parts of the catalyst particles is sufficiently humbled, so that they begin to sinter and the cracking catalysts are ineffective. enrichments Vanadin and other heavy metals, in particular Nickel, also poison the catalyst. They tend differently strong, excessive dehydration and aromatic condensation which leads to excessive production of Carbon and gases and thus to a deterioration of the Yield of liquid fuel leads. An oil, like a crude oil or a crude oil fraction, or any other oil containing one particularly rich content of nickel and / or other metals, which show a similar behavior, and at the same time  contains relatively large amounts of coke precursors is here as carbo-metallic oil, and such an oil provides a Special challenge for the petroleum refinery specialist represents.

In general, the coking tendency or the content of Coke precursors of an oil are determined by dividing the weight percent Carbon determines which will remain if you have one Sample of this oil pyrolyzed. The industry takes this value as a measure of the extent to which a given oil contributes to Formation of non-catalytic coke tends when used as a starting material used in a catcracker. Two established Test methods are recognized, namely the Conradson carbon test method and the Ramsbottom carbon test method, wherein the latter is described in ASTM Test No. D 524-76. In the conventional FCC practice will reduce Ramsbottom carbon values in of the order of 0.1 to 1.0 as an indication of acceptable starting material. The present invention is concerned with the use of hydrocarbon feedstocks, have the higher Ramsbottom carbon values and thus a much greater potential for coke formation than have conventional starting materials.

Since the different heavy metals do not have the same catalyst Have poisoning activity, one presses expediently the poisoning activity of an oil containing a given poisoning metal or given poisoning metals, than the amount of a single metal believed to be one has equivalent poisoning activity. As a result, the Heavy metal content of an oil by the following Relationship (the relationship served as a model by W.L. Nelson in the Oile and Gas Journal, p. 143, 23rd October 1961), in which the content of each metal present in Share per million of this metal, as a metal on a weight basis, based on the weight of the starting material, indicated is:

According to the conventional FCC practice, the heavy metal content becomes of the starting material for the FCC process on a relative low level, for example, 0.25 parts per million Nickel equivalents or less. The present invention is concerned with the processing of raw materials, have the metal contents lying substantially above this value and therefore a much greater potential in terms of Enrichment on the catalyst and the poisoning of the catalyst respectively.

The above relationship can also be used as a measure of enrichment of heavy metals on the cracking catalyst, with the exception that the amount of metal used in the relationship on the weight of the catalyst (moisture-free basis) instead of based on the weight of the starting material. at the conventional FCC practice, in which a circulating Catalyst stock repeatedly for the treatment of fresh Starting material is reused, with periodic or continuous Addition or removal of small amounts of fresh or spent catalyst, the metal content of the Catalyst maintained at a level which, for example, in Range from 200 to 600 parts per million nickel equivalents lies. The inventive method is concerned with the use of catalysts that are much higher Have metal content, and therefore a much greater tendency compared to the normal case, to promote dehydration, aromatic condensation, gas generation or coke formation respectively. Such higher metal enrichments therefore become normally considered highly undesirable in the FCC process.

There has been a great deal of interest in the transformation for a long time from carbo-metallic oils to gasoline and other liquid ones Fuels. For example, it was suggested in the fifties that a variety of carbo-metallic oils are successful in gasoline and other products using the Houdresid method can be converted. The Houdresid method  differs from the FCC process in that it is catalyst particles with "granular grain size" (much larger than the particle size from conventional FCC catalysts) in a compact, under the influence of gravity moving bed used, in contrast to the suspension of catalyst particles in the starting material and the product vapors in one Fluidized bed.

Although the Houdresid process obviously takes a step forward meant with regard to the effects of metal contaminants and coke formation on the performance of the Catalyst, the productivity of this process was limitations subjected. Since its implementation was not economical, The first Houdresid plant is no longer in operation. While the 25 years since the first commercial application of the Houdresid method have passed, according to the experts her eager search for suitable modifications and changes continued the FCC process, which is a commercially successful Application of the method to Topprückstände and the like would allow. During this period is a variety have been made by proposals, and some of them are up to to a certain extent have been used commercially.

Some proposals include the treatment of heavy oil feedstock, to remove the metal from the cracking process, such as hydrotreating, solvent extraction and complex formation with Friedel-Crafts catalysts, however These techniques have been kiritized as they are not economical. Another suggestion is a combined cracking process used with "dirty oil" units and "pure oil" units. at In another proposal, residual oil is mixed with gasoil and the amount of residual oil in the mixture depending on the flash evaporation equilibrium temperature at the bottom the riser-cracker unit used in the process controlled. In yet another proposal, the starting material a mild, preparatory hydrocracking or hydrotreating stage subjected before being introduced into the cracker unit  becomes. For the production of gasoline is also proposed been a carbo-metallic oil, such as hot top residue To bring into contact takonite pellets. This only represents one small selection of proposals that are in the patent literature and technical reports have been described.

Despite the great efforts that have been made here, and despite the fact that each of these proposals is a part solves the encountered difficulties, is the conventional FCC practice today a mute witness to the lack of carbo-metallic Oil cracking process, in terms of technical Feasibility are both economical and highly practical. Some crude oils are relatively free of coke precursors and / or Heavy metals, and the disturbing components of crude oil are mostly concentrated in the highest boiling fractions. So it was possible through the coke precursors and heavy metals To avoid problems that occur mostly by the Yield of liquid fuel, which potentially from the sacrificed at the highest boiling fractions. In the conventional FCC practice is as starting material in particular the crude fraction has been used between Boils 343.3 ° C and 537.8 ° C, with such Fractions relatively free of coke precursor and heavy metal contaminants are. Such, known as "vacuum gas oil" (VGO) Starting material is generally made from crude oil, by mixing the fractions below 343.3 ° C distilled off at atmospheric pressure and then a between 343.3 ° C and 482.2 ° C to 551.7 ° C boiling fraction by a further vacuum distillation separated from the heavier fractions.

The vacuum gas oil is used as starting material for the conventional Used FCC processing. The heavier fractions will be normally used for a number of other purposes, such as For example, for the production of asphalt, residual fuel oil, # 6 fuel oil or marine bunker C fuel oil, which is a big waste represents the potential value of this crude oil fraction,  especially with regard to the great efforts and Expenses one was willing to afford to try out Coal and shale oils are essentially similar materials manufacture.

The present invention is based on the object at the same time these heavy fractions, the considerable Amounts of both coke precursors and heavy metals and possibly also have other disturbing components, in Cracking compound with the lighter oils and doing the Total yield of gasoline and other liquid hydrocarbons Fuels from a given amount of crude oil or crude product to increase. As already mentioned above, the present Invention by no means the first attempt, such a method However, the longstanding desire to develop carbo-metallic starting materials to undergo a cracking process, along with the slow progress of the industry in In this respect, a continuing need for such Method. The method of the present invention appears uniquely advantageous in terms of the problem of treatment Such carbo-metallic oils on an economical and technical advantageous way.

The task is solved by a method with the characterizing features of claim 1. In the dependent claims FIGS. 2 to 38 show embodiments of the method according to claim 1.

The present invention provides a simple, relatively straightforward and highly productive process for the conversion of carbo-metallic Starting material, such as Topprückstände or the like, to various lighter products, such as gasoline, available. The carbo-metallic starting material comprises or consists of an oil which boils above 343.3 ° C. Such Oil, or at least the 343.3 ° C + portion thereof, is indicated by a heavy metal content of at least 4, preferably more than 5, and in particular at least 5.5 parts per million nickel equivalents by weight, and a carbon residue in the pyrolysis of at least 1 wt .-% and preferably at least 2 wt .-%. According to the invention  The carbo-metallic starting material is in shape a pumpable liquid with a hot conversion catalyst contacted, the weight ratio from catalyst to starting material in the range of 3 is up to 18 and preferably more than 6.

The starting material in this mixture becomes a conversion step which includes cracking while mixing as feedstock and catalyst through a fluidized bed reactor flows. The starting material, the catalyst and others Materials can be introduced at one or more points become. The reactor comprises an elongated or elongated Reaction chamber, at least partially perpendicular or inclined is arranged and in which the starting material, the obtained Products and the catalyst kept in contact with each other while being used as a dilute phase or as a current at one predetermined riser residence time in the range of 0.5 to Flow for 10 seconds.

The reaction is carried out at a temperature of 482.2 ° C up to 760 ° C, measured at the exit of the reaction chamber, at a total absolute pressure of 0.69 to 3.45 bar performed under such conditions, which are sufficiently severe to produce one conversion per pass Range of 50% or more and a deposition of coke on the catalyst in an amount in the range of 0.3 to 3 wt .-%, preferably at least 0.5 wt .-%, to obtain. The total amount of coke production, based on the weight of the fresh starting material, is in the range of 4 to 14% by weight.

At the end of the predetermined residence time, the catalyst of separated from the products, subjected to a strip stage to high boiling components and other entrained or adsorbed Removing hydrocarbons, and then regenerating, by coke in at least one regeneration zone with an oxygen-containing, the combustion-entertaining gas under such time, temperature and atmosphere conditions  burns, which are sufficient to regenerate the carbon on the Catalyst to 0.25 wt .-% or less, preferably to 0.05% by weight or less, wherein at least the main weight fraction of the coke in a Zone is burned, in which a molar ratio of CO: CO₂ of at least 0.25, preferably at least 0.3, and especially at least 1, is maintained. The Regenerated catalyst is then used for contact with fresh Feedstock recycled to the reactor.

Depending on how the method according to the invention is practiced, may have one or more of the advantages described below be achieved. Preferably, and if so desired The process can be carried out without hydrogen feeds into the reaction chamber. Preferably, and if desired is the process without prior hydrotreating of the Starting material and / or previous removal stages of asphaltenes or metals from the starting material be, and this is possible even if the carbo-metallic Total oil more than 4 or more than 5, or even more than 5.5 parts per million nickel equivalents heavy metal by weight, and a carbon residue in the pyrolysis of more than 1 wt .-%, has more than 1.4 wt .-% or more than 2 wt .-%. In addition, all the starting material that is the conversion should be subjected to, as described above, in a and the same conversion chamber will be cracked. The cracking reaction can be done with a catalyst that already previously used (and has been recycled, wherein a necessary complement to compensate for the usual losses and deactivation was made) to be among the above conditions described a carbo-metallic starting material to crack. In a first round not cracked to gas Heavy hydrocarbons can be used with or without hydrotreating be returned to another cracking stage in contact with the same kind of starting material in which they first used the Cracking conditions were subjected, and under the same kind of conditions; however, the method is preferably used in the  significant one-time throughput or in accordance with the single pass procedure (for example, fewer than 15% by volume, based on the volume of fresh starting material, recycled).

According to a preferred embodiment or a preferred Aspect of the present invention will be the catalyst in the end the above-mentioned, predetermined residence time in one direction hurled through the elongated reaction chamber or an extension of this is formed while the products, which have a lower pulse, to an abrupt change in direction be forced, resulting in an abrupt, essentially instantaneous ballistic separation of the products of leads to the catalyst. The thus separated catalyst is then subjected to a strip stage as described above, regenerated and returned to the reactor.

According to another preferred embodiment or a preferred Aspect of the present invention is the carbo-metallic Starting material not only with the catalyst in Brought in contact, but also with one or more additional Materials, including and especially liquid water, at a weight ratio of additional materials to starting material in the range of 0.04 to 0.15, preferably 0.04 to 0.1, and especially 0.05 to 0.1. Such additional materials, including the liquid water, before, during or after mixing the starting material with the mentioned catalyst and either after or preferably before the evaporation of the starting material mixed with the starting material. The starting material, the catalyst and the water (for example in the form of liquid water or in the form of water vapor, obtained by Evaporation of the liquid water, which with the starting material has come into contact with one or more Places introduced along the reactor in the fluidized bed reactor, which may be a reactor in which the separation is as above described, carried out by ballistic means, or not. While  the mixture of starting material, catalyst and water vapor, obtained by evaporation of the liquid water, by the Reactor flows, subject to the starting material of the above-mentioned Transformation stage that includes cracking. The starting material, the catalyst, the water vapor and the obtained Products become together in the mentioned elongated reaction chamber kept in contact while as a dilute phase or as electricity during the above, predetermined Riser residence time, which is in the range of 0.5 to 10 seconds lies, flow.  

The method described above may be used in conjunction with others preferred alternatives, improvements and more commonly used Conditions will be carried out, and some of them will described below.

In the drawings shows:

Fig. 1 is a schematic diagram of a first apparatus for performing the method according to the invention,

Fig. 2 is a schematic diagram of a second device for carrying out the method according to the invention and

Figs. 3 to 5 are graphs showing results obtained by carrying out the method of the present invention.

The present invention provides a method for continuous catalytic conversion of a large variety of carbo-metallic Oils into products of smaller molecular weight available, with the production of high-quality liquid Products is raised to a maximum value, and where it is is possible, if desired, a vacuum distillation or other Avoid expensive treatments, such as hydrotreating. The The term "oils" includes not only those compositions which consist mainly of hydrocarbons and at room temperature are liquid (for example 20 ° C), but also such compositions consisting mainly of hydrocarbon exist and at ambient temperature represent asphalts or tars, however, when heated to temperatures ranging up to 426.7 ° C become liquid. The present invention is Applicable to carbo-metallic oils, whether they are from Paraffin derived or not. Provided they have the required boiling range, the carbon residue at the Pyrolysis and the heavy metal content, it is possible the principle of the invention to the processing of highly diverse materials apply, such as heavy sump products from crude oil, heavy bitumen crude oil, to such crude oils as "heavy crude" are known and have approximate properties such as top residues, shale oil, tar sands extract, products of  coal liquefaction and solvated coal, more atmospheric Top residue and vacuum top residue, extracts and / or bottoms (Raffinate) of solvent deasphalting, aromatic Extract of oil refining, tar sump products, heavy return oil, slop oil, other refinery waste streams and Mixtures of the above products. Such mixtures can For example, be prepared by the available Hydrocarbon fraction, including oils, tars, pitches and the like, mixes. Also can powdered coal in be suspended in the carbo-metallic oil. Using the present invention can be demetallized oils converted the person skilled in techniques for Entmetallisierung of knows carbo-metallic oils; however, it is an advantage of this Invention, that uses as starting material carbo-metallic oils which can not be any previous demetallization treatment have been subjected. Similarly, the Invention are also applied to starting materials, the previously hydrotreated; However, it is Again, an advantage of this invention is that it succeeds the conversion of carbo-metallic oils can be applied which have not previously been subjected to hydrotreating. The preferred Application of the present invention, however, takes place Topprückstände, that is, on the crude oil fraction, the at and above 343.3 ° C, either alone or in admixture with pure gas oils. While the use of materials that previously subjected to vacuum distillation, according to the invention are not excluded, it provides an advantage of this Invention is that in a satisfactory way materials can process or treat the previously no vacuum distillation and less capital is invested must save and operating costs, compared to the conventional FCC process in which a vacuum distillation unit is required.

Table 1 below shows a comparison between a typical vacuum gas oil (VGO) heretofore used in fluid catalytic cracking and various top stocks which are but a few examples of the numerous top stocks that can be used in the present invention.

From the table it can be seen that the heavier or the higher boiling starting materials by relatively lower API density values are marked as the example given Vacuum gas oil (VGO). In general, those were catalytic Cracking process starting materials with lower boiling temperatures and / or higher API densities than far superior viewed over starting materials with higher boiling temperatures and / or lower API densities. Comparisons between the Gasoline yield of high-boiling starting materials and starting materials with a medium boiling range at constant coke yield have shown that the starting materials with the middle Boiling range for a given coke yield a superior Gasoline yield.

According to the invention, a carbo-metallic oil starting material is prepared of which at least 70%, preferably at least 85%, and especially 100% (vol.%) At and above Boil at 343.3 ° C. All boiling temperatures given here are based on standard conditions at atmospheric pressure. For carbo-metallic oil, partially or completely off a material which is at and above 343.3 ° C Such material is referred to herein as 343.3 ° C + material; and 343.3 ° C + material, the is part of an oil or has been separated from an oil, which contains constituents above and below 343.3 ° C boiling, may be referred to as 343.3 ° C + fraction become. However, the terms "boil above" and "343.3 ° C +" does not mean that all the material associated with these Expressing is called, which has the ability to boil. The carbo-metallic oils suitable for the present invention can also contain material under no conditions boiling; For example, certain asphalts and asphaltenes can thermally cracked during the distillation, obviously without boiling. Therefore, for example, when it is said that the Starting material comprises at least 70 vol .-% material, the above 343.3 ° C boiling, then meant by it be that the 70% in question may include a little material,  that does not boil or evaporate at any temperature. If Such non-boiling materials may be present often or for the most part in parts of the starting material which are not below 537.8 ° C, Boil 551.7 ° C or higher. Therefore, it is said that at least 10%, preferably 15% and in particular at least 20% (vol.%) of the 343.3 ° C + fraction not boiling below 537.8 ° C 551.7 ° C, then it should be meant that all material or each Part of the material not below 537.8 ° C or 551.7 ° C boils, and at and above the specified Temperatures may be volatile or non-volatile.

Preferably, the contemplated starting materials, or at least the 343.3 ° C + material contained therein a carbon residue in the pyrolysis of at least 2 or more. For example, the Ramsbottom carbon content range from 2 to 12, and it is common at least 4. A particularly common area is between 4 to 8. It is noteworthy that this is exemplary indicated VGO in Table 1 a Ramsbottom carbon residue value of 0.38 and the 343.3 ° to 551.7 ° C fractions of various top-residues Ramsbottom carbon values between 0.3 and 0.5 while the various top residues, each as a whole (343.3+) upwards in the Ramsbottom carbon values of 4 to 16.8 vary, and there may be even higher values be contemplated.

Preferably, the starting material has an average composition, by an atomic ratio of hydrogen to carbon in the range of 1.2 to 1.9, preferably 1.3 to 1.8 is characterized.

The carbo-metallic starting materials used according to the invention or at least the 343.3 ° C + materials contained therein  can be at least 4 parts per million Nickel equivalents as defined above, of which wengistens 2 parts per million of nickel are (as metal, based on the weight). Carbo-metallic oils, within the above range, may be mixtures of two or more Oils are made, some of which are the above Contain amounts of nickel equivalents and nickel, and others not. It should also be noted that the above Values for nickel equivalents and nickel temporal and weight averages for a significant period of operation the conversion plant, such as a Month, are. It should also be taken into account that the Heavy metals in certain circumstances after repeated oxidation and reductions on the catalyst a lower Poisoning tendency show, and in the literature criteria for setting "effective metal" values. In This is, for example, an article by Cimbalo et al., entitled "Deposited Metals Poison FCC Catalyst", published in Oil and Gas Journal, May 15, 1972, pages 112-122, to mention, whose entire content should be included here. If necessary or even desirable, the contents of Nickel equivalents and nickel in the invention to be processed carbo-metallic oils also in the form of "effective In spite of the fact that Cimbalo et al. observed gradual reduction in poisoning activity It can be, and is usually, that regeneration of the catalyst under normal FCC regeneration conditions the dehydration, demethanization and aromatic Condensation activity of enriched on the cracking catalyst Heavy metals not reduced.

It is known that 0.2 to 5 wt .-% "sulfur" in Form of elemental sulfur and / or its compounds (however given as elemental sulfur, by weight the starting material) in the FCC starting materials, and that the sulfur or modified forms of sulfur their Way to find in the obtained gasoline product, and, where  Lead is added, its sensitivity to the To reduce octane enhancement. If crudes or toppings to be processed with high sulfur levels, requires in Often, the sulfur present in the gasoline product is a sweetener. In that Extent in which the sulfur is present in the coke, he notes also a potential air pollution, since the regenerator burns it to SO₂ and SO₃. However, within the scope of the invention found that the located in the starting material Sulfur in the inventive method on the other hand in the Able to inhibit the heavy metal activity in by adding metals as Ni, V, Cu and Fe are kept in the sulfide form in the reactor become. These Sufides are far less active than the metals even in favor of dehydration and coking reactions. Accordingly, it is acceptable to use the invention Carry out a process with a carbo-metallic oil, the at least 0.3, preferably more than 0.8, and in particular at least 1.5% by weight of sulfur in the 343.3 ° C + fraction contains.

For the purposes of the present invention suitable carbo-metallic Oils can and usually are significant amounts contain nitrogenous compounds, with a considerable Proportion thereof is present as basic nitrogen. For example can be the total nitrogen content of carbo-metallic Oils at least 0.05 wt .-% amount. Because the cracking activity of cracking catalysts on acid sites on the catalyst surface or in whose pores is due, can basic nitrogenous compounds temporarily these sites neutralize and poison the catalyst with it. However, that is the catalyst is not permanently destroyed as the nitrogen burned away from the catalyst during regeneration can, as a consequence of which the acidity of the active sites is restored.

The carbo-metallic oils can also produce significant amounts contain pentane-soluble substances, for example at least 0.5% by weight, typically 2% by weight or more, and  even 4% by weight or more. These can be, for example Asphaltenes and other materials include.

Alkaline and alkaline earth metals are generally not prone to evaporate in large quantities under the distillation conditions, in the distillation of crude oil for the production of Vacuum gas oils are commonly used as FCC starting materials be used. These metals remain for the most part in the "bottom" or "bottom" fractions (the not vaporized, high-boiling fraction), which for example used for the production of asphalt and other by-products were. However, top residues and other carbo-metallic ones are Oils in many cases soil products and can therefore considerable Amounts of alkali and alkaline earth metals, such as Sodium, included. These metals settle during the Cracking on the catalyst. Depending on the composition the catalyst and the regeneration temperatures, Those exposed to these metals can interact and undergo reactions with the catalyst or enter (Including the catalyst support), which normally when processing VGO under conventional FCC processing conditions not be observed. When the catalyst properties and the regeneration conditions required Of course, you will take the necessary precautions meet the amounts of alkali and alkaline earth metals in to limit the starting materials, these metals are not only as brine, with the crude oil in its natural state occur together, get into the starting material, but also as constituents of the water or the water vapor that enters the Cracking be performed. When the catalyst is exposed to alkali and alkaline earth metal is particularly sensitive, therefore, a careful desalting of the crude oil used to prepare the carbo-metallic starting material to be important. Among such In some circumstances, the content of such metals (hereinafter the For the sake of simplicity, referred to as "sodium") in the starting material at 1 part per million or less, based on the Weight of the starting material to be kept. Alternatively to this  the sodium content of the starting material can be in line with be brought to that of the catalyst, so the sodium content of the catalyst which is in use is substantially equal to or less than the one the replacement catalytic converter with which the system is loaded.

According to a particularly preferred embodiment of the invention contains the carbo-metallic oil starting material at least 70 vol .-% of material, which is above 343.3 ° C. boils, wherein at least 10% of the material, which boiling above 343.3 ° C, not below Boil 551.7 ° C. The average composition this 343.3 ° C + material can still be as follows characterized by: (a) an atomic ratio of hydrogen to carbon in the range of 1.3 to 1.8; (b) a Ramsbottom carbon value of at least 2; (c) at least 4 parts per million nickel equivalents as defined above which are at least 2 parts per million nickel (as metal, by weight); and (d) by at least one of the following Characteristics: (i) at least 0.3% by weight of sulfur, (ii) at least 0.05% by weight of nitrogen, and (iii) at least 0.5% by weight of pentane-soluble compounds. Very often the preferred starting material will have all the characteristics (i), (ii) and (iii), and other components, those in oils of petroleum origin or non-petroleum origin be present in varying amounts, provided that they do not prevent the implementation of the procedure.

Although the possibility of using a starting material, that has been cracked to some extent before, should not be excluded, one has the inventive method the definite advantage of being successful with it extensive conversions and very substantial yields liquid hydrocarbons from carbo-metallic Oils that previously did not appreciably undergo a cracking process have been subjected. Accordingly, this is in the inventive Method used carbo-metallic starting material  for example, and preferably at least 85%, especially preferably at least 90%, and especially in the essentially completely an oil that was previously not with a cracking catalyst under cracking conditions is. In addition, the inventive method is suitable for single-pass or single-pass process execution. The return volume is thus, if at all a reduction takes place, based on the volume fresh starting material, preferably 15% or less, and in particular 10% or less.

In general, the weight ratio of catalyst is too fresh starting material (starting material not previously with a cracking catalyst under cracking conditions come into contact is) in the process in the range of 3 to 18. Preferred ratios are between 4 and 12, especially preferred between 5 and 10, in particular between 6 and 10, with a ratio of 6 to 8 is currently considered to be the near-optimal ratio. Within the limits imposed by product requirements can be set, the coke yield of the process, based on fresh starting material, be degraded when the ratio from catalyst to oil at relatively low levels, within the above ranges, is maintained.

In the conventional FCC processing of VGO, the ratio between the number of barrels per day throughput of the plant and the total number of tons of catalyst passing through the circulation all stages of the procedure are subject to considerable variation. For the present purposes, the daily investment throughput defined as the number of barrels of fresh initial product that above 343.3 ° C, which boils the plant per average Operating day to liquid products below Boiled at 221.1 ° C, processed. For example in a commercially successful type of FCC-VGO process implementation 8 to 12 tons of catalyst circulates in a process with a plant throughput of 1000 barrels  per day. In another commercially successful process this ratio ranges from 2 to 3. While the present invention in the range of 2 to 30, typically between 2 to 12 tons of catalyst stock per 1000 barrels of daily plant throughput can be practiced the process of the invention is preferably at a very small ratio of catalyst weight to daily plant throughput carried out. It is particularly preferred that the inventive To carry out a process with a catalyst stock, for contact with the starting material for the desired residence time at the above ratio of Sufficient catalyst to oil while the amount of catalyst stock, relative to plant throughput, to a minimum with the catalyst stock circulating or in other stages of the treatment, such as while stripping, regenerating, and the like. It will Therefore, particularly preferred, the inventive method with 2 to 5 and in particular 2 tons of catalyst inventory or less per 1000 barrels of daily plant throughput perform.

In carrying out the method according to the invention, the Catalyst can be added continuously or periodically for example, to normal losses of catalyst from the system compensate. In addition, the catalyst addition in conjunction be carried out with the catalyst removal, for example the average activity level of the catalyst maintain or increase in the investment. For example can the speed with which the virgin Catalyst is introduced into the plant, in the range of 0.0454 to 1.361, preferably 0.068 to 0.907 and in particular 0.0907 to 0.068 kg per barrel Starting material lie. If on the other hand equilibrium catalyst used from the FCC operation can be so high Replacement speeds such as 2.268 kg per barrel be applied. If the circumstances are such that  the catalyst used in the plant with regard to Resistance to deactivation below the Average and / or prevailing conditions in the installation can also result in a faster deactivation faster addition rates than those specified above applied become; On the other hand, in other circumstances Even smaller rates of addition can be applied.

Without wishing to be bound by any theory, it seems that as if a set of procedural features, detailed below described, such as the residence time and optionally mixing water vapor and starting material, reduce the extent to which the cracking conditions Metals are generated in a reduced state on the catalyst, of heavy metal sulphide (s), sulphate (s) or oxide (s) occurring on the catalyst particles by the previous contact with carbo-metallic starting material and regeneration conditions are separated. It thus appears that the process is a significant one Control of the poisoning effect of heavy metals allows the catalyst, even if the enrichments of such Metals are considerable.

Consequently, the process can be carried out with catalysts, have the heavy metal enrichments, which so far in conventional FCC-VGO operation as completely inadmissible would have been viewed. For the reasons mentioned, the implementation of the process with catalysts are envisaged, the heavy metal enrichments in the range of 3000 to 70,000 parts per million nickel equivalents on average respectively. The enrichment may preferably be in the range of 4000 to 50 000 parts per million, and in particular more than 5,000 to 30,000 parts per million. These ranges are based on parts per million nickel equivalents, where the metals are given as metal and by weight and moreover on regenerated equilibrium catalyst measured and related to these. In the case however, that a catalyst of suitable activity is too low Cost should be available, which is very high  Catalyst replacement rates would be possible, could carbo-metallic oil also with a catalyst that is less than Has 3000 parts per million nickel equivalents of heavy metals, be converted to lower boiling liquid products For example, one could use an equilibrium catalyst of another plant, such as an FCC plant, which was used to crack a starting material, For example, a vacuum gas oil, which in the pyrolysis a Carbon residue of less than 1 gives and less than Contains 4 parts per million nickel equivalents of heavy metals.

In any case, the equilibrium concentration of heavy metals in the circulating catalyst inventory by arbitrary Change in the catalyst addition rate discussed above controlled (including maintenance or variation, if desired or required). So, for example the catalyst addition is kept at a speed in which the heavy metal enrichment on the catalyst in one the above ranges is maintained.

In general, it is preferred to use a catalyst, which has a high degree of cracking activity, high conversion rates and high productivity with low residence times. The conversion efficiency of the catalyst can be expressed be as generated transformation during the actual process implementation and / or as generated conversion in standard tests for the catalyst activity. For example, it is preferable a catalyst used in the course of an extended Procedural execution is sufficiently active in order for a conversion level of at least 50%, preferably at least 60%, to worry. In this context, the transformation as liquid vol .-%, based on fresh starting material, expressed. For example, a preferred catalyst may also be to be defined as one who, in his virgin Condition or in equilibrium a specified activity shows, expressed in the form of a vol .-% statement, available through MAT (micro-activity test). In the context of the present invention  the aforementioned percentage means the percentage Volume fraction of the standard starting material, which is 221.1 ° C End point petrol and lighter products at 482.2 ° C, a weight hourly space velocity of 16, calculated on the basis of one at 593.3 ° C dried catalyst, and a 3 C / O (ratio of catalyst to oil) measured by ASTM-MAT test D-32, using a suitable standard starting material, for example, the Davison WHPS-12 primary gas oil, which has the following analysis values and properties:

API density at 15.56 ° C, degree | 31.0 Specific gravity at 15.56 ° C, g / cc .8708 Ramsbottom carbon, wt% 0.09 Conradson carbon, wt% (estimated) 0.04 Carbon, wt% 84.92 Hydrogen, wt.% 12.94 Sulfur,% by weight 0.68 Nitrogen, parts per million 305 Viscosity at 37.8 ° C, m² / s 10.36 x 10 ^-6 Watson K factor 11.93 aniline point 182 bromine number 2.2 Paraffins, Vol .-% 31.7 Olefins, Vol .-% 1.8 Naphthenes,% by volume 44.0 Aromatics, Vol .-% 22.7 Average molecular weight 284 nickel traces vanadium traces iron traces sodium traces Chloride traces BS & W traces

Distillation, ° C ASTM D-1160 IBP 229.4 10% 316.1 30% 351.1 50% 371.7 70% 390.0 90% 419.4 FBP 445.6

The endpoint of the gasoline produced in the MAT test becomes often as 221.1 ° C wS (true boiling point) defines what corresponds to standard laboratory distillation, however, other endpoints may as well be used for this purpose serve. The conversion is calculated by taking from 100% by volume (based on fresh starting material) of those Products that are heavier than gasoline, and won in the Product remain, peel off.

The catalyst may be in its virgin or original Form or, as indicated above, in any other Form be introduced into the procedure; for example, you can use an equilibrium catalyst derived from another Was removed, such as a catalyst, the previously used to crack a different starting material has been. Unless the characterization is based on the MAT activity occurs, the preferred catalysts can be added The basis of their MAT activity can either be described as they are "introduced" into the process of the invention, or how they are "extracted" or based on their equilibrium MAT activity in the method according to the invention, or They can also be made using both the one and the other other basis. A preferred MAT activity for original and non-original catalysts, as well they are "introduced" into the process of the invention, is at least 60%, but it should be noted that in particular in the case of non-original catalysts, which are supplied at high rates of addition, too  lower levels of MAT activity are acceptable. An acceptable MAT activity of the catalyst as it is "withdrawn", respectively an acceptable equilibrium MAT activity level of the catalyst used in the process according to the invention is 20% or more, with 40% being or more, and more preferably 60% or more, preferred values represent.

Any hydrocarbon cracking catalyst can be used which has the above-mentioned conversion capabilities. A special preferred class of catalysts comprises such catalysts, which have a pore structure into which starting material molecules for adsorption and / or contact with active catalytic sites within or adjacent to the pores can enter. Different types of catalysts with this Classifications are available, including, for example the layered silicates, such as the soap tonics. Although the most common available catalysts within this classification the well-known zeolite-containing catalysts are, can Non-zeolite-containing catalysts are envisaged.

The preferred zeolite-containing catalysts may be any Zeolite, whether it is a natural, semisynthetic or synthetic zeolite, alone or in Mixture with other materials, the suitability of the catalyst do not deteriorate to a significant degree, provided that the catalyst obtained was as indicated above Activity and pore structure. For example, if the Catalyst is a mixture, he can use a zeolite component comprise together with or dispersed in a porous, heat-resistant, inorganic oxide carrier; in such a case, the Catalyst, for example, 1 to 60 wt .-%, preferably 1 to 40% by weight, and especially 5 to 25 wt .-%, based on the total weight of the zeolite catalyst (anhydrous basis), with the remainder of the catalyst consists of porous, heat-resistant, inorganic oxide, either alone or in combination with any known additives  to speed up or suppress various desired ones and unwanted reactions. For general explanation of Class of zeolite molecular sieve catalysts used in the framework of the present invention is made to the disclosures the article "Refinery Catalysts Are a Fluid Business", and "Making Cat Crackers Work on Varied Diet," referring to the on July 26, 1978 and September 13, 1978 in Chemical Week Magazine have appeared. The revelations of these two publications should be included here.

In most cases, the zeolite constituents of the zeolite-containing Catalysts are those that are involved in FCC cracking have proved to be suitable. In general, these are crystalline aluminosilicates, typically fourfold Coordinated aluminum atoms consist of oxygen atoms connected to the adjacent silicon atoms in the crystal structure are. However, the term "zeolite" in the context of present invention not only aluminosilicates, but also Substances in which the aluminum is partly or completely has been replaced, such as by gallium and / or other metal atoms, and it further includes substances in which the silicon has been partially or completely replaced, such as by germanium. A replacement by titanium and Zirconium is also suitable.

Most zeolites are produced in the sodium form and also occur in nature in this form, the sodium cations with the electronegative sites in the crystal structure are connected. The sodium cations tend to be the zeolites to be inactive and much less stable if this is the case Conditions of hydrocarbon conversion, especially at high temperatures. As a result, the zeolite be subjected to ion exchange, and when the zeolite a Component of a catalyst composition, such Ion exchange before or after the incorporation of the zeolite as Component of the composition take place. Suitable cations for the replacement of sodium in the zeolite crystal structure  Ammonium (decomposable to hydrogen), hydrogen, the rare Earth metals, alkaline earth metals, etc. In the professional world are different suitable ion exchange processes and also cations known as exchange material in the zeolite crystal structure can be introduced.

Examples of naturally occurring, crystalline aluminosilicate zeolites, used in the context of the present invention or in which catalysts can be incorporated are faujasite, Mordenite, clinoptilot, chabazite, analcite, erionite, and as well Levyn, Dachiardite, Paulingite, Noselith, Ferriorite, Heulandite, Skolezite, Stibit, Harmotom, Phillipsite, Brewsterite, Flarit, Datolite, Gmelinite, Caumnite, Leucite, Lasurstein, Scaplite, Mesolith, Ptholite, Nepheline, Matrolith, Offretite and Sodalite.

Examples of synthetic, crystalline aluminosilicate zeolites, as or in catalysts for carrying out the invention Are suitable: Zeolite X, US-PS 28 82 244, zeolite Y, US Pat. No. 3,130,007 and zeolite A, US Pat 28 82 243; as well as zeolite B, US Pat. No. 3,008,803; Zeolite D, CA-PS 6 61 981; Zeolite E, CA-PS 6 14 495; Zeolite F, US PS 29 96 358; Zeolite H, U.S. Patent 3,010,789; Zeolite J, U.S. Patent 3,011,869; Zeolite L, BE-PS 5 75 177; Zeolite M, US Pat. No. 2,995,423; Zeolite O, U.S. Patent No. 3,140,252; Zeolite Q, U.S. Patent No. 2,991,151; Zeolite S, US-PS 30 54 657; Zeolite T, U.S. Patent No. 2,950,952; Zeolite W, US Pat. No. 3,012,853; Zeolite Z, CA-PS 6 14 495; and Zeolite Omega, CA-PS 8 17 915. Also suitable are the ZK-4HJ zeolite, alpha-beta zeolite and the zeolites of the ZSM type. In addition, those in the U.S. Patent Nos. 3,140,249, 3,140,253, 3,944,482 and 4,137,151 Zeolites suitable, the disclosures of these patents should be included here.

The crystalline aluminosilicate zeolites with a faujasite Crystal structure are particularly within the scope of the present invention suitable. This includes in particular natural Faujasite and zeolite X and zeolite Y.  

The crystalline aluminosilicate zeolites, such as synthetic Faujasite, under normal conditions in the form of regular shaped, discrete particles of size 1 crystallize to 10 microns, and this is also the size that frequently encountered in commercially available catalysts is, and which are suitable in the context of the invention. Preferably the particle size of the zeolites is 0.5 to 10 microns, and in particular 0.1 to 2 microns or fewer. For example, in situ calcined kaolin prepared zeolites characterized by even smaller crystallites his. Crystalline zeolites have both an inner and a also an outer surface, which here as a "portal" surface is designated, wherein the greater part of the total surface area through the inner surface. With the portal surface is herewith the outer surface of the zeolite crystal meant by which the reactants pass need to be converted to low-boiling products. The Blocking the inner channels by, for example, coke formation, the blocking of the inputs to the inner channels by deposition of coke on the portal surface, and the pollution By metal poisoning, the entire zeolite surface to a considerable extent. Therefore, the effects contamination and pore clogging to a minimum keep crystals that are larger than usual, as above indicated, preferably in the invention to be used Catalysts not used.

Commercially available zeolite-containing catalysts with supports, a variety of different metal oxides and combinations including, for example, including Silica, alumina, magnesia and mixtures of this as well as mixtures of these oxides with clays, like this For example, in US-PS 30 34 948 is described. For example one can use any of the zeolite-containing molecular sieve Use fluid cracking catalysts for the preparation gasoline from vacuum gas oils are suitable. However, certain can Benefits can be achieved through sensible selection of  Catalysts with a considerable resistance to Metals. A metal-stable zeolite catalyst, for example described in US-PS 39 44 482, wherein the Catalyst 1 to 40 wt .-% of a rare earth-exchanged Contains zeolite and the rest of a refractory metal oxide with a specified pore volume and size distribution. Other catalysts called "metal tolerant" are described in the above-mentioned article by Cimbalo et al. described.

In general, preference is given to using catalysts which a total particle size in the range of 5 to 160 microns, especially 40 to 120, and especially preferably 40 to 80 microns, have.

The catalyst composition may also include one or more Include combustion promoters that are suitable for the subsequent stage the regeneration of the catalyst are suitable. The cracking of carbo-metallic oils leads to a considerable separation of coke on the catalyst, causing a loss of activity of the catalyst. Therefore, the activity To restore the catalyst, the coke is in a Regeneration stage burned away, in which the coke in combustion gases including carbon monoxide and / or carbon dioxide is transferred. There are various substances known to the conversion of coke in carbon monoxide and / or carbon dioxide and / or carbon dioxide, when incorporated in small quantities in cracking catalysts become. The promoters for the combustion of coke to carbon monoxide tend to lower the temperature at which one given degree of coke removal can be achieved, and they reduce the potential for thermal deactivation of the catalyst. Such promoters normally found in effective amounts of trace amounts up to 10 or 20% by weight of the  Catalyst can be used, for example, any Be kind, usually the burning of carbon under regeneration conditions to carbon monoxide, preferably Carbon dioxide, promotes.

Although a wide variety of other catalysts, including zeolite-containing, as well as non-zeolite-containing catalysts usable in the context of the present invention, Below are some examples of commercially available Catalysts specified in the practical application of have been used in the present invention:

Table 2

The above properties are properties of original Catalysts and are, except in the case of Zeolite content, based on an anhydrous basis, ie to a material that has been fired at 954.4 ° C. The zeolite content was determined by comparing the x-ray intensities a catalyst sample and a standard material, which was made of high purity Natium-Y zeolite according to the design # 6, dated 9 January 1978, of the proposed ASTM standard  Procedure entitled "Determination of the Faujasite Content of a Catalyst. "It is considered an advantage that the inventive method in the practical absence of Tin and / or antimony or at least in the presence of one Catalyst can be carried out, which is substantially free of one or both of these metals.

The inventive method can with the above-described carbo-metallic oil and catalyst as the substantially single materials entered into the reaction zone, be performed. However, the charge is additional Materials not excluded. The feed of the reaction zone with recirculated oil has already been mentioned above. As will be described in more detail below, can Also other materials can be added, the one Can fulfill a variety of functions. In such a case Usually put the carbo-metallic oil and the catalyst the majority of the total, entered into the reaction zone Materials dar.

Some of the additional materials used can, fulfill functions that face considerable advantages To offer the procedure that only with the carbo-metallic oil and the catalyst. Among these functions These include: Controlling the effects of heavy metals and other catalyst contaminants; Enhancement of catalyst efficiency; Absorb the excess heat in the Catalyst as it is obtained from the regenerator; disposal environmentally polluting substances or their transformation into a shape or forms in which they are easier to remove Products can be separated and / or disposed of; Kontrollierung the catalyst temperature; Dilution of carbo-metallic Oil vapors to reduce their partial vapor pressure and to increase the yield of desired products; regulation the starting material / catalyst contact time; Zurverfügungsstellung of hydrogen for a low-hydrogen carbo-metallic Starting material; Assistance in the dispersion of the starting material;  and possibly also distillation of the products. Certain metals in the heavy metal enrichment on the catalyst are more active in favoring unwanted ones Reactions, if they are in the form of elemental metal, as if in contact with oxygen in the catalyst regenerator produced, oxidized form. However, that was enough the contact time between catalyst and starting material vapors and product in the conventional catalytic cracking, so that the hydrogen released in the cracking reaction in the Location was a considerable part of the less harmful oxides due to the more harmful elemental heavy metal form. One can take advantage of this situation to his advantage, if one introduces additional materials in the reaction zone in Mixture with the catalyst, the starting material vapors and the products in a gaseous form (including vaporous Form) are present. The increased volume of material in the Reaction zone caused by the presence of additional Materials, leads to an increase in the flow rate through the reaction zone and thus has a corresponding decrease the residence time of the catalyst and the resulting oxidized Heavy metals result. Due to the shortened residence time exists for the reduction of oxidized heavy metals too elementary form less opportunity, and thus stand less elemental, harmful metals for contact with the starting material and the products available.

The materials to be added may be of any suitable type Way into the process, with some examples described below. For example, you can use be mixed with the carbo-metallic oil starting material before the latter is brought into contact with the catalyst. alternative For this, the materials to be added, if it is desired to be mixed with the catalyst before this comes into contact with the starting material. Separated parts The materials to be added can also be separated with both Catalyst and mixed with the carbo-metallic oil become. In addition, the starting material, the catalyst  and the additional materials also, if desired will be merged, essentially simultaneously. On Part of the materials to be added can also be used with the catalyst and / or the carbo-metallic oil to any of those described Species are mixed while additional parts follow be mixed while additional parts below be mixed. For example, part of the to be added Materials for the carbo-metallic oil and / or to added to the catalyst before passing the reaction zone reach while another part of the materials to be added is introduced directly into the reaction zone. The to be added Materials can be in a variety of spaced locations into the reaction zone or along its extension, if they elongated, be introduced.

The amount of additional materials present in the starting material, Catalyst or in the reaction zone to meet the above described functions and also other functions present can be varied to the desired extent; however the said amount will preferably be sufficient to be in the essential to ensure a heat balance of the process. These materials may, for example, in the reaction zone with a weight ratio of materials to starting material of up to 0.4, preferably from 0.02 to 0.4, in particular From 0.03 to 0.3, and most preferably from 0.05 to 0.25.

For example, many or all of the above-mentioned desirable ones Functions are achieved when H₂O in the form of water vapor or in the form of liquid water, or in the form a combination of these, in the reaction zone with a weight ratio of H₂O to starting material in the range of 0.04 or more, and preferably 0.05 to 0.1 or more introduces. Without wanting to be tied to any theory, The use of H₂O seems the reduction of on the catalyst oxides, sulfites and sulfides in the free metal form which is believed to inhibit condensation dehydration with detailed promotion of coke and  Hydrogen yield and associated product loss favors. In addition, H₂O can also to some extent reduce the deposition of metals on the catalyst surface. There may also be a slight tendency containing nitrogenous and other heavy impurities Desorb molecules from the surface of the catalyst particles, or it may have at least some tendency to inhibit consist of their adsorption by the catalyst. It will also believed that added H₂O the acidity of the catalyst Bronsted acidification increases, resulting in a Reinforcement of the catalyst efficiency leads. Under the assumption, that the supplied H₂O is colder than the regenerated catalyst and / or the temperature in the reaction zone, can through the noticeable heat, which increases the temperature of the H₂O by contact with the catalyst in the reaction zone or elsewhere, excess heat from the catalyst is released subtracted from. The liquid or vaporous water contains less than 100 parts per million of sodium and less than 500 parts per million of each calcium and Magnesium. All or part of H₂O can and will preferably from the products of a previous catalytic Conversion of a carbo-metallic oil condensed. When the H₂O is recycled water or such comprising, for example, 500 to 5000 parts contains per million H₂S dissolved in it, a number of additional benefits can be achieved. That in ecological terms Unloved H₂S does not have to be released into the atmosphere, the recycled water requires no further treatment for the removal of H₂S, and the H₂S can contribute to the reduction the coking of the catalyst afford by the Heavy metals passivated, that is, by placing them in the Converted sulfite form, which has a lower effectiveness for reinforcement coke formation and hydrogen production have, as the  free metals. In the reaction zone, the presence of Water dilute the carbo-metallic oil vapor and thereby their Partial vapor pressure decrease and thus to an increase in the Yield of the desired products. It was reported that the H₂O in conjunction with other materials for the production of hydrogen during cracking is suitable; that's the way it can be to be able to act as a hydrogen donor for low hydrogen to serve carbo-metallic oil starting materials. The H₂O can also fulfill purely mechanical purposes, such as: assistance in the atomization or dispersion of the starting material;  Competition over the high molecular weight molecules in terms of adsorption on the surface of the catalyst, wherein coke formation is interrupted; Steam distillation vaporizable product of non-volatile starting material; and separating the product from the catalyst after completion of the Cracking reaction. In a particularly preferred extent, the H₂O, the Catalyst and the carbo-metallic oil substantially simultaneously brought together. For example, you can H₂O and starting material in an atomizing nozzle and the resulting Spray immediately at the downstream end of the spray Contact the reaction zone with the catalyst.

The addition of water vapor to the reaction zone is reported in the literature Of fluid-catalytic cracking frequently mentioned. The addition from liquid water to the starting material becomes relatively rare mentioned, compared to the direct introduction of water vapor in the reaction zone. Within the scope of the present invention However, it is particularly preferred that an intimate mixture with liquid water and carbo-metallic oil at a weight ratio from 0.04 to 0.15 at the moment or just before the introduction of the oil is formed in the reaction zone, wherein the water (for example in the form of liquid water or in Form of water vapor, obtained by evaporation of the liquid Water by contact with the oil) the reaction zone as part the feedstock flow introduced into the reaction zone is, enters. Without wanting to be tied to any theory, It is believed that the above-described measure is advantageous for promoting the dispersion of the starting material is. Also, the heat of evaporation of the water, by the Catalyst, the starting material or both, is withdrawn, Cause that water is an effective heat trap, as water vapor alone. Preferably, the weight ratio from liquid water to starting material 0.04 to 0.1, in particular 0.05 to 0.1.

Of course, the liquid water in the manner described above or otherwise introduced into the process be, and in any case, the introduction of the liquid  Water also by introducing additional amounts of water in Form of water vapor in equal or different areas of the Reaction zone or in the catalyst and / or the starting material be accompanied. For example, the amount of additional Water vapor, expressed as the weight ratio of water vapor to starting material, 0.01 to 0.25, wherein the weight ratio of total water (as water vapor and as liquid water) to starting material 0.3 or less is. The feed weight ratios of liquid Water to steam in such a combined use of liquid water and water vapor can range from 5 to 0.2 lie. Such a relationship may be on a predetermined Level kept within such a range or, if necessary or desired, be varied to the heat balance to regulate or maintain the response.

Other functions can be used to fulfill the functions described above Materials are added to the reaction zone. For example can reduce the dehydration-condensation efficiency of Heavy metals by introduction of hydrogen sulphide gas in the reaction zone are inhibited. For low-hydrogen carbo-metallic Oil feedstocks can be hydrogen available be made either by using a conventional hydrogen Donor diluents, such as heavy fuel, or including relatively low molecular weight hydrocarbon fragments, including for example: light paraffins; low molecular weight Alcohols and other compounds that undergo intermolecular hydrogen transfer allow or favor; and connections, which chemically generate hydrogen in the Combine reaction zone, such as by reaction of Carbon monoxide with water, with alcohols, with olefins or with other materials or mixtures of the aforementioned substances.

All of the above, additional materials (including Water) may be used alone or in conjunction with each other or in Connection with other materials; like nitrogen or others Inert gases, light hydrocarbons and other compounds  any of the features described above for which they are appropriate are, fulfill, and include, without limitation, as a diluent to lower the starting material Partial vapor pressure and / or as a heat trap for the absorption of Excess heat from the catalyst, as seen from the regeneration stage is received serve. The above statements present a discussion of some features that are going through other materials introduced into the reaction zone than the Catalyst and the carbo-metallic oil starting material, fulfilled Of course, other materials can also be used added and other functions are fulfilled without the Leave the framework of the present invention.

The present invention can be used in a wide variety of ways Devices are realized. However, a preferred Device Means for rapid evaporation of as much as possible starting material and for effective mixing of starting material and catalyst (although not necessarily in this order), means to give the resulting mixture as a dilute suspension in a kind of fluidized bed to flow and means for separating the catalyst from cracking products and uncracked or only partially cracked starting material at the end of a predetermined residence time or Residence times, it being preferred that all or at least a substantial proportion of product abruptly from at least a part of the catalyst is separated.

For example, the device may be along the elongate reaction chamber one or more points for the introduction of carbo-metallic Starting material, one or more points to Introduction of catalyst, one or more introductory points of additional material, one or more points to Removal of products and one or more points for removal of the catalyst. The means of introducing the Starting material, the catalyst and other materials can range from open piping to advanced nozzles or spray cans, preferably using agents which are capable of producing liquid starting materials divide into fine droplets.  

Preferably, the reaction chamber, or at least a major part the same, more vertical than horizontal arranged and has a Length to diameter ratio of at least 10, preferably 20 or 25 or more. The application of vertical Riser reactors are preferred. When the reactor is tubular is, he can consistently a uniform diameter or he may be continuous or gradual Have diameter increase along the reaction path to the Maintain speed along the flow path or to vary.

In general, the feeds (for the catalyst and the starting material) and the construction of the reactor such, that a relatively high flow rate and a diluted Suspension of the catalyst is obtained. For example the steam or catalyst rate in the riser usually at least 7.6 m / sec and typically at least 10.64 m / sec. This speed can reach up to 16.72 m / sec or 22.8 m / sec or more. The speed capabilities of the reactor will generally be sufficient to build up or the accumulation of a substantial catalyst bed in the To prevent floor area or other parts of the riser, the catalyst loading in the riser being upstream End (for example, on the ground) and at the downstream end (for example, on the head) of the riser below 64.6 or 80.7 kg / m³, or below 32.3 kg / m³ can be maintained.  

The fluidized bed process includes, for example, the flow of Catalyst, starting material and products as a stream in a positively controlled and sustained direction, which is determined by the elongated nature of the reaction zone. This does not mean, however, that a strictly linear flux is maintained must become. To some extent a turbulent flow and a "slip" of the catalyst occur as is known, especially in certain vapor velocity ranges and catalyst loadings, though It has been reported that it is advisable to meet low catalyst loadings apply to a slip and mix back prevent.

The preferred reactor is one in which all or an essential part of the evaporated, cracked products one or more locations along the riser of the catalyst be separated, wherein preferably substantially all evaporated, cracked products at the downstream end of the riser are separated from the catalyst. In a preferred Reactor type is the separation of catalyst and Products by ballistic means; that is, the catalyst is thrown in a direction through the riser tube is fixed, and is forced to move in the so general continue to set the direction, while the products, which have a lower momentum, to an abrupt change of direction be forced, resulting in an abrupt, essentially immediate separation of product and catalyst. at a preferred embodiment, here as ventilated Riser is called, the riser tube has a virtually unhindered Outlet opening at the downstream end for discharge of the catalyst. Through an exit opening in the side the tube, which is the downstream end of the riser adjacent, the products are removed. The outlet opening for the catalyst is by a catalyst flow path with the usual stripper and regenerator connected while the outlet for the products associated with a product flow path that is substantially or completely off the catalyst flow path  is separated, and to separation devices for separation the products of relatively small amounts of catalyst which, if any, exists succeeded in finding its way through the product exit opening. Examples of a ballistic separation device and technique, as described above, can be found in US-PS 40 66 533 and 40 70 159 to Myers et al. be found, their entire revelations should be included hereby.

Preferred conditions for carrying out the method are described below. Among these are: starting material, Catalyst and reaction temperatures, reaction and Starting material pressures, residence times and conversion levels, Coke production and coke deposition on the catalyst.

In conventional FCC operation with VGO, the feedstock becomes Usually preheated, often at temperatures that are considerably higher than required to the starting material for pumping and for introduction into the reactor are sufficient liquid close. For example, preheating temperatures are reported after all, at 371.1 ° C or 426.7 ° C lay. In the context of the method according to the invention, as it is currently used in practice, the preheating of the starting material limited so that the starting material is capable of a larger amount of heat from the catalyst absorb, wherein the catalyst, the starting material on the Conversion temperature heated, and at the same time the use of external fuels for heating the starting material kept to a minimum. As a result, the starting material be supplied at ambient temperature, provided that Nature of the starting material allowed this. Heavier starting materials can be used at elevated preheat temperatures of up to 315.6 ° C, typically from 93.3 ° C to 260 ° C are fed, with higher Preheat temperatures are not necessarily excluded.

The catalyst feed to the reactor can be quite different  Temperatures occur, for example from 593.3 ° C to 871.1 ° C, preferably from 648.9 ° C to 815.6 ° C, and in particular from 704.4 ° C to 760 ° C, currently temperatures from 718.3 ° C to 746.1 ° C are considered optimal.

As mentioned above, the transformation of the carbo-metallic Oil to low molecular weight products at a temperature be carried out from 482.2 ° C to 760 ° C, which at the reaction chamber outlet is measured. The measured at this outlet Reaction temperature is preferably in the range of 523.9 ° C to 704.4 ° C, especially from 529.5 ° C to 648.9 ° C, and completely more preferably maintained from 537.8 ° to 621.1 ° C. Dependent on from the selected temperature and properties the starting material can all the starting material evaporate in the riser or not.

Although, as indicated above, the reactor pressure in one Range from about 0.69 to about 3.45 bar, lie the preferred and the most preferred pressures in the field from 1.04 to 2.41 bar, or from 1.38 to 2.41 bar. in the In general, the partial (or total) pressure of the starting material in the range of 0.21 to 2.07, preferably 0.48 to 1.72, and in particular from 0.69 to 1.18 bar. The starting material Partialdampfd 69985 00070 552 001000280000000200012000285916987400040 0002003043107 00004 69866ruck can through the introduction of gaseous (including vaporous) materials be controlled or decreased in the reactor, such as for example, by introducing water vapor, water and other additional materials as described above. The procedure was calculated, for example, at a ratio of starting material  Partial pressure to total pressure in the riser in the range of 0.2 to 0.8, preferably 0.3 to 0.7, and in particular 0.4 to 0.6, wherein the Ratio of supplied gaseous material (which recycled Gases and / or water vapor, by introduction of H₂O in the riser in the form of water vapor and / or liquid Water was obtained) to total pressure in the riser accordingly in a range of 0.8 to 0.2, preferably 0.7 to 0.3 and especially 0.6 to 0.4. In the just described exemplary operation of the invention Procedure was the ratio of partial pressure of the added gaseous material to the partial pressure of the starting material 0.25 to 2.5, preferably 0.4 to 2, and especially 0.7 to 1.7.

Although the residence time of the starting material and product vapors in the riser in the range of 0.5 to 10 seconds can, as described above, are preferred and quite particularly preferred values between 0.5 and 6 or between 1 and 4 seconds, with a range of 1.5 to 3.0 seconds currently regarded as the optimal range becomes. For example, the process has a vapor-riser residence time of 2.5 seconds or less, under Supply of abundant amounts of gaseous materials in the riser, these quantities have been sufficient, for example a partial pressure ratio of supplied gaseous materials to hydrocarbon starting material of 0.8 or to give more. The process was continued with a residence time of 2 seconds or less and with an aforementioned Ratio in the range of 1 to 2 performed. The Combination of low starting material partial pressure, one very small residence time and a ballistic separation of Products of the catalyst is considered extremely cheap considered for the conversion of carbo-metallic oils. additional Benefits may be in the context of the aforementioned combination be achieved when a substantial partial pressure of supplied gaseous material, in particular H₂O prevails, as above has been described.  

Depending on whether a sliding between the catalyst and the Hydrocarbon vapors occur in the riser, the catalyst Riser dwell time may or may not be the same like the riser residence time of the vapors. Demand can be the ratio from average catalyst reactor residence time to Steam reactor residence time, that is, the sliding, in the range from 1 to 5, preferably from 1 to 4, and in particular from 1.2 to 3, being an area from 1.2 to 2 is currently considered optimal.

Certain types of known FCC equipment is a riser present the catalyst and the product vapors together into an expanded chamber, which is commonly referred to as Part of the reactor is considered, in which the catalyst separated from the product and collected. The continued Contact the catalyst with non-cracked starting material (if any) and cracked products in such an extended chamber leads to a catalytic converter Starting material total contact time, which is noticeably above the Riser residence times of the vapors and the catalysts is. If the inventive method with a ballistic separation of catalyst and vapors at the downstream end (for example, at the top) of the riser, as described in the above-mentioned Myers et al. described is, then the riser residence time and the catalyst contact time for a major part of the starting material and the Product vapors are essentially the same. It will be beneficial considered when the steam riser residence time and the steam Catalyst contact time for at least 80, preferably at least 90, and in particular at least 95 vol .-% of the entire starting material and of the product vapors containing the Risers happen to be essentially the same. By the prevention continuous contact of these vapors with the catalyst in a catalyst separation and collection chamber the tendency to re-cracking and reduced selectivity be avoided.  

In general, the combination of catalyst to oil ratio, Temperatures, pressures and residence times are aligned be that one has an essential transformation of the carbo-metallic Oil starting material causes. It is an advantage the process of the invention that in a single pass very high levels of conversion can be achieved; for example the conversion can be over 50% and up to 90% or more. Preferably, the above-mentioned Conditions are kept at such levels that are sufficient around the conversion in the range of 60 to 90% and preferably to keep in the range of 70 to 85%. The These conversion values are calculated by subtracting from 100% deducts the percentage by dividing the liquid volume of the fresh starting material by the hundredfold of the volume of liquid Product boiling at or above 221,1 ° C (wS, Standard atmospheric pressure).

These considerable conversion values can become relatively large Yields of coke lead, which usually happens, for example to yields of 4 to 14 wt .-%, based to fresh starting material, more often from 6 to 12%, and mostly from 6 to 10%. The coke yield can be deposit more or less quantitatively on the catalyst. at eligible catalyst to oil ratios, the obtained Coke deposit more than 0.3, more often more than 0.5, and usually more than 1 wt .-% coke, based on the Weight of regenerated, moisture-free catalyst, amount. Such coke deposition can be at 2% or 3%, or even higher.

As with conventional FCC methods with VGO, the present invention includes Reverse the stripping of spent catalyst the separation of the catalyst from the product vapors. With the Those skilled in the art are familiar with suitable stripping means and suitable conditions for stripping spent Catalyst, however, the inventive method can in make a few stricter conditions necessary in some cases,  than previously used. This can be done, for example, by the Use of a carbo-metallic oil, the ingredients which is under the conditions prevailing in the reactor do not volatilize and get these ingredients even, at least partially, settle on the catalyst. so adsorbed, unvaporized material can at least in two ways View disturbing. When the gases (including the Vapors) used to strip the catalyst in can enter a catalyst separation or collection chamber, which is connected to the downstream end of the riser, and if in such a chamber an accumulation of catalyst is present, first of all, the evaporation of this unevaporated hydrocarbons must be followed in the stripper of adsorption thereof on the catalyst bed which is located in the chamber. When the catalyst is in the stripper of freed of adsorbed starting material, the obtained Feedstock vapors pass through the catalyst bed, the accumulated in the catalyst collection and / or separation chamber has, and in the form of coke and / or condensed material deposit on the catalyst bed. Because of these deposits carrying catalyst from the bed into the stripper and from There in the regenerator can move, the condensed products require a larger stripping capacity during the Coke increased regeneration temperatures and / or a larger Regeneration capacity may be necessary. From the above mentioned reasons, preferably the contact between the Stripping and the catalyst accumulations in the catalyst separation or collection chamber prevented or restricted. apart from a catalyst amount consisting essentially of the Circuit fails and at the bottom of the separation and / or collection chamber This can be done, for example, by that the formation of such enrichments is prevented by, for example, the circulating catalyst immediately after weaning on the bottom of this chamber this chamber removed. At the same time, it may be appropriate such time, temperature and atmosphere conditions in the Apply strippers sufficient to potentially volatile  Hydrocarbon material derived from the stripped catalyst is carried down to 10% by weight or less, based on the total weight of carbon on the Catalyst to the regeneration temperatures and the regeneration capacity to keep to a minimum. Such For example, stripping can reheat the catalyst an extensive stripping with steam and the use of Include gases that have a higher temperature than they usual for FCC / VGO process control, such as Flue gas from the regenerator, as well as other refinery gas streams, as hydrotreater off-gas (H₂S-containing), hydrogen and other gases. For example, the stripper may be at a temperature of 551.7 ° C or at higher temperatures operate.

The essential transformation of carbo-metallic oils to lighter ones Products according to the present invention, rightly so high coke yields and significant coke deposition lead on the catalyst, and requires some care at the catalyst regeneration. To be sufficiently effective the zeolite-containing and non-zeolite-containing catalysts It is desirable to keep the catalyst under to regenerate such time, temperature and atmospheric conditions, which are sufficient to the percentage by weight to carbon remaining on the catalyst 0.25% or less, regardless of whether the catalyst a large accumulation of heavy metals or not. Preferably, this percentage weight fraction is 0.1% or less, and more preferably 0.05% or less, in particular in zeolite catalysts. The quantities of coke, therefore must be burned away from the catalysts when carbo-metallic Oils are usually substantial greater than in the case of cracking VGO. In the context of the present Invention is the term "coke" also any residual, unevaporated starting material or cracking product when such material after stripping on the Catalyst remains.  

The regeneration of the catalyst, that is the burning away on the catalyst during the conversion of the starting material settled coke, can be at any suitable temperature in the range of 593.3 ° to 871.1 ° C, measured at the Regeneratorauslaß for the catalyst. This temperature is preferably 648.9 ° to 815.6 ° C, in particular 690.6 ° to 773.9 ° C, and they is most preferably 718.3 ° to 746.1 ° C. The inventive method is for example with a flow regenerator at a temperature the dense catalyst phase in the range of 704.4 ° up to 760 ° C has been performed.

If regenerated catalyst for cracking carbo-metallic Oil was used, it was previously believed that the success cracking of the burning of the coke in contact with the Combustion-generating gases containing excess oxygen, is dependent. By the term "excess oxygen" meant such an amount of oxygen be greater than the stoichiometrically required amount to burn all hydrogen, all carbon and all other combustibles, if any is present, which is selected within the above-mentioned Coke content are present immediately before regeneration. The gaseous products of combustion, which in the presence of excess Oxygen is normally carried out include a significant amount of free oxygen. This free Oxygen is, if not by means or another  Process as the regeneration removed from the by-product gases or converted into any other form, usually as free oxygen in the regenerator system coming flue gas occur. In order for sufficient driving force to complete the combustion of the coke to low Maintained if all the coke or a major portion the coke is burned with excess oxygen, Normally, the amount of free oxygen will not just be be noticeable, but considerable, that is, in the whole Regeneration flue gas coming from the entire, closed Regeneration level is obtained, a concentration free oxygen of at least 2 mol .-% present. While such a method is effective to achieve the desired low To obtain carbon contents on the regenerated catalyst, it is subject to restrictions and difficulties arise on, as will be explained in more detail below.

In conventional practice, combustion of the coke during regeneration produces some H₂O, as usually one small amount of hydrogen is present in the coke; however, will be in general, carbon monoxide and carbon dioxide as the main products considered. The conversion of the carbon content of the coke into Carbon monoxide and carbon dioxide are highly exothermic reactions. For example, the reaction between oxygen and Coke with formation of carbon dioxide 32 816 kJ / kg coke, while the reaction between oxygen and Coke or carbon to form carbon monoxide approximate 9228 kJ / kg coke produced. The bigger the amount of coke is that of a given catalyst Weight has to be burned away, the bigger the while the amount of heat released by the combustion in the regenerator.

The liberated in the regenerator by the combustion of the coke Heat is absorbed by the catalyst and can easily be removed by This is withheld until the regenerated catalyst is brought into contact with fresh starting material. at the processing of carbo-metallic oils up to relatively  high degrees of conversion, in the context of the present invention can be achieved, the amount of regenerator heat, by the recycling of the regenerated catalyst to the fresh Starting material is transferred, the extent of that heat Substantially exceed, which is suitable to in the Riser to heat the starting material and other materials and to vaporize the heat for the exothermic cracking reaction To make available to compensate for the heat losses of the plant and the same. According to the invention, therefore, on the fresh Starting material transferred Regenratorwärme within certain controlled areas or, if necessary, be restricted. The heat transferred in this way can for example, in the range of 9538 to 2791, preferably from 1395 to 2093, and especially from 361.1 to 1977 kJ / kg of fresh starting material. The above indicated ranges refer to the combined Heat, expressed in kJ / kg of fresh starting material, which through the catalyst to the starting material and the reaction products (between bringing the starting material into contact with the catalyst and the separation of the product from the catalyst) for providing the heat for the reaction (for example for cracking) and the enthalpy difference between the products and the fresh starting material is transferred. In the above indicated areas are not included the heat, in the reactor by the adsorption of the coke on the catalyst is provided, nor the heat that is consumed is by heating, evaporating or reacting the Recycle streams and supplied materials such as water, water vapor, Naphtha and other hydrogen donors, fumes and Inert gases, or by radiation loss or other losses.

It may be a method or a combination of methods according to the invention applied to the over the catalyst the fresh starting material transferred regeneration heat amount  to control or limit. For example, you can add a combustion promoter to the cracking catalyst to produce the Combustion temperature of coke to carbon dioxide and / or carbon monoxide in the regenerator. Furthermore you can Catalyst through heat exchanger extract heat, including for example, by heat exchangers (for example, steam queues), which are installed in the regenerator itself, whereby heat is removed from the catalyst during the regeneration can. The heat exchangers may also be in the catalyst transport lines be incorporated, for example, in the of Regenerator to the reactor running catalyst recirculation line, wherein the catalyst after its regeneration heat can be withdrawn. The catalyst abandoned in the regenerator Amount of heat can be reduced by the Isolation of the regenerator reduced so that heat loss takes place to the surrounding atmosphere, especially if provided is, starting materials with an extremely high coking potential to edit; however, heat loss generally occurs to the atmosphere in economic terms as less considered appropriate, as other alternatives described here. Furthermore, it is also possible to feed cooling liquids into the reactor, For example, water and / or water vapor, wherein the amount inert gas contained in the regenerator for heat absorption and Distance is available is increased.

Regardless of whether the methods described above are used, For example, the present invention includes a method of control or limitation of the returned, regenerated Catalyst transferred to the fresh starting material heat by maintaining a certain relationship between the carbon monoxide that is in the regenerator be formed while these gases with the catalyst, which is regenerated in a heat exchange contact or relationship stand. In general, all coke or a Main weight fraction of coke on the catalyst immediately is present before regeneration, in at least one combustion zone removed, in which the above ratio is controlled as described below. In particular is at least a major portion, preferably at least  65 wt .-%, and in particular at least 80 wt .-% of Coke on the catalyst removed in a combustion zone, in which the molar ratio of CO₂ to CO at a value is kept substantially below 5, for example at 4 or less. Considering the CO₂ / CO ratio of the other side, so is the molar CO / CO₂ ratio preferably at least 0.25, in particular at least 0.3, and most preferably 1 or more, or even 1.5 or more. While the professional knows ways and means to to inhibit the combustion of CO to CO₂ has been proposed that the molar ratio of CO to CO₂ kept below 0.2 If you want a catalyst with one regenerated high heavy metal enrichment, resulting from the processing derived from carbo-metallic oils. In this context For example, US Pat. No. 4,162,231 issued to Zrinscak, Sr. et al. to be named. According to the invention, however, the Maximizing CO generation is a particularly preferred embodiment in the regeneration of the catalyst to a carbon content of 0.1% or less, preferably 0.05% Or less. In addition, the regeneration by-pass process in its entirety, according to a preferred implementation of the invention, to the above-mentioned low carbon contents on the regenerated catalyst with a deficiency of oxygen be performed; In particular, the one to the one or total oxygen supplied to the plurality of regeneration stages preferably less than the stoichiometric amount, which is required to all hydrogen in the coke to H₂O and to burn all the carbon in the coke to CO₂. If the coke contains other combustible ingredients, the be stoichiometric amount set so that the amount of oxygen needed to burn these components is included.

Another, also particularly preferred method of control and restriction by the recycled catalyst transferred to the fresh starting material amount of heat includes the discharge of a portion of the heat that is returned from the  Catalyst is carried by, in addition to the Reactor introduced materials such as water, water vapor, Naphtha or other hydrogen donors, flue gases, Inert gases and other gaseous and vaporizable materials, which can be introduced into the reactor.

The greater the amount of coke that is of a catalyst given weight must be burned away, the greater the danger of leaving the catalyst at excessive temperatures exposes. Many otherwise desirable and suitable cracking catalysts are against deactivation at high temperatures especially sensitive, and among these catalysts there are a considerable number of expensive molecular sieve or zeolite Catalysts. The crystal structures of zeolites and the Pore structures of the catalyst supports are generally opposite sensitive to thermal and / or hydrothermal degradation. The use of such catalysts in catalytic Conversion process of carbo-metallic starting materials creates a need for regeneration processes which the catalyst is not destroyed by the fact that he very much high temperatures and water vapor is exposed. This need can with a multi-stage regeneration process be countered, which is the feed of a first regeneration zone with the spent catalyst and the supply of includes oxidizing gas. The amount of oxidizing gas, which in this first zone is introduced, and the concentration of oxygen or oxygen-carrying gas is sufficient only to the desired Conversion of the coke on the catalyst to carbon dioxide gases partially effect. The partially regenerated catalyst is then removed from the first regeneration zone and introduced into a second regeneration zone. The oxidizing Gas is introduced into the second regeneration zone to a higher concentration of oxygen or oxygen-containing gas to provide as in the first zone, and the distance of the carbon to the desired degree. The regenerated catalyst can then from the second Zone away and to contact with fresh starting material in  be returned to the reactor. An example of such Multi-stage regeneration process is described in US-PS 29 38 739 described.

The multi-stage regeneration offers the possibility of combination a regeneration with a deficit of oxygen and the control of the molar CO: CO₂ ratio. So can 50% by weight or more, preferably 65 to 95% by weight, and especially 80 to 95% by weight of the catalyst coke in. immediately before regeneration one or more regeneration stages are removed, in which the molar ratio of CO: CO₂ to the above described Way is controlled. In conjunction with the above statements can the last five percent by weight or more or also 10 wt .-% or more of the original coke up to the total amount of coke after the previous one Stage or previous stages is to be removed in a subsequent regeneration stage, in which more oxygen is present. Such a procedure can be carried out so that the entire flue gas, the from the complete, completed regeneration process is obtained, little or no surplus Contains oxygen, that is of the order of 0.2 mol% or less, or even 0.1 mol% or less, which is considerably less than those suggested elsewhere 2 mol%. As a result, the multi-stage regeneration is so far especially valuable, as they another, suitable procedure to limit the heat of regeneration, regenerated by the Transfer the catalyst to the fresh starting material is, and / or reduce the risk of thermal Disactivation represents, while at the same time the possibility consists of the carbon content on the regenerated catalyst to the very low percentages (for example 0.1% or less), which is the catalyst efficiency improve considerably. In addition, the one becomes  Part of the regeneration sequence, in which the hottest Conditions prevail, while still a noticeable Amount of coke on the catalyst is present when the regeneration conditions, for example the temperature or the atmosphere, in the second zone are much less spicy than in the first zone (for example at least 5.6 ° C and preferably at least 11.1 ° C). Such a process procedure can protect the catalyst pose in the strict conditions. A particularly preferred Embodiment of the invention consists in a two-stage Flow regeneration at a maximum temperature of 815.6 ° C with a reduced temperature of at least 5.6 or 11.1 ° C in the dense phase of second stage, compared to the dense phase of the first stage, and with a reduction of the carbon on the catalyst to 0.05% by weight or less or even 0.025% by weight or less in the second zone. In fact, the catalyst can by this method easily to carbon contents of 0.01 wt .-% to be regenerated, even if the carbon on the catalyst prior to regeneration as high a value as 1% has.

In some cases, it is important to make sure that none Adsorbed oxygen-containing gases through the recycled Catalyst can be dragged into the riser. When ever such a measure is considered necessary, the catalyst, which is removed from the regenerator, with appropriate Stripping gases for removing the oxygen-containing gases of a stripping step be subjected. The stripping can, for example, at relatively high temperatures, for example, at 732.2 ° to 743 ° C, using Water vapor, nitrogen or any other inert gas as Stripping gas (s) are performed. The use of nitrogen or other inert gases is favorable in so far as doing the Danger of hydrothermal catalyst deactivation avoided which can occur when using Wasserdasmpf.  

The following remarks concerning the metal, carbon and heat management or process guidance should help to achieve the best results in the implementation of the present invention. As these comments are largely to refer to the procedure, which is considered the best is to be expressed thereby, that the invention is not limited to the process guides described below is limited. As some of these remarks necessarily based on theoretical considerations, should continue be expressed that thereby no binding It is intended to some theory, whether it be here explicitly mentioned or implicit in the subsequent proposals for the conduct of the procedure.

Although the metal, carbon and heat management or procedure subsequently separately addressed and are discussed, they are interconnected and different from each other dependent objects, both in theory and in the Practice. While the coke yield and coke deposition on the Catalyst primarily by the relatively large amounts of Coke precursors are created in the carbo-metallic Oils are present, the coke is produced by high metal enrichment aggravates, which in turn also one considerable negative impact on catalyst performance can have. In addition, the and carbon handling / process management achieved a level of success a direct influence on the extent to which a Heat process control is necessary have. Finally have steps that support the metal handling or been found to be very helpful in With regard to carbon and heat management or process management proved.

As mentioned above, the presence of a large one tends to be great Heavy metal accumulation on the catalyst to a complication the problem of dehydration and aromatic condensation, what leads to an increased production of gases and coke, at one  Starting material of a given Ramsbottom carbon value. The introduction of considerable amounts of H₂O in the reactor, either in the form of water vapor or in the form of liquid Water, seems extremely favorable in terms of heavy metals to keep it in a less harmful form, that is in the oxide form instead of the metallic form. It will be at the same time supporting the maintenance of the desired selectivity.

Similarly, a system in which the system components and Residence times are selected so that the ratio of Catalyst reactor residence time to catalyst regenerator residence time be suitable for the periods of time during which the catalyst under reducing conditions or oxidation conditions is maintained. This can likewise the maintenance of desired selectivity levels support.

Whether the metal content of the catalyst successfully handled can, by monitoring the total generated hydrogen plus methane in the reactor and / or the ratio of hydrogen to methane, which are produced in this way observed become. In general, the molar ratio of Hydrogen to methane less than about 1, preferably about 0.6 or less, with a value of about 0.4 or less than is considered optimal.

Careful carbon handling and management can be both the selectivity (the ability to increase the production of to maximize valuable products) as well as heat productivity improve. In general also support the above described method for controlling the metal content of the Carbon handling or process management. The expediency the addition of water with regard to the carbon process is already detailed in the paragraphs above been described, dealing with additional materials for Introduction to the reaction zone. In general, should those processes involving the dispersion of the starting material  in the reaction zone, also helpful turn out; These methods include, for example, the Application of misting devices to the dispersion of the starting material.

The ratio of catalyst to oil is also one in the Thermal process factor to be considered. As with the conventional FCC practice of VGO, the reactor temperature can be at the implementation of the present invention thereby controlled be that one the flow of hot regenerated catalyst as appropriate, increased or decreased to the reactor temperature In the case of a riser reactor typically is the outlet temperature. If the automatic control device for catalyst introduction is set so that an excessive ratio of Catalyst to oil is maintained can be expected that unnecessarily large amounts of carbon produced and unnecessary large amounts of heat are released with respect to the Reaction zone fed fresh starting material.

With regard to carbon handling and process management Relatively high reactor temperatures are also considered favorable considered. Such higher temperatures favor a more complete one Evaporation of the starting material and separation of the Product from the catalyst.

Carbon handling or process management may be carried out by appropriate means Restriction of the total pressure in the reactor and the Partialdruckes the starting material are also facilitated. For a given degree of conversion, in general, relative small decreases in the above-mentioned pressures already to a considerable extent Decrease in coke production. This may possibly be be attributed to the fact that the restriction of the Total pressure to increased evaporation of the high-boiling Components of the starting material that promotes cracking and the separation of both unreacted starting material and higher boiling, cracked products from the catalyst.  In this regard, it can also be helpful to Pressure drop downstream with respect to the reactor and associated with the reactor equipment restrict. However, if it is desirable or necessary to run the system at a higher total pressure, for example Operational constraints (e.g. because of a pressure drop of the downstream equipment), The advantages described above can also be achieved thereby Be sure to set the starting material partial pressure restrictions subjects. Suitable ranges for the total reactor pressure and the starting material partial pressure are already mentioned above been, and it is generally desirable to try the pressures within these areas to a minimum hold.

The abrupt separation of the catalyst from product vapors and unreacted starting material (if any is) also a great help. For this reason is the so-called ventilated riser device and technique, disclosed in US Pat. Nos. 4,070,159 and 4,066,533 to George D. Myers et al., The preferred type of device for performing the inventive method. For similar reasons it is advantageous between the separation of the catalyst from the Product steaming and the beginning of stripping time passing shortened as much as possible. The application of a ventilated Risers and prompt stripping give less cause for coking unreacted starting material and higher boiling, cracked products adsorbed on the catalyst.

A particularly expedient procedure with regard to the carbon handling or procedure is the procedure in the ventilated riser using a Hydrogen donors, if necessary, perform while the starting material partial pressure and the total reactor pressure as low as possible, and relatively large amounts of water, Steam and, if desired, other diluents introduces the numerous benefits discussed above  have as a consequence. When liquid water, water vapor, hydrogen Donors, hydrogen or other gaseous or vaporizable Materials are introduced into the reaction zone, which allows Addition of these materials beyond, an additional control the ratio of catalyst to oil exercise. Therefore For example, the practice of increasing or decreasing the Ratio of catalyst to oil at a given increasing or decreasing amount of reactor temperature decreases or can be omitted by either a suitable humiliation or increasing the proportion of water, water vapor and other gaseous or vaporizable materials or, suitably, the ratio of water to steam and / or other gaseous materials entering the reaction zone introduced, reduced or increased.

The heat treatment or process comprises measures which are taken to different sections of the Control the amount of heat released and / or order Such heat as it can be released succeeds to handle. In contrast to the conventional FCC practice under Using VGO where it generally poses a problem while the regeneration to generate enough heat to heat balance in the reactor, the processing of carbo-metallic oils generally have so much heat that one careful handling and process control of the heat necessary becomes.

The heat treatment can be facilitated by various methods which are related to the materials introduced into the reactor. Thus, the heat absorption by the starting material be brought to a maximum when preheating the starting material is kept to a minimum, only necessary is that the temperature of the starting material is so high that it is sufficiently liquid to be pumped into the reactor and to be dispersed there. If the catalyst in one highly active state and the coking is suppressed (Metal control), to achieve higher conversions, the  obtained higher conversion and greater selectivity heat absorption increase the reaction. In general, favor higher reactor temperatures increase catalyst conversion efficiency with regard to more heat-resistant and higher-boiling constituents high coking potential. While so does the catalyst deactivation rate can be increased, the higher process temperature tends to compensate for this loss of effectiveness. Higher temperatures in the reactor also contribute to enlargement the octane number and thus equal to the octane degrading Effects of high carbon capture. Other Methods for the absorption of heat have already been mentioned above with the introduction of water, steam and others gaseous or vaporizable materials are discussed in the reactor.

Sharp stripping and various regeneration methods described above are suitable for controlling the heat release in the Raktor. While the removal of heat from the catalyst in the regenerator or at a downstream point, in relating to the regenerator, by heat exchangers (including Steam queues) as a way to control the released Heat has been proposed is the procedure described above the multi-stage regeneration and control of the CO / CO₂ ratio (either in a single-stage or in a multi-stage Regeneration), however, considered more advantageous. The application of steam snakes can be considered as a sort of own goal be as a steam coil or a heat exchanger in the regenerator or in a catalyst recycle line generally an increase in catalyst-to-oil Ratio and an increase in carbon production in the reactor and the heat release in the regenerator result.

As mentioned above, the invention may be practiced in the ways described above and in many other ways. Two exemplary embodiments are explained in more detail with reference to the schematic diagrams of FIGS. 1 and 2 and with reference to the following descriptions thereof, but this does not mean any restriction.

Fig. 1 shows a schematic diagram of a plant for carrying out the method according to the invention. The carbo-metallic oil feedstock (which may have been heated in a raw material pre-heater, not shown) and water supplied through the supply line 9 (if used) are fed through the feedstock supply line 10 , which has a check valve 11 , into a C 12 , where they are mixed with a catalyst flow supplied through the supply line 13 , controlled by the valve 14 . Of course, a variety of different mixing devices may be employed, and devices may further be provided to introduce the other additional materials discussed above. The mixture of catalyst and starting material, with or without such additional materials, is then introduced into the riser 18 .

Although the riser 18 is shown vertically in the drawing, it will be apparent to those skilled in the art that the riser need not necessarily be vertical since riser reactors are known in which a fair amount of the riser is not disposed vertically. Thus, riser tubes with an upwardly directed directional component are contemplated, and usually the upward component of their upwardly flowing inclined portions is substantial, that is, at least 30 °. There are also known risers which have downwardly flowing, inclined or vertical sections as well as horizontal sections. Furthermore, folded risers are known which have both upwardly and downwardly extending portions. Finally, it is possible to carry out the process according to the invention in an inclined and / or vertically arranged tube, into which the starting material and the catalyst are introduced from above, and in which the starting material and the catalyst under the influence of gravity and the outflow of the Move starting material down to a lower level. In the context of the present invention are generally those reaction chambers in question, which have a large L / D ratio, and where there is a significant deviation from the horizontal.

At the upper end of the riser 18 , a chamber 19 is arranged which receives the catalyst coming out of the riser. While the chamber 19 may be a conventional separation and collection chamber, means are preferably provided to force the product struggles to make a sufficient change in direction with respect to the direction taken by the catalyst particles, thereby suddenly and efficiently separating the vapors from the catalyst. Preferably, as described above, a "ballistic" separation of the catalyst particles from the product vapors is made.

In the schematic diagram, the separation chamber 19 comprises an upwardly directed extension 20 of the riser tube 18 with an open upper end 21 through which the catalyst particles are removed. In this embodiment, use is made of the so-called ventilated riser disclosed in the Myers et al. Patents described above. is described. Because of the refractory nature of the carbo-metallic fractions, relatively severe conditions are required, but rapid separation of the catalyst from the lighter cracked products in the vented riser prevents overcracking of the desired liquid products, such as gasoline, to gaseous products. The product vapors are forced to make a sudden change in direction through the side opening 22 located in the side of the riser extension 20 , the majority of the catalyst particles being unable to follow the product vapors into the opening 22 .

The vapors and the few particles that have succeeded in following the vapors into the opening 22 are transferred by the cross-line 23 into a cyclone separator 24 . It is an advantage of the illustrated ventilated riser system that it can operate satisfactorily with a single stage cyclone separation device. However, in the present embodiment, the cyclone separator 24 is used as a first cyclone separator connected to a selectively disposed second cyclone separator 25 via a transfer line 17 . The cyclone separator, whether single-stage or multi-stage, separates those small amounts of catalyst from the product vapors which have been able to pass through the side opening 22 . The product vapors are removed from the separation chamber 19 through the product discharge line 26 .

The catalyst particles discharged from the open upper end 21 of the riser extension 20 and those catalyst particles discharged from the discharge legs 27 and 28 of the first and second cyclones 24 and 25 , respectively, fall on the bottom of the separation chamber 19 . The catalyst inventory and the residence time of the catalyst in the chamber 19 are preferably kept to a minimum. During startup, the catalyst particles present can be kept in limbo by loosening nozzles 30 , which are supplied with steam via the steam feed line 29 . From the bottom of the separation chamber 19 overflowing, spent catalyst passes through the downpipe 31 in a stripper chamber 32 which is equipped with baffles 33 and into which a steam jet 34 leads. Any other stripping gas mentioned above can be used with or instead of water vapor.

The carbon is, wegggebrannt the combustion device 38, in which the treated catalyst by stripping through the downcomer 39 and the check valve 40 is received from the surface of the catalyst. The fans 41 and 42 , in conjunction with a valve and piping system, generally designated by reference numeral 44 , provide the air for the combustion air nozzles 48 at the bottom of the combustor and for the loosening nozzles 49 which are located at a higher position. A preheater 43 may be employed when starting up the plant with VGO, although the preheater is usually not needed when processing heavy hydrocarbons in accordance with the present invention; then, when the plant is switched to carbo-metallic feedstock, the operation of the preheater can be stopped (or at least limited). Additional fuel means may be provided to supply fuel through the combustion air nozzles 48 ; however, it is usually not necessary because the carbon precipitate on the catalyst provides more than enough fuel to maintain the temperatures required in the regeneration section. The regenerated catalyst from which most of the carbon has been burned leaves the combustor through an upper outlet 50 and passes through a transverse conduit 51 into a second chamber 52 where it is deflected by means of a baffle 53 into the lower part of the chamber. Although the use of two-stage regeneration is possible and preferred, in this particular embodiment, the second chamber 52 serves primarily as a separation chamber, although it may be used to further carbon down to 0.01% or less in the final stages to remove the regeneration.

The catalyst may be supplied from the second chamber 52 in up to three different directions. A portion of the catalyst may be returned to the combustor 38 via the catalyst recirculation loop 55 and the control valve 56 to control the heat in the combustor. A portion of the catalyst is entrained by the product gases, such as CO and / or CO₂, produced by burning the carbon on the catalyst in the combustor, and the entrained catalyst dust passes in the upper portion of the chamber 52 to two sets of first and second Cyclones, generally designated by reference numerals 57 and 58 , in which this catalyst dust is separated from the combustion gases. The catalyst discharged in the cyclones 57 and 58 and through their downcomers is directed to the bottom of the chamber 52 where the catalyst is suspended by inert gas and / or water vapor nozzles 59 and baffle assembly 54 , the latter being the discharge of regenerated catalyst through the outlet 69 into the catalyst replenishment line 13 , through which it is recirculated for contact with fresh feedstock in the C-piece 12 as described above.

The combustion product gases produced by regeneration of the catalyst and separated from the entrained catalyst dust by the sets 57 and 58 at primary and secondary cyclones in chamber 52 are exhausted through the exhaust conduits 61 and 62 and the heat exchangers 60 and 63 . Since these gases contain significant amounts of CO 2, they may be fed via the gas feed 64 into an optional furnace 65 in which the CO is burned to heat the heating coil 66 connected to the steam boiler 67 . Additional heat may be supplied to the contents of the boilers through the conduit loop 68 , which circulates liquid from the boiler 67 to the heat exchangers 60 and 63 and back to the boiler. This, of course, is only one of many possible examples of regeneration systems. The heat returned from the regenerator via the regenerated catalyst to the riser may be controlled in any other manner as described above; however, the present invention controls the relative proportions of carbon monoxide and carbon dioxide that are produced while the catalyst is in heat exchange relationship with the combustion gases resulting from the regeneration. The same method is also implemented in the particularly preferred embodiment illustrated by FIG. 2.

In Fig. 2, reference numeral 80 stands for a raw material control valve in the raw material supply line 82 . Through the feed line 83 (if needed), liquid water is fed into the feedstock. A heat exchanger 81 disposed in the supply line 82 serves as a raw material preheater, whereby preheated starting material can be fed into the bottom of the riser reactor 91 . The catalyst is passed into the reactor through the catalyst standpipe 86 , the catalyst flow being regulated by a check valve 87 and an appropriate automatic control device (not shown) familiar to those skilled in the art of planning and operating riser crackers. The riser 91 may optionally include means for injecting water, water vapor and, if desired, other gaseous and / or vaporizable materials for the purposes mentioned above. The reactor is equipped with a separation chamber 92 similar to the separation chamber 19 of the reactor shown in Fig. 1, and thus the embodiment of Fig. 2 comprises means for forcing the vapors to change direction for a sudden and effective separation from the catalyst as in the embodiment described above. The catalyst exits the separation chamber 92 through the stripper 94 which operates in a similar manner to the stripper 32 shown in FIG . The spent catalyst passes from the stripper 94 through the spent catalyst transfer line 97 , which has a check valve 98 to control flow, into the regenerator 101 .

The regenerator 101 is divided into an upper chamber 102 and a lower chamber 103 by a partition plate 104 mounted between the upper and lower ends of the regenerator. The spent catalyst coming from the transfer line 97 enters the upper chamber 102 , in which the catalyst is partially regenerated. A funnel-shaped collector 106 having a slanted upper edge receives the partially regenerated catalyst from the upper surface of the dense phase of the catalyst in the upper chamber 102 and introduces it through the downcomer 107 with an outlet 110 below the upper surface of the dense phase of the catalyst the lower regeneration chamber 103 . Instead of the internal catalyst downpipe 107 , it is also possible to use an externally attached downpipe. Valves in such an externally mounted downcomer can control catalyst residence time and flow rate in and between the upper and lower chambers.

Through the air supply line 113 , the air is brought to the regenerator. A portion of the air passes through a branch supply line 114 to the bayonet 115 which extends upwardly into the interior of the storage space 111 along the central axis thereof. The catalyst in chamber 103 has access to the space within the storage space 111 between its side walls and the bayonet 115 . A narrow (not shown) bayonet in the mentioned space relaxes the catalyst and forces it upward against a horizontally disposed ring manifold (not shown) at the open end of the storage space 111 which opens into the chamber 103 . The remaining air, which is supplied through the air supply line 113 , can be heated in an air heater 117 (at least during start-up with VGO) and then introduced through the inlet 118 of the above-mentioned ring manifold, which is provided with holes, nozzles or other openings, which generate an upward gas flow to agitate the partially regenerated catalyst in chamber 103 .

The air supplied in this way completes in chamber 103 the regeneration of the partially regenerated catalyst obtained from the downpipe 107 . The amount of air supplied is sufficient so that the air and / or the combustion gases obtained are still able to assist combustion when they reach the top of the chamber 103 . The above-mentioned drop tube 107 extends through an enlarged opening in the partition plate 104 , on which a gas distributor 120 is arranged, which is arranged concentrically with respect to the downpipe and surrounds it. Through the gas distributor 120 , the combustion-sustaining gases now partially depleted in combustion-sustaining gas pass into the upper regenerator chamber 102 where they are contacted with the spent catalyst from the transfer line 97 for its partial oxidation. Apertured probes or other suitable means in the gas distributor 120 assist in the uniform distribution of the partially combustion-sustaining gas-depleted gas in the upper chamber 102 . Additional air or other fluid may be introduced into the upper chamber 102 , if desired, through the supply line 122 which leads into or through the gas distributor 120 . Completely regenerated catalyst having less than 0.25% carbon, preferably less than 0.1%, and more preferably less than 0.05%, is discharged from the lower regenerator chamber 103 through a regenerated catalyst stripper 128 , the outlet of which is in the above-mentioned Catalyst leased line 86 leads. In this way, the regenerated catalyst is returned to the riser 91 for contact with further fresh feed material supplied via the feedstock feed line 82 . Any heat received by the recycled catalyst in the regenerator 101 is available for transfer to the fresh feedstock in the riser.

The partitioning of the regenerator into upper and lower regeneration chambers 102 and 103, respectively, not only compensates for variations in the catalyst-regenerator residence time, but also provides unique assistance in limiting the amount of regeneration heat transferred to the fresh stock while at the same time regenerated catalyst with low residual carbon values for recycle to the reactor. Due to the location of the regenerator, spent catalyst from transfer line 97, with its high carbon content in chamber 102, contacts the combustion assisting gases which are at least partially depleted of oxygen by burning the carbon from the partially regenerated catalyst in the lower regenerator chamber 103 . For this reason, it is possible to control both the combustion and the amount of generated carbon dioxide in the upper regenerator chamber 102 . Although the air or other regeneration gas supplied through the air supply line 113 and the branch line 114 may contain a relatively large amount of oxygen, some of the carbon of the partially regenerated catalyst with which they come into contact in the lower regeneration chamber 103 is already removed , The high concentration of oxygen and the temperature of the partially regenerated catalyst together are the cause of rapid removal of residual carbon in the catalyst, yielding a clean, regenerated catalyst with a minimum of heat release. So here, too, the combustion temperatures and the CO: CO₂ ratio in the lower regeneration chamber can be easily controlled. The regeneration exhaust gases are discharged from the upper regenerator chamber 102 through the exhaust pipe 123 , the regulation valve 124 , the catalyst dust trap 125, and the outlet 126 .

The product vapors obtained from the separation chamber 92 may be processed in any suitable manner, for example, by discharge through the vapor extraction lines 131 to the inlet of the fractionating column 132 . The said fractionating column comprises a bottom product outlet 133 , a side outlet 134, a flushing oil stripper 135 , a stripper bottom outlet and a discharge line 136 connected to a pump 137 for discharging flushing oil. The top product of stripper 135 is recycled to stripping column 132 via stripping head product recycle line 138 .

The main overhead product discharge line 139 of the fractionating column is connected to the overhead receiver 142 which has a bottom product outlet line 143 which leads to the pump 144 for the removal of gasoline product. If desired, a portion of this product may be recycled to the fractionation column 132 via the recirculation line 145 , the flow being controlled by the recirculation valve 146 . The overhead receiver also includes a water receiver 147 , and a water discharge line 148 . Through the gas outlet 150 of the overhead product receiver, a product stream is discharged, which contains mainly material below C₅, but also some C₅-, C₆- and C₇ material. If desired, the C₅ material and heavier material present in the gas product stream may be separated by pressure, cooling and fractionation and recycled to the overhead receiver with a compressor, condenser and a fractionating column (not shown).

Examples

The following examples are merely illustrative and are not to be construed as limiting the present invention. The data of the catalysts used in these examples are given in Table 2 above.

The practice to date in some refineries includes the mixing of relatively small amounts of carbo-metallic Oils with vacuum gas oils, usually as starting material used for fluid catalytic cracking. It should, however be underlined that the ordinary practice in it consisted of the amounts of carbo-metallic oil in such mixtures to obtain a starting material by relatively low levels of nickel equivalents of heavy metals and by relatively low levels of carbon residue the pyrolysis was characterized. Surprisingly, it has become however, shown that the degree of conversion of carbo-metallic Oils are larger if such oils are in such sufficient quantities be used that the nickel equivalents of heavy metals and the carbon residues have the relatively high levels disclosed herein Achieve values, for example when the amount of carbo-metallic Oil a major weight fraction of the hydrocarbon cracking reactant in the starting material or Include the hydrocarbon cracking reactant in the starting material forms.

Examples 1A-1D

In these examples, essentially the system shown in Fig. 1 and described above is used. Examples 1A through 1C illustrate operation with blends containing various relative amounts of vacuum gas oil (VGO) and topping residues. In Examples 1C and 1D, the operation with a mixture on the one hand and with 100% Topp residue on the other hand compared. With regard to the analyzes of the vacuum gas oils and the top residues, reference is made to the following Table 3. With regard to the operating conditions and the summary of the results, reference is made to the following Table 3.

Comparison of the results of Examples 1A and 1B

At a temperature in the range of 523.9 to 526.7 ° C you get with the system used here is known to have a degree of conversion of 78% when using an equivalent catalyst and VGO is worked, which similar to the vacuum gas oils exemplified in Table 3 is. A comparison of the results of Examples 1A and 1B shows that by assuming that the vacuum gas oil in each mixture too converted to the previously established conversion rate of 78% which is present to a lesser extent (40%) Topp residue converted to only 44% in the experiment of Example 1A while processing a mixture, the a higher proportion of top residue (66%) as in Example 1B, contains a 63% conversion of the top residue is reached. Also noteworthy is the increase in volume yield. Thus, the invention can be used to higher Conversion to top residues and / or higher volume yields to get at very good octane levels when the top-lag is increased in the blends compared to blends significantly larger amounts of VGO and much smaller amounts contained in top residues.

Comparison of the results of Examples 1C and 1D

A comparison of the results of Examples 1C and 1D shows that assuming that the VGO in the mixture of Example 1C converted to the previously determined conversion rate of 78% is converted, the top-back only to 58%, if it makes up 42% of the starting material while up to 64% is converted when it is 100% of the starting material accounts. Again, the increase in percent volume yield remarkable. Thus, the invention can be so applied be higher conversions of top residue and / or increased percent volume yields of liquid products very good octane levels are achievable, if as starting material Topp residues alone are used in comparison  to a mixture of top residue and VGO.

Examples 2 and 3

Using the Topp residue of Example 1D given in Table 3 and using a plant as shown in FIG. 1 and described above, the results given in Table 4 were also given in Table 4 achieved.

Examples 4-6

These examples were carried out using equipment as shown in Fig. 2 and described above. In the operation of this plant as described above and in compliance with the conditions given in Table 4, and using a two-stage regeneration process, the results also shown in Table 4 were obtained.

Examples 7-10

These examples were carried out using a pilot plant and using the starting material, catalyst and operating conditions given in Tables 1, 2 and 4. FIGS. 3 to 5 show the yield in percent by volume of (3) C₃-olefins, (4) C₄-saturated compounds and olefins, and (5) Gasoline, respectively versus conversion in percent by volume, obtained by using the starting materials and Catalysts of Examples 7 to 10 with repetition at different values.

Claims (38)

1. A process for the economic conversion of carbo-metallic oils in lighter products, characterized in that

• I. Providing a conversion raw material containing 343.3 ° C + material, wherein the 343.3 ° C + material is characterized by a carbon residue at pyrolysis of at least 1% by weight and at least 4 parts per million nickel equivalents Contains heavy metal (s);
• II. This raw material for conversion with a cracking catalyst to form a stream comprising a suspension of the catalyst in the starting material, and the resulting stream through a fluidized bed reactor having an elongate reaction chamber which is at least partially perpendicular or inclined, for a predetermined steam -Riser residence time in the range of 0.5 to 10 seconds at a temperature of 482.2 ° C to 760 ° C an absolute pressure of 0.69 to 3.45 bar, which represents a conversion per pass in the range of 50% to 90% is sufficient to flow, with coke in amounts of 6 to 14 wt .-%, based on fresh starting material, forms and deposited in amounts of 0.3 to 3 wt .-% on the catalyst;
• III. separating the catalyst from the obtained cracking products;
• IV. Freeing the separated catalyst by stripping of the adsorbed hydrocarbons;
• V. regenerating the catalyst by combusting the coke in at least one regeneration zone with an oxygen-containing combustion-sustaining gas under conditions of time, temperature and atmosphere sufficient to reduce the carbon on the catalyst to 0.25 wt. to reduce% or less, wherein gaseous combustion products comprising CO and / or CO₂, are formed, and wherein at least the main weight fraction of the coke is burned in one of the regeneration zones, in which the molar ratio of CO: CO₂ at a level of at least 0th , 25 is held; and
• VI. recycling the regenerated catalyst for contact with fresh feedstock to the reactor.

2. The method according to claim 1, characterized in that a 343.3 ° C + material is used which is at least 70 vol .-% of the starting material and at least Contains 10 vol .-% of material which is not below 537.8 ° C boiling. 3. The method according to claim 1, characterized in that a starting material is used whose carbon residue a total Ramsbottom carbon value of at least 1%. 4. The method according to claim 1, characterized in that a starting material is used whose carbon residue altogether a Ramsbottom carbon remainder in the Range from 2 to 12 corresponds. 5. The method according to claim 1, characterized in that a starting material is used, the total at least 4 parts per million nickel equivalents of heavy metal (s) contains, of which at least 2 parts per million Nickel are (as metal, by weight). 6. The method according to claim 1, characterized in that a starting material is used, the total at least 5.5 parts per million nickel equivalents of heavy metal (s) contains. 7. The method according to claim 1, characterized in that Supplementary catalyst is added to lost or replacing catalyst removed from the system, wherein the supplemental catalyst as it is introduced, a Microactivity of at least 60% by volume, and any taken out of the system catalyst, as he removed will, a microactivity of at least 20% by volume.   8. The method according to claim 1, characterized in that the accumulation of heavy metals on the catalyst ranging from 3000 parts per million to 70,000 parts per million nickel equivalents of heavy metal (s), based on the weight and measured on regenerated Equilibrium catalyst is maintained. 9. The method according to claim 1, characterized in that the catalyst used is a zeolite molecular sirb catalyst which contains at least 5% by weight of sieve. 10. The method according to claim 1, characterized in that a predetermined riser residence time of the starting material and the product vapor of 3 seconds or less is selected. 11. The method according to claim 1, characterized in that the temperature in the reactor in a range of 529.5 ° C to 648.9 ° C is maintained. 12. The method according to claim 1, characterized in that the starting material partial pressure or the total absolute pressure is maintained in a range of 0.21 to 2.07 bar. 13. The method according to claim 1, characterized in that the conversion is kept within a range of 60 to 90% becomes. 14. The method according to claim 1, characterized in that the conversion is kept within a range of 70 to 85% becomes. 15. The method according to claim 1, characterized in that it in the presence, in the reaction zone, of additional gaseous and / or vaporized material at a Weight ratio of 0.02 to 0.4 is performed.   16. The method according to claim 1, characterized in that it is carried out without addition of hydrogen to the cracking zone becomes. 17. The method according to claim 1, characterized in that it without previous hydrotreating of the starting material is carried out. 18. The method according to claim 1, characterized in that it without previous removal of asphaltenes from the Starting material is performed. 19. The method according to claim 1, characterized in that it without prior removal of heavy metals the starting material is carried out. 20. The method according to claim 1, characterized in that the cracking reaction is carried out with a catalyst, which has been previously used to be a carbo-metallic Starting material under the conditions specified in claim 1 to crack. 21. The method according to claim 1, characterized in that all starting material for conversion into and the same conversion chamber is cracked. 22. The method according to claim 1, characterized in that the starting material for the transformation in a substantially Single pass method is cracked. 23. The method according to claim 22, characterized in that less than 15% by volume based on the volume of fresh starting material, be recycled.   24. The method according to claim 1, characterized in that the starting material for the transformation with liquid Water at a weight ratio of water to starting material ranging from 0.04 to 0.15 and a stream is formed, which is a mixture from the starting material, the catalyst and water vapor, obtained by the evaporation of the liquid water, contains and to convert this current through the reactor the starting material flows. 25. The method according to claim 24, characterized in that a weight ratio of liquid water to starting material For the conversion from 0.04 to 0.1 is chosen. 26. The method according to claim 24, characterized in that a weight ratio of liquid water to starting material is selected for the conversion of 0.05 to 0.1. 27. The method according to claim 24, characterized in that the water and the starting material before or at the same time with the contacting of the starting material with be brought together the cracking catalyst. 28. The method according to claim 24, characterized in that the water is brought together with the starting material for the conversion is before the starting material for the conversion is brought into contact with the cracking catalyst. 29. The method according to claim 1, characterized in that the catalyst at the end of the predetermined residence time flung in a direction that is through the elongated Reaction chamber or an extension determined by this while the products are giving a lower pulse have to be forced to make a sudden change of direction what an abrupt, essentially instantaneous ballistic separation of the products from the catalyst.   30. The method according to claim 1, characterized in that the starting material for the transformation with liquid water at a weight ratio of water to starting material in the range of 0.04 to 0.15 and brought together a stream is formed, which is a mixture of starting material, Catalyst and water vapor obtained by evaporation of the liquid water, and you can see this stream through the Flow reactor for converting the starting material, wherein the catalyst is at the end of the above-mentioned predetermined Residence time is thrown in one direction, the through the elongated reaction chamber or an extension determined or determined by the latter while the products, which have a lower momentum, to an abrupt change of direction be forced, what an abrupt, im essential instantaneous ballistic separation of Products of the catalyst leads. 31. The method according to claim 30, characterized in that the Regeneration at a temperature in the range of 537.8 ° C to 815.6 ° C is performed. 32. The method according to claim 30, characterized in that Regeneration at a temperature in the range of 690.6 ° C to 773.9 ° C is performed. 33. The method according to claim 30, characterized in that the Catalyst up to a carbon content of 0.1% or less is regenerated. 34. The method according to claim 30, characterized in that the Catalyst up to a carbon content of 0.05% or less is regenerated. 35. The method according to claim 30, characterized in that the Combustion conditions are controlled to the presence excess oxygen, if any is present in the entire flue gas coming out of the  obtained complete, completed regeneration process is limited to 0.2 mol% or less. 36. The method according to claim 30, characterized in that the Combustion conditions are controlled to the presence excess oxygen, if any is present in the entire flue gas coming out of the obtained complete, completed regeneration process is limited to 0.1 mol% or less. 37. The method according to claim 30, characterized in that the Regeneration is carried out so that the catalyst successively through a plurality of regeneration zones leads, with 65 to 95% of the coke, the immediate before regeneration on the catalyst, removed be, wherein the molar ratio of CO: CO₂ on a Level of at least 0.25 is maintained. 38. The method according to claim 30, characterized in that the Regeneration is carried out so that the catalyst successively through a plurality of regeneration zones 80% to 95% of the coke, which is immediately prior to regeneration on the catalyst, are removed, and the molar ratio of CO: CO₂ a level of at least 0.3, and the Catalyst while a carbon content on the catalyst of 0.05 wt% or less is regenerated.