DE3043107A1 - METHOD FOR CONVERTING CARBO METALLIC OIL WITH CONTROLLED CO: CO (DOWN ARROW) 2 (DOWN ARROW) RATIO REGENERATION - Google Patents

Description

Tm generally boiling gasoline and other liquid hydrocarbon fuels in the range of about 37.8 ° to about 343.3 ° C (about 100 ° to about 65O ⁰ F). However, the crude oil from which these fuels are made contains a diverse mixture of hydrocarbons and other compounds that have very different molecular weights and therefore boil over a wide range. There are, for example, crude oils are known in which 30 to 60% or more of the total oil volume composed of compounds boiling at temperatures above 343.3 ° C (650 ⁰ F). Under these crude oils, there are those which bcs'tehen to about 10% to about 30% or more of their total volume of compounds with such high molecular weight that they boil above 551.7 ° C (1025 ⁰ F), or at least not below 551 Boil, 7 ° C (1025 ⁰ F) at atmospheric pressure.

As this relatively abundant, high-boiling component of crude oil for inclusion in gasoline or other liquid hydrocarbon fuels unsuitable, the petroleum refining industry has methods of cracking or breaking up the molecules the high-molecular, high-boiling compounds into smaller molecules, which boil over a suitable boiling range, developed. That about this. The most commonly used cracking process is known as fluid catalytic cracking (FCC). Although the FCC process has reached a very advanced stage and has developed numerous modified forms and variations What they all have in common is that a vaporized hydrocarbon feedstock in a elevated temperature in contact with a cracking catalyst suspended in the feedstock vapors, a cracking process; is subjected. As soon as the desired level of molecular weight and boiling point reduction is reached, the catalyst becomes separated from the desired products.

The crude oil in its natural state contains a large number of materials that have a very disruptive influence on the FCC process and only a portion of these interfering materials can be economically removed from the crude oil.

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Among these interfering materials are coke precursors (such as Asphaltene, non-nuclear aromatics, etc.), heavy metals (such as nickel, vanadium, iron, copper, etc.), lighter metals (such as sodium, potassium, etc.), sulfur, Nitrogen and other substances. Of these materials, certain, such as the lighter metals, can be economically produced Desalination processes will be removed, which is part of the normal process of pretreating crude oil for fluid catalytic cracking are. Other materials, such as coke precursors, asphaltenes, and the like, tend to degrade into coke during the Cracking process, which settles on the catalyst and thereby deteriorates the contact between the hydrocarbon feedstock and the catalyst, and generally the same Reduced performance or activity level. The heavy metals go almost quantitatively from the starting material onto the catalyst surface above.

If the catalyst is reused over and over again to treat further raw material, which is normally is the case, then the heavy metals can accumulate on the catalyst to such an extent that they are unfavorable Way to change the composition of the catalyst and / or the nature of the catalyst effect on the starting material. For example Vanadium tends to form rivers or melts with certain components of commonly used FCC catalysts, wherein the melting point of parts of the catalyst particles is lowered enough that they begin to sinter and the cracking catalysts become ineffective. Enrichments of vanadium and other heavy metals, in particular Nickel, also poison the catalyst. They have different tendencies, excessive dehydration and aromatic condensation to favor, which leads to an 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 fraction of crude oil, or any other oil, that one particularly rich content of nickel and / or other metals that show a similar behavior, and at the same time

relative (containing large amounts of coke precursors is referred to here as Carbo-metallic oil is called, and such an oil represents one poses a particular challenge for the petroleum refinery specialist.

In general, the tendency to coke or the coke precursor content of an oil can be determined by calculating the percent by weight Carbon that remains when a sample of this oil is pyrolyzed. The industry takes this value as a measure of the extent to which a given oil tends to form non-catalytic coke when used as a starting material used in a catcracker. Two established test procedures are recognized, namely the Conradson carbon test procedure and the Ramsbottom Carbon Test Method, the latter being described in ASTM Test No. D524-76. In the Conventional FCC practice uses Ramsbottom carbon values on the order of about 0.1 to about 1.0 as an indication of a considered acceptable starting material. The present invention is concerned with the use of hydrocarbon feedstocks, which have higher Ramsbottom carbon values and thus a much greater potential for coke formation than have conventional starting materials.

Since the various heavy metals do not have the same catalyst poisoning activity, the poisoning activity of an oil containing a given poisoning metal or metals is expediently expressed as the amount of a single metal which is assumed to have an equivalent poisoning activity. Accordingly, the heavy metal content of an oil can be expressed by the relationship given below (model was the relationship of WL Nelson in Oil and Gas Journal, page 143, October 23, 1961), in which the content of each metal present in parts per million thereof Metal, expressed as metal on a weight basis based on the weight of the starting material

V Fe Cu

Nickel equivalents = Ni + - _A -5 · + · = -r + - \ -5- ^

* »Fö '/ ·. i / ' ^J

In accordance with conventional FCC practice, the heavy metal content is determined of the feedstock for the FCC process at a relatively low level, for example about 0.25 parts per million Nickel equivalents or less. The present invention is concerned with the processing of raw materials, which have metal contents significantly above this value and which therefore have a significantly greater potential in terms of Have accumulation on the catalyst and poisoning of the catalyst.

The above relationship can also be used as a measure of the enrichment of heavy metals serve 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. In conventional FCC practice, where a circulating Catalyst inventory is reused over and over again for the treatment of fresh starting material, with periodic or continuous Adding or removing small amounts of fresh or used catalyst, the metal content of the Maintained catalyst at a level which, for example, in the range of about 200 to about 600 parts per million nickel equivalents lies. The inventive method is concerned with the use of catalysts which have a much higher metal content and which therefore have a much greater tendency to compared to the normal case, to promote dehydration, aromatic condensation, gas generation or coke formation exhibit. Such higher metal concentrations are therefore normally considered highly undesirable in the FCC process.

There has been a great deal of interest in the conversion for a long time of carbo-metallic oils in gasoline and other liquid fuels. For example, in the 1950s it was suggested that a variety of carbo-metallic oils are successfully used in gasoline and other products using the Houdresid process can be converted. The Houdresid method

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differs from the FCC process in that it is catalyst particles with "granular grain size" (much larger than the partial. · size of conventional FCC catalysts) in a compact, be used under the influence of gravity moving bed, in contrast to the suspension of catalyst! particles in the starting material and the product vapors in a fluidized bed.

Although the Houdresid process is obviously a step forward meant in terms of the effects of metal contamination and coke formation on the performance of the Catalyst, the productivity of this process was limited. Since its implementation was not economical, the first Houdresid system is no longer in operation. During the 25 years since the Houdresid proceedings have elapsed, the experts have accordingly; their eager search for appropriate modifications and changes of the FCC process, demonstrating a commercially successful application of the process to top residues and the like would allow. During this period, a variety of suggestions have been made, and some of them are up to has been used commercially to some extent.

Some suggestions include treating the heavy fuel oil feedstock, to remove the metal from it before the cracking process, such as hydrotreating, solvent extraction and complexing with Friedel-Crafts catalysts, however, these techniques have been criticized for being uneconomical. Another proposal uses a combined "dirty oil" and "clean oil" unit cracking process. at Another proposal is to mix residual oil with gas oil and the amount of residual oil in the mixture as a function of the flash evaporation equilibrium temperature at the bottom the riser-cracker unit used in the process. Another suggestion is the raw material subjected to a mild, preparatory hydrocracking or hydrotreating stage before entering the cracking unit

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to be led. For the production of gasoline it has also been proposed to use a carbo-metallic oil such as top residue with hot Bringing taconite pellets into contact. This is only a small selection of the proposals found in the patent literature and technical reports have been described.

Despite the great efforts that have been made here, and in spite of the fact that each of these proposals solves some of the difficulties encountered, conventional FCC practice today is a silent witness to the lack of carbo-metallic oil cracking processes, which are both economical and highly practical in terms of technical feasibility. Some crude oils are relatively free of coke precursors and / or heavy metals, and the offending components of the crude oil are mostly concentrated in the highest boiling fractions. It was thus possible to largely avoid the problems caused by the coke precursors and heavy metals by sacrificing the yield of liquid fuel which could potentially be obtained from the highest boiling fractions. In conventional FCC practice, in particular crude oil fraction is as a starting material have been used, the (650 ⁰ F) and about 537,8 ⁰ C (1000 ⁰ F) boiling between about 343.3 ° C, such fractions being relatively free of Koksvorläufer- and heavy metal impurities. Such a, known as "vacuum gas oil" (VGO) feedstock is generally prepared from crude oil by the below about 34 3.3 ⁰ C (650 ⁰ F) boiling fractions distilled off at atmospheric pressure and then a between about 343.3 ° C (650 ⁰ F) and about 482.2 ⁰ C to 551.7 ° C (900 to 1025 ⁰ F) is separated from the heavier fractions by a further vacuum distillation.

The vacuum gas oil is used as the starting material for the conventional FCC processing used. The heavier fractions are usually used for a number of other purposes, such as for example for the production of asphalt, residual heating oil, # 6 heating oil or marine bunker C heating oil, which is a big waste represents the potential value of this crude oil component,

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especially in view of the great effort and expense that one was willing to make to try to get out. ^: Coal and shale oils to produce essentially similar materials. The present invention is based on the object of simultaneously cracking these heavy fractions, which contain considerable amounts of both coke precursors and heavy metals and possibly also of other interfering constituents, in conjunction with the lighter oils, thereby increasing the overall yield of gasoline and other liquid hydrocarbons. : To increase fuels from a given amount of crude oil or crude product. As mentioned above, the present invention ι no means the first attempt,] to develop such a method, however, is the long-standing desire! to subject carbo-metallic raw materials to a cracking process! drag, along with the slow progress of the industry in | in this regard, there is a continuing need for such a process. The method of the present invention appears! uniquely advantageous with regard to the problem of treating i such: carbo-metallic "oils on an economical and technical basis j

i beneficial way. . j

The present invention provides a simple, relatively straightforward, and highly productive process for converting carboj metallic feedstock, such as top residues or the like, to various lighter products such as gasoline. The carbo-metallic starting material comprises or consists of j an oil which boils above about 343.3 ° C (650 ⁰ F). Such an oil, or at least the 343.3 ° C + (650 ° F +) portion thereof, is characterized by a heavy metal content of at least about 4, preferably more than about 5, and in particular at least about | 5.5 parts per million nickel equivalents by weight, j and a carbon residue on pyrolysis of at least about 1 weight percent, and preferably at least about 2 weight percent. According to the invention, the carbo-metallic starting material in the form of a pumpable liquid is brought into contact with a hot conversion catalyst, the weight ratio of catalyst to starting material being in the range from about 3 to about 18 and preferably more than about 6.

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The feedstock in this mixture is subjected to a conversion step which includes cracking while the feedstock / catalyst mixture flows through a fluidized bed reactor. The feedstock, catalyst, and other materials can be introduced at one or more points. The reactor comprises an elongated reaction chamber which is at least partially arranged vertically or inclined and in which the starting material, the products obtained and the catalyst are kept in contact with one another while they are as a dilute phase or as a flow at a predetermined riser residence time flow in the range of about 0.5 to about 10 seconds. ^;

The reaction is conducted at a temperature of about 482.2 ° C (900 ⁰ F) to about 760 ⁰ C (1400 ⁰ F), measured at the outlet of the reaction chamber at a total absolute pressure of from about 0.70 to about 3.52 kg / cm (about 10 to about 50 psia) is carried out under conditions sufficiently severe to produce a conversion per pass in the range of about 50% or more and a deposition of coke on the catalyst in an amount in the range of about 0. 3 to about 3% by weight, preferably at least about 0.5% by weight. The total amount of coke production based on the weight of fresh feedstock ranges from about 4 to about 14 weight percent. .

At the end of the predetermined residence time, the catalyst is removed from the products separately, subjected to a stripping stage in order to remove high-boiling components and other entrained or adsorbed To remove hydrocarbons, and then regenerated by using the coke in at least one regeneration zone an oxygen-containing gas that maintains combustion under such time, temperature and atmosphere conditions

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burns that are sufficient to keep the carbon on the regenerated Reducing the catalyst to about 0.25% by weight or less, preferably to about 0.05% by weight or less, wherein at least the major part of the weight of the coke is burned in a zone in which a molar ratio of COrCO at least about 0.25, preferably at least about 0.3, and more preferably at least about 1 is maintained. Of the regenerated catalyst is then returned to the reactor for contact with fresh feedstock.

Depending on how the method according to the invention is practiced, one or more of the advantages described below can be achieved. Preferably, and if so desired, the process can be carried out without supplying hydrogen to the reaction chamber. Preferably, and if so desired the process can be carried out without prior hydrotreating the starting material and / or without prior removal steps of asphaltenes or metals can be carried out from the starting material, and this is possible even if the carbometallic total oil greater than about 4, or greater than about 5, or even greater than about 5.5 parts per million nickel equivalents of heavy metal by weight and a carbon residue in the pyrolysis of more than about 1% by weight, "has more than about 1.4% by weight or even more than about 2% by weight .; In addition, all of the starting material that is converting is to be subjected, as described above, to be cracked in one and the same conversion chamber. The crack reaction can be carried out with a catalyst that has been used previously (and recycled, with a necessary addition has been made to compensate for the usual losses and deactivation). order under the above conditions described to crack a carbo-metallic starting material. Not cracked to gasoline in a first run heavy hydrocarbons can be recycled to a further cracking stage in contact with, with or without hydrotreating the same type of starting material in which they were first subjected to the cracking conditions and under the same type of conditions; however, the method is preferably used for im

substantial one-time throughput respectively. according to the single pass procedure carried out (for example, less than 15% by volume, based on the volume of fresh starting material, returned).

According to a preferred embodiment or a preferred Aspect of the present invention becomes the one-way catalyst at the end of the above-mentioned predetermined residence time centrifuged, which is formed by the elongated reaction chamber or an extension of this, while the products, which have a lower momentum, are forced to an abrupt change of direction, resulting in an abrupt, essentially results in instant ballistic separation of the products from the catalyst. The catalyst separated in this way is then stripped as described above, regenerated and returned to the reactor.

According to a further preferred embodiment or a preferred one Aspect of the present invention is the carbometallic starting material not only with the catalyst in Brought into 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 from about 0.04 to about 0.15, preferably about 0.04 to about 0.1, and especially about 0.05 to about 0.1. Such additional materials, including the liquid water, can before, during or after mixing the starting material with the mentioned catalyst and either after or preferably before the evaporation of the starting material are mixed with the starting material. The source material, the catalyst and the water (for example in the form of liquid water or in the form of steam, obtained by Evaporation of the liquid water that has come into contact with the starting material) are carried out on one or more Places along the reactor are introduced into the fluidized bed reactor, which can be a reactor in which the separation as above described, done by ballistic means, or not. While

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

In the drawings show:

Fig. 1 is a schematic diagram of a first device for

Implementation of the method according to the invention; Fig. 2 is a schematic diagram of a second device for

Implementation of the method according to the invention; and Figures 3 to 5 are graphical representations of results that when carrying out the method according to the invention

can be obtained.

The present invention provides a process for the continuous catalytic conversion of a wide variety of carbometallic oils into products with. a smaller molecular weight, thereby maximizing the production of high quality liquid products, and allowing, if desired, to avoid vacuum distillation or other costly treatments such as hydrotreating. The term "oils" encompasses not only those compositions which consist primarily of hydrocarbons and are liquid at room temperature (for example 20 ^° C. (68 ^° F)), but also those compositions which consist primarily of hydrocarbons and are asphalts or tars at ambient temperature but up to etwa426,7 ° C (800 ⁰ F) become liquid when heated to temperatures in the range of. The present invention is applicable to carbo-metallic oils whether or not derived from petroleum. Provided they have the required boiling range, the carbon residue from pyrolysis and the heavy metal content, it is possible to apply the principle of the invention to the processing of a wide variety of materials, such as heavy sumps of crude oil, heavy biturcene crude oil, crude oils which are known as "heavy crude" and have approximate properties such as top residue, shale oil, tar sand extract, products of

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of coal liquefaction and solvated coal, atmospheric top residue and vacuum top residue, extracts and / or sump products (raffinate) from solvent deasphalting, aromatic extract from Schinierölraf f ination, tar sump products, heavy recycle oil, slop oil, other refinery waste streams and mixtures of the above products. Such mixtures can be made, for example, by mixing available hydrocarbon fractions including oils, tars, pitches and the like. Powdered coal can also be suspended in the carbo-metallic oil. Using the present invention, demetallized oils can be converted, those skilled in the art being familiar with techniques for demetallizing carbo-metallic oils; however, it is an advantage of this invention that carbometallic oils which have not previously been subjected to a demetallizing treatment can be used as the starting material. Similarly, the invention can also be applied to starting materials which have previously been hydrotreated; however, it is an advantage of this invention that it can be successfully applied to the conversion of carbo-metallic oils that have not previously been hydrotreated. However, if the preferred application of the present invention topped crudes, that is to the crude oil fraction boiling at and above 343.3 ° C (650 ⁰ F), either alone or in mixture with pure gas oils. While the use of materials which have previously been subjected to vacuum distillation are not excluded according to the invention, it is an advantage of this invention that one can process or treat in a satisfactory manner materials that have not previously been subjected to vacuum distillation, and thus one can has to invest less capital and operating costs compared to traditional FCC processes which require a vacuum distillation unit.

Table 1 below shows a comparison between a typical vacuum gas oil (VGO) that has been used so far in fluid catalytic cracking was used, and various top residues that only

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API density

3433+ (2)

all in all

% By volume of

343 ^ + - parliamentary group,

3433-

Ramsbottom Carbon-

3433-

oil or top residue

551.7 551.7+ 551.7 343.3+

TABEL Metals wt% S Parts by weight per million (3) 343.3+

Nickel - total Ni V Fe equivalent.

Parts by weight of nitrogen per million of 3433+ fraction overall more basic part

N / A-

Parts by weight per million

28.4 16.9

100 65.3

OjO 34.7

038 0.49 4.96

0.2 2.5+

0.1 33.8

2.6 1.9

17.4

23.1 19.1 14.5 22.7

930 35 /) 99.0 17.0 58.02

0.83 2.75

2.94

260 450

723

78.7 213 0.49 3.99 3X) + I ^ 11.9 4J99 1.64 512 200 64.7 353 0.47 6 ^ 6 6.4 24.7 3 ^ 12.00 239 940 507 51.8 48.2 0.46 9 /) 0 19.6 63 ^ 2.9 33.13 4.43 1853 72.8 27 2. 0.36 4.42 1.4 3.0 2.4 236 038 2063 43.6 56.4 0.42 16.81 48.8 119/3 3.1 74.03 4.22 1845 60.8 39.2 0.48 9 /) 1 21.9 60.0 3.1 34J84 2 ^ 0 (4) 80.2 19.8 033 4 ^ 6 2.7+ - 8.5 3 ^ 0 0 ^ 6 40.7 593 032 15.1 0.8 70X) 2JO 15.47 3J4

0.8 6.9

1.8

7.5 9.2

Mexican isthmus

Mexican Kirkuk (D

Murban

- “Arabian Light ^ Arabian Med. ^ Ekofisk ■ "Fosterton

^ Iranian Light 17.4

^ La ^ Miss Sweet 23.7 Wyoming Sour 12.4 35 ^ ⁵ U) A refined blend of Mexican and Kirkuk topp residues

^V (2) In the table mean 3433 and 551 J 3433 ° C (650 ⁰ F) or 551.7 ⁰ C (1025 ⁰ F); 3433+ means 3433 ° C + (650 ° + -) material. as explained below.

(3) The copper content was below 0.5%, with one exception: the Mexican Kirkuk had a copper content of 0.6%. All metal contents are in parts per Million stated, based on the weight of the 3433 + fraction.

(4) Beredinet.

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From the table it can be seen that the heavier or the higher-boiling starting materials are replaced by relatively lower ones API density values are marked as the vacuum gas oil (VGO) given as an example. In general, those were catalytic Cracking process feedstocks with lower boiling temperatures and / or higher API densities than far superior viewed compared to starting materials with higher boiling temperatures and / or lower API densities. Comparisons between the Gasoline yield of high-boiling raw materials and raw materials materials with an average boiling range with constant coke yield have shown that the starting materials with the average Boiling range for a given coke yield result in a superior gasoline yield.

According to the invention one prepares a carbo-metallic oil feedstock prior to, of which at least about 70%, preferably at least about 85%, and especially approximately 100% (vol .-%) at and boiling above about 343.3 ° C (650 ⁰ F). All boiling temperatures given here are based on standard conditions at atmospheric pressure. In carbo-metallic oil, which consists partially or completely of a material which boils at and above about 34 3.3 ° C (650 ⁰ F), such material is designated herein as 343.3 ° C + - (650 ⁰ F + - ) Denotes material; and 343.3 ° C + (650 ° F + -) contains material which is part of an oil or has been separated from an oil, the components which boil below and above 343.3 ° C (650 ⁰ F), can be used as 343.3 ° C + - (650 ⁰ F + -) fraction. However, the terms "boils above" and "343.3 ° C + (650 F + ^0)" is not that all material which is referred to with these terms, has the ability to boiling mean. The carbometallic oils suitable for the present invention can also contain material that does not boil under any conditions; for example, certain asphalts and asphaltenes can be thermally cracked during distillation, apparently without boiling. Therefore, when, for example, specifically, that the starting material comprises at least about 70% by volume of material (F 650 ⁰⁾ boils above about 343.3 ° C, then should thus be meant that the question 70% may comprise a small amount of material,

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that does not boil or volatilize at any temperature. If such non-boiling materials are present, they may often be concentrated or for the most part in the parts of the. Feedstock that do not below about 537.8 ° C (1000 ⁰ F), 551.7 ⁰ C (1025 ⁰ F) or higher boiling. Therefore, when it is said that at least about 10%, preferably about 15%, and more preferably at least about 20% (vol%) of the 343.3 ⁰ C + (650 ⁰ F +) fraction not below about 537.8 ° C or 551, Boiling 7 ° C (1000 ° F - or 1025 ⁰ F) is intended to mean that all or any part of the material does not boil below about 537.8 ° C or 551.7 ° C (1000 ⁰ F or 1025 ⁰ F) boils, and can be volatile or non-volatile at and above the specified temperatures.

Preferably, the contemplated starting materials, or at least the 343.3 ° C + (650 ° F + -) material therein, have a carbon residue on pyrolysis of at least about 2 or more. For example, the Ramsbottom carbon content can range from about 2 to about 12, and it is often at least about 4. A particularly common range is from about 4 to about 8. It is noteworthy that the exemplary VGO in Table 1 is a Ramsbottom -Kohlenstoffrückstandswert of 0.38 and 343.3 ° to 551.7 ° C (650 ⁰ F to 1025 ⁰ F) fractions of the various top-residues Ramsbottom carbon values between about 0.3 and about 0.5 have , while the various top residues, each as a whole (343.3+ (650+)), vary upward in Ramsbottom carbon values from about 4 to about 16.8, and even higher values can be envisaged.

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

The carbometallic starting materials used according to the invention or at least the 343.3 ⁰ C + contained therein

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(650 ⁰ F +) materials can contain at least about 4 parts per million nickel equivalents as defined above, of which at least about 2 parts per million are nickel (as metal by weight). Carbo-metallic oils, within the above range, can be prepared from mixtures of two or more oils, some of which contain the amounts of nickel equivalents and nickel given above and some of which do not. It must also be taken into account that the values given above for the nickel equivalents and nickel are average values in terms of time and weight for a substantial operating period of the conversion plant, such as one month. It should also be taken into account that under certain circumstances the heavy metals show a lower tendency to poison after repeated oxidations and reductions on the catalyst, and criteria for establishing "effective metal" values are described in the literature. For example, an article by Cimbalo et al., Entitled "Deposited Metals Poison FCC Catalyst", published in the Oil and Gas Journal, May 15, 1972, pages 112-122, the entire content of which is included here, should be mentioned in this context should be. If necessary or also desirable, the contents of nickel equivalents and nickel in the carbometallic oils to be processed according to the invention can also be expressed in the form of the "effective metal" values. Despite the fact that Cimbalo et al. The gradual decrease in poisoning activity observed may, and usually is, such that regeneration of the catalyst under normal FCC regeneration conditions does not decrease the dehydrogenation, demethanization and aromatic condensation activity of heavy metals accumulated on the cracking catalyst.

It is known that about 0.2 to about 5 weight percent "sulfur" is present in Form of elemental sulfur and / or its compounds (but expressed as elemental sulfur based on weight of the starting material) are present in the FCC starting materials, and that the sulfur or modified forms of sulfur are theirs Can find way down to the gasoline product obtained, and where

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Adding lead tends to reduce its sensitivity to octane amplification. When crude oils or top residues with high sulfur contents are processed, the sulfur present in the gasoline product often requires sweetening. To the extent that the sulfur i "" · coke is present, it also represents potential air pollution, as the regenerator _{burns it to SO 2} and SO. In the context of the invention, however, it was found that the sulfur in the starting material in the process according to the invention is, on the other hand, able to inhibit heavy metal activity by keeping metals such as Ni, V, Cu and Fe in the sulfide form in the reactor. These sulfides are far less active than the metals themselves in promoting dehydration and coking reactions. Accordingly, it is acceptable to carry out the process according to the invention with a carbometallic oil which contains at least about 0.3, preferably more than about 0.8, and in particular at least about 1.5% by weight of sulfur at 343.3 ° C + (650 ⁰ F +) fraction contains.

Carbo-metal Iishe suitable for the purposes of the present invention Oils can and usually will contain significant amounts of nitrogenous compounds, with a considerable amount Part of it is present as basic nitrogen. For example, the total nitrogen content of carbo-metallic oils be at least about 0.05% by weight. Because the cracking activity of cracking catalysts on acid sites on the catalyst surface or in its pores', basic nitrogen-containing compounds can temporarily these places neutralize and poison the catalyst. However, the catalyst is not permanently destroyed because the nitrogen can be burned away from the catalyst during regeneration, the acidity of the active sites as a result is restored.

The carbo-metallic oils can also contain significant amounts of contain pentane-insolubles, for example at least about 0.5% by weight, typically about 2% by weight or more, and

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even about 4% by weight or more. These can include, for example, asphalt and other materials.

Alkali and alkaline earth metals generally do not tend to evaporate in large amounts under the distillation conditions used in the distillation of crude oil to produce vacuum gas oils which are commonly used as FCC feedstocks. These metals remain for the most part in the "bottom" or "sump" fractions (the non-evaporated, high-boiling portion) which were used, for example, for the production of asphalt and other by-products. However, top residues and other carbometallic oils are in many cases byproducts and therefore can contain significant amounts of alkali and alkaline earth metals such as sodium. These metals settle on the catalyst during cracking. Depending on the composition of the catalyst and the regeneration temperatures to which it is exposed, these metals can undergo interactions and reactions with the catalyst (including the catalyst support) that are normally not observed in the processing of VGO under conventional FCC processing conditions . If the catalyst properties and the regeneration conditions make it necessary, the necessary precautionary measures will of course be taken to limit the amounts of alkali and alkaline earth metals in the starting materials, these metals not only occurring as brines with the crude oil in its natural state , get into the starting material, but also as constituents of the water or steam that are fed into the cracking unit. If the catalyst is particularly sensitive to alkali and alkaline earth metals, careful desalting of the crude oil used to prepare the carbometallic starting material can therefore be important. Under such circumstances, the content of such metals (hereinafter referred to as "sodium" for convenience) _% in the starting material can be maintained at about 1 part per million or less based on the weight of the starting material. Alternatively to this

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the sodium content of the starting material can be in line with that of the catalyst so as to maintain the sodium content of the catalyst, which in use is essentially the same size or smaller than that of the replacement catalytic converter with which the system is being loaded.

According to a particularly preferred embodiment of the invention, the carbo-metallic oil feedstock containing at least about 70% by volume of material which (F 650 ⁰⁾ boils above about 343.3 ° C, at least about 10% of the material above about 343, Boiling 3 ⁰ C (650 ⁰ F), not boiling below about 551.7 ° C (1025 ⁰ F). The average composition of 343.3 ° C + (65O ⁰ F +) this - material may be further characterized as follows: (a) an atomic ratio of hydrogen to carbon in the range of about 1.3 to about 1.8; (b) a Ramsbottom carbon value of at least about 2; (c) at least about 4 parts per million nickel equivalents as defined above, of which at least about 2 parts per million are nickel (as metal by weight); and (d) by at least one of the following features: (i) at least about 0.3% by weight sulfur, (ii) at least about 0.05% by weight nitrogen, and (iii) at least about 0.5% by weight. -% of pentane-insoluble compounds. Very often the preferred starting material will include all of features (i), (ii) and (iii) and other components found in petroleum or non-petroleum origin oils may be present in varying amounts provided they do not prevent them Implementation of the procedure.

Although the possibility of using a starting material, ' that has already been cracked to a certain extent before, should not be excluded, has the inventive method the definite advantage of being successful in extensive conversions and very substantial yields liquid hydrocarbon fuels made from carbo-metallic can receive oils that have not previously undergone a noticeable cracking process. Accordingly, this is the case with the one according to the invention Process used carbo-metallic starting material

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ORIGINAL INSPECTED

for example, and preferably at least about 85%, particularly preferably at least about 90%, and most preferably substantially entirely, an oil that has not previously been treated with a cracking catalyst has been brought into contact under cracking conditions. The method according to the invention is also suitable for process implementation with a single throughput or single pass. The return volume, if any return takes place at all, is based on the volume fresh starting material, preferably about 15% or less, and especially about 10% or less.

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

In traditional VGO FCC processing, the ratio between the number of barrels per day throughput of the plant and the total number of tons of catalyst circulated through all stages of the process can vary considerably. For present purposes, the daily · throughput is defined as the number of barrels of fresh starting material that boils above about 343.3 ⁰ C (650 ⁰ P), the plant per average day of operation to liquid products below about 221.1 ⁰ C (43O ⁰ F) boil, processed. For example, in a commercially successful way of performing the FCC-VGO process, about 8 to about 12 tons of catalyst are circulated in a process with a plant throughput of 1000 barrels

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per day. In another commercially successful process, this ratio is in the range of about 2 to 3. While the; present invention in the range of about 2 to about 30, typically between about 2 to about 12 tons of catalyst inventory per · 1000 barrels of daily plant throughput can be practiced.; the process according to the invention is preferably carried out with a very small ratio of catalyst weight to daily plant throughput carried out. It is particularly preferred that the invention To carry out the process with a catalyst inventory that is suitable for contact with the starting material for the desired residence time at the above-specified ratio of catalyst to oil is sufficient, while the amount of catalyst was in place, relative to the plant throughput, is kept to a minimum with the catalyst inventory being circulated or in other process phases is held for treatment, such as stripping, regenerating, and the like. It will therefore particularly preferred to use the method according to the invention about 2 to about 5, and especially about 2 tons or less of catalyst inventory per 1000 barrels of daily plant throughput perform.

When carrying out the process according to the invention, the catalyst can be added continuously or periodically, for example to compensate for normal losses of catalyst from the system. In addition, the addition of the catalyst can be carried out in connection with the removal of the catalyst in order, for example, to maintain or increase the average activity level of the catalyst in the plant. For example, the rate at which the virgin catalyst is introduced into the plant can range from about 0.0454 to about 1.361 (about 0.1 to about 3), preferably about 0.068 to 0.907 (about 0.15 to about 2) and especially about; 0.0907 to about 0.068 kg (0.2 to about 1.5 pounds) per barrel of ton of feedstock. If we on the other side direct \ weight catalyst from the FCC operation used, such high speeds j substitution such as 2.268 kg to (5 pounds per barrel) applied per barrel. When the circumstances are like that

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the catalyst used in the plant in terms of Resistance to deactivation below the Average and / or the prevailing conditions in the system result in faster deactivation, can also faster addition rates than those indicated above are used; on the other hand, in contrary circumstances lower addition rates can also be used.

Without wishing to be bound by any theory, it seems as if a number of procedural features, which are detailed below be described, such as the residence time and the optional mixing of steam and starting material, reduce the extent to which metals are produced in the reduced state on the catalyst under the cracking conditions, from heavy metal sulphide (s), sulphate (s) or oxide (s), which on the catalyst particles through previous contact with carbometallic starting material and regeneration conditions are deposited. It thus appears that the process has a significant control over the effects of heavy metals on poisoning allowed the catalyst even if the accumulations in such metals are considerable.

As a result, the process can be carried out with catalysts that have heavy metal accumulations, which up to now would have been regarded as completely inadmissible in conventional FCC-VGO operation. For the reasons mentioned, it is possible to envisage carrying out the process with catalysts which have heavy metal enrichments in the range from about 3,000 to about 70,000 parts per million nickel equivalents on average. The enrichment can preferably range from about 4,000 to about 50,000 parts per million, and more preferably greater than about 5,000 to about 30,000 parts per million. These ranges are in terms of parts per million nickel equivalents, with metals expressed as metal and by weight, and also measured on and related to regenerated equilibrium catalyst. In the event, however, that a catalyst of suitable activity should be available at very low cost, which means that it is very high

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Catalyst replacement rates were possible, the carbonic acidallic oil could also be used with a catalyst that is less than Contains 3,000 parts per million nickel equivalents of heavy heavy metals, converted to lower-boiling liquid products. For example, an equilibrium catalyst could be: use another plant, for example an FCC plant, which was used to crack a feedstock, for example a vacuum gas oil which on pyrolysis gives a carbon residue of less than 1 and less than about 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 arbitrarily changing the catalyst addition rate discussed above controlled (including maintaining or varying if desired or necessary). For example the catalyst addition can be kept at a rate in which the heavy metal accumulation on the catalyst is kept in one of the ranges given above.

In general, it is preferred to employ a catalyst which has a high level of cracking activity, gives high conversion rates and high productivity with low residence times. The conversion efficiency of the catalyst can be expressed as the conversion produced during the actual operation of the process and / or as conversion produced in standard tests for catalyst activity. For example, is preferred a catalyst is employed which is sufficiently active in the course of an extended process operation to achieve a level of conversion of at least about 50%, preferably at least about 60%. In this context, the conversion expressed as liquid volume% based on fresh starting material. For example, a preferred catalyst is also chin be defined as having a specified activity in its virgin or equilibrium state shows, expressed in the form of a vol .-% indication, obtainable by MAT (micro-activity test). Within the scope of the present invention

• * · »■» n ~ n on 7 r » α ο.0
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■ 31

means the percentage aforementioned the volume percentage of standard feedstock to 221.1 ⁰ C (4 30 ⁰ F) end point gasoline and lighter products at 482.2 ⁰ C (900 ⁰ F), an up, the weight hourly space velocity of 16 was calculated based on a (1100 ⁰ F) the dried catalyst at 593.3 ° C, and 3C / O (catalyst to oil ratio) as measured by ASTM MAT test D-32, converted, namely using a suitable standard feedstock such as Davison WHPS-12 primary gas oil that has the following analytical values and properties:

API density at 15.56 ° C (60 ⁰ F), degree 31.0

Specific density at 15.56 ° C

(60 ° F), g / cm ^3, 0.8708

Ramsbottom carbon, wt% 0.09

Conradson carbon, wt% (estimated) 0.04

Carbon, wt% 84.92

Hydrogen, wt% 12.94

Sulfur, wt% 0.68

Nitrogen, parts per million 305

Viscosity at 37.8 ° C (100 ° F), centistokes 10.36

Watson K factor 11.93

Aniline point 182

Bromine number 2.2

Paraffins,% by volume 31.7

Olefins, volume percent 1.8

Naphthenes, vol% 44.0

Aromatics / vol% 22.7

Average molecular weight 284

Nickel traces

Vanadium traces

Iron traces

Sodium traces

Chloride _t traces

B&W tracks

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« Mm- " ■ 3043107 ASTM-D- 1160 229.4 (445) 316.1 (601) 351.1 (664) 371.7 (701) 390.0 (734) 419.4 (787) 445.6 (834)

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Distillation, ⁰ C ( ⁰ F)

IBP

10%

30%

50%

70%

90%

FBP

The end point of the gasoline produced in the MAT test is often referred to as 221.1 ⁰ C (430 ⁰ F) tbp (true boiling point, true boiling point) defines what a standard laboratory distillation corresponds to, but may for this purpose as well, other Serve endpoints. The conversion is calculated that one of the 100 Vol .-% (based on fresh feedstock) of those products heavier than gasoline, remain _un d ^ _n the product obtained, subtract.

The catalyst can in its virgin or ursorünlichen Form or, as already indicated above, in any other / form can be introduced into the process; for example you can use an equilibrium catalyst taken from another facility, such as a catalyst that was previously used to crack a different starting material. If the characterization is based on the MAT activity occurs, the preferred catalysts can be described as either based on their MAT activity they are "introduced" into the process according to the invention, or how they are "withdrawn" or on the basis of their equilibrium MAT activity in the inventive method, or they can also using both the one and the other basis. A preferred MAT activity for parent and non-parent catalysts, such as they are "introduced" into the process according to the invention, is at least about 60%, however, it should be noted that, especially in the case of non-original catalysts, which are fed at high addition rates, too

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lower MAT activity levels are acceptable. An acceptable one MAT activity of the catalyst as it is "withdrawn", respectively an acceptable equilibrium MAT activity level of the catalyst used in the process of the invention about 20% or more, with about 40% or more, and especially about 60% or more being preferred values represent.' .

Any hydrocarbon cracking catalyst can be used that has has the conversion abilities given above. A particularly preferred class of catalysts includes those catalysts which have a pore structure in which starting material molecules for adsorption and / or for contact with active catalytic sites within or adjacent to the pores can enter. Various types of catalysts with this classification are available including, for example the layered silicates, such as the soap clays. Although the most common available catalysts within this classification are the well-known zeolite-containing catalysts Non-zeolite-containing catalysts should also be considered.

The preferred zeolite-containing catalysts can contain any zeolite, regardless of whether it is a natural, semi-synthetic one or synthetic zeloith, alone or in admixture with other materials, affects the suitability of the catalyst do not deteriorate to a significant extent, provided that the. obtained catalyst the above Has activity and pore structure. For example, if the catalyst is a mixture, it can be a zeolite component comprise together with or dispersed in a porous, refractory, inorganic oxide support; in such a case the Catalyst, for example, from about 1% to about 60% by weight, preferably about 1 to about 40% by weight, and in particular about 5 to about 25% by weight, based on the total weight of the zeolite catalyst (anhydrous base), with the remainder of the catalyst consisting of porous, refractory, inorganic oxide, either alone or in combination with any known additives

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to speed up or suppress various desired i and adverse reactions. For a general explanation of the class of zeolite molecular sieve catalysts. the in the frame of the present invention, reference is made to the disclosures of the articles "Refinery Catalysts Are a Fluid Business",> and "Making Cat Crackers Work on Varied Diet", respectively, 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 components of the zeolite-containing catalysts will be those found useful in FCC cracking processes. In general, these are crystalline aluminosilicates, which typically consist of four-coordinate aluminum atoms which are linked by oxygen atoms to the neighboring silicon atoms in the crystal structure. However, the term "zeolite" in the context of the present invention not only includes aluminosilicates, but also ^: substances in which the aluminum has been partially or completely replaced, such as, for example, by gallium and / or other metal atoms, and it also includes substances in which the silicon has been partially or completely replaced, for example by germanium. A replacement by titanium and ^; Zirconium is also suitable. _:

i Most zeolites are produced in the sodium form and \ occur naturally in this form _f where the sodium | cations are connected to the electronegative sites in the crystal structure i. The sodium cations tend to render the zeolites inactive and much less stable when exposed to hydrocarbon conversion conditions, particularly at high temperatures. Accordingly, the zeolite can be ion exchanged, and when the zeolite is a component of a catalyst composition, such ion exchange can occur before or after the zeolite is incorporated as a component of the composition. Suitable cations for replacing the sodium in the zeolite crystal structure include

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Ammonium (decomposable to hydrogen), hydrogen, the rare ones Earth metals, alkaline earth metals, etc. In the professional world are different suitable ion exchange processes and also known cations that act as exchange material in the zeolite crystal structure can be introduced.

Examples of Naturally Occurring, Crystalline Aluminosilicate Zeolites / which can be used in the context of the present invention or incorporated into the catalysts are Faüjasit, Mordenite, Clinoptilot, Chabazite, Analcite, Erionite, and also Levyn, Dachiardite, Paulingite, Noselite, Ferriorite, Heulandite, Scolezite, stibite, harmotome, phillip'site, brewsterite, flarite, Datolite, gmelinite, caumnite, leucite, glaze stone, scaplite, mesolite, Ptholite, nepheline, matrolite, offretite and sodalite.

Examples of synthetic, crystalline aluminosiliate zeolites which are used as or in catalysts for carrying out the inventive Process suitable are: Zeolite X, US Pat. No. 2,882,244, Zeolite Y, US Pat. No. 3,130,007 and Zeolite A, US Pat 2,882,243; as well as Zeolite B, U.S. Patent 3,008,803; Zeolite D, Canadian Patent 661,981; Zeolite E, Canadian Patent 614,495; Zeolite F, U.S. Patent

2,996,358; Zeolite H U.S. Patent 3,010,789; Zeolite J, U.S. Patent 3,011,869; Zeolite L, BE-PS 575 177; Zeloith M, U.S. Patent 2,995,423; Zeolite O, U.S. Patent 3,140,252; Zeolite Q, U.S. Patent 2,991,151; Zeolite S, U.S. Patent

3,054,657; Zeolite T, U.S. Patent 2,950,952; Zeolite W, U.S. Patent 3,012,853; Zeolite Z, Canadian Patent 614,495; and Zeolite Omega, CA-PS 817 915. Also suitable are the ZK-4HJ-Zeloith, alpha beta-zeolite and the Zeloithe of the ZSM type. Additionally, there are also those described in U.S. Patents 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 suitable in the context of the present invention. This includes, in particular, more natural ones Faüjasite and Zeolite X and Zeolite Y.

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The crystalline aluminosilicate zeolites, such as synthetic
Faujasite, under normal conditions, will be in regular shape
shaped, discrete particles ranging in size from about 1 to about
10 microns crystallize, and this is also the size that
is often encountered in commercially available catalysts, and which are suitable within the scope of the invention. Preferably
the particle size of the zeolites is about 0.5 to about
10 microns, and more particularly from about 0.1 to about 2 microns or
fewer. For example, in situ from calcined kaolin
produced zeolites be characterized by even smaller crystallites. Crystalline zeolites have both an internal and a
also an outer surface, which is called the "portal" surface here

is referred to, with the greater part of the total surface
is put by the inner surface. The portal surface means the outer surface of the zeolite crystal through which the reactants have to pass in order to be converted into low-boiling products. the
Blockage of the inner channels through, for example, coke formation,
the blockage of the entrances to the inner channels through the deposition of coke on the portal surface, and the contamination through metal poisoning, the entire zeolite surface!

reduce to a considerable extent. Therefore, in order to reduce the impact i

contamination and pore clogging to a minimum to j

hold, will crystals that are larger than usual, as above;

indicated, preferably in the to be used according to the invention!

Catalysts not used. ■: · ~ · j

Zeolite-containing catalysts with supports are commercially available

borrowed a variety of different metal oxides and grain:

contain combinations of these, including, for example, j

Silica, alumina, magnesia and mixtures of I.

these and mixtures of these oxides with clays, as described, for example, in US Pat. No. 034,948. Example!

wise you can use any of the zeolite-containing molecular sieve;

Use fluid cracking catalysts designed for the manufacture of J

from gasoline from vacuum gas oils are suitable. However, ■

certain advantages can be achieved by sensible selection of j

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Catalysts with considerable resistance to metals. A metal-resistant zeolite catalyst is for example in US Pat. No. 3,944,482, the catalyst being 1 to 40% by weight of a rare earth-exchanged Contains zeolite and the remainder is a heat-resistant metal oxide with a specified pore volume and size distribution. Other catalysts referred to as "metal tolerant" are discussed in the above-referenced article by Cimbalo et al. described.

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

The catalyst composition can also comprise one or more combustion promoters which are necessary for the subsequent stage the regeneration of the catalyst are suitable. The cracking of carbo-metallic oils leads to considerable deposition of coke on the catalyst, which results in a loss of activity of the catalyst. Hence the activity To restore the catalyst, the coke is burned away in a regeneration stage in which the coke is released into combustion gases including carbon monoxide and / or carbon dioxide is transferred. There are various substances known to cause the transformation favor of coke in carbon monoxide and / or carbon dioxide when incorporated in small amounts in cracking catalysts will. The promoters for the combustion of the coke to carbon monoxide tend to lower the temperature at which a given level of coke removal can be achieved, and they do thus reduce the potential for thermal deactivation of the catalyst. Such promoters normally found in effective amounts of trace up to about 10 or 20% by weight of the

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Catalyst can be used, for example, any Be kind that usually involves the combustion of carbon under regeneration conditions to carbon monoxide, preferably Carbon dioxide, promotes.

Although a great variety of other catalysts, including Zeloith-containing as well as non-zeolite-containing catalysts is useful in the present invention, the following are some examples of commercially available Catalysts indicated which have been used in the practice of the present invention:

Table 2

Specific weight percent

Surface of zeolite. ,,. “.

j / r, u n. Al-O, SiO ₀ Na _n O Fe ₀ O TiO ₀ m '/ g content 2 3 2_ 2 2 2_

AGZ-290 300 11.0 29.5 59.0 0.40 0.11 0.59

GRZ-I 162 14.0 23.4 69.0 0.10 0.4 0.9

CCZ-220 129 11.0 34.6 60.0 0.60 0.57 1.9

Super DX 155 13.0 31.0 65.0 0.80 0.57 1.6

F-87 240 10.0 44.0 50.0 0.80 0.70 1.6

FOC-90 240 8.0 44.0 52.0 0.65 0.65 1.1

HFZ 20 310 20.0 59.0 40.0 0.47 0.54 2.75

HEZ-55 210 19.0 59.0 35.2 0.60 0.60 2.5

The catalysts identified in the table as AGZ-290, GRZ-I, CCZ-220 and Super DX are products of WR Grace & Co. The catalysts F-87 and FOC-90 are products of Filtrol, while HFZ-20 and HEZ- 55 Engelhard / Houdry products are. The above properties are properties of the original catalysts and are, that is, a material which is based except in the case of zeolite content, on an anhydrous basis been calcined at 954.4 ⁰ C (1750 ⁰ F). The zeolite content was obtained by comparing the X-ray intensities of a catalyst sample and a standard material consisting of high purity sodium Y zeolite according to draft # 6, dated January 9, 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 a catalyst can be carried out which is essentially free of one or both of these metals.

The method according to the invention can be carried out with that described above carbo-metallic oil and catalyst as that essentially single materials added to the reaction zone. However, the loading is with additional Materials not excluded. Feeding the reaction zone with recycled oil has already been mentioned above. As will be described in more detail below, can other materials can also be added which can fulfill a variety of functions. In such a case Carbo-metallic oil and a catalyst usually put represents the majority by weight of the total materials fed into the reaction zone.

Some of the additional materials that can be employed perform functions that are significant advantages over offer the process performed only with the carbo-metallic oil and the catalyst. Among these functions to mention are: control of the effects of heavy metal and other catalyst contamination; Enhancement of catalyst efficiency; Absorbing the excess heat in the catalyst as it is obtained from the regenerator; disposal of substances polluting the environment or transforming them into a form or forms in which they can be more easily removed Products can be separated and / or disposed of; Control of the catalyst temperature; Dilution of the carbo-metallic oil vapors to reduce their partial vapor pressure and to increase the yield of desired products; regulation the feedstock / catalyst contact time; Provision of hydrogen for a low-hydrogen carbo-metallic Starting material; Assistance in dispersing the starting material

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materials; and possibly also distillation of the products. Certain metals in the heavy metal accumulation on the catalyst are more active in favoring ψοη undesirable reactions when they are in the form of elemental | m metal, as if they were in the through contact with oxygen in the catalyst regenerator generated, oxidized form. However, the contact time between the catalyst and the starting material vapors was sufficient and product in the conventional catalytic cracking, so that the hydrogen released in the cracking reaction in the It was able to return a considerable part of the less harmful oxides to the more harmful elemental heavy metal form. One can use this situation to one's advantage if one introduces additional materials in the reaction zone in admixture with the catalyst, the starting material vapors and the products in a gaseous form (including vapor Form) are available. The increased volume of material in the 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 oxidized heavy metals generated thereby. As a result of the shortened dwell time exists for the reduction of oxidized heavy metals

f the elementary form less opportunity, ljmd there are thus less elementary, harmful metals for contact with the starting material and the products available.

The materials to be added can be any suitable Way to be introduced to the procedure, with some examples are described below. For example, they can be mixed with the carbo-metallic oil feedstock before the latter is brought into contact with the catalyst *. Alternatively for this purpose, the materials to be added can, if desired, be mixed with the catalyst before it comes into contact with the starting material. Separate parts of the materials to be added can also be used separately with both the Catalyst as well as with the carbo-metallic oil. In addition, the starting material, the catalyst

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ORIGINAL INSPECTED

Sator and the additional materials can also, if so desired, be brought together substantially simultaneously. A Part of the materials to be added can also with the catalyst and / or the carbo-metallic oil on any of the described Types are mixed while additional parts are subsequently mixed in. For example, some of the Materials are added to the carbo-metallic oil and / or to the catalyst before they enter the reaction zone while another part of the materials to be added is introduced directly into the reaction zone. The ones to be added Materials can be in a variety of spaced apart locations in the reaction zone or along its extension if they are is elongated, to be introduced.

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

For example, many or all of the above-mentioned desirable functions can be achieved if H_O in the form of water vapor or in the form of liquid water, or in the form of a combination of these, in the reaction zone with a weight ratio of H2O to starting material in the range of about 0 .04 or more, and preferably from about 0.05 to about 0.1 or more. Without wishing to be bound by any theory, the use of HjO appears to inhibit the reduction of oxides, sulphites and sulphides on the catalyst to the free metal form, which is believed to cause condensation -dehydrogenation with accompanying promotion of coke- and

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Hydrogen yield and associated product loss favored; stigt. In addition, H ₂ O can also reduce the deposition of metals on the catalyst surface to a certain extent. There may also be a slight tendency to; desorb nitrogenous and other heavy contaminant containing molecules from the surface of the catalyst particles, or at least some tendency to inhibit them. Adsorption by the catalyst exist. It is also assumed that added HO increases the acidity of the catalyst through Bronsted acid formation, which leads to an increase in the efficiency of the catalyst. Under the annalame that the supplied H_O is colder than the regenerated catalyst and / or the temperature in the reaction zone, the noticeable heat that increases the temperature of the H ₃ O through contact with the catalyst in the reaction zone or elsewhere is released, excess heat is removed from the catalyst. The liquid or vaporous water contains less than about 100 parts per million of sodium and less than 500 parts per million of each calcium and; Magnesium. All or part of the H ₃ O can and is preferably condensed from the products of a previous catalytic conversion of a carbo-metallic oil. j If the HO is recirculated water or such ^:

containing dissolved, for example, about 500 to about 5000 parts \ per million HJS therein comprises a number of j additional advantages can be achieved. The ecologically unpopular HjS does not have to be released into the atmosphere, the returned water does not require any further treatment to remove HS, and the H ₃ S can make a contribution to the! ringerung the coking of the catalyst afford by passivates the j heavy metals, that is, by converting this into the [sulphite, which have a lower activity for reinforce-, kung the coke and hydrogen production, as the

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free metals. In the reaction zone, the presence of water can dilute the carbo-metallic oil droplets and thereby lower their partial pressure and thus lead to an increase in the yield of the desired products. The H ₃ O, in conjunction with other materials, has been reported to be useful in generating hydrogen during cracking; so it may be able to serve as a hydrogen donor for low-hydrogen carbo-metallic oil feedstocks. The HO can also serve purely mechanical purposes, such as: helping with the atomization or dispersion of the starting material

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t materials; Competition with the high molecular weight molecules in terms of adsorption on the surface of the catalyst, with the formation of coke being interrupted; Steam distillation of evaporable product from non-digestible starting material; and separation of the product from the catalyst! after the end of the; Cracking reaction. In a particularly preferred measure, the H ₉ O, the catalyst and the carbo-metallic oil are brought together essentially simultaneously. For example, the HO and starting material can be mixed in an atomizing nozzle and the spray obtained can be brought into contact with the catalyst at the downstream end of the reaction zone.

The addition of water vapor into the reaction zone is frequently mentioned in the literature on fluid catalytic cracking. The addition of liquid water to the starting material is mentioned relatively rarely compared to the direct introduction of water vapor into the reaction zone. In the context of the present invention; however, it is particularly preferred that an intimate mixture with liquid water and carbometallic oil is formed at a weight ratio of about aoyO4 to about 0.15 at the moment or just before the introduction of the oil into the reaction zone, the water (e.g. in the form of of liquid water or in the form of water vapor obtained by evaporation of the liquid water through contact with the oil) enters the reaction zone as part of the feedstock flow introduced into the reaction zone. Without wishing to be bound by any theory ¹ , it is assumed that the measure described above is advantageous for promoting the dispersion of the starting material. The heat of vaporization of the water, which is generated by the catalyst, the starting material or by! both of which are withdrawn cause the water to be a more effective heat trap than water vapor alone. The weight ratio of liquid water to starting material is preferably about 0.04 to about 0.1, in particular about 0.05 to about 0.1. \

Λ ϊ i

Of course, the liquid water can be used in the manner described above or introduced into the process in some other way be, and in any case can be the introduction of the liquid

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Water also includes the introduction of additional amounts of water in the form of water vapor into the same 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, from about 0.01 to about 0.25, the weight ratio of total water (as water vapor and as liquid water) to starting material is about 0.3 or less. The feed weight ratios of liquid Water to water vapor with such a combined use of liquid water and water vapor can range from about 5 to about 0.2. Such a ratio may be maintained at a predetermined level within such a range or, if necessary or desired, can be varied to regulate or maintain the thermal balance of the reaction.

To fulfill the functions described above, others can also Materials are added to the reaction zone. For example, the dehydrogenation-condensation efficiency of Heavy metals can be inhibited by introducing hydrogen sulfide gas into the reaction zone. For low-hydrogen carbometallic oil feedstocks can be made available to hydrogen by using either a conventional hydrogen donor Adding diluents, such as heavy gasoline, or relatively low molecular weight hydrocarbon fragments, including for example: light paraffins; low molecular weight alcohols and other compounds that allow intermolecular hydrogen transfer allow or favor; and compounds that chemically produce hydrogen in the Combine reaction zone, for example by reacting 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) can be used alone or in combination with one another or in combination with other materials, such as nitrogen or others Inert gases, light hydrocarbons and other compounds

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any of the functions described above for which they are suitable are, meet, and including and without limitation, as a diluent for lowering the starting material partial vapor pressure and / or as a heat trap to absorb excess heat from the catalyst as it comes from the regeneration stage is obtained, serve. The above represent a discussion of some of the functions performed by materials other than the catalyst and the carbo-metallic oil feedstock introduced into the reaction zone can be, and of course, other materials can be added and other functions can be performed without the Is left within the scope of the present invention.

The present invention can be embodied in a wide variety of devices. However, a preferred one includes Apparatus Means for the rapid evaporation of as much raw material as possible and: for the effective mixing of raw material and catalyst (although not necessarily in that order), means to make the resulting mixture as to allow a dilute suspension to flow in a kind of fluidized bed, and means for separating the catalyst from cracked 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 the product abruptly of at least part of the catalyst is separated.

For example, the device can be positioned along the elongated reaction chamber one or more points for the introduction of carbometallic starting material, one or more points for Introduction of catalyst, one or more points for introducing additional material, one or more points for Include removal of products and one or more points for removal of the catalyst. The means of introducing the Feedstock, catalyst, and other materials can range from open piping to sophisticated nozzles or spray nozzles are sufficient, preferably means are used which are capable of the liquid starting materials to be divided into fine droplets.

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Preferably the reaction chamber is, or at least a main part the same, arranged vertically rather than horizontally, and has a length to diameter ratio of at least about 10, preferably about 20 or 25 or more. The use of vertical riser reactors is preferred. If the reactor is tubular it can have a uniform diameter throughout, or it can be continuous or stepwise Have an increase in diameter along the reaction path in order to maintain the speed along the flow path or to vary.

In general, the feed means (for the catalyst and the feedstock) and the design of the reactor are such that a relatively high flow rate and a dilute suspension of the catalyst is obtained. For example, the steam or catalyst velocity in the riser will usually be at least about 7.6 m / sec (25 feet / sec) and typically at least about 10.64 m / sec (35 feet / sec). This speed can be up to 16.72 m / sec (55 feet / sec) or about 22.8 m / sec (75 feet / sec) or more. The speed capabilities of the reactor will generally be sufficient to prevent the build-up or accumulation of a substantial bed of catalyst in the bottom or other parts of the riser, with the catalyst loading in the riser at the upstream end (e.g., the bottom) and downstream The end (for example, at the head) of the riser is held below about 64.6 or 80.7 kg / m ³ (4 or 5 pounds per cubic foot), or below about 32.3 kg / m ³ (2 pounds per cubic foot) can be.

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The fluidized bed process includes, for example, the flow of Catalyst, feedstock and products as one stream in a positively controlled and sustained direction, which is determined by the elongated nature of the reaction zone. However, that does not mean that a strictly linear flow is maintained must become. To a certain extent, turbulent flow and "sliding" of the catalyst can occur, as is known, particularly in certain vapor velocity ranges and catalyst loadings, though it has been reported that it is advisable to have sufficiently low catalyst loadings apply to prevent slipping and backmixing.

The most preferred reactor is one in which all or a substantial part of the vaporized, cracked products on are separated from the catalyst at one or more locations along the riser, preferably substantially all of them vaporized cracked products are separated from the catalyst at the downstream end of the riser. With a preferred one Reactor type, the separation of catalyst and products takes place ballistic; that is, the catalyst is thrown in a direction determined by the riser tube and is forced to stop its movement in the so general set direction, while the products, which have less momentum, make an abrupt change in direction be forced, resulting in an abrupt, essentially instantaneous separation of product and catalyst. at In a preferred embodiment, which is referred to here as a ventilated riser, the riser tube has a practically un- obstructed outlet opening at downstream end for discharge of the catalytic converter. Through an exit opening in the side of the tube that is the downstream end of the riser is adjacent, the products are removed. The outlet opening for the catalyst is through a catalyst flow path with the usual stripper and regenerator connected while the outlet port connected to a product flow path for the products is, which is substantially or completely from the catalyst

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fliossweg is separated, and to Trennumjsvnrrichtunqen for separation dor products of relatively small mummies, tn K.iial ysator which, if any, has succeeded in finding its way through the product outlet opening. Examples of a ballistic separation device and technique as described above can be found in U.S. Patents 4,066,533 and US Pat 4,070,159 to Myers et al. can be found, the entire disclosures of which are intended to be included here.

Preferred conditions for carrying out the process are described below. Among these, to name _r: starting material, catalyst and reaction temperatures, reaction and raw material pressures, residence and conversion levels, coke on the catalyst and Kbksabscheidung ·.

In conventional FCC operation with VGO, the feedstock is usually preheated, often to temperatures considerably higher than necessary to make the feedstock sufficiently fluid for pumping and introduction into the reactor. For example, preheat temperatures have been reported, which, after all, at about 371.1 ⁰ C or 426.7 ⁰ C (700 ⁰ F ⁰ F or 800) layers. In the context of the process according to the invention, as it is currently used in practice, the preheating of the starting material is restricted so that the starting material is able to absorb a greater amount of heat from the catalyst, the catalyst heating the starting material to the transition temperature , while minimizing the use of external fuels to heat the feedstock. Accordingly, the feedstock can be fed at ambient temperature if the nature of the feedstock allows it. Heavier feedstocks may at elevated preheat temperatures of up to about 315.6 ° C (600 ⁰ F), (200 ⁰ F to about 500 ⁰ F) are supplied typically from about 93.3 ° C to about 260 ⁰ C, with higher Preheating temperatures are not necessarily excluded.

The catalyst feed to the reactor can be

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different temperatures take place, for example from about
593.3 ° C to about 871.1 ° C (about 1600 to about 1100 ° F ^0), preferably from about 648.9 ° to about 815, 6 ° C (about 1200 ° to about
1500 ⁰ F), and in particular from about 704.4 to about 760 ⁰ C (about
1300 ° to about 1400 ° F), with temperatures of about .718.3 ° to about 746.1 ° C (about 1325 ° to about 1375 ° F) currently being optimal
be considered.

As already mentioned above, the conversion of the carbo-metallic oil to low molecular weight products can take place at one temperature
which is measured at the Reaktionskammerauslass be performed: (up to about 1400 ⁰ F about 900 °) throughput of about 482.2 ° to about 760 ⁰ C.
The reaction temperature measured at this outlet is preferably in the range of about 523.9 ° to about 704.4 ° C (about 975 ° C
to about 1300 ⁰ F), especially from about 529.5 ° to about 648.9 ° C
(about S85 ° to about 1200 ° F), and most preferably from about; 537.8 ° held to about 621.1 ° C (about 1000 ° to about 1150 ⁰ F). ^! Depending on the selected temperature and the intrinsic. ; Shafts of the starting material can be any starting material; may or may not evaporate in the riser. i

. ■ - ■■■■ i

Although, as indicated above, the reactor pressure in a

Range from about 0.70 to about 3.52 kg / cm ² (about 10 to about ^:

50 psia), the preferred and the very special are:

the most preferred pressures in the range of about 1.06 to about j

2.46 kg / cm ² (about 15 to about 35 psia), or from about 1.41 to about 2.46 kg / cm ² (about 20 to about 35 psia). In general, can

the partial (or total) pressure of the source material in the area!

from about 0.21 to about 2.11 (about 3 to about 30), preferably J. from about 0.49 to about 1.76 (about 7 to about 25), and especially:

at about 0.70 to about 1.20 kg / cm * (about 10 to about 17 psia) |

lie. The starting material partial vapor pressure can be determined by the;

Introduction of gaseous (including vapor) ''

Materials in the reactor are controlled or lowered;

such as by introducing steam, water and!

other additional materials as described above. The J

The procedure was, for example, with a ratio of initial:

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material partial pressure to total pressure in the dam riser in the range of about 0.2 to about 0.8, preferably about 0.3 to about 0.7, and especially about 0.4 to about 0.6, the ratio of fed gaseous materini (which includes recycled gases and / or water vapor obtained by introducing H ₂ O into the riser in the form of water vapor and / or liquid water) corresponding to a total pressure in the riser in a range of approximately O ₇ 8 to about 0.2, preferably about 0.7 to about 0.3, and especially about 0.6 to about 0.4. In the exemplary operation of the method according to the invention just described, the ratio of the partial pressure of the added gaseous material to the partial pressure of the starting material was approximately 0.25 to approximately 2.5 / preferably approximately 0.4 to approximately 2, and in particular approximately 0.7 to approximately 1 , 7.

Although the residence time of the starting material and product vapors in which risers can range from about 0.5 to about 10 seconds, as described above, are preferred and entirely particularly preferred values between about 0.5 and about 6 or between about 1 and about 4 seconds, with a range of about 1.5 to about 3.0 seconds is currently considered the optimal range will. For example, the process was performed with a steam riser residence time of about 2.5 seconds or less, below Feeding copious amounts of gaseous materials into the riser, these amounts being sufficient to, for example a partial pressure ratio of supplied gaseous materials to give hydrocarbon feedstock of about 0.8 or more. The procedure was continued with a dwell time of about 2 seconds or less and at an aforementioned ratio in the range of about 1 to about 2. the Combination of low starting material partial pressure, a very short dwell time and a ballistic separation of the Products from the catalyst are considered to be extremely beneficial for the conversion of carbo-metallic oils. Additional Advantages can be achieved within the framework of the aforementioned combination if a substantial partial pressure of the supplied gaseous material, especially H-O, prevails, as described above.

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Depending on whether there is sliding between the catalytic converter and the
Hydrocarbon vapors occur in the riser, the catalyst riser residence time may or may not be the same,
like the riser residence time of the vapors. Accordingly, the ratio of average catalyst-reactor residence time to steam-reactor residence time, i.e. sliding, can range from about 1 to about 5, preferably from about 1 to about 4, and especially from about 1.2 to about 3, with a range of about 1.2 to about 2 currently considered optimal.

Certain types of known FCC systems have a riser
present, which releases the catalyst and product vapors together into an enlarged chamber, which is usually called
Part of the reactor is considered to be in which the catalyst
separated from the product and collected. Continued contact of the catalyst with uncracked feedstock (if any) and cracked products in
such an enlarged chamber leads to a catalytic converter. Total feedstock contact time which is well above the riser residence times of the vapors and catalysts. If the inventive method with a ballistic separation of catalyst and vapors at the downstream end
(e.g., at the top) of the riser, as described in the aforementioned Myers, et al. is described, the riser residence time and catalyst contact time are essentially the same for a majority of the feedstock and product vapors. It is believed advantageous if the steam riser residence time and steam catalyst contact time are at least about 80, preferably
at least about 90, and especially at least about 95 percent by volume of the total feedstock and product vapors passing through the riser are substantially the same. By preventing prolonged contact of these vapors with the catalyst in a catalyst separation and collection chamber, the tendency towards re-cracking and decreased selectivity can be avoided.

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In general, the combination of catalyst to oil ratio, temperatures, pressures and residence times should be tailored to cause substantial conversion of the carbometallic oil feedstock. It is an advantage of the method according to the invention that very high conversion levels can be achieved in a single pass; for example, the conversion can be over 50% and up to about 90% or more. Preferably, the aforementioned conditions are maintained at levels sufficient to keep the conversion in the range of about 60 to about 90%, and preferably in the range of about 70 to about 85%. The conversion values above are calculated by subtracting from 100% the prozentualen'Anteil which boils by dividing the liquid volume by one hundred times the volume of liquid product that is at or above 221.1 ⁰ C (430 ⁰ F, tbp, standard Atmospheric pressure j, is obtained.

These considerable conversion values can lead to relatively large yields of coke, which is what usually happens, for example for yields of about 4 to about 14% by weight, based on fresh starting material, more often from about 6 to about 12%, and most often from about 6 to about 10%. The coke yield can be deposited more or less quantitatively on the catalyst. at eligible catalyst-to-oil ratios can be obtained Coke deposition greater than about 0.3, more often greater than about 0.5, and most often greater than about 1 weight percent coke based on that Weight of regenerated, moisture-free catalyst. Such coke deposition can be about 2% or about 3%, or even higher.

As with traditional FCC procedures with VGO, this includes Process of stripping spent catalyst after separating the catalyst from the product vapors. With the Those skilled in the art will know suitable stripping agents and suitable conditions for stripping used Catalyst, however, the process according to the invention may in some cases require somewhat more stringent conditions,

■ * of the fresh starting material

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than were previously used. This can result, for example, from the use of a carbo-metallic oil, the constituents contains, which are not volatilized under the conditions prevailing in the reactor and these components settle themselves, at least partially, on the catalyst. Such adsorbed, non-evaporated material can at least in two ways Be disturbing to sight. When the gases (including vapors) used to strip the catalyst are in a catalyst separation or collection chamber connected to the downstream end of the riser, and if there is an accumulation of catalyst in such a chamber, this can first of all be vaporized not followed by vaporized hydrocarbons in the stripper adsorption of the same on the catalyst bed located in the chamber. If the catalyst is in the stripper from adsorbed starting material is freed, the resulting starting material vapors can pass through the catalyst bed, the has accumulated in the catalyst collection and / or separation chamber and is in the form of coke and / or condensed material settle on the catalyst bed. As the catalyst carrying these deposits moves from the bed to the stripper and from Moved there into the regenerator, the condensed products may require a larger stripping capacity during the Coke can make increased regeneration temperatures and / or a greater regeneration capacity necessary. From the above For reasons mentioned, the contact between the stripping vapors and the catalyst accumulations in the catalyst separation or collection chamber prevented or limited. Except for an amount of catalyst that consists essentially of the Circuit fails and remains at the bottom of the separation and / or collection chamber, this can be done, for example, by that the formation of such accumulations is prevented by, for example, the catalyst in the circuit removed from this chamber immediately after settling on the bottom of this chamber. At the same time, it can be useful to apply such time, temperature and atmosphere conditions in the stripper that are sufficient to avoid potentially volatile

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term hydrocarbon material carried by the striated catalyst to about 10 weight percent or less based on the total weight of carbon on the catalyst in order to keep regeneration temperature and capacity to a minimum. Such stripping can include, for example, reheating of the catalyst, extensive stripping with steam and the use of gases that have a higher temperature than is usual for FCC / VGO process management, such as flue gas from the regenerator, as well as other refinery gas streams such as hydrotreater waste gas ( _{containing H 2} S), hydrogen and other gases. For example, the stripper at a Temneratur of about 551.7 ° C can be operated or at higher temperatures (1025 F ^0). . -

The essential conversion of carbo-metallic oils to lighter ones Products, according to the present invention, can lead to quite high coke yields and considerable coke deposition on the catalyst and requires some care when regenerating the catalyst. To have sufficient effectiveness the zeolite-containing and non-zeolite-containing catalysts to maintain, it is desirable to regenerate the catalyst under such time, temperature and atmosphere conditions, sufficient to reduce the weight percentage of carbon remaining on the catalyst to about Depress 0.25% or less, regardless of whether the catalyst has a high concentration of heavy metals or not. This percentage by weight is preferably approximately 0.1% or less, and in particular approximately 0.05% or less, in particular in zeolite catalysts.- The amounts of coke that must therefore be burned away by the catalysts, if carbometallic Oils processed are usually considerably larger than in the case of cracking VGO. In the context of the present In the invention, the term "coke" is intended to include any residual, unevaporated feedstock or cracked product if such material remains on the catalyst after stripping.

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The regeneration of the catalyst, that is, the burning off of coke deposited on the catalyst during the conversion of the feedstock, can be carried out at any suitable temperature in the range of about 593.3 ° to about 871.1 ° C (about 1100 to about 1600 ° F). measured at the regenerator outlet for the catalyst. This temperature is up to about 815.6 ° C (about 1200 to about 1500 ⁰ F), more preferably about 690.6 ° to about 773.9 ⁰ C (about 1275 to about 1425 ⁰ F), and preferably 648.9 ° most preferably is about 718.3 ° to about 746.1 ⁰ C (about 1325 ° to about 1375 ° F). The inventive method has been carried out, for example, with a flow regenerator at a temperature of the dense catalyst phase in the range from about 704.4 ° to about 760 ° C (about 1300 ° to about 1400 ° F).

Provided regenerated catalyst for cracking carbo-metallic oil was used, it was previously believed that the success cracking from burning coke in contact with combustion producing gases containing excess oxygen, is dependent. By the term "excess oxygen" it is intended to mean such an amount of oxygen

be greater than the stoichiometrically required amount to burn all hydrogen, all carbon and all other combustible ingredients, if any, are those selected within those mentioned above Coke content are present immediately before regeneration. The gaseous products of combustion, in the presence of excess Oxygen will normally include a significant amount of free oxygen. This free one Oxygen is, unless it is by means or another

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Process other than regeneration removed from the by-product gases or converted to some other form, usually as free oxygen in that from the regenerator unit occurring smoke gas. To ensure sufficient driving force to complete the combustion of the coke to low levels, if all coke or a part of the coke Of the coke is burned with excess oxygen, the amount of free oxygen usually not only becomes noticeable, but rather considerable, that is to say in the entire regeneration flue gas that comes from the entire, enclosed Regeneration step is obtained, there will be a free oxygen concentration of at least about 2 mole percent. While such a process is effective to obtain the desired low carbon contents on the regenerated catalyst, it has limitations and difficulties, as will be explained below.

In conventional practice, when the coke is burned during regeneration, some P ^ O is produced, since it is usually a there is a small amount of hydrogen in the coke; however, carbon monoxide and carbon dioxide are generally used as the main products viewed. 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 to form carbon dioxide produces 7838 kcal / kg of coke (14,108 BTU per pound of coke), while the reaction between oxygen and coke or carbon with the formation of carbon monoxide approximately 2204 kcal / kg of coke (3967 BTU per pound of coke) was generated. The greater the amount of coke that is given by a catalyst Weight has to be burned away, the greater the amount of heat released during combustion in the regenerator.

The heat released in the regenerator by the combustion of the coke ¹ is absorbed by the catalyst and can easily be retained by the latter until the regenerated catalyst is brought into contact with fresh starting material. When processing carbo-metallic oils up to relatively

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high degree of conversion, within the scope of the present invention can be achieved, the amount of regenerator heat that can be achieved by returning the regenerated catalyst to the fresh Starting material is transferred, the extent of that heat supply significantly exceed which is suitable for in the j Risers heat the feedstock and other materials and vaporize the heat used for the exothermic cracking reaction To make available, to compensate for the heat losses of the system and the like. According to the invention, therefore, on the fresh Regenerator heat transferred to raw material is controlled within certain approximate ranges or, if necessary, be restricted. For example, the heat transferred in this manner can range from about 277.8 to about 666.7 (approx 500 to about 1200), preferably from about 333.3 to about 500 (about 600 to about 900), and especially from about 361.1 to about 472.2 kcal / kg of fresh starting material (about 650 to about; 850 BTUs per pound of fresh starting material). The above The ranges given relate to the combined heat, expressed in kcal / kg of fresh starting material, which through the catalyst to the starting material and the reaction products (between the contacting of the starting material with the catalyst and the separation of the product from the catalyst) to provide the heat for the reaction (e.g. for cracking) and the enthalpy difference between the products and transferred to the fresh starting material. In the above The ranges given do not include the heat generated in the reactor by the adsorption of the coke on the catalyst is made available, nor the heat that is consumed by heating, evaporating or converting the Recycle streams and input materials such as water, steam, naphtha and other hydrogen donors, flue gases and Inert gases, or by radiation loss or other losses.

A method or a combination of methods according to the invention can be used applied to the amount of regeneration heat transferred via the catalyst to the fresh feedstock

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to control or limit. For example, a combustion promoter can be added to the cracking catalyst to reduce the Combustion temperature from coke to carbon dioxide and / or carbon monoxide decrease in the regenerator. Furthermore, heat can be extracted from the catalyst by means of heat exchangers, including for example through heat exchangers (e.g. steam coils) built into the regenerator itself, which removes heat from the catalyst during regeneration can. The heat exchangers can also be installed in the catalyst transport lines, for example in the from Regenerator to the reactor running catalyst return line, wherein the catalyst after its regeneration heat can be withdrawn. The amount of heat given to the catalyst in the regenerator can be reduced by using the Insulation of the regenerator reduced in size, so that there is a loss of heat to the surrounding atmosphere, especially if provided is to process raw materials with an extremely high coking potential; however, there is generally heat loss to the atmosphere from an economic point of view as less expedient than other alternatives described here. Furthermore, cooling liquids can also be fed into the reactor, for example water and / or water vapor, with the amount of inert gas available in the regenerator for heat absorption and removal is increased.

Regardless of whether the procedures described above are used, the present invention includes a method of control or limiting the heat transferred to the fresh feedstock via the recycled, regenerated catalyst by maintaining a certain ratio between the carbon dioxide and the carbon monoxide in the regenerator are formed while these gases are in heat exchange contact or relationship with the catalyst being regenerated stand. In general, all of the coke or a major portion by weight of the coke that is on the catalyst is immediately is present prior to regeneration, removed in at least one combustion zone in which the above-mentioned ratio is controlled as described below. In particular, at least a major portion, preferably at least

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about 65% by weight, and in particular at least about 80% by weight, of the coke on the catalyst is removed in a combustion zone in which the molar ratio of CO2 to CO is kept at a value substantially below 5, for example is about 4 or less. If the CC ^ / CO ratio is viewed from the other side, the molar CO / CO ^ ratio is ^: preferably at least about 0.25, in particular at least about 0.3, and very particularly preferably about 1 or more, or even 1.5 or more. While the expert knows ways and means to convert the combustion of CO to CO _? To inhibit, it has been proposed that the molar ratio of CO to CO- should be kept below 0.2 when regenerating a catalyst with a high heavy metal enrichment, which results from the processing of carbometallic oils. In this connection, for example, US Pat. No. 4,162,231 to Zrinscak, Sr. et al. to be named. According to the invention, however, the maximization of CO generation is a particularly preferred embodiment in the regeneration of the catalyst to a carbon content of 0.1% or less, preferably about 0.05% or less. In addition, the regeneration addition method may / be in accordance with a preferred implementation of the invention to the above-mentioned low carbon contents on regenerated catalyst with a deficiency of oxygen \ material carried out in its entirety; In particular, the total oxygen supplied to the one or more regeneration stages can preferably be less than the stoichiometric amount required to burn _{all the hydrogen in the coke to HO and all the carbon in the coke to CO 2.} If the coke contains other combustible constituents, the stoichiometric amount mentioned can be adjusted so that the amount of oxygen required for the combustion of these constituents is included.

Another, likewise particularly preferred method for checking and limiting the amount of heat transferred to the fresh feedstock by the recycled catalyst includes the dissipation of part of the heat generated by the return

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guided catalyst is carried by additionally in the Materials introduced into the reactor, such as water, steam, 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 released by a catalyst given weight has to be burned away, the greater the risk of exposing the catalytic converter to excessive temperatures suspends. Many otherwise desirable and suitable cracking catalysts are particularly sensitive to deactivation at high temperatures, and among these are catalysts a handsome number of expensive molecular sieve or zeolite catalysts. The crystal structures of zeolites and the pore structures of the catalyst supports are generally opposite somewhat sensitive to thermal and / or hydrothermal degradation. The use of such catalysts in catalytic conversion processes of carbo-metallic starting materials creates a need for regeneration processes in which the catalyst is not destroyed by being very exposed to high temperatures and water vapor. This need can be met with a multi-stage regeneration process be encountered, which requires the charging of a first regeneration zone with the spent catalyst and the supply of oxidizing gas includes * The amount of oxidizing gas contained in this first zone is introduced and the concentration of oxygen or oxygen-bearing gas is only sufficient to achieve the desired conversion of the coke on the catalyst to carbon oxide 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 than to provide in the first zone, and the distance of carbon to the desired level. The regenerated catalyst can then from the second Zone removed and placed in contact with fresh starting material

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been returned to the reactor. An example of such a thing The multi-stage regeneration process is disclosed in US Pat. No. 2,938,739 described. ':>

The multi-stage regeneration offers the possibility of combining a regeneration with a deficit of oxygen and the control of the molar COrCC ^ ratio. Thus, about 50% by weight or more, preferably about 65 to about 95% by weight, and in particular about 80 to about 95% by weight, of the coke present on the catalyst immediately before the regeneration can be removed in one or more regeneration stages in which the molar ratio of CO: COj is controlled in the manner described above. In connection with the above, the last five percent by weight or more or even 10 percent by weight or more of the coke originally present up to the total amount of coke that has remained after the previous stage or stages can be used in a subsequent regeneration stage be removed in which more oxygen is present. Such a process can be carried out in such a way that all of the flue gas obtained from the complete, closed regeneration process contains little or no excess oxygen, that is to say of the order of magnitude of about 0.2 mol% or less , or even about 0.1 mole percent or less, which is considerably less than the 2 mole percent suggested elsewhere. Accordingly, multi-stage regeneration is particularly valuable in that it is another convenient method of limiting the heat of regeneration transferred to the fresh feedstock by the regenerated catalyst and / or reducing the risk of thermal deactivation while at the same time providing the possibility to reduce the carbon content on the regenerated catalyst to the very low percentages (e.g. 0.1% or less) that will significantly improve the catalyst efficiency. In addition, will be the one

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Part of the regeneration sequence in which the most severe conditions prevail, carried out while a significant amount of coke is still present on the catalyst, if the regeneration conditions, for example the temperature or the atmosphere, are much less severe in the second zone than in the first zone (For example by at least about 5.6 ° C. ("1O ⁰ F) 'and preferably by at least about 11, 1 ⁰ C (20 ⁰ F)). Such a process procedure can represent a protection of the catalyst from the stricter conditions. A particularly preferred embodiment of the invention is a two-stage fluidized regeneration at a maximum temperature of about 815.6 ° C (1500 ⁰ F) with a reduced temperature of at least about 5.6, or 11.1 ⁰ C (10 or 20 ⁰ F) in the dense phase of the second stage compared to the dense phase of the first stage, and with a reduction in carbon on the catalyst to about 0.05 wt.% or less, or sec or about 0.025 wt% or less in the second zone. In fact, the catalyst can easily be regenerated to carbon contents of 0.01% by weight by this method, even if the carbon on the catalyst prior to regeneration is as high as about 1%.

In some cases it is important to ensure that adsorbed oxygen-containing gases are not entrained into the riser by the recycled catalyst. Whenever such a measure is deemed necessary, the catalyst removed from the regenerator can be subjected to a stripping step with suitable stripping gases to remove the oxygen-containing gases. The stripping may for example at relatively high temperatures, for example at about 732.2 ° C. to about 743.3 ° C (about 1350 ° to about 1370 ⁰ F), using steam, nitrogen or any other inert gas as the stripping gas (e) will. The use of nitrogen or other inert gases is beneficial in that it avoids the risk of hydrothermal catalyst deactivation, which can occur when using steam.

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The following explanations regarding the handling of metal, carbon and heat or the management of the process are intended to provide assistance in achieving the best results when carrying out the
be the present invention. As these remarks largely relate to the conduct of the procedure which is believed to be the best, it is intended to indicate that
the invention is not limited to the procedures described below. Since some of these remarks are necessarily based on theoretical considerations, it should also be emphasized that this is not binding
any theory is intended, whether or not it is here. is expressly mentioned or implicitly expressed in the following proposals for the conduct of the proceedings.

Although the metal, carbon and heat handling resp.
- procedural guidance is addressed separately below and
discussed, these are interrelated and interdependent subjects, both in theory and in
Practice. While the coke yield and coke deposition on the
Catalyst primarily caused by the relatively large amounts of _: Coke precursors that are present in the carbo-metallic! oils are present, the coke production is aggravated by high metal- '- enrichments, which in turn also have a
can have a significant negative impact on catalyst performance. In addition, the success achieved in metal and carbon handling or process management will be achieved! degree has a direct influence on the extent to which one
Heat processing is necessary have; Schiiesslich _"(have steps that have been taken to support the metal handling or j -Verfahrensführung to be very helpful in the I with regard to the carbon and heat handling or -Verfahrens-;

leadership proven. j

As mentioned above, the presence of a large one tends to be! Heavy metal accumulation on the catalyst makes it difficult J the problem of dehydration and aromatic condensation, which ί leads to an increased production of gases and coke, with a j

ORIGINAL INSPECTED ^C0PY

Starting material for a given Ramsbottorn carbon value. The introduction of significant amounts of H-O into the reactor, either in the form of water vapor or in the form of liquid Water appears extremely beneficial in terms of heavy metals in a less harmful form, i.e. in the oxide form instead of the metallic form. At the same time supports the maintenance of the desired selectivity.

Likewise, a system in which the system components and dwell times are selected so that the ratio of If the catalyst-reactor residence time is decreased to the catalyst-regenerator residence time, the time spans should be suitable to lower, during which the catalyst is kept under reduction conditions or oxidation conditions. This can also help maintain desired levels of selectivity.

Whether the metal content of the catalyst is being handled successfully can be determined by monitoring the total hydrogen produced plus methane in the reactor and / or the ratio of hydrogen to methane produced in this way will. In general, the hydrogen to methane molar ratio should be less than about 1, preferably about 0.6 or less, with a value of about 0.4 or less being considered optimal.

Careful carbon handling or process management can both selectivity (the ability to maximize the production of valuable products) and ■ heat productivity to enhance. In general, the metal content control methods described above also aid Carbon handling or process management. The expediency the addition of water with regard to the carbon process management has already been described in detail in the paragraphs above, which deal with additional materials for Introduction to the reaction zone deal. In general, those processes that reduce the dispersion of the starting material should

130-0 Si7 / 0622

improve materials in the reaction zone, also helpful prove; these methods include, for example, the use of misting devices to promote dispersion of the source material.

The ratio of catalyst to oil is also at the Thermal process management factor to be considered. As with VGO's traditional FCC practice, the reactor temperature can be at The practice of the present invention can be controlled by allowing the flow of hot regenerated catalyst depending on whether it is increased or decreased in order to lower or increase the reactor temperature, which is the case in the case of a riser reactor typically the outlet temperature. When the automatic control device for the introduction of the catalyst adjusted to maintain an excessive catalyst to oil ratio, it can be expected that unnecessarily large amounts of carbon are generated and unnecessarily large amounts of heat are released in relation to the Fresh starting material fed into the reaction zone.

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

The carbon handling or process management can be carried out by suitable Limitation of the total pressure in the reactor and the partial pressure of the starting material are also facilitated. In general, for a given degree of conversion, relatively small decreases in the above-mentioned pressures can lead to a substantial one Lead to a decrease in coke production. This could possibly be due to the limitation of the Overall pressure leads to increased evaporation of the high-boiling components of the starting material, which promotes cracking and the separation of both unreacted feedstock and higher boiling cracked products from the catalyst

- 62 -

• bo

loif-htort. In this regard, it can nuc: h helpful soin, den Pressure drop in the equipment downstream of the reactor and in communication with the reactor restrict. However, when it is desirable or necessary to run the system at a higher total pressure, for example because of Operational restrictions (e.g. due to a pressure drop in downstream equipment), The advantages described above can also be achieved by restricting the starting material partial pressure subject. Suitable ranges for the total reactor pressure and the partial pressure of the starting material have already been given above and it is generally desirable to try to keep pressures within these ranges to a minimum keep.

The abrupt separation of the catalyst from product vapors and Unreacted starting material (if one is available) is also of great help. For this reason is the so-called ventilated riser apparatus and technique disclosed in U.S. Patents 4,070,159 and 4,066,533 to George D. Myers et al., The preferred type of device for carrying out the method according to the invention. For similar reasons it is advantageous is the time elapsing between the separation of the catalyst from the product vapors and the start of the stripping shorten as much as possible. The use of a ventilated riser and prompt stripping are less likely to cause coking of unreacted feedstock and higher boiling cracked products adsorbed on the catalyst.

A particularly expedient procedure with regard to the carbon handling or process control is to run the process in the ventilated riser using a Hydrogen donor, if necessary, to carry out while keeping 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 advantages discussed above

130037/0622 _{BAD 0RIG | NAL}

COPV

6049 CD, - & + -; LQ. 3 OA 3 1 07

have as a consequence. When liquid water; Water vapor, hydrogen donors, Hydrogen or other gaseous or vaporizable materials are introduced into the reaction zone, allows the In addition, adding these materials, an additional control the ratio of catalyst to oil. Therefore, for example, the practice of increasing or decreasing the Ratio of catalyst to oil at a given increasing or decreasing amount of the reactor temperature can be reduced or omitted by either a suitable lowering for it or increases the feed proportions of water, steam and other gaseous or vaporizable materials or, appropriately, the ratio of water to Damof and / or other gaseous materials entering the reaction zone be introduced, decreased or increased.

The heat handling or process management includes measures which are taken to control and / or to control the amount of heat released in different stages of the process to successfully handle such heat as can be released. Contrary to the traditional FCC practice under Use of VGO where it is generally a problem while generating enough heat during regeneration to ensure heat balance in the reactor is generated by the processing of Carbo-metallic oils generally have so much heat that a careful handling and process management of the heat necessary

Heat handling can be facilitated by various methods related to the materials introduced into the reactor. In this way, the heat absorption by the starting material can be maximized when the starting material is preheated is kept to a minimum, it is only necessary that the temperature of the starting material is high enough that it is sufficiently liquid to be pumped into the reactor and dispersed there. If the catalyst is in a highly active state is kept and the coking is suppressed (metal control), in order to achieve higher conversions, the

- 64 ORIGINAL INSPECTED COPY

obtained higher conversion and greater selectivity the heat absorption increase the response. In general, higher reactor temperatures will benefit catalyst conversion efficiency with regard to heat-solid and higher-boiling components with a high coking potential. While so the KdLnly.satord deactivation speed can be increased, the higher process temperature does not compensate for this loss of effectiveness. Higher temperatures in the reactor also contribute to an increase in the octane number, thus equaling the cetane number rigorous effects of high carbon deposition. Other Methods for absorbing heat have already been related above discussed with the introduction of water, water vapor and other gaseous or vaporizable materials into the reactor. ■ '

Sharp stripping and various regeneration methods described above are suitable for controlling the release of heat in the reactor. During the removal of heat from the catalyst in the regenerator or at a downstream point, with respect to the regenerator, through heat exchangers (including Water vapor coils) as a way to control the released Heat has been proposed, the method of multi-stage regeneration and control of the CO / CC ^ ratio described above is used (either in a single-stage or in a multi-stage regeneration), however, viewed as more advantageous. The application of water vapor coils can in part be viewed as a kind of own gate, as a water vapor coil or a heat exchanger generally an increase in the catalyst-to-oil ratio in the regenerator or in a catalyst recycle line causing an increase in carbon production in the reactor and heat release in the regenerator.

As noted above, the invention can be practiced in the ways described above and in many other ways. Two examples Embodiments are based on the schematic diagrams of Figures 1 and 2 and on the basis of their subsequent descriptions explained in more detail, but this is not a restriction.

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BAD-QRiGfNAL _o q? 1

Figure 1 shows a schematic diagram of a system for Implementation of the method according to the invention. The carbo-. ■ metallic oil starting material (which is in a not shown Raw material preheater may have been heated) and water supplied through the feed line 9 (if such is used) are through the starting material supply line 10, which has a control valve 11, into a C-piece 12 conveyed, where they are mixed with a catalyst flow fed in through the supply line 13, controlled by the valve 14. Of course, a variety of different Mixing devices are used, and devices can also be provided to mix the other additional materials, discussed above. The mixture of catalyst and feedstock, with or without such additional ones Materials, is then fed 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 is not necessarily must be arranged vertically, since riser reactors j are known in which a reasonable proportion of the riser tube is not | is arranged vertically. There are thus riser pipes with a ' upward directional component in question, and is usually the upward component of their upward flowing, ' inclined areas considerably, that is to say it is at least 30 °. There are also known risers which flow downwards. inclined or vertical sections, as well as horizontal descents! cuts. Furthermore, folded risers are known which; have both upwardly and downwardly extending portions. Finally, it is possible that the invention Process in an inclined and / or vertically arranged tube ■ to carry out, in which the starting material and the catalyst j Sator are introduced from above, and in which the starting material and the catalyst are under the influence of the Gravity and the drainage of the starting material move down to a deeper level. In the context of the present In general, those reaction chambers that have a large L / D ratio are suitable for the invention, and in which one there is a clear deviation from the horizontal.

- «rt Λ /» - CT # rt -

COPY

At the upper end of the riser 18, a chamber 19 is arranged which picks up the catalyst coming out of the riser. While chamber 19 can be a conventional separation and collection chamber can, means are preferably provided to cause the product vapors to change direction sufficiently with respect to that of force the catalyst particles to go in the direction they are taking, causing the vapors to suddenly and effectively escape from the catalyst. be separated. Preferably, as described above, there is a "ballistic" separation of the catalyst particles from the product vapors performed. . ■

In the schematic diagram, the separation chamber 19 includes a upward extension 20 of the riser tube 18 with an open upper end 21 through which the catalyst particles be discharged. In this embodiment, the so-called ventilated riser, which is disclosed in the Myers et al. patents described above. is described. Because The refractory nature of the carbo-metallic fractions requires relatively severe conditions, but prevents them the quick separation of the catalyst from the lighter cracked ones Products in the ventilated riser crack the desired liquid products, such as gasoline, into gaseous ones Products. The product vapors are forced to suddenly change direction through the side opening 22, which is shown in FIG the side of the riser extension 20 is arranged, the catalyst particles predominantly in the product vapors cannot follow into the opening 22.

The vapors and the few particles that have succeeded in following the vapors into the opening 22 are passed through the cross line 23 transferred to a cyclone separator 24. It is an advantage of the illustrated ventilated riser system that it can operate satisfactorily with a single stage cyclone separator. However, the cyclone separator 24 in the present embodiment as a first cyclone separator used, which via a transfer line 17 with an optionally arranged, second cyclone separator

- 67 -

130037/0622

BATH ORIGINAL

6049 CD - «* - ·, 3Q431Q7

device 25 is connected. The cyclone separator, regardless of whether it is single-stage or multi-stage, separates those small amounts of catalyst from the product vapors that it. has succeeded in getting through the lateral opening 22. The product fumes are discharged from the separation chamber 19 through the product discharge line 26.

The catalyst particles emerging from the open top 21 of the riser extension 20, and those catalyst particles emerging from the are discharged from the discharge legs 27 and 28 of the first and second cyclones 24 and 25, respectively, fall to the bottom of the Separation chamber 19. The catalyst inventory and the residence time of the catalyst in chamber 19 are preferably on one Kept to a minimum. During the start-up, the catalyst particles present can be blown through the loosening nozzles 30, which are via the Steam supply line 29 are fed with steam, in Be held in limbo. Used catalyst overflowing from the bottom of the separation chamber passes through the Downpipe 31 into a stripper chamber 32, which is equipped with baffles 33 and into which a steam jet 34 leads. Each other stripping gas mentioned above can be used in conjunction with or in place of water vapor.

The carbon is in the combustion device 38, in which the stripped catalyst is picked up via the downcomer and control valve 40 from the surface of the catalytic converter burned away. The fans 41 and 42 provide in conjunction with a valve and piping system, which generally indicated by the reference numeral 44, the air for the combustion air nozzles 48 at the bottom of the combustion apparatus and for the loosening nozzle 49, which is in a higher position are arranged. A preheater 4 3 can be used if the system is started up with VGO, although the preheater usually not needed if the invention is heavy Hydrocarbons are processed; if the system is then converted to carbo-metallic starting material, the Operation of the preheater stopped (or at least limited)

BAD ORfGfMAL

been. Additional fuel means are to be provided, to supply fuel through the combustion air nozzles 48; however, it is usually not necessary as the carbon precipitate on the catalyst will produce more than enough fuel Provides to those required in the regeneration section Maintain temperatures. The regenerated catalyst from which most of the carbon has been burned away leaves the combustion device through an upper outlet and enters a second chamber 52 through a cross line 51, where it is deflected into the lower part of the chamber by means of a baffle plate 53. Although the application of a two-stage Regeneration is possible and also preferred, the second chamber 52 serves primarily in this special embodiment as a separation chamber, although it can also be used to further carbon down to about 0.01% or less to be removed in the final stages of regeneration.

The catalyst can be guided out of the second chamber 52 in up to three different directions. Part of the catalyst can be returned to incinerator 38 via catalyst recirculation loop 55 and the like Control valve 56 for controlling the heat in the combustion device. Part of the catalyst is used by the Product gases entrained, such as CO and / or CO- produced by burning the carbon on the catalyst in the Combustion device are generated, and the entrained Catalyst dust arrives at the top of chamber 52 to two sets of first and second cyclones generally associated with the Reference numerals 57 and 58 are denoted in which this catalyst dust is separated from the combustion gases. The catalyst collected in the cyclones 57 and 58 and through their Catalyst discharged downstairs is directed to the bottom of the chamber where the catalyst is passed through inert gas and / or steam nozzles 59 and is held in suspension by a baffle plate arrangement 54, the latter being responsible for the removal of regenerated Catalyst facilitated through the outlet 69 in the catalyst supply line 13, through which it for contact with fresh starting material in the C-piece 12, as described above, is recirculated.

13003770622

COPY

Λ L

6049CD

Those generated by the regeneration of the catalyst and by the catalyst dust carried over by the sets 57 and 58 Combustion product gases separated at primary and secondary cyclones in chamber 52 are passed through exhaust lines 61 and 62 and the heat exchangers 60 and 63 removed. This one Gases contain significant amounts of CO, they can be via the gas supply line 64 are fed into an optional oven 65 in which the CO is used to heat the heating coil 66, the is connected to the steam boiler 67, is burned. Additional Heat can be added to the contents of the boilers through the conduit loop 68, the liquid from the boiler 67 to the heat exchangers 60 and 63 and back to the boiler. Of course, this is just one of many possible examples of regeneration systems. Those from the regenerator via the regenerated catalyst to the riser Recirculated heat can be controlled in any of the other ways described above; however, according to the invention, the controls relative proportions of carbon monoxide and carbon dioxide that are generated while the catalyst is in a heat exchange relationship to the combustion gases coming from the regeneration. The same procedure is also in the Realized by Fig. 2 explained, particularly preferred embodiment. · ■ ■

In FIG. 2, the reference numeral 80 stands for a starting material control valve in the starting material supply line Through the supply line 83 (if required) liquid is produced Water fed into the feedstock. A heat exchanger 81 arranged in the supply line 82 serves as the starting material, al-preheater, whereby preheated feedstock can be fed into the bottom of the riser reactor 91. The catalyst is fed into the reactor through the catalyst standpipe 86, the catalyst flow through a control valve 87 and a suitable automatic control device (not shown) regulates which professionals are familiar with in the field of planning and operating riser crackers.

- 70 -

-Ήρ ·

The riser 91 can optionally comprise means for the injection of water, water vapor and, if desired, other gaseous and / or vaporizable materials for the purposes mentioned above. The reactor is provided with a separation chamber 32 similar to the separation chamber 19 of the reactor shown in Figure 1 and thus the embodiment of Figure 2 includes means for forcing the vapors to change direction in order to achieve 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 manner similar to that of the stripper 32 shown in FIG. The used catalyst passes from the stripper 94 through the transfer line 97 for used catalyst, which has a shut-off valve 98 for controlling the flow, into the regenerator 101.

The regenerator 101 is supported by a partition plate 104, which is attached between the upper and lower ends of the regenerator, divided into an upper chamber 102 and a lower chamber 103. The spent catalyst coming from transfer line 97 enters the upper chamber 102 in which the catalyst is partially regenerated. A funnel-shaped collection device 106 with a bevel cut top edge takes the partially regenerated catalyst. From the top surface the dense phase of the catalyst in the upper chamber 102 and brings it through the downpipe 107 with an outlet 110 below the upper surface of the dense phase of the catalyst into the lower regeneration chamber 103. Instead of the internal Catalyst downpipe 107 can also be used an externally attached downpipe. Through valves in such an external Attached downpipe can control the catalyst residence time and the flow rate in and between the upper and lower Chamber controlled.

Air is supplied to the regenerator through the air supply line 113 brought. A part of the air reaches the bayonet 115 through a two supply line 114, which extends upwards into the

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130037/0622

BATH ORIGINAL

6049cd -> a— j ^. 30A31 07

Interior of the storage space 111, along its central axis, extends into it. 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 bayonet (not shown) in the space mentioned loosens the catalyst and forces it upwards against a horizontally arranged ring distributor (not shown) at the end that is open at the top of the storage space 111 which opens into the chamber 103. The remaining air that is supplied through the air supply line 113 can be installed in an air heater 117 (at least during start-up with VGO) and then heated through inlet 118 of the above mentioned ring distributor are introduced, which is provided with holes, nozzles or other openings, which one to the top generate directed gas flow to fluidize the partially regenerated catalyst in chamber 103.

The air supplied in this way completes in chamber 103 the regeneration of the partial regeneration of the air obtained from the downpipe 107 regenerated catalyst. The amount of air supplied is sufficient that the air and / or the combustion gases obtained are still able to support the combustion if they reach the top of chamber 103. The above-mentioned downpipe 107 extends through an enlarged opening in the Separating plate 104, on which a gas distributor 120 is arranged, which is arranged concentrically with respect to the downpipe and surrounds this. The gases maintaining the combustion pass through the gas distributor 120, some of which are now used for the combustion entertaining gas are depleted, in the upper regenerator chamber 102, where they are with the incoming from the overhead line 97, spent catalyst are brought into contact for its partial oxidation. Apertured probes or other suitable means in gas manifold 120 will assist in evenly distributing the partial to the combustion entertaining »gas depleted gas in the upper chamber 102. Additional air or other fluids can be in the upper Chamber 102, if desired, can be introduced through the supply line 122 which leads into or through the gas manifold 120.

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Λ * ·% Λ »« · t ** PS

Fully regenerated catalyst with less than about 0.25% carbon, preferably less than 0.1%, and more preferably less than about 0.05 % _r is removed from the lower regenerator chamber 103 by a regenerated catalyst stripper 128, the outlet of which is shown in FIG the above-mentioned catalytic converter stand-alone line 86 leads. In this way, the regenerated catalyst is returned to the riser 91 for contact with further fresh starting material which is supplied via the starting material supply line 82. Any heat that the recycled catalyst has picked up in regenerator 101 is available for transfer to the fresh feedstock in the riser.

The division of the regenerator into an upper and a lower regeneration chamber 102 or 103 is not only equal to fluctuations the catalyst-regenerator residence time, it also provides unique support in terms of restriction the amount of regeneration heat transferred to the fresh feedstock while a regenerated catalyst with low residual carbon values for recycling in the reactor is obtained. Due to the arrangement of the regenerator, the spent catalyst comes out of the transfer line 97 with its high carbon content in the chamber 102 in contact with the combustion assisting gases, the at least are already partially depleted of oxygen by burning the carbon from the partially regenerated catalyst in the lower regenerator chamber 103. Because of this, it is possible to monitor both the combustion and the amount of generated Control carbon dioxide in the upper regenerator chamber 102. Although the air or something else, through the air supply line 113 and the branch line 114 are supplied with regeneration gas can contain a relatively large amount of oxygen, is already part of the carbon of the partially regenerated catalyst, with which they come into contact in the lower regeneration chamber 103 is removed. The high concentration of oxygen and the Temperature of the partially regenerated catalyst are common Cause of rapid removal of the remaining carbon

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130037/0622

cop *

i r

Substance in the catalyst, with a clean, regenerated catalyst with a minimultr? of heat release is obtained. - ^: The combustion temperatures and the COrCCU ratio in the lower regeneration chamber can therefore also be easily checked here. The regeneration exhaust gases are discharged from the upper regenerator chamber 102 through the exhaust line 123, the regulating valve 124, the catalyst dust trap 125 and outlet 126. :

The product vapors obtained from the separating canister 92 can on processed in any suitable manner, for example by evacuation through vapor discharge lines 131 to the inlet fractionation column 132. Said fractionation column comprises a bottoms outlet 133, a side outlet 134, a flushing oil stripper 135, a stripper bottom outlet, and drain line 136, which is connected to a pump 137, for the discharge of flushing oil. The overhead product of the stripper 135 becomes; via the stripper head product return line 138 into the ' Fractionation column 132 recycled.

The main overhead product discharge line 139 of fractionation column j is connected to the overhead product receiver 142, which has an outlet line 143 for bottoms which "leads to pump 144 for the discharge of gasoline product. If desired, a portion of this product can be discharged via the recirculation line 145 \ can be returned to the fractionation column 132, the flow being controlled by means of the recirculation valve 146. The overhead product receiver also comprises a water receiver 147 and a water discharge line 148. A product stream is discharged through the gas outlet 150] of the overhead product receiver, the \ mainly material below C _5, but also some C ₅ -., ^c c ~ -.! desired and C _'7 material Falls, the C ^ material and heavier material loading in the gas product stream can j takes place, separated by pressure, cooling and fractionation and to the overhead product receiver with a compressor, cooler and! a Fraktionierko lonne (not shown) are returned. -

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ORIGINAL INSPECTED COPY

For games

The following examples serve only for illustration and are not to be interpreted as a restriction of the present invention. The data for the catalysts used in these examples are given in Table 2 above.

The conventional practice to date in some refineries involves blending relatively small amounts of carbo-metallic oils with vacuum gas oils, which were commonly used as starting material for fluid catalytic cracking. It should, however It should be emphasized that the common practice has been to control the amounts of carbo-metallic oil in such mixtures to restrict in order to obtain a starting material, which by relatively low contents of nickel equivalents of heavy metals and was characterized by relatively low levels of carbon residues from pyrolysis. Surprisingly, it has However, it has been shown that the degree of conversion of carbo-metallic oiling is greater when such oils are in such sufficient quantities be used that the nickel equivalents of heavy metals and the carbon residues are the relatively high disclosed here Reach values, for example, when the amount of carbo-metallic oil is a major proportion by weight of the hydrocarbon cracking reactant in the feedstock constitutes or all of the hydrocarbon cracking reactant in the feedstock forms.

Examples 1A-1D

In these examples, that shown in FIG. 1 is essentially used and the system described above is used. Examples 1A to 1C illustrate the operation with mixtures which are different Contain relative amounts of vacuum gas oil (VGO) and top residues. In Examples 1C and 1D, the operation with a Mixture on the one hand and with 100% top residue on the other hand compared with each other. With regard to the analyzes of vacuum gas oils and the top residues are referred to in Table 3 below. With regard to the operating conditions and the

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130037/0622

For a summary of the results, reference is made to Table 3 below.

Comparison of the Ergebni sse of Examples 1A and 1B at a temperature in the range of about 523.9 to 526.7 ° C (about 975-980 ⁰ F) is obtained with the system used here is known to a degree of conversion of about 78% when using an equivalent catalyst and VGO is used, which is similar to the vacuum gas oils exemplified in Table 3. A comparison of the results of Examples IA and 1B shows that assuming that the vacuum gas oil in each mixture is converted to the previously determined conversion rate of 78%, the top residue present in a smaller proportion (about 40%) in the experiment of Example 1A was only converted to about 44%, while processing a mixture containing a higher proportion of Topp residue (about 66%) as in Example 1B achieves 63% conversion of Topp residue. Also noteworthy is the increase in volume yield. Thus, the invention can be used to obtain higher conversion at top residues and / or higher volume yields at very good octane levels when the top residue in the blends is increased compared to blends that contain much larger amounts of VGO and much smaller amounts of top residue.

Comparison of the results of Examples IC and 1D

A comparison of the results of Examples 1C and 1D shows that assuming that the VGO in the mixture of Example 1C is converted to the previously determined conversion rate of 78%, the top residue is only converted to about 58 % when it is makes up about 42% of the starting material, while it is converted up to about 64% when it makes up 100 % of the starting material. Here again, the increase in volume percentage yield is remarkable. Thus, the invention can be applied in such a way that higher conversions of the top residue and / or increased percentage volume yields of liquid products with very good octane levels can be achieved when only top residues are used as starting material, in comparison

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to a mixture of top residue and VGO.

Examples 2 and 3

Using the top residue from Example 1D given in Table 3 and using equipment such as this is shown in Fig. 1 and has been described above, while maintaining the conditions given in Table 4, the also obtained in Table 4 results.

Examples 4-6

These examples were carried out using a facility as shown in Fig. 2 and described above. When operating this system as described above and in compliance with the conditions given in Table 4, and using a two-stage regeneration process, the results also given in Table 4 were obtained.

Examples 7-10

These examples were carried out using a pilot plant and using that given in Tables 1, 2 and 4 Starting material / catalyst and operating conditions carried out Figures 3 to 5 show the yield in percent by volume of (3) co ~ olefins, (4) C.-saturated compounds and olefins, and (5) gasoline, each plotted against volume percent conversion obtained by using the raw materials and catalysts of Examples 7-10, repeating at different values.

13003 ~ 7 ^7/0622

example 1A TABLE 3
Example 1B VGO Top residue VGO example 1C (492)
(818)
[1000) Example 1D en VGO Top residue 26.1 233 25.9 Top residue 049 API density 26.1 23.6 Top residue 22.9 O
σ Distillation, Vol.%
⁰ C ( ⁰ F) 287.8 (550)
415.0 (779) 235.6 (456)
423.9 (795)
526.7 (980) 291.1
411.1 23.1 5%
50 %
80% 301.1 (574)
411.7 (773) . 243.3 (470)
440 JO (824)
529.4 (985) 506.1 (943) 515.6 (556)
(772) 243.3 (470)
433 ^ (813)
526.1 (979) End point (EP) 509.6 (949) 0.36 0.42 0.50 (960) 255.6
436.7
537.8I Sulfur, wt.% 0.38 0.30 3.94 0.33 0.69 ι Ramsbottom
Carbon value 0.36 4.12 0.6 4.25 f 4.2

Heptane-insoluble

Links,

Wt%.

0.04

Metals, parts by weight pwo million

Fe 1.2

Ni < 0.5

V <03

Well 6.5

Weight portion

0396

0.91

33 73 4.7 22

0.404

0.03

<0.5

< 03

<r 0.5

<03

0.34

0.77

2.5

43 4.2 0.8

0.66

< 1.0

<

1.1 1.0

0.583

134

113 113

2.0

100%

CO

CD

CO '

API-Oich » 1 -A - 534.4 (994) 1 -B TABLE 4 EXAMPLES 2 3 4th S. distillation (40% R.C) 137 (28.0) (66% R.C.) 1 -O (100% R.C) (100% R.C) ABL R.C. (5) CO
r> IBP 42,016 (92,630) 33592 (74540) 1 -C (100% R.C.) 33,782 (74,478) 32,753 (72,209) 1029 12268) tf Source material 50% 426 (940) 6.1 417 (920) (42% R.C) 34,042 (75,050) 1,742 (3,840) 1,774! 3.91Oi 87.5 (193.01 Starting material, kg (pounds) / hr (1) 95% 4.2051 9.270) 23 2,740 (6,040) 48,642 (107537) 1,837 (4,050) 4,187 (9,230) 4,255 (9,380) 43.7 (96.4) Water vapor, kg (poundsl / hr RONC F-87 6.7 F-87 1512 1 4,215) 3,724 (8,210) GRZ-I GRZ-I Eq. SDX (4) Water, kg (pounds) / hr MONC 8.2 13th 83 2,457 (5,417) GRZ-I 7.1 73 9.3 catalyst Regeneration ^{temperature, 0} C ( ⁰ F) 73 GRZ-I 73 2.6 Catalyst / oil ratio Upper regeneration temp., ⁰ C ( ⁰ F) 45.5 540.6 (1005) 6.0 525.0 (977) 523.9 (975) 526.7 (980) Oampf-Riser-Varweilzait (see) Lower regeneration temp., ⁰ C ( ⁰ F) 6.4 130 (27.0) 526.7 (980) 2.55 (36.3) 2.43 (34.6) 2.47 I 35.1) Rx temperature, ⁰ C ( ⁰ F) Spent catalyst, wt% C 1003 5235 (975) 1.76 (25.0) Pressure, kg / cm2 (psia) Regenerated catalyst,% C 0.72 7.2 2.02 (28.7) 4.9 5.6 4.3 Product" Circulating catalyst,% C 623 23 6.1 3.2 25th 2.7 Drying gas, wt .-% 02-Abgai, mol% d. entire Rauchgaut 1193 93 4.6 3.5 5.4 53 9.2 C3-saturated compounds, vol .-% C0 ₂ / C0, kg / kg 2.2 3.0 83 6.8 3.5 7.0 C3-Olifine, vol .-% 53.4 9.5 8.7 33 73 8.3 9.7 I. Cj-saturated «Compounds, Vol. ·?» 453 53 7.1 31.4 42.9 52.0 f C4-Ola (ina, VoI .-% 92 8.2 73 433 8.9 10.0 11.6 • C5-221.1 ° C, Vol.% 248 1033 48.4 10.0 97.4 102.7 95.1 Kokt, G «w .-% 444 038 73 1053 0.53 0.67 0.63 Material balance, Giw .-% 93.1 67.5 101.7 038 593 64.3 78.5 * selectivity . 773 124.7 0.71 63.6 III3 118.1 111.0 Conversion, vol.% 742.2 (1368) 673 1233 Volume expansiona,% - 54.4 1193 53.0 52.7 47.8 petrol - 54 ^! 031 95 54.7 94 104 168 032 248 94 254 255 264 - 432 108 238 438 435 420 03 893 235 434 89.4 895 92.3 00 783 440 91.6 78.7 783 82.7 7423 (1369) 92.2 803 724.4 (1336) 721.1 (1330I N / A CO - 82.0 737.2 (1359) N / A N / A 698.9 (12901 ⁰ - 705.6 (1302) N / A N / A N / A 718.3 113251 038 - N / A 1.72 1.72 1.21 CO 0.015 - 1.67 0.53 0.53 0.01 - * -, 136 0.43 - - 0.34 O 2.0 032 - 0.0 0.0 0.0 00 - 0.0 2.43 3.19 3.81 0.0 2.67 33

Table 4 - continued

API density 5 6th EXAMPLE 7th IELE 8th 9 10 O)
O I. * distillation ABL R.C. * Murb. Mex. (2) Murb.VGOO) Murb. R.C. ABL R.C Mex. R.C CD Φ Source material IBP 1,225.8 (2,702.4) 1-243.62 (2,741.72) 1.89 (4.16) 2.26 (4.981 1.03 (2.27) 2.05 (4.52) O T CO, Starting material, kg (pounds) / hr (1) 50% 85.46 (188.4) 113X) (249.2) - - - - T f— S i Water vapor, kg (pounds) / hr 95% 0 0 - - - - t * * Water, kg (pounds) / hr RONC. Eq. SDX Eq. SDX Eq. SDX Eq. SDX Eq. SDX Eq. SDX \ CO catalyst MONC 5.8 7.1 10.32 8.46 12.5 12.35 irs Catalyst / oil ratio Regeneration temperature.oc ("F) 1.6 2.3 Dempf Riser Residence Time (see) Upper regeneration temp., ⁰ C ( ⁰ F) 538.9 (1002) 651.7 (1025) 568.9 (1056) 566.1 (1051) 568.3 (1055) 593.3 (1100) CD Rx temperature, ⁰ C ( ⁰ F) Lower regeneration temp., ⁰ C ( ⁰ F) 2.47 (35.1) 2.50 (35.6). Pressure, kg / cm ^ (psia) Used catalyst. Wt. * C Products Regenerated catalyst,% C 4.9 SJS 3.5 5.5 Drying gas, wt .-% Circulating catalyst,% C 3.2 2.7 3.5 2.2 C3-gosaturated compounds,% by volume Oj exhaust gas, MoL% d. total flue gas 10.5 9.6 13.7 11.4 C3 "olefins,% by volume CO ^ / CO, kg / kg 7ß 5.9 8.9 4.2 Cij-saturated compounds, vol .-% N / A - do not specify 10.8 10.5 11.0 11.8 C4 olefins,% by volume *) »... top residue 45.5 52.1 53.50 53.44 45.85 46.55 C5-221.1 ° C,% by volume (1) Only fresh raw material, with dei 9.9 8.4 7.22 8.1 16.47 9.53 Coke, wt% 98.2 100.0 98.81 96.7 96.6 99.4 Material balance,% by weight 0.63 0.68 0.64 0.73 0.57 0.63 selectivity 71.4 75.7 83.2 72.95 79.96 74.1 Conversion, Vol. * 118.2 118.8 Volume yield,% petrol 60.5 47.7 42.5 36.9 36.3 37.8 95 152 212 258 398 398 93 pounds 93 ü 92.0 93.2 95.4 94 82.2 80.8 70.7 78.1 80.1 N / A N / A 695 (1283) 737.8 (13601 701.7 (1295) • 737.8 (1360) 763.9 (1407) 676.1 (1249) NVA N / A N / A N / A 772.2 (1422) 735.0 (1355) N / A N / A N / A N / A 1.63 1.14 0.87 1.49 2.54 0.94 OJOI 0 /) 1 0.17 033 0.73 0.17 0/42 0.49 0 0 2.51 4.9 2.32 2.52 4.7 5.8 4.43 18.2 3.84 20th Exception, the * Example 3 the return of 9.477 # / hour of return heavy oil which has an API density of 18.3 UOD (up to 775 ° F 550) boils at about 287.3 to 412.8 ⁰ C and Zufuhrungsleitung Topp-residue-is injected into the riser in the. (2) Mixture of 67 % Mexican and 33% Murban ToDD residue • n (% by volume).

The VGO Davison Gletchoewichts-Super DX given in Table 1

r _n ^ :. μ 1: .. * .. T-

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Claims (38)

DR.-ING. WALTER ABlTZ 30431 07 ^M ~
DR. DIETER F. MORF Π """ I I'oKtfach Bf) OlOO, 8000 Münchon 8β DIPL.-PHYS. M. GRITSCHNEDER ' HtaiiBChrift / T'ONtnl AdiiriiHn Patent attorneys T Telegrams: Chemindus Munich Telex: (O) 523992 . 6049 CD Ashland Oil, Inc.
Russell, Kentucky, V.St.A. Process for converting carbo-metallic oil with a controlled CO: CO ₂ ratio during regeneration Claims Process for the economical conversion of carbo-metallic oils into lighter products, characterized in that one I. provides a feedstock for the conversion which contains 343.3 ° C + material, the 343.3 ° C + material being characterized by a carbon residue on pyrolysis of at least about 1% by weight and at least about 4 parts per Million nickel equivalent «contains heavy metal (s);
II. Comprising this feedstock for conversion with a cracking catalyst to form a stream 130ö3 ¹ 770622 BATH ORIGINAL 6049 CD - 2 - a suspension of the catalyst in dom starting material, which brings together and the current obtained by a fluidized bed reactor having an elongated reaction chamber which is at least partially disposed vertically or inclined for a predetermined vapor Riserv ^erwe ü ~ time ranging from about 0.5 to about 10 Seconds at a temperature of about 482.2 ° C to about 760 ° C and an absolute pressure of about 0.70 to about 3.52 kg / cm ² , which corresponds to a conversion per pass in the range of about 50% to about 90% is sufficient, can flow, with coke being formed in amounts of about 6 to about 14% by weight, based on fresh starting material, and being deposited on the catalyst in amounts of about 0.3 to 3% by weight; III. separating the catalyst from the cracked products obtained;
IV. The separated catalyst is freed from the adsorbed hydrocarbons by stripping; V. regenerates the catalyst by burning the coke in at least one regeneration zone with an oxygen-containing, the combustion maintaining gas under such time, temperature and atmosphere conditions, which are sufficient to the carbon on the catalyst to about 0.25 wt .-% or less, wherein gaseous combustion products, comprising CO and / or CO ₂ / are formed, and wherein at least the main part by weight of the coke is burned in one of the regeneration zones in which the molar ratio of COrCO _{2 is} at a level of at least held about 0.25; and VI. returning the regenerated catalyst to the reactor for contact with fresh feedstock. 13QQ37 / 0622 2. The method according to claim 1, characterized in that the 34 3.3 ° C + material is at least about 70% by volume of the starting material and contains at least about 10% by volume of material not below about 537.8 ° C boils. 3. The method according to claim 1, characterized in that the total carbon residue of the starting material has a Ramsbottom carbon value of at least about 1% is equivalent to. 4. The method according to claim 1, characterized in that the carbon residue of the starting material as a whole a Ramsbottom carbon value in the range of about 2 to about 12. 5. The method according to claim 1, characterized in that the total starting material is at least about 4 parts per Contains a million nickel equivalents of heavy metal (s) of which at least about 2 parts per million is nickel (as metal, based on weight). 6. The method according to claim 1, characterized in that all of the starting material is at least about 5.5 parts contains heavy metal (s) per million nickel equivalents. 7. The method according to claim 1, characterized in that supplementary catalyst is added to or lost to replace the catalyst removed from the system, the supplementary catalyst as it is introduced, a Microactivity of at least 60% by volume, and any catalyst withdrawn from the system as it is withdrawn will have a micro-activity of at least about Have 20 vol .-%. BATH ORIGINAL 6049CD - 4 - 30 A3 1 8. The method according to claim 1, characterized in that an accumulation of heavy metals on the catalyst in the range of about 3000 parts per million to about
70,000 parts per million nickel equivalents of heavy metal (s) by weight and measured on regenerated equilibrium catalyst occurs. 9. The method according to claim 1, characterized in that the catalyst is a zeolite molecular sieve catalyst, containing at least about 5% by weight sieve. 10. The method according to claim 1, characterized in that the predetermined riser residence time of the feedstock and product vapors is about 3 seconds or less. 11. The method according to claim 1, characterized in that the temperature is maintained in the reactor in a range from about 529.5 ° C to about 648.9 C ^0. 12. The method according to claim 1, characterized in that the starting material partial pressure or the total pressure in a range from about 0.21 to about 2.11 kg / cm ² abs. lie. 13. The method according to claim 1, characterized in that the conversion is in a range of. about 60 to about 90% lies. 14. The method according to claim 1, characterized in that the conversion in a range from about 70 to about 8 5% lies. 15. The method according to claim 1, characterized in that it is in the presence, in the reaction zone, of additional
gaseous and / or vaporizable material in one
The weight ratio of this material to the starting material is in the range of about 0.02 to about 0.4. 1300p / 0622 6049 CD - 5 - 16. The method according to claim 1, characterized in that it is carried out without adding hydrogen to the cracking zone. 17. The method according to claim 1, characterized in that it is carried out without prior hydrotreating of the starting material. 18. The method according to claim 1, characterized in that it without prior removal of asphaltenes from the Starting material is carried out. 19. The method according to claim 1, characterized in that it is made without prior removal of heavy metals the starting material is carried out. 20. The method according to claim 1, characterized / that the cracking reaction is carried out with a catalyst that has previously been used to produce a carbo-metallic To crack starting material under the conditions specified in claim 1. 21. The method according to claim 1, characterized in that all the starting material for die'Umwandlung in a
and the same conversion chamber is cracked. 22. The method according to claim 1, characterized in that the feedstock for conversion is cracked in an essentially single pass process. 23. The method according to claim 22, characterized in that less than about 15 vol .-%, based on the volume of the fresh starting material. 130_0 | 7_ / 0622 24. The method according to claim 1, characterized in that the starting material for the conversion with liquid Water at a weight ratio of water to starting material in the range of about 0.04 to about 0.15 and a stream is formed which is a mixture from the raw material, the catalyst and water vapor obtained by the evaporation of the liquid water, and this stream is allowed to flow through the reactor to convert the feedstock. 25. The method according to claim 24, characterized in that the weight ratio of liquid water to starting material for conversion is from about 0.04 to about 0.1. 26. The method according to claim 24, characterized in that the weight ratio of liquid water to starting material for the conversion is about 0.05 to about 0.1. 27. The method according to claim 24, characterized in that the water before or simultaneously with the bringing into contact the raw material for the conversion with the cracking catalyst with the raw material for the conversion is brought together. 28. The method according to claim 24, characterized in that the water is brought together with the starting material for the conversion before the feedstock is contacted with the cracking catalyst for conversion. 29. The method according to claim 1, characterized in that the catalyst at the end of the predetermined residence time is thrown in a direction which is determined by the elongated reaction chamber or an extension of this is, while the products, which have a lower momentum, are forced to an abrupt change of direction, resulting in an abrupt, essentially instantaneous, ballistic separation of the products from the catalyst, GOPY 30. The method according to claim 1, characterized in that the starting material for the conversion with liquid water. ^: at a weight ratio of water to starting material in the range from about 0.04 to about 0.15 and a stream is formed which is a mixture of starting material ^! rial, catalyst and steam obtained by evaporation of the liquid water, contains, and is allowed to flow through dei reactor, conversion of the starting material this stream, wherein the catalyst at the end of the above-mentioned ^vorherbe-: voted residence time is flung in a direction is determined or fixed by the elongated reaction chamber or an extension j of this, while the product! which have a lower pulse, j-Rich direction changes will be forced to an abrupt, which leads to an abrupt, instantaneous in \ substantially ballistic separation of products from the catalyst. 31. The method according to claim 30, characterized in that the j Regeneration at a temperature in the range of about . 537.8 ⁰ C is performed to about 815.6 ⁰ C. ' 32. The method according to claim 30, characterized in that the j regeneration is carried out at a temperature in the range of about ⁰ j 690.6 C to about 773.9 ° C. ι 33. The method according to claim 30, characterized in that the: Catalyst up to a carbon content of about 0.1% or less is regenerated. 34. The method according to claim 30, characterized in that the ' Catalyst up to a carbon content of about 0.05% j or less is regenerated. 35. The method according to claim 30, characterized in that the j Combustion conditions are controlled to ensure the presence of excess oxygen, if excess oxygen is present at all in all the flue gas that comes out of the! 130Q3 & / - 0622 j ORIGINAL INSPECTED entire, completed regeneration process is to be limited to 0.2 mol% or less. 36. The method according to claim 30, characterized in that the Combustion conditions are controlled to ensure the presence of excess oxygen, if any is present in all of the flue gas obtained from the entire, 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 in such a way that the catalyst is successively passed through a plurality of regeneration zones, with about 65 to about "95% of the coke that was on the catalyst immediately before the regeneration , while maintaining the molar ratio of CO: CO ₂ at a level of at least about 0.25. 38. The method according to claim 30, characterized in that the regeneration is carried out in such a way that the catalyst is successively passed through a plurality of regeneration zones, about 80% to 95% of the coke which was present on the catalyst immediately before the regeneration being removed and the molar ratio of CO: CO ₂ . at a level of at least about 0.3 while regenerating the catalyst to a carbon content on the catalyst of about 0.05% by weight or less. 1300 ^ 7-0622