NL8006227A - PROCESS FOR THE CONVERSION OF CARBON AND METAL CONTAINING OIL WITH A REGULATED CO: CO2 RATIO IN THE REGENERATION. - Google Patents

Description

1 / * N.O. 29,568

Process for the conversion of carbon and metal-containing oil with a controlled CO: CC> 2 ratio during regeneration, _____

Generally, gasoline and other liquid hydrocarbon fuels boil in the range of about 57 to about 545 ° C. However, the crude from which these fuels are prepared contains a different mixture of hydrocarbons and other compounds, which vary widely in molecular weight and therefore boil over a wide range.

For example, crudes are known in which 50 to 60% or more of the total volume of the oil consists of compounds boiling at temperatures above 54-5 ° C. Below 10 are crude oils, in which about 10% to about 50% or more of the total volume consists of compounds having such a high molecular weight that they will boil above 552 ° C or at least will not boil below 552 ° C at atmospheric pressure.

Because these relatively abundant high boiling components of crude oil are unsuitable for inclusion in gasoline or other liquid hydrocarbon fuels, the petroleum refining industry has developed methods for cracking or breaking the molecules of the high molecular weight high boiling compounds to smaller molecules that boil in a suitable boiling range.

The cracking process, which is most widely used for this purpose is known as catalytic flow cracking (ECO). Although the ECC process has reached a very advanced state and many modified shapes and variations have been developed, their unifying factor is that an evaporated hydrocarbon feed is cracked at an elevated temperature in contact with a cracking catalyst suspended in the feed dam-50. pen. After reaching the desired degree of molecular weight and boiling point decrease, the catalyst is separated from the desired products.

Crude oil in its natural state contains various products which tend to have quite unpleasant influences on FCC processes and only some of these difficult materials can be economically removed from the crude oil. Among these difficult materials are coke precursors (such as asphaltenes, multinucleated aromatics, etc.), heavy metals (such as nickel, vanadium, iron, copper, etc.), fairly light metals (such as Na-5, potassium, etc.), sulfur , nitrogen and others. Certain materials, such as the relatively light metals, can be economically removed by desalting operations, which are part of the normal crude oil pretreatment procedure for FCC, Other materials such as coke precursors, asphaltenes and the like tend to decomposing to coke during the cracking operation, which coke is deposited on the catalyst, impeding contact between the hydrocarbon feed and the catalyst and generally reducing the strength or activity level. The heavy metals transfer almost quantitatively from the feed to the catalyst surface.

When the catalyst is used over and over to process additional feed, which is usually the case, the heavy metals on the catalyst can accumulate to the point that they adversely affect the composition of the catalyst and / or the nature of its effect on supply. For example, vanadium tends to form fluxes with certain components of the commonly used FCC catalysts, sufficiently lowering the melting point of portions of the catalyst particles to begin to sinter and become ineffective cracking catalysts. Accumulations of vanadium and other heavy metals, especially nickel, also poison the catalyst. They tend, in varying degrees, to promote excessive dehydrogenation and aromatic condensation, resulting in an excessive production of carbon and gases with consequent disadvantage of the liquid fuel yield. An oil such as a crude oil or crude fraction or other oil, which is particularly rich in nickel and / or other metals, which exhibit a similar behavior, while containing relatively large amounts of coke precursors, is referred to herein as a 40 carbon metal oil and is a special challenge for 8 0 06 22 7 3 * petroleum refining.

Generally, the coke-forming tendency or coke precursor content of an oil can be determined by determining the weight percentage of carbon remaining after a sample of that oil has been pyrolyzed. The industry accepts this value as a measure of the degree in which a given oil tends not to form catalytic coke when used as a feed in a catalytic cracker. Two established 10 trials are recognized, the Oonradson carbon and the

Ramsbottom carbon tests, the latter of which is described in ASTM D524-76. In conventional PCC practice, Ramsbottom carbon values in the order of about 0.1 to about 1.0 are considered indicative of an acceptable feed. The present invention relates to the use of hydrocarbon feeds which have higher Ramsbottom carbon values and thus exhibit considerably greater coking power than conventional feeds.

Since the various heavy metals do not have a similar catalyst poisoning activity, it is effective to poison an oil, which is one. given poisoning metal or metals to be expressed as the amount of a single metal determined to have equivalent poisoning activity. Therefore, the heavy metal content of an oil can be expressed by the following formula (formed after that of 77 L. Nelson in Oil and Gas Journal of October 23, 1961, pages 14-3), in which the content of any metal present 30 language is expressed in parts per million of such a metal, as metal, on a weight basis, based on the weight of the feed:

Nickel equivalents = Ni + jjyg + + "TIE *

According to conventional PCC practice, the heavy metal content of the feed for the PCC processing is regulated at a relatively low level, for example about 0.25 ppm nickel equivalents or less. The present invention relates to the processing of feeds containing metals significantly above this value and therefore 4-0 have a substantially greater capacity for collection and poisoning of the catalyst.

The aforementioned formula can also be used as a measure of heavy metal accumulation on the cracking catalyst, except that the amount of metal 5 used in the formula is based on the weight of the catalyst (on an anhydrous basis) rather than on the weight of the supply. In conventional FCC practice, where a circulating stock of catalyst is used over and over in fresh feed processing, with periodic or continuous minor addition and withdrawal of fresh and spent catalyst, the metal content of the catalyst is maintained at a level, e.g. in the range may be from about 200 to about 600 ppm nickel equivalents. The process of the present invention relates to the use of catalysts with a significantly greater metal content, and therefore have a much greater than normal tendency to promote dehydrogenation, aromatic condensation, gas production and coking. Therefore, such a collection of more metals is usually considered to be quite undesirable in FCC processing.

There is a longstanding interest in the conversion of carbon-metal oils to petrol and other liquid fuels. For example, in the 1950's it has been suggested that various carbon metal oils could be successfully converted to gasoline and other products by the Houdresid process. Unlike the FCC embodiment, the Houdresid process utilizes "granular size" catalyst particles (much larger than the usual 50 FCC catalyst particle size) in a dense gravitational bed, rather than suspended catalyst particles in the feed and product vapors in a fluidized bed .

Although the Houdresid process clearly represented a step forward in dealing with the influences of metal contamination and coke formation on the catalyst behavior, its productivity was limited. Because its operation was not economical, the first Houdresid unit is no longer in operation. Therefore, the technique has been 40 over the 25 years that have passed since 8006227

The Hold Resid Process was first technically introduced, continuing with the difficult investigation of suitable modifications or alternatives to the FCC process, which would permit technically successful treatment on reduced crude oil and the like. A number of proposals were made during this period; some have been used to some degree technically.

Several proposals involve the treatment of the heavy oil feed to remove the metal therefrom prior to the cracking treatment, such as by treatment with water, solvent extraction and complexation with Friede-Crafts catalysts, but these techniques have not been criticized as economically justified. In another proposal, a combination cracking process is used with "dirty oil" and "clean oil" units. In yet another proposal, residual oil is mixed with gas oil and the amount of residual oil in the mixture is related to the Equilibrium flash evaporation temperature at the bottom of the riser-type cracking unit used in the process 20. In yet another proposal, the feed is subjected to a careful preliminary hydrocracking treatment or water treatment before the feed is introduced into the cracking unit. it has been proposed to contact a carbon metal oil, such as a reduced crude oil, with hot taconite granules to prepare gasoline, which is a small selection of the many proposals that have appeared in patent literature and technical reports.

Notwithstanding the great effort spent and the fact that each of these proposals overcomes some of the difficulties involved, today's customary FCC practice contributes tacit witness to the scarcity of carbon metal oil cracking techniques, which are both economical and highly practical the point of view of technical feasibility. Some crudes are relatively free of coke precursors or heavy metals or both, and the difficult components of the crude are largely concentrated in the highest boiling fractions. As a result, it has been largely possible to avoid the problems of cooking precursors and heavy metals α η n fi ·> 9 7

V

-s by sacrificing the liquid fuel yield, which would potentially be available from the highest boiling fractions. More particularly, in conventional FCC practice, the feed has been that fraction of crude oil boiling at about 343 to about 538 ° C, which fractions are relatively free of coke precursors and heavy metal contamination. Such a feed, known as "vacuum gas oil" (VGO), is generally prepared from crude oil by distillation of the fractions boiling below about 343 ° C at atmospheric pressure and then separation by further vacuum distillation from the heavier fractions of a fraction boiling between about 343 ° C and about 482 ° C to 552 ° C.

The vacuum gas oil is used as a feed for a conventional FCC processing. The heavier fractions are usually used for various other purposes, such as, for example, preparation of asphalt, residual fuel oil, fuel oil number 6 or fuel oil marine Bunker C, which represents a large loss of the potential value of this part of the crude oil, especially in view of the great effort and expense that the art is willing to spend in an attempt to prepare generally similar materials from coal and slate oils. The present invention is directed to the simultaneous cracking of these heavier fractions containing significant amounts of both coke precursors and heavy metals, and optionally other difficult constituents, along with the lighter oils, giving the total yield of gasoline and other liquid hydrocarbon -30 fuels from a given amount of crude oil is increased. As indicated above, the present invention is in no way the first attempt to develop such a method, but the long-standing recognition of the desirability of cracking carbon metal feeds, along with the slow advancement of the industry for its implementation , demonstrates the continuing need for such a process. It is believed that the present process is uniquely effective in treating the problem of treating such carbon-metal oils in an economically and technically sound manner.

The present invention is notable in providing a simple, relatively direct and highly productive approach to converting a carbon-metal feed, such as a reduced crude or the like, to various lighter products such as gasoline. The hydrocarbon metal feed contains an oil which boils above or is composed of about 343 ° C.

Such an oil or at least the 34-3 ° C + portion thereof is characterized by a heavy metal content of at least about 4, preferably more than about 5 and most preferably at least about 5 * 5 ppm nickel equi valent (weight delery and by a carbon residue after pyrolysis of at least about 1% and more preferably at least about 2%. According to the invention, the carbon-metal feed, in the form of a pumpable liquid, is contacted with hot conversion catalyst in a catalyst to feed weight ratio in the range of from about 3 to about 18 and preferably 20 over about 6.

The feed in this mixture undergoes a conversion step which involves cracking, while the feed and catalyst mixture flows through a progressive flow reactor. The feed, catalyst and other products can be introduced in one or more places.

The reactor includes an elongated reaction space, which is at least partially vertical or inclined and in which the feedstock, resulting products and catalyst are kept in contact with each other as they are a dilute phase or stream for a pre- certain residence times in the riser flow in the range of from about 0.5 to about 10 seconds.

The reaction is carried out at a temperature from about 4-80 ° to about 760 ° C, measured at the reaction chamber outlet 35 under a total pressure of about 70 to about 350 kPa under conditions sufficient to permit a conversion per pass in the range of about 50% or more and coke to deposit on the catalyst in an amount in the range of from about 0.3 to about 3% by weight> - $, and preferably about 09 7 κ *> select at least about 0.5%. The total amount of coke production based on the weight of the fresh feed is in the range of about 4 to about 14% by weight.

At the end of the predetermined residence time 5, the catalyst is separated from the products, stripped to remove the high boiling components and other entrained or adsorbed hydrocarbons, and then regenerated by removing the coke in at least one regeneration zone with oxygen. containing the combustion support gas under conditions of time, temperature and atmosphere sufficient to reduce the carbon on the regenerated catalyst to about 0.25 wt% or less and preferably about 0.05 wt% or less, and at least 15% of the weight of the coke is burned in a zone in which the CO: CO2 molar ratio is maintained at a level of at least about 0.25, more preferably at least about 0.3 and even more preferably at least about 1.

The regenerated catalyst is recycled to the reactor for contact with fresh feed.

Depending on how the method of the invention is carried out, one or more of the following advantages can be realized. If desired and preferably, the process can be carried out without adding hydrogen to the reaction space. If desired and preferred, the process can be carried out without prior treatment with water from the feed and / or without another process for removing asphaltenes or metals from the feed and this is the case even when the carbon metal oil as a whole exceeds about 4, or more than about 5 or even more than about 5.5 ppm nickel, eiviva spring weight parts of heavy metal and a carbon residue after pyrolysis greater than about 1%, greater than about 1.4% or greater than about 2 wt. % has. In addition, all conversion feed, as described above, can be cracked in one and the same conversion space. The cracking reaction can be carried out with a catalyst which has been used before (recycle except 40 replacement as required to compensate for normal losses and 8006227 9 D deactivation) to crack a carbon-metal feed under the conditions described above. Heavy hydrocarbons, which have not been cracked to "gasoline" a first pass may be recycled with or without treatment with water for further cracking in contact with the same type of feed in which they are first subject to cracking conditions and under the same type of conditions; however, treatment according to an in. Substantial one-off or single pass (10, for example, less than about 15 volume percent cycle based on fresh feed volume) is preferred.

According to an embodiment or aspect of the invention, at the end of the predetermined residence time, as mentioned above, the catalyst is driven in a direction determined by the extended reaction space or an extension thereof, while the products , with a smaller impulse, are brought to an abrupt direction change, resulting in an abrupt substantially instantaneous ballistic separation of products from the catalyst. The catalyst thus separated is then stripped, regenerated and recycled to the reactor described above.

According to another preferred embodiment or another aspect of the invention, the carbon-metal feed is contacted not only with the catalyst, but also with one or more additional products, including in particular liquid water in a weight ratio with respect to to the feed ranging from about 0.04 to about 0.15, more preferably about 50 to about 0.1, and even more preferably about 0.05 to about 0.1. Such additional products, including the liquid water, may be mixed with the feed before, during or after mixing the feed with the aforementioned catalyst, and either 55 after or preferably before evaporation of the feed.

The feed, the catalyst and the water (for example, in the form of liquid water or in the form of steam obtained by evaporation of liquid water in contact with the feed) are introduced into the reactor of the progressive 4-0 flow type, which is already not a reactor can be 8006227%, which embodies the above-described ballistic separation, in one or more places along the reactor.

While the mixture of feed, catalyst and steam obtained by evaporation of the liquid water flows through the reactor, the feed undergoes the aforementioned conversion step, which involves cracking. The feedstock, catalyst, steam and the products obtained are kept in contact in the aforementioned elongated reaction chamber, while flow occurs as a dilute phase or stream for the aforementioned predetermined residence time in the riser. is in the range of about 0.5 to about 10 seconds.

The method as described above can be carried out in conjunction with other preferred alternatives, refining operations or more conventional conditions, some of which will be mentioned under the heading "Description of different and preferred embodiments 8006227".

Short attribution of the figures

Fig. 1 is a schematic representation of a first device for the practice of the invention.

FIG. 2 is a schematic representation of a second device for carrying out the invention.

Fig. 3 to 5 are graphs of data obtained from the practice of the method of the invention. Description of Various and Preferred Embodiments The present invention provides a process for the continuous catalytic conversion of a wide variety of carbon metal oils to lower molecular weight products while maximizing the products of highly valuable liquid products and optionally allowing avoid vacuum distillation and other expensive treatments such as water treatment.

The term "oils" includes not only those predominant hydrocarbon compositions which are liquid at room temperature (i.e. 20 ° C), but also those predominant; Hydrocarbon compositions which are asphalts or tars at ambient temperature, but which liquefy upon heating to temperatures in the range up to about 427 ° C. The invention is applicable to carbon metal oils, of petroleum origin or not. For example, provided the oils have the required boiling range, the carbon residue after pyrolysis and the heavy metal content, the invention can be applied to the processing of very different products, such as heavy crude products from crude oil, heavy bitumen crude oil, which crude oils are known as "heavy crudes" which approximate the properties of reduced crudes, slate oil, tar sands extract, liquefied coal and dissolved coal products, atmospheric and vacuum reduced crudes, extracts and / or bottoms (raffinate) of the deasphalting with solvent, aromatic extract of lubricating oil refining, tar bottoms, heavy ground running oil, contaminated oil, other refinery waste streams and mixtures of the foregoing products. Such mixtures can be prepared, for example, by mixing available hydrocarbon fractions, including oils, tar products, 8008227% pitches, and the like. Powdered carbon can also be suspended in the carbon-metal oil. Those skilled in the art are aware of techniques for de-metallizing carbon-metal oils and de-metallized oils can be converted using the invention; it is, however, an advantage of the invention that carbon-metal oils which have not undergone prior demetallation treatment can be used as feed. The invention can also be used with water-treated feeds; however, it is an advantage of the invention that it can successfully convert carbon metal oils which have undergone virtually no prior treatment with water. However, the preferred application of the process to reduced crude oil, ie, that crude oil fraction boiling at and above 343 ° C, is alone or mixed with untreated gas oils. While the use of product subjected to a preliminary vacuum distillation is not excluded, it is an advantage of the invention that it can satisfactorily process product which has not undergone prior vacuum distillation, thus capital investment and processing costs are saved compared to the usual FCC processes, which require a vacuum distillation unit.

Table A provides a comparison between a conventional vacuum gas oil (VGO), which has hitherto been used at ECC, with various reduced crudes, which are a single example of the many reduced crudes that can be used in the present invention 30 uses.

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As can be seen from the table, the sulfur or higher boiling feeds are characterized by relatively higher API density values than the illustrative vacuum gas oil (VGO). In general, those catalytic cracking process feeds with lower boiling temperatures and / or higher API densities are much better. considered feeding with higher cooking temperatures and / or a lower API density. Comparisons of the gasoline yield of high boiling feeds compared to medium boiling feeds at a constant coke yield have shown that the medium boiling feeds give a better gasoline yield for a given coke yield.

According to the invention there is provided a carbon metal oil feed, of which at least about 70%, more preferably at least about 85% and even more preferably about 100% (volume%) boils at and above about 545 ° C. All cooking temperatures are based on standard atmospheric pressure conditions. Carbon metal oil, which is partially or wholly composed of a product boiling at and above about 34-3 ° C, designates such a product as a 343 ° C + product; and 343 ° C + product, which is part of or separated from an oil, containing components boiling above and below 34-3 ° C may be referred to as a 34-3 ° C + fraction. However, the terms "cooking above" and "34 -3 ° C +" do not imply that all the product characterized by these terms will have the boiling power. The carbon metal oils contemplated by the invention may contain product which cannot boil under arbitrary conditions, for example, certain asphalts and asphaltenes can thermally crack during distillation, apparently without boiling, when it is therefore stated that the feed contains at least about 70% by volume of product boiling above about 343 ° C , it is to be understood that the 70% in question may contain some product which will not boil or volatilize at any temperature These non-boiling products, if present, can usually or for the most part be concentrated in parts of the feed, which does not boil below about 53 ° C, 552 ° C or higher-4-0. Thus, if it is stated that at least about 8006227 14%, more preferably about 15%, and even more preferably at least about 20% (volume%) of the 343 ° C + fraction will not boil below about 538 ° C or 552 ° C, it should be understood that all or any portion of the product , which does not boil at about 538 ° C or 552 ° G, may or may not be volatile at times, and will warp the indicated temperatures.

Preferably, the cup feed or at least the 343 ° C + product therein gives a carbon residue after pyrolysis of at least about 2 or more. For example, the Ramsbottom carbon content can range from about 2 to about 12 and more preferably at least about 4. A particularly common range is about 4 to about 8. It should be noted that the illustrative VGO 15 in Table A has a Ramsbottom carbon residue value of 0.38 and that the 343 ° C to 552 ° C fraction of the various reduced crudes have Ramsbottom carbon values. between about 0.3 and about 0.5, while the various reduced crudes as a whole (343+ total) 20 in Ramsbottom carbon value range from about 4 to about 16.8 and still higher values are envisaged.

Preferably, the feed has an average composition characterized by an atomic ratio of hydrogen to carbon in the range of about 1.2 to about 1.9, and preferably about 1.3 to about 1.8.

The carbon-metal feeds used in accordance with the invention, or at least the 343 ° + product therein, may contain at least about 4 parts per million nickel equivalents, as defined above, of which at least about 30 parts per million nickel (as metal, divide weight). Carbon metal oils within the previous range may be prepared from mixtures of two or more oils, some of which may or may not contain the amounts of nickel equivalents and nickel as set forth above. It should also be noted that the previous values for nickel equivalents and nickel are time-weighted averages for a significant operating period of the conversion unit, such as, for example, a month. It should also be noted that the heavy 40 metal conditions reduce some 8006227 vol. * have shown a tendency to poison after repeated oxidations and reductions on the catalyst and the literature describes criteria for determining "effective metal" values. See, for example, the article by Cimbalo 5 et al. Entitled "Deposited Metals Poison FCC Catalyst",

Oil and Gas Journal, May 1972, pp. 112-122. When considered necessary and desirable, the contents of nickel equivalents and nickel in the carbon metal oils processed according to the invention can be expressed in "effective metal" values. Notwithstanding the gradual reduction in poisoning activity determined by Cimbalo et al., Catalyst regeneration under normal FCC regeneration conditions cannot seriously impede and does not hinder and dehydrogenate, deethanize, and oxidate condensation activity of heavy metals collected on the cracking catalyst. usually not either.

It is known that from about 0.2% to about 5% by weight of "sulfur" in the form of elemental sulfur and / or compounds thereof (however reported as elemental sulfur relative to the weight of the feed) appears in FCC feeds and that the sulfur and the modified forms of sulfur find their way into the resulting gasoline product and, when lead is added, tend to reduce their susceptibility to octane enhancement. Sulfur in the gasoline product often requires the release of odors when processing crude oils containing a lot of sulfur. To the extent that sulfur is present in the coke, this also represents a potential air pollutant as the regenerator removes the sulfur burns to SO ^ and 30 SO ^. However, it has been found that, in the present process, the sulfur in the feed, on the other hand, is capable of inhibiting heavy metal activity by maintaining metals such as Ni, V, Cu and Fe in the sulfide form in the reactor.

These sulfides are much less active than the metals themselves in promoting dehydrogenation and coking reactions. Consequently, it is acceptable to practice the invention with a carbon metal oil with at least about 0.3 acceptable above about 0.8% and more acceptable at least about 1.5% by weight of sulfur 40 in the 34-3 ° G + fraction.

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The carbon metal oils suitable for the invention may "contain and" usually contain substantial amounts of nitrogen-containing compounds, a substantial portion of which may be basic nitrogen. For example, the total nitrogen content of the carbon-metal oils can be at least about 0.05 wt%. Since cracking catalysts owe their cracking activity to acidic sites on the catalyst surface or in its pores, basic nitrogen-containing compounds may temporarily remove them. neutralize sites 10, thereby poisoning the catalyst.

However, the catalyst is not permanently damaged as the nitrogen can be burned from the catalyst during regeneration, thereby restoring the acidity of the active sites.

The carbon metal oils may also contain significant amounts of pentane insolubles, for example at least about 0.5% by weight and more usually "about 2% or more and even about 4% or more.

These may include, for example, asphalting and other products.

Alkali metals 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 prepare the vacuum gas oils commonly used as FCC feeds. Rather, most of these metals remain in the "bottom product" fraction (the non-evaporated high boiling part), which can be used, for example, in the preparation of asphalt or other by-products. However, reduced crudes and other carbon metal oils in many fall soils and therefore may contain significant amounts of alkali and alkaline earth metals such as sodium These metals are deposited on the catalyst during cracking Depending on the catalyst composition and the size of the regeneration temperatures at which it is exposed, these metals may undergo interactions and reactions with the catalyst (including the catalyst support), which are not usually experienced in the processing of VGO under usual ECC processing conditions. When the catalyst 8006227 lysator properties and the regeneration conditions so require, one will of course take the necessary precautions take measures to limit the amounts of alkali metal and alkaline earth metal in the feed, which metals can enter the feed not only as saline together with the crude oil in its natural state, but also as components of water or steam, which are supplied to the cracking unit . Therefore, careful desalination of the preparation of the carbon can be done. Crude oil used in metal feed is important when the catalyst is particularly sensitive to alkali metals and alkaline earth metals. In such circumstances, the content of such metals (hereinafter collectively referred to as "sodium") in the feed can be maintained at about 1 ppm or less, based on the weight of the feed. Also, the sodium content of the feed can be tuned to that of the catalyst to maintain the sodium content of the catalyst used, substantially equal to or less than that of the replacement catalyst fed to the unit.

According to a particular embodiment of the invention, the carbon metal metal oil feed constitutes at least about 70% by volume of the product boiling above about 343 ° C and at least about 10% of the product above about 3ζί · 3Ο0 boils will not boil below about 552 ° C. The average composition of this 343 ° C + product may further be characterized by: (a) an atomic hydrogen to carbon ratio 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, parts by weight) and (d) at least one of the following: (i) at least about 0.3 wt% sulfur, (ii) at least about 0.05 wt% nitrogen, and (iii) at least about 0.5 wt% of pentane insolubles.

Very commonly, the preferred feed will contain all components (i), (ii) and (iii) and other components found in oils of petroleum and non-petroleum origin 40 may also be present in varying amounts 8006227 18 r provided they do not exhibit the action of the prevent process.

While it is not intended to exclude the possibility of using a feed which has been subject to some cracking beforehand, the present invention has the clear advantage of being able to successfully produce large conversions and very significant yields of liquid hydrocarbon fuels produce from carbon metal oils, which have not been subjected to any essential · ... ····. ··, fce mata of · cracking · "Thus, for example, is - and at. preferably at least about 85% <> more preferably at least about 90% and most preferably almost all carbon metal feed introduced in the present process, oil not previously contacted with a cracking catalyst under cracking conditions.

In addition, the method of the invention is suitable for application in a substantially one-off or single pass manner. Therefore, the volume of the optional recycle based on the volume of the fresh feed is preferably about 15% or less, and more preferably about 10% or less.

Generally, the weight ratio of catalyst to fresh feed (feed not previously exposed to a cracking catalyst under cracking conditions) used in the process is in the range of about 5 to about 18. Preferred ratios are about 4 to about 12 more preferably about 5 to about 10 and even more preferably about 6 to about 10, with a ratio of about 6 to about 8 now considered to be nearly optimal. Within the constraints of product quality requirements, controlling the catalyst to oil ratio at relatively low levels within the aforementioned ranges tends to reduce the coke yield of the process based on fresh feed.

55 In the conventional FCC processing of VGO, the ratio between the number of barrels of 159 liters per day of the factory feed and the total number of tons of catalyst undergoing circulation through all phases of the process may vary. For the purposes of the present invention, the daily factory throughput is defined as the number of barrels of 159 liters of fresh feed, boiling above about 343 ° C, which this factory processes per average business day into liquid products, which cook below about 221 ° C. For example, in a technically successful type of FCC-VGO treatment, about 8 to about 12 tons of catalyst are circulated in the process at 1000 barrels of 159 liters per day of factory throughput. In another technically successful process, this is. ratio in the range of about 2 to 3.

While the present invention can be practiced in the range of about 2 to about 30 and more usually about 2 to about 12 tons of catalyst stock per 1000 barrels of 159 liters of daily factory throughput, it is preferable to practice the process of the present invention with a very low catalyst weight to daily factory throughput ratio. More particularly, it is preferable to carry out the process of the present invention with a supply of catalyst sufficient to contact the feed for the desired residence time within the aforementioned catalyst to oil ratio, while increasing the amount of catalyst stock, with respect to factory throughput, that is under circulation or stored for treatment at other stages of the process, such as, for example, stripping, regeneration and the like, is kept as small as possible. More particularly, it is therefore preferable to carry out the process of the present invention with about 2 to about 5 and more preferably about 2 tons of catalyst stock or less per 1000 vabsn of 159 liters per factory daily wafer.

In the practice of the invention, catalyst can be added continuously or periodically, such as, for example, to supplement normal catalyst losses from the system. In addition, the catalyst addition can be carried out in conjunction with the extraction of catalyst, for example to maintain or increase the average activity level of the catalyst in the unit. For example, the amount of unused catalyst added to the unit can range from about 0.29 to about 8.7, more preferably about 8006227, 4.3 to about 5, 8, and most preferably about 0.58 to about 4.4 g / l feed. On the other hand, when equilibrium catalyst of the FCC treatment is to be used, replacement amounts of about 14.5 g / l may be used. When the conditions are such that the catalyst used in the unit is below average in resistance to deactivation and / or conditions prevailing in the unit tend. -to promote faster deactivation, one can add 10 amounts that are greater than the aforementioned; however, in the opposite circumstances, lower addition amounts may be used.

Without wishing to be bound by any theory, it seems that some features of the method described in detail below, such as, for example, residence time and any mixing of steam with the feed, tend to limit the extent wherein cracking conditions generate metals in the reduced state on the catalyst from one or more heavy metal sulfides, sulfates or oxides deposited on the catalyst particles by prior exposures to carbon metal feed and regeneration conditions. Therefore, the method appears to provide substantial control over the poisoning effect of heavy metals on the catalyst, even when the accumulation of such metals is quite significant.

As a result, the process can be carried out with heavy metal catalyst-bearing accumulations, which have hitherto been considered to be rather impermissible in the conventional IC-VGO treatments. For these reasons, use of the catalyst bearing heavy metal accumulation process in the range of from about 3000 to about 70,000 ppm nickel equivalents on average is contemplated. More particularly, the accumulation can be in the range from about 4000 to about 50,000 ppm and more particularly about 5000 to about 30,000 ppm. The foregoing ranges are based on parts per million nickel equivalents, the metals being expressed as parts by weight of metal measured with and based on 40 regenerated equilibrium catalyst. However, in the event that 8006227% that catalyst of suitable activity is available at very low cost, allowing very high catalyst replacement rates, the carbon metal oil could be converted to lower boiling liquid products with a catalyst less than 5000 ppm carries nickel equivalents of heavy metals. For example, one may use equilibrium catalyst from another unit, for example, an FCC unit, which has been used for cracking a feed, for example, vacuum gas oil, with a carbon residue after pyrolysis of less than 1 and containing less than about 4 ppm nickel equivalents to heavy metals.

In any case, the equilibrium concentration of heavy metals in the circulating catalyst stock can be controlled (including maintenance or variation if desired or required) by manipulating the degree of catalyst addition discussed above. Thus, for example, the addition of catalyst can be maintained at such a rate that will control the accumulation of the heavy metals on the catalyst in one of the ranges set forth above.

In general, it is preferred to use a catalyst with a relatively high cracking activity content, which gives a high degree of conversion and productivity at low residence times. The conversion capacities of the catalyst can be expressed as the conversion generated during the actual operation of the process and / or as conversion produced during standard catalyst activity tests. For example, it is preferable to use a catalyst which is sufficiently active during an extended process operation to maintain a conversion level of at least about 50% and more preferably at least about 60%. In this context, the conversion is expressed in liquid volume percentage based on fresh feed.

For example, the preferred catalyst can also be defined as one which, in the unused or equilibrium state, shows a specified activity expressed as a volume percentage obtained from the MAT (microactivity test). For the purposes of the present invention 40, the foregoing percentage is the volume percentage of standard 8006227 22 standard feed, which is converted to gasoline with an end point of 221 ° G and lighter products at 482 ° C, a space velocity of 16 (weight space rate, whsv), calculated on the basis of the catalyst dried at 595 ° C and 3C / O (catalyst to oil ratio) according to the preliminary ASTK MAT test D-32, using an appropriate standard feed, for example Davison WHPS-12 primary gas oil, with the following analysis and properties: API density at 15.6 ° C, degrees 3 ^ .0 10 specific density at 15.6 ° C, g / cm ^ 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, wt.% 305 viscosity at 37.8 ° C, cS 10.36 "Watson K factor 11.93 aniline point 182 20 bromine number 2.2 alkanes, vol.%. 3i, 7 olefins, vol.% 1.8 naphthenes, vol.% 44.0 aromatics, vol.% 22.7 25 average molecular weight 284 nickel trace vanadium trace iron trace sodium trace 30 chlorides trace BS&W trace

Distillation, ° C ASTM D-1160 initial boiling point 229.5, 10% 316.5 35 50% 351 50% 572 70% 390 90% 419.5.

final boiling point 445.5 8006227

a

The gasoline endpoint generated in the MAT test is often defined as 221 ° C wpp (true boiling point), which is a standard laboratory distillation, but other endpoints may equally serve the present purposes. The conversion is calculated by subtracting from 100 the percentage by volume (based on fresh feed) of those products which are heavier than gasoline and which remain in the recovered product.

The catalyst can be introduced into the process in the unused form or, as indicated above, in a form other than the unused form; for example, one can use a balancing catalyst withdrawn from another unit, such as a catalyst used in cracking another feed. When characterized based on the MAT activity, the preferred catalysts can be described based on their MAT activity "as introduced" in the method of the present invention, or based on their "as withdrawn" or equilibrium MAT activity in the method of the present invention, or on both of these bases. A preferred MAT activity for unused and unused catalyst "as introduced" in the process of the present invention is at least about 60%, but it will be appreciated that, especially in the case of unused catalysts, that are fed in a high degree of addition, lower MAT activity levels are acceptable. An acceptable "such as withdrawn" or equilibrium MAT activity level of catalyst used in the method of the present invention is about 20% or more, however about 40% or more, and preferably about 60% or more, the preference.

Any hydrocarbon cracking catalyst of the above conversion capacities can be used. A particularly preferred class of catalysts includes those catalysts having pore structures into which molecules of feedstock can enter for adsorption and / or for contact with active catalyst sites in or adjacent to the pores. Different types of catalyst are available within 8006227 24-r this classification, including, for example, layered silicates, for example, smectites. While the most widely available catalysts within this classification are known zeolite-containing catalysts, non-zeolite-like catalysts are also contemplated.

The preferred zeolite-containing catalysts may contain any zeolite, whether natural, semi-synthetic or synthetic, alone or in admixture with other products, which do not substantially impair the suitability of the catalyst provided that the resulting catalyst has the has listed activity and pore structure.

For example, when the catalyst is a mixture, it can include the zeolite component along with or dispersed in a porous refractory inorganic oxide support; in such a case, the catalyst may, for example, be about 1% to about 60%, more preferably about 1 to about 4-0%, and most preferably about 5 'to about 25%, based on the total weight of the catalyst. catalyst (on an anhydrous basis) of the zeolite, the remainder of the catalyst being the porous refractory inorganic oxide alone or in combination with any of the known additives to promote or suppress various desired or undesired reactions. For a general explanation of the genus zeolite, molecular sieve type catalysts useful in the invention, reference is made to the articles entitled "Refinery Catalysts Are a Fluid Business" and "Making Cat Crackers Work on Varied Diet", which respectively appeared in the July 26, 1978, and September 13, 1978, 30 episodes of Chemical Week magazine.

For the most part, the zeolite components of the zeolite-containing catalysts will be those known to be suitable for FCC cracking processes. Generally, these are crystalline aluminosilicates, usually composed of tetra-coordinated aluminum atoms joined by oxygen atoms with adjacent silicon atoms in the crystal structure. However, the term "zeolite" as used herein is intended to include not only aluminosilicates, but also products in which the aluminum 4-0 has been replaced in whole or in part, such as, for example, by Ω η n fi 9 9 7 \ gallium and / or other metal atoms and further includes products in which all or part of the silicon has been replaced, such as, for example, by germanium. Titanium and zircon substitution can also be used.

Most zeolites are prepared or occur naturally in the sodium form, so that sodium cations are associated with the electro-negative sites in the crystal structure. The sodium cations tend to render zeolites inactive and much less stable when exposed to hydrocarbon conversion conditions, especially high temperatures. Accordingly, the zeolite can be exchanged with ions, and when the zeolite is a component of a catalyst composition, such ion exchange can take place before or after incorporation of the zeolite as a component of the composition. Suitable cations to replace sodium in the zeolite crystal structure include ammonium (decomposable to hydrogen), hydrogen, rare earths, alkaline earth metals, etc. Various suitable ion exchange methods and cations, which can be exchanged in the zeolite crystal structure are known to the expert.

To examples of naturally occurring crystals. Linear aluminosilicate zeolites that may be used or incorporated in the catalyst for the present invention are faujasite, mordenite, clinoptilot, chabazite, analycite, erionite, as well as levynite, dachiardite, paulingite, noselite, ferriorite, heulandite, scolccite, stibite, harmotome, phillipsite, brewsterite, flarite, datolite, gmelinite, caumnite, leucite, lazurite, scaplite, mesolite, ptholite, nefeline, matrolite, offretite and sodalite.

Examples of synthetic crystalline aluminosilicate zeolites suitable as such or in the catalyst for the practice of the present invention are zeolite X, U.S. Patent 2,882,244, zeolite Y, U.S. Patent 3,130,007, and zeolite A , U.S. Patent 2,882,243, as well as Zeolite B, U.S. Patent 3,008,803, Zeolite D, Canadian Patent 661,981, Zeolite E, Canadian Patent 40,614,495, Zeolite F, U.S. Patent 2,996,358, 8 0 06 22 7 26 Zeolite H, U.S. Patent 3,010,789, Zeolite J, U.S. Patent 3,011,869, Zeolite L, Belgian Patent 575,177, Zeolite M, U.S. Patent 2,995,423, Zeolite 0, 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 3,012,855, Zeolite Z, Canadian Patent 614,495 and zeolite omega, Ganadees patent 10 817,915 * ZK-4HJ, alpha beta and ZSM type zeolites are also suitable. In addition, the zeolites described in U.S. Pat. Nos. 3,140,249, 3,140,253, 3,944,482 and 4,137 * 151 are also suitable.

The crystalline faujasite-type aluminosilicate rzeolites having a crystal structure are particularly preferred for use in the present invention. In particular, these include natural fauja-site and zeolite X and zeolite Y.

The crystalline aluminosilicate zeolites, such as synthetic faujasite, will crystallize under normal conditions as regularly formed, discrete particles of about 1 to about 10 microns in size and therefore this is the trafficking commonly found in technical catalysts which can be used in the invention. Preferably, the particle size of zeolites is from about 0.5 to about 10 microns and more preferably from about 0.1 to about 2 microns or less. For example, zeolites prepared in situ from calcined kaolin may be characterized by even smaller crystallites. Crystalline zeolites display both an internal and an external specific surface, which is defined as a "gate" specific surface, with most of the total specific surface area present internally. The gate specific surface 35 refers to the outer surface of the zeolite crystal through which reagents are expected to pass to convert the lower boiling products. Blocking of the internal channels for, for example, coke formation, blocking of the entrance to the internal channels 40 by depositing coke in the gate-specific surface 8006227 c- (

a

> surface and contamination from metal poisoning, will significantly reduce the total zeolite specific surface. Therefore, preferably to minimize the effect of contamination and pore-blocking, crystals larger than the normal size, as mentioned above, are not used, for example, in the catalysts of the present invention.

Commercial zeolite-containing catalysts are available with supports containing a variety of metal oxides and a combination thereof, including, for example, silica, alumina, magnesium oxide, and mixtures thereof and mixtures of such oxides with clays, as described, for example, in U.S. U.S. Patent 3,034,94-8. For example, one can choose any of the zeolite-containing molecular sieve cracking catalysts suitable for the production of gasoline from vacuum gas oils. However, certain advantages can be achieved through judicious selection of catalysts with appreciable metal resistance. A metal-resistant zeolite catalyst is described, for example, in U.S. Pat. No. 3,944,482, wherein the catalyst contains 1-40 wt% of a rare earth exchanged zeolite, the remainder being refractory nonaloxide with a specified pore volume / volume / size distribution. Other catalysts described as "metal tolerant" are described in the aforementioned article by Cimbalo et al.

In general, it is preferred to use catalysts with a total particle size in the range of about 5 to about 160, more preferably about 4-0 to about 120, and most preferably about 40 to about 80 microns. .

The catalyst composition may also contain one or more combustion promoters used in the subsequent catalyst regeneration step. Cracking of carbon metal oils results in a significant deposition of coke on the catalyst, which coke reduces the activity of the catalyst. Therefore, in order to restore the 4C activity of the catalyst, the coke 8006227 28 is burned at a regeneration stage, the coke being converted to combustion gases containing carbon monoxide and carbon dioxide. Several products are known which, when incorporated into cracking catalysts in small amounts, tend to promote the conversion of the coke to carbon monoxide and / or carbon dioxide. Combustion to carbon monoxide promoters tend to lower the temperature, whereby a given degree of coke removal can be achieved, thereby reducing the ability for thermal deactivation of the catalyst. Such promoters, commonly used in effective amounts ranging from a trace to about 10 to 20% by weight of the catalyst, may be of some type, for example, which generally support the combustion of carbon under regeneration conditions. then promotes to carbon dioxide.

While a wide variety of other catalysts, including both zeolite-containing and non-zeolite-containing, may be used in the practice of the invention, the following catalysts are examples of commercially available catalysts used in the practice of the invention.

Table B

Specific wt.% _ Specific area "_" 2 / g PT, A12 ° 3 3iO2 ^ 2 ° Fe2 ° TiO2 AG2-290 300 11.0 29.5 59.0 0.40 0.11 0.59 GHZ-1 162 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 FCC-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 8 0 06 22 7

The AGS-290, GRZ-1, CCZ-220 and Super DX catalysts mentioned above are products of W.R. Grace and. Co. £ -87 and FOC-90 are products from Filtrol, while HF2-20 and HEZ-55 are products from Engelhard / Houdry. The above mentioned are properties of unused catalysts and, except in the case of the zeolite content, are set on an anhydrous basis, i.e. based on material ignited at 954 ° C. The zeolite content is obtained by comparing the X-ray intensities of catalyst sample and a standard product consisting of a high purity sodium Y zeolite of design No. 6, dated January 9, 1978 of the proposed ASÜ method entitled " Determination of the Faujasite Content of a Catalyst ”.

It is understood as an advantage that the process of the present invention can be carried out in the substantial absence of tin and / or antimony or at least in the presence of a catalyst substantially free of one or both of these metals.

The method of the present invention can be

Conducted with the above-described carbon-metal oil and catalyst as essentially the only products fed to the reaction zone. However, the supply of additional products is not excluded. The addition of recycled oil after the reaction zone has already been reported. As described in more detail below, other products which perform different functions can also be supplied. In such a case, the carbon metal oil and the catalyst usually make up the largest weight amount of the total of all products fed to the reaction zone.

Certain additional products that can be used perform functions that offer significant advantages over the process performed with the carbon metal oil and catalyst alone. Among these functions are: control of the influence of heavy metals and other catalyst impurities; increasing the catalyst activity; absorption of excess heat in the catalyst obtained from the regenerator; removal of contaminants or conversion thereof 8006227 to form or forms in which they can be more easily separated from products and / or disposed of; control of the catalyst temperature; dilution of the carbon metal oil vapors to reduce their partial pressure and increase the yield of desired products; control of the feed / catalyst contact time; supplying hydrogen to a hydrogen-deficient carbon metal oil feed; promoting dispersion of the feed and possibly also distillation of products. Certain metals in the heavy metal accumulation on the catalyst are more active in promoting undesirable reactions when they are in the form of elemental metal than when they are in the oxidized form, as generated by contact with oxygen in the kata-15 lysator regenerator. However, the contact time between catalyst and supply and product vapors in the prior conventional catalytic cracking was sufficient so that hydrogen released in the cracking reaction was able to convert again a significant portion of the less harmful oxides to the more harmful elemental heavy metals. This situation can be taken advantage of by the addition of additional products which are in gaseous form (including vapor form) in the reaction zone mixed with the catalyst and vapors of feed and products. The increased volume of product in the reaction zone, resulting from the presence of such additional products, tends to increase the flow rate through the reaction zone with a corresponding decrease in the residence time of the catalyst and oxidized heavy metals formed thereby. Because of this reduced residence time, there is less opportunity for reduction of the oxidized heavy metals to the elemental form, and therefore less harmful elemental metals are available for contact with the feed and products.

Products can be introduced into the process in any suitable manner, some examples of which follow. For example, the products can be mixed with the carbon metal oil feed prior to the latter's contact with the catalyst. Also, the 40 added products may, if desired, be mixed with the catalyst prior to contact of the latter with the feed. Separate portions of the added products can be mixed separately with both catalyst and carbon metal oil. Moreover, if desired, the feed, catalyst and additional products can be brought together substantially simultaneously. A portion of the added products can be mixed with catalyst and / or carbon metal oil in any of the ways described above, while additional portions can then be added to the mixture. For example, a portion of the added products can be added to the carbon metal oil and / or the catalyst before they reach the reaction zone, while another portion of the added products are introduced directly into the reaction zone. The added products may be added in the reaction zone at a plurality of spaced positions or along its length, if in an extended state.

The amount of added products, which may be present in the feed, the catalyst or the reaction zone to perform the aforementioned functions and others, may be varied if desired; however, this amount will preferably be sufficient to balance the heat balance of the process. For example, these products may be introduced into the reaction zone in a feed weight ratio of up to about 0.4, preferably in the range of from about 0.02 to about 0.4, more preferably from about 0.03 to about 0.3 and most preferably about 0.05 to about 0.25.

For example, parts or all of the functions considered desirable above can be achieved by introducing water into the reaction zone in the form of steam or liquid water or a combination thereof in a weight ratio with respect to the feed in the range of about 0 , 04- or more, or more preferably about 0.05 to about 0.1 or more. Without wishing to be bound by any theory, it appears that the use of water tends to inhibit the reduction of 0-0 catalyst supported oxides, sulfites and sulfides 8006227 32 tot to the free metal form, which is assumed promote condensation dehydrogenation with subsequent promotion of coke and hydrogen yield and accompanying loss of product. In addition, water can also somewhat reduce the deposition of metals on the catalyst surface. There may also be some tendency to nitrogen containing and other heavy impurity molecules to desorb from the surface of the catalyst particles or at least some tendency to inhibit their absorption by the catalyst. It is observed that added water tends to increase the acidity of the catalyst by Bronsted acid formation, which in turn increases the activity of the catalyst. Assuming that the water as supplied is colder than the regenerated catalyst and / or the temperature of the reaction zone, the observable heat involved in the rise in the temperature of the water after contact with the catalyst in the reaction zone or elsewhere may release excess heat. absorb the catalyst. Preferably, the liquid or vaporous H 2 O contains less than about 100 ppm sodium and less than about 300 ppm of both calcium and magnesium. The total amount or part of the water can and is preferably condensed from the products of a previous catalytic conversion of a carbon metal oil. When the water is recycled water or contains recycled water containing, for example, about 500 to about 5000 ppm IL> S dissolved therein, a number of additional advantages can be cultivated. The ecologically unattractive H 2 S does not need to be discharged to the atmosphere, the recirculated water requires no further treatment to remove 50 sn, it may help reduce the coking of the catalyst by passivation of the heavy metals, that is, by converting it to the sulfide form, which has a less tendency than the free metals to increase the coke and hydrogen production. In the reaction zone, the presence of water can dilute the carbon-metal oil vapors, reducing their partial pressures and increasing the yield of desired products. Water has been reported to be suitable in combination with other products to generate hydrogen during cracking; therefore, the water may be able to act as a hydrogen donor for hydrogen-deficient carbon metal oil feeds. The water can also perform certain pure mechanical functions 7.λοΊ o ·> \ n η η τ> οπ * αη in r! o for> noTrftl * i ncr nf ^ i Qrvör »era ncr of the supply; compete with high molecular weight molecules for adsorption on the surface of the catalyst, thereby interrupting coking; steam distillation of evaporable product from non-evaporated feed product and liberation of product from catalyst after completion of the cracking reaction. It is particularly preferred to combine water, catalyst and carbon-metal oil almost simultaneously. For example, water and feed can be mixed in a spray nozzle and the resulting spray liquid immediately contacted with the catalyst at the downstream end of the reaction zone.

The addition of steam to the reaction zone is widely reported in FCC literature. Addition of liquid water to the feed is discussed relatively little compared to the supply of steam directly into the reaction zone. However, it is particularly preferred according to the present invention that liquid water is introduced into an intimate mixture with the carbon-metal oil in a weight ratio of about 0.4 to about 0.15 at or prior to the time of addition of the oil to the reaction zone, the water (for example, in the form of liquid water or in the form of steam generated by evaporation of liquid water in contact with the oil) entering the reaction zone as part of the feed stream, which enters such a zone. While not wishing to be bound by any theory, the foregoing is believed to be effective in promoting feed dispersion.

Also, the heat of evaporation of the water, which is absorbed from the catalyst, from the feed or from both, causes the water to produce a more effective heat drop than steam alone. Preferably, the liquid water to feed weight ratio is about 0.04 to about 0.1, more preferably about 0.05 to about 0.1.

Obviously, the liquid water can be introduced into the process in the manner described above or in other ways, and in any case, the introduction of 4-0 liquid water may be accompanied by the introduction of additional amounts of water as 8 0 06 22 7 34 steam in the same or different parts of the reaction zone or in the catalyst and / or feed. For example, the amount of additional steam can be in a weight ratio with respect to the feed in the range of about 0.01 to about 0.25, with the weight ratio of total water (as steam and liquid water) to the feed as about 0 , 3 or less. Thus, the feed weight ratio of liquid water to steam in such a combined use of liquid water and steam can range from about 5 to about 0.2. Such a ratio can be maintained at a predetermined level within such a range or varied as necessary or desired to control or maintain the heat balance of the reaction.

Other products can be added to the reaction zone to perform one or more of the functions described above. For example, the dehydrogenation condensation activity of heavy metals can be inhibited by introducing hydrogen sulfide gas into the reaction zone. Hydrogen can be made available for metal-deficient carbon-metal-oil feeds by introducing into the reaction zone either a conventional hydrogen donor diluent such as a heavy naphtha or low molecular weight carbon-hydrogen fragment contributors such as for example: light alkanes; alcohols and other compounds. low molecular weight things that allow or favor intermolecular hydrogen transfer; and compounds that chemically combine to develop hydrogen in the reaction zone such as by reaction of carbon monoxide with water or with alcohols or with olefins or with other products or mixtures of the foregoing products.

Any of the aforementioned additional products (including water), alone or together or together with other products, such as nitrogen or other inert gases, light hydrocarbons and other products, may perform any of the functions described above for which they are suitable. , including without limitation, act as diluents for reducing the feed partial pressure and / or as heat reduction annfi means for absorbing excess heat contained in the catalyst obtained from the regeneration stage.

The foregoing is a discussion of some functions which can be performed by products other than catalyst and carbon metal oil feed which are introduced into the reaction zone and it will be appreciated that other products may be added or other functions are practiced without departing from the scope of the invention.

The invention can be practiced in a wide variety of equipment. The preferred equipment, however, includes means for rapidly evaporating as much of the feed as possible and efficiently mixing the feed and catalyst (although not necessarily in that order) to flow the resulting mixture as a dilute slurry in a progressive flow mode and for separating the catalyst from cracked products and any uncracked or only partially cracked feed at the end of a predetermined residence time or predetermined residence times, it being preferred that the total or at least a substantial portion of the product must be separated abruptly from at least part of the catalyst.

For example, along the extended reaction space, the equipment may have one or more points for the addition of carbon metal feed, one or more points for the feed. ring of catalyst, one or more points for additional product addition, one or more points for product withdrawal and one or more points for catalyst withdrawal. The means for supplying the feed, catalyst and other product can vary from open pipes to refined nozzles or nozzles, it being preferred to use means capable of breaking the liquid supply into fine droplets.

It is preferred that the reaction space, or at least most of it, is more near vertical than horizontal and has a length to diameter ratio of at least about 10, more preferably about 20 or 25 or more. The use of a vertical riser type reactor 5 is preferred. If tubular, the reactor may generally have a uniform diameter or may have a continuous or stepped increase in diameter along the reaction path to maintain or vary the velocity along the flow path.

Generally, the fillers (for catalyst and feed) and reactor configuration are such as to provide a relatively high flow rate and a dilute catalyst slurry. For example, the vapor or catalyst velocity in the riser will usually be at least about 750 and more usually at least about 1050 cm / sec. to be. This speed can be up to about 1650 or about 2250 cm / sec. or higher. The reactor speed capacities will generally be sufficient to prevent significant build-up of a catalyst bed in the bottom portion or other portion of the riser, whereby the catalyst charge in the riser can be maintained below about 0.064- or 0. 08 g / m 2 below about 0.032 g / cm 2 at the upstream (eg bottom) and downstream (eg top) ends of the riser, respectively.

For example, the progressive flow mode involves the flow of catalyst, feed and products as a flow in a positively controlled and sustained direction, which is determined by the extended nature of the reaction zone. However, this does not suggest that there should be a strict linear flow. As is known, turbulent flow and catalyst slippage may occur to some extent, especially in certain vapor velocity ranges and some catalyst fillings, although it has been reported to be advisable, to use sufficiently low catalyst fillings to limit slippage and back mixing.

Most preferably, the reactor is a reactor, which abruptly separates a substantial portion or all of the evaporated cracked products from the catalyst at one or more points 4-0 along the riser, and preferably separates substantially all of the evaporated 8006227 cracked products from the catalyst. the downstream end of the riser. A preferred type of reactor embodies ballistic separation of catalyst and products; that is, catalyst 5 is propelled in a direction defined by the riser and is forced to continue its movement in the general direction thus established, while the products must make an abrupt change of direction with a less impulse, resulting in an abrupt, · .. ·. 10 almost instantaneous separation of product from catalyst. In a preferred embodiment, referred to as an escaping riser, the riser includes a substantially unobstructed discharge opening at the downstream end for catalyst removal. An outlet opening in the wall of the tube adjacent to the downstream end receives the products. The discharge opening communicates with a catalyst flow path. extending to the conventional stripping device and the regenerator, the outlet opening communicating with a product flow path substantially or wholly separated from the catalyst flow path and leading to separators for separating the products from any relatively small portion of catalyst leading to entry to the product outlet port. Examples of a ballistic separator and technique as described above are found in U.S. Pat. Nos. 4,066,533 and 4,070,159. Preferred conditions for carrying out the method are described below. These include feed, 50 catalyst and reaction temperatures, reaction and feed pressures, residence time and conversion levels, coke production and coke deposit on catalyst.

In the conventional ECO operations with VGO, the feed is usually preheated, often to temperatures that are significantly higher than required to make the feed sufficiently flowable for pumping and for feeding to the reactor. For example, preheating temperatures of about 30 ° C or 430 ° C have been reported. However, in the present process, as practiced today, it is preferable to limit the preheating of the feed so that the feed is able to absorb a greater amount of heat from the catalyst while the catalyst increases the feed. to conversion temperature, while simultaneously minimizing the use of external fuels to heat the feed. Therefore, if the nature of the feed allows, it can be fed at ambient temperature. Heavier feeds can be fed at preheating temperatures up to about 516 ° C, usually about 90 ° C to about 260 ° C, but higher preheating temperatures are not necessarily excluded.

The catalyst feed to the reactor can vary very widely in temperature, for example from about 590 ° C to about 8 ° 0 ° C, more preferably about 650 ° C to about 815 ° 0, and more preferably about 705 ° 0 to about 760 ° C, with about 720 ° C to about 74-6 ° C now considered optimum.

As indicated above, the conversion of the carbon metal oil to relatively low molecular weight products can be carried out at a temperature from about 480 ° C to about 780 ° C, measured at the outlet of the reaction space. The reaction temperature, as measured at this outlet, is more preferably maintained in the range from about 525 ° C to about 705 ° C, more preferably about 530 ° C to about 650 ° C, and most preferably about 538 ° C to about 621 ° C. Depending on the selected temperature and the properties of the feed, all feed may or may not evaporate in the riser. Although the pressure in the reactor as indicated above can range from about 70 to about 550 kPa, preferred and more preferred pressure ranges are from about 105 to about 245 and from about 140 to about 245 kPa. Generally, the partial (or total-55 le) of the feed can be in the range of about 21 to about 210, more preferably about 50 to about 175, and most preferably about 70 to about 120 kPa. The partial pressure of the feed can be controlled or suppressed by feeding gaseous (including vaporous) products into the reactor, such as, for example, steam, water and other additional products described above. For example, the process has been conducted with the feed partial pressure ratio to the total riser pressure in the range of from about 0.2 to about 0.8, more usually about 0.3 to about 0.7, and still more usually about 0.4 to about 0.6, with the ratio of added gaseous product (containing recycle gases and / or steam from the addition of water to the riser in the form of steam and / or liquid water with respect to the total pressure in the riser ranging accordingly from about 0.8 to about 0.2, more usually about 0.7 to about 0.3, and even more usually about 0.6 to about 0.4. In the illustrative embodiments just described, the ratio of the partial pressure of the added gaseous product to the partial pressure of the feed has been in the range of about 0.25 to about 2.5, more usually about 0, 4 to about 2 and more usually about 0.7 to about 1.7. Although the residence time of feed and product vapors in the riser can range in the range of from about 0.5 to about 10 seconds, as described above, preferred and more preferred values are about 0.5 to about 6 and about 1 to about 25 seconds, with about 1.5 to about 30 seconds now being considered about optimal. For example, the process has been conducted with a vapor residence time in the riser of about 2.5 seconds or less by adding significant amounts of gaseous products into the riser, which amounts are sufficient to provide, for example, a partial pressure ratio of added gaseous products with respect to the hydrocarbon feed of about 0.8 or more. For further explanation, the process has been carried out with a residence time of about 2 seconds or less with the aforementioned ratio in the range of about 1 to about 2. The combination of low feed partial pressure, very short residence time and ballistic separation of products of the catalyst are particularly favored by the conversion of carbon metal oils.

8006227 40

Other advantages can be obtained in the preceding combination, when there is a substantial partial pressure of added gaseous product, especially water, as described above. Depending on whether slippage occurs between the catalyst and hydrocarbon vapors in the riser. catalyst residence time in the riser may or may not equal that of the vapors. Therefore, the ratio of the average catalyst residence time in the reactor 10 to the vapor residence time in the reactor, i.e. slipping, can be in the range of about 1 to about 5, more preferably about 1 to about 4, and the most preferably about 1.2 to about 3> with about 1.2 to 2 now considered optimum.

In certain types of known ICC units, there is a riser which dissolves catalyst and product vapors together in an enlarged space, which is usually considered to be part of the reactor, in which the catalyst is freed from product and collected. Continued contact of catalyst, optionally uncracked feed and cracked products in such an enlarged space results in a total catalyst feed contact time that noticeably exceeds the residence time of the vapors and catalysts in the riser. In the practice of the process of the present invention with ballistic separation of catalyst and vapors at the downstream (eg, top) end of the riser, as taught in U.S. Pat. Nos. 4,066,533 and 4,070,159, the riser residence time and catalyst contact time are substantially 30 equal for a large part of the supply and product vapors. It is considered expedient if the vapor residence time in the riser and the vapor catalyst contact time are substantially equal to at least about 80/0, more preferably at least about 90%, and most preferably at least about 95% by volume. total supply and product vapors passing through the riser. When depriving such vapors of continued contact with catalyst in a catalyst liberation and collection space, a tendency toward re-cracking and reduced selectivity can be avoided.

ο η n fi? ? 7

Generally, the combination of catalyst to oil ratio, temperatures, pressures, and residence times should be such that substantial conversion of the carbon-metal oil feed is accomplished. It is an advantage of the method that very high conversion levels can be achieved in a single step; for example, the conversion can be greater than 50% and can be up to about 90% or higher. Preferably, the aforementioned conditions are maintained at sufficient levels to allow the conversion levels in the range of about 60 to about 90% and more at preferable to keep about 70 to about 85%. The previous conversion levels are calculated by subtracting from 100% the percentage obtained by dividing the liquid volume of fresh feed 15 into 100 times the volume of liquid product boiling at and above 221 ° C (true boiling point, standard atmospheric pressure ).

These significant conversion levels can and will usually result in relatively high yields of coke, such as, for example, about 4 to about 14 wt% based on fresh feed, more usually about 6 to about 12 wt%, and usually about 6 to about 10 wt%. %. The coke yield can be deposited more or less quantitatively on the catalyst. At the intended catalyst to oil ratios, the resulting coke deposit may be greater than about 0.37, more usually greater than about 0.5, and often greater than about 1% by weight, based on the anhydrous weight of regenerated catalyst.

Zen such coke deposits can reach about 2%, or about 3% or even higher.

Like the conventional ECO operations on VGO, the present process involves stripping spent catalyst after liberating the catalyst from product vapors. Those skilled in the art are familiar with suitable stripping agents and spent catalyst stripping conditions, 55 but in some instances the present process may require somewhat more severe conditions than those commonly employed. This may result, for example, from the use of a carbon metal oil with components which do not volatilize under reactor conditions, which components themselves are deposited at least in part on the catalyst. Such an adsorbed, non-evaporated product can be difficult from at least two points of view. First, when the gases (including vapors) used for stripping the catalyst 5 can access a catalyst liberation or collection space connected to the downstream end of the riser and when there is an accumulation of catalyst in such a space, evaporation can of these unevaporated hydrocarbons in the stripper are followed by adsorption on the catalyst bed in space. More specifically, when the catalyst in the stripper is stripped of adsorbed feed material, the resulting fumes of feed material pass through the catalyst bed accumulated in the catalyst collection and / or liberation space and may contain coke and / or condensed product deposit on the catalyst in this bed. When the catalyst carrying such deposits is moved from the bed in the stripper and from there to the regenerator, the condensed products may create a demand for more stripping capacity, while the coke may tend to regenerate - increase temperatures and / or request a greater regeneration capacity. For the foregoing reasons, it is preferable to prevent or limit the contact between stripping vapors and catalyst accumulations in the catalyst liberation or collection space. This can be done, for example, by preventing the formation of such accumulations, for example with the exception of an amount of catalyst, which essentially disappears from the circulation and may remain behind in the liberation and / or collection space, the catalyst, which is circulation, can be removed from space promptly after deposition on the bottom of the room. Also, in order to minimize regeneration temperatures and the regeneration capacity demand, it may be desirable to employ conditions of time, temperature and atmosphere in the stripper sufficient to remove the potentially volatile hydrocarbon product obtained by the stripped catalyst. to about 10 wt% or less of the total carbon load on the catalyst. A similar no 6 2 2 7 * equal stripping treatment can, for example, re-heating the catalyst, an extensive stripping treatment with steam, the use of gases with a temperature considered to be higher than normal for FCC / VGO treatments, such as, for example, waste gas. from the regenerator, as well as other refining stream gases such as waste gas from the hydrotreater (containing E 2 S), hydrogen and other contents. For example, the stripping device can be used at a temperature of about 555 ° C or 10 higher.

Substantial conversion of carbon metal oils to lighter products of the invention tends to produce sufficiently high coke yields and coke deposition on catalyst to require some care in catalyst regeneration. In order to maintain a suitable activity in zeolite and non-zeolite catalysts, it is desirable to regenerate the catalyst under conditions of time, temperature and atmosphere sufficient to reduce the weight percent of carbon remaining on the catalyst to about 0. 25% or less, whether the catalyst has a strong heavy metal accumulation or not. Preferably, this weight percentage is about 0.1% or less, and more preferably about 0.05% or less, especially with zeolite catalysts. The amounts of coke, which must therefore be burned from the catalysts in the processing of carbon-metal oils, are usually considerably greater than would be the case in VGO cracking. The term coke, as used in the present invention, includes any residual unevaporated feed or cracked product when such product is present on the catalyst after stripping.

The regeneration of catalysts, the burning off of coke deposited on the catalyst during the conversion of the feed, can be carried out at any suitable temperature in the range of about 590 to about 870 ° C, measured at the catalyst outlet of the regenerator. This temperature is preferably in the range from about 650 ° C to about 815 ° C, more preferably from about 690 ° C to about 775 ° C, and optimally about 720 ° C

80 06 22 7 44 to about 745 ° C. For example, the process can be carried out with a fluidized regenerator with the dense phase temperature of the catalyst in the range of about 705 to about 760 ° C.

It has therefore been suggested in the regeneration of catalyst used in the cracking of carbon metal oils that the success of the cracking treatment depended on the combustion of the coke in contact with combustion-producing gases containing excess oxygen. By excess oxygen 10 is meant an amount in excess of the stoichiometric requirements for the combustion of all hydrogen, all carbon and any optional combustible components present in the aforementioned selected portion of the coke immediately prior to regeneration. The gaseous products of the compound, which are conducted in the presence of excess oxygen, will usually contain a significant amount of free oxygen. Such free oxygen, unless removed from the by-products or converted to another form by an apparatus or method other than regemination, will usually manifest itself as free oxygen in the waste gas from the regenerator unit. In order to provide sufficient driving force to complete the combustion of coke to low levels, when burning all or part of the coke with excess oxygen, the amount of free oxygen will usually not only be noticeable, but substantial. say there will be a concentration of at least about 2 moles of free oxygen in the total regeneration waste gas obtained in the total completed regeneration operation. While such a technique is effective in achieving the desired low carbon levels of 8006227 on regenerated catalyst, it has its limitations and difficulties, which will become apparent from the following discussion.

As usually done, the combustion of 5 coke during regeneration generates some H 2 O because of the small amount of hydrogen commonly found in coke; however, carbon monoxide and carbon dioxide are generally considered to be the major products. The conversion of the carbon content of coke to carbon-10 monoxide and carbon dioxide are highly exothermic reactions. For example, the reaction of oxygen with coke to prepare carbon dioxide gives 3284-1 kJ / kg of coke, while the reaction of oxygen with coke or carbon to form carbon monoxide gives about 9234-kJ / kg of coke. The greater the amount of coke to be burned from a given weight of catalyst, the greater the amount of heat released during combustion in the regenerator.

Heat, which is released by burning 20 coke in the regenerator, is absorbed by the catalyst and can easily be retained until the regenerated catalyst is contacted with fresh feed. When processing carbon metal oils to the relatively high conversion levels involved in the present invention, the amount of regenerator heat transferred to the fresh feed through regenerated catalyst recirculation can significantly increase the level of heat exceed input which is suitable in the riser for heating and evaporation of the feed and other products, for supplying the endothermic reaction heat to the cracking, for replenishing heat losses of the unit, etc. Therefore According to the invention, the amount of regenerator heat transferred to the fresh feed can be controlled or, if necessary, limited within certain approximate ranges. For example, the amount of heat thus transferred may range from about 1160 to about 2795, more particularly about 14-00 to about 2100, and more particularly about 1510 to about 1980 kJ / kg fresh feed. The aforementioned ranges 8 0 06 22 7 * 46 refers to the combined heat, in kJ / kg fresh feed, which is transferred from the catalyst to the feed and reaction products (between the contact of the feed with the catalyst and the separation of product 5 from the catalyst) to provide the heat of reaction (e.g. for cracking) and the difference in ethalpy between the products and the fresh feed. Not included in the foregoing is the heat made available in the reactor by the adsorption of coke on the catalyst, nor the heat consumed by heating, evaporating or reacting circulating currents and such additional products such as water, steam, naphtha and other hydrogen supplying compounds , waste gases and inert gases, or from radiation or other losses.

One olefin combination techniques may or may be used in the present invention to control or limit the amount of regeneration heat transferred via catalyst to fresh feed.

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 in the regenerator. In addition, heat can be removed from the catalyst with heat exchangers, including, for example, heat exchangers (eg steam coils) built in the reactor itself, whereby heat can be extracted from the catalyst during regeneration. Heat exchangers can be incorporated into catalyst transfer lines, such as, for example, the catalyst return from the regenerator to the reactor, whereby heat can be removed from the catalyst after it has been regenerated. The amount of heat imparted to the catalyst in the reactor can be limited by reducing the amount of insulation on the regenerator to allow any heat loss to the surrounding atmosphere, especially when it is intended to process feeds with an exceptionally high coking potential. ; in general, such heat loss to the atmosphere is considered less economically desirable than certain other alternatives set forth herein. It is also possible to inject cooling streams into the regenerator, for example water and / or steam, to increase the amount of inert gas available in the regenerator for heat absorption and removal.

Practiced or not practiced with the foregoing techniques, the present invention encompasses the technique of controlling or limiting the heat which is transferred to the fresh feed via recycle regenerated catalyst while maintaining a specified carbon dioxide to carbon ratio monoxide ΊΟ formed in the regenerator, while such gases are maintained in heat exchange contact or relationship with regenerating catalyst. Generally, all or a major part of the coke weight present on the catalyst is removed immediately prior to regeneration in at least one combustion zone, controlling the aforementioned ratio as described below. More particularly, at least the majority, more preferably at least about 65% by weight, and even more preferably 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 until CO is maintained at a level significantly below 5, for example, about 4 or less. When considering the CO2 / CO ratio from the reverse viewpoint, it is preferable that the CO / CO2 molar ratio be at least about 0.25 and preferably at least about 0.5 and even more preferably about 1 or more or is even 1.5 or more. While those skilled in the art are aware of techniques for inhibiting the combustion of CO to 30 CO2, it has been proposed that the CO: CO2 molar ratio should be kept less than 0.2 when regenerating catalyst with large heavy metal accumulations from the processing of carbon metal oils; see, for example, U.S. Pat. No. 35 4,162,215. In the present invention, however, maximizing CO production while regenerating the catalyst to about 0.1% carbon or less, and preferably about 0.05 ° / ° carbon or less, is an embodiment of the present invention, which is particularly preferred. In addition, according to a preferred method for carrying out the invention, it is possible to do this

4-S

• regeneration sub-process as a whole is carried out to the aforementioned low carbon levels on regenerated oxygen deficient catalyst; more specifically, the total oxygen supplied to one or more regeneration steps may be the stoichiometric amount, and is preferably less than the stoichiometric amount, which would be required to burn all hydrogen in the coke to E 2 O and all carbon in burn the coke to GOg. When the coke contains other flammable ingredients, the aforementioned stoichiometric amount can be controlled to include the amount of oxygen required to burn it.

Yet another particularly preferred technique for regenerating or limiting the regeneration heat imparted to fresh feed via recycled catalyst involves the bypass of some of the heat carried by the recycled catalyst to additives introduced into the reactor, such as water, steam, naphtha, other hydrogen-providing compounds, waste gases, inert gases, and other gaseous or evaporable products, which may be introduced into the reactor.

The greater the amount of coke to be burned from a given weight of catalyst, the greater the ability to expose the catalyst to excessive temperatures. Many otherwise desirable and suitable cracking catalysts are particularly sensitive to high temperature deactivation, among which are quite few of the expensive molecular sieve or zeolite type catalysts. The crystal structures of zeolites and the pore structures of the catalyst supports are generally somewhat sensitive to thermal and / or hydrothermal degradation. The use of such catalysts in catalytic conversion processes for carbon-metal-35 feeds creates a need for regeneration technique which will not destroy the catalyst by exposure to very severe temperatures and steam treatments.

Such a need can be met by a multi-stage regeneration process, which involves the transport of spent catalyst to a first regeneration zone and 8006227 supply of oxidizing gas thereto. The amount of oxidizing gas entering the first zone and the concentration of oxygen or oxygen carrying gas therein are sufficient for only partial implementation of the desired conversion of coke on the catalyst to carbon oxide gases. The partially regenerated catalyst is then removed from the first regeneration zone and transferred to a second regeneration zone. Oxidizing gas is introduced into the second regeneration zone to give a higher concentration of oxygen or oxygen-containing gas than in the first zone to complete the. removal of carbon to the desired level. The regenerated catalyst can then be removed from the second zone and recycled to the reactor for contact with fresh feed. An example of such a multi-stage regeneration process is described in U.S. Pat. No. 2,958,759 *. The multi-stage regeneration provides the option of combining low oxygen regeneration with the control of the CO: CO2 molar ratio. For example, about 50 wt% or more, more preferably about 65 to about 95 wt%, and even more preferably about 80 to about 95 wt%, of the coke on the catalyst can be removed in a catalyst immediately prior to regeneration. or more regeneration steps, wherein the CO: CO2 molar ratio is controlled / in the manner described above. In combination with the foregoing, the last 5 wt% or more, or 10 wt%, or 50 or more of the coke originally present up to the total amount of coke remaining after the previous step or steps can be removed in a subsequent regeneration -stage, in which more oxygen is present. Such a process is susceptible to use in such a way that the total exhaust gas recovered from the entire completed regeneration operation contains little or no excess oxygen, ie, in the order of about 0.2 mole / o or less, or about 0.1 mole percent or less, which is considerably less than the 2 mole percent suggested elsewhere. Therefore, the multi-stage regeneration is particularly advantageous in that it provides another suitable technique for limiting the regeneration heat transferred to fresh feed via regenerated catalyst and / or reducing the thermal deactivation capability while simultaneously providing an opportunity. becomes for Θ 3? lowering the carbon content on the regenerated catalyst to those very low percentages (e.g., about 0.1% or less), which particularly increase the catalyst activity. In addition, when the regeneration conditions, e.g., temperature or atmosphere, are considerably less heavy in the second zone than in the first zone (for example with at least about 5> 5 and preferably at least about 11 ° C), that part of the regeneration sequence, which involves the most severe conditions, while there is still a noticeable amount of coke on the catalyst. Such an operation can provide some protection of the catalyst from the more severe conditions. A particularly preferred embodiment of the invention is the two to 20 stage fluidized regeneration at a maximum temperature of about 815 ° C with a reduced temperature of at least about 5> 5 or 11 ° C in the dense phase of the second stage compared to the dense phase of the first stage and with reduction of carbon on catalyst 25 to about 0.05 wt% or less or even about 0.25 wt% or less in the second zone. In fact, the catalyst can be easily regenerated to carbon contents of 0.01 wt% by this technique, even though the carbon on the catalyst prior to regeneration is about 1%,

In most circumstances it will be important to ensure that no adsorbed oxygen-containing gases are transferred to the riser by recycled catalyst. Thus, if such an operation is deemed necessary, the catalyst discharged from the regenerator can be stripped with suitable stripping gases to remove oxygen-containing gases. Such a stripping treatment can be performed, for example, at relatively high temperatures, for example, about 750 ° C to about 745 ° C, using steam, 8006227 nitrogen or other inert gases as the stripping gas (s). The use of nitrogen and other inert gases is beneficial from the viewpoint of avoiding a tendency to hydrothermal catalyst deactivation which may arise from the use of steam.

The following comments and discussion regarding metal management, carbon management, and heat management may assist in obtaining the best. results from the use of the invention. Since these comments are largely directed to what is considered the best embodiment, it will be understood that the invention is not limited to the particular embodiments discussed here. In addition, there is no intention to be bound by any theory as expressed or implied herein in the performance suggestions as described below, since certain comments are necessarily based on theoretical considerations.

Although discussed separately below, it will be readily apparent that the management of metals, carbon and heat are interrelated and dependent topics both theoretically and practically. While the coke yield and catalyst deposition are primarily the result of the relatively large amounts of coke precursors found in carbon-metal oils, coke production is aggravated by large metal accumulations, which can also significantly affect catalyst behavior. Moreover, the degree of success experienced in the management of the metals and the carbon will have a direct influence on the extent to which heat management is necessary. In addition, some of the steps taken to support the management of the metals have been found to be very helpful with regard to carbon and heat management.

As mentioned above, the presence of a large heavy metal accumulation on the catalyst tends to exacerbate the problem of dehydrogenation and aromatic condensation, resulting in an increased 4-0 of gases and coke products for a feed of 8 0 06 22 7 52 a given Ramsbottom carbon value. The addition of substantial amounts of watchman to the reactor, either in the form of steam or liquid water, appears very advantageous from the viewpoint of keeping the heavy metals in a less harmful form, ie the oxide instead of the metal form. This contributes to maintaining the desired selectivity.

Also, a unit design in which system components, residence times and residence times are chosen to reduce the ratio residence time of the catalyst in the reactor with respect to the residence time of the catalyst in the regenerator will tend to reduce the ratio of the times during which the catalyst is under reduction conditions and under oxidation conditions, respectively. This can also contribute to maintaining desired selectivity levels.

Whether the metal content of the catalyst is successfully managed can be observed by recording the total amount of hydrogen plus methane generated in the reactor and / or the ratio of hydrogen to methane thus generated. It is generally believed that the hydrogen to methane molar ratio should be less than about 1 and preferably about 0.6 or less, with about 0.4 or less being considered about optimal.

Careful carbon management can reduce selectivity.

(the ability to make the production of valuable products made ximal) and improve heat productivity. In general, the above-described metal control techniques also assist in carbon management. The suitability of water addition for carbon management has already been explained in considerable detail in that part of the description which relates to added products for introduction into the reaction zone. In general, these techniques, which improve the dispersion of the feed in the reaction zone, will also prove helpful; these include, for example, the use of misting or mist-forming devices to help disperse the feed.

40 The catalyst to oil ratio is also an o η η β o o i

V

factor in the warnte management. In accordance with prior FCC practice with VGO, the reactor temperature in the practice of the present invention can be controlled by the flow of hot regenerated catalyst to the reactor, respectively, in response to decreases and increases in the reactor temperature, usually the outlet temperature in the case of a riser-type reactor. When the automatic catalyst feed control is set to maintain excess catalyst to oil ratio, unnecessarily large amounts of carbon production and heat release due to the weight of fresh feed entering the reaction zone can be expected. will be added.

Relatively high reactor temperatures are also favorable from the viewpoint of carbon management. Such relatively high temperatures provide more complete evaporation of feed product catalyst release.

Carbon management can also be facilitated by an appropriate restriction of the total pressure in the reactor and the partial pressure of the feed. In general, at a given conversion level, relatively small reductions in the aforementioned pressures can significantly reduce cooking output. This may be due to the fact that limiting the total pressure tends to increase the evaporation of high boiling components of the feed, to encourage cracking and the release of both unconverted feed and relatively high boiling cracking products at the catalyst. In this context, it may be useful to limit the pressure drop of the equipment downstream from and in communication with the reactor. However, when it is desired or necessary to operate the system at a fairly high total pressure, such as, for example, due to processing limitations (e.g., pressure drop in the 55 downstream equipment), the advantages described above can be obtained by limiting the partial pressure of the feed. Suitable ranges for the total reactor pressure and partial feed pressure have been set forth above, and generally it is desirable to attempt to keep the pressures as low as possible within these ranges.

8006227 4 54 *

The abrupt separation of catalyst from product vapors and any unconverted feed is also of great help. It is for this reason that the so-called vented riser equipment and technique described in U.S. Pat. Nos. 4,070,159 and 4,066,555 is the preferred type of equipment for the practice of the present process. For similar reasons, it is advantageous to minimize the elapsed time between separation of catalyst from product vapors and the start of stripping. The vented riser and instant stripping tend to reduce the opportunity to coke unconverted feed and relatively high boiling cracking products adsorbed on the catalyst.

A particularly desirable mode of implementation from the carbon management standpoint is to carry out the process in the vented riser using a hydrogenating agent, if necessary, while keeping the partial feed pressure and the total reactor pressure as low as possible, and to incorporate relatively large amounts of water, steam and other diluents as desired, giving the numerous advantages discussed in more detail above. In addition, when liquid water, steam, hydrogenating agents, hydrogen, and other gaseous or evaporable products are supplied to the reaction zone, the addition of these products provides an opportunity to exert additional control of the catalyst. to oil ratio. Thus, for example, the practice of increasing or decreasing the catalyst-to-oil ratio for a given amount of decrease or increase in reactor temperature may be reduced or eliminated by either an appropriate reduction or increase in the addition ratios of water, steam and other gaseous or evaporable material to substitute either a suitable reduction or increase in the ratio of water to steam and / or other gaseous products introduced into the reaction zone.

The heat management involves measures taken to control the amount of heat released in various parts of the processes and / or 8006227% successfully treating such heat as can be released. In contrast to the conventional FCC practice using VGO, where it is usually a problem to generate sufficient heat during regeneration to equilibrate the reactor, the processing of carbon-metal oils generally so much heat that careful management is required. Heat management can be facilitated by various techniques associated with the products being introduced into the reactor. Therefore, heat absorption by feed can be maximized by minimal preheating of the feed, it only being necessary that the feed temperature is sufficiently high so that the feed is sufficiently flowable for successful pumping and dispersion in the reactor. When the catalyst is kept in a highly active state with the coking suppression (control of metals) to achieve higher conversion, the resulting higher conversion and greater selectivity can increase the heat absorption of the reaction. Generally, relatively high reactor temperatures promote catalyst conversion activity despite more refractory and higher boiling components with high coking capabilities. While the rate of catalyst deactivation can therefore be increased, the rather high treatment temperatures tend to reverse this loss of activity. Fairly high temperatures in the reactor also contribute to the increase in the octane number, thereby eliminating the octane-lowering effect of a large carbon deposit. Other techniques for absorbing heat have also been described above in connection with the introduction of water, steam and other gaseous or evaporable products into the reactor.

The heavy-duty stripping treatment and various regeneration techniques discussed above are suitable for controlling heat release in the regenerator. While removal of heat from catalyst in or downstream of the regenerator by heat exchanger (including steam coils) has been proposed as 8006227 56 a means of controlling heat output, the above described techniques of multi-stage regeneration and control over the C0 / CC> 2 ratio (in either a single or a multi-stage regeneration) are considered more effective. The use of steam coils is considered partially self-destructive in that a steam coil or heat exchanger in the regenerator or catalyst return line will generally cause an increase. in the catalyst to oil ratio with a resulting increase in the degree of carbon production in the reactor and heat release in the regenerator.

As mentioned above, the invention can be practiced by the methods described above or by many other methods. Two illustrative, non-limiting examples are described with reference to the accompanying diagrams in Figures 1 and 2 and the description of these Figures which follows.

Fig. 1 is a schematic representation of an apparatus for carrying out the method of the present invention. The carbon metal oil feed (which may have been heated in a feed preheater not shown) and water (if used) supplied by the feed line 9} are fed through the feed line 10 with a control valve 11 to a fork 12, in which they mixing with a stream of catalyst supplied through supply line 13 and controlled by valve 14. Of course, a variety of mixing arrangements may be employed and arrangements may be made to supply the other additives discussed above. The mixture of catalyst and feed, with or without such additional materials, is then fed to the riser 18.

While the riser 18 appears vertical in the figure, those skilled in the art will note that the riser need not be vertical since riser-house type reactors are known in which a noticeable portion of the riser pipe is not vertical. Thus, upwardly rising riser tubing is contemplated, and usually the upward component of their upwardly flowing ramps is, i.e., at least about 0 ° to about 30 °. It is also known to supply risers 8 0 06 22 7 «

V

shafts having downwardly flowing inclined or vertical portions as well as horizontal portions. Coiled risers are also known in which both upwardly extending and downwardly extending segments are present. In addition, it is entirely suitable to carry out the method of the invention in an inclined and / or vertical pipe, into which the feed and catalyst are introduced at an upper elevation and in which the feed and catalyst move under the influence of gravity. 10 force and the downward flow of the feed to a lower elevation. Therefore, the invention generally contemplates the use of reaction chambers with a long L / D ratio and with a significant deviation from horizontal.

At the top of the riser 18 is a chamber 19 which receives the catalyst from the riser. While chamber 19 is a conventional release and collection chamber, it is preferable to provide means for product vapors to undergo a sufficient direction change with respect to the direction followed by the catalyst particles, with the vapors suddenly and effectively separated of the catalyst.

Preferably, there is a "ballistic" separation of catalyst particles and product vapors as described above. In the accompanying schematic diagram, the release chamber 19 comprises an upward extension 20 of the riser pipe 18 with an open top end 21 through which the catalyst talcator particles are discarded. This embodiment utilizes the so-called vented riser described in U.S. Pat. Nos. 4,066,533 and 4,070,159.

Due to the refractory nature of carbon-metal fractions, a relatively large gravity is required, but the rapid release of catalyst from the lighter cracked products into the vented riser prevents overcracking of desirable liquid products such as gasoline into gaseous products. The product vapors are forced to undergo a sudden change of direction in the transverse opening 22 on the side of the riser extension 20, where the catalyst particles are largely unable to follow the product vapors in the opening 22.

The vapors and those few particles that still follow these vapors in the opening 22 are transferred by cross pipe 23 to a cyclone separator 24. It is an advantage of the vented riser system shown that it can function satisfactorily with a single stage cyclone separator. In the present embodiment, however, the cyclone separator 24 is used as a cyclone separator of the first stage connected via a transfer line 17 to an optional second cyclone separator. The cyclone separators, either of the one-stage or multistage type, separate from the products that small amounts of catalyst, which nevertheless enter the cross gate 22. Product vapors are discharged from the release chamber 19 through product discharge line 26.

The catalyst particles discharged from the open top end 21 of the riser from conduit 20, and those catalyst particles discharged from the discharge branches 27 and 28 of primary and secondary cyclones 24 and 20 fall to the bottom of the clearance space 19. Preferably, the stock and residence time of the catalyst in chamber 18 is as short as possible. During start-up, those catalyst particles, which are present, may be kept in suspension by agitation-causing nozzles 30, to which steam is supplied through the steam supply line 29. Spent catalyst that overflows from the bottom of the release chamber 18 passes through the downcomer 31 to a stripping space 32, which is provided with baffles 33 and a steam jet pipe 34. Any of the above 30 other stripping gases can be used with or instead of the steam.

Carbon is burned from the surface of the catalyst in the combustion device 38, which receives stripped catalyst through the downcomer line 39 and control valve 35. Blowers 41 and 42 in conjunction with a valve and line arrangement, generally indicated by 44 , supply air to the combustion air nozzles 48 at the bottom of the combustion device and to the shaking nozzles 49 "at an elevated 40 position. The air preheater 43, although not usually used in the processing of heavy hydrocarbons of the invention can be used at start-up of the unit with VGO, then, when the unit is switched to the carbon-metal supply, the preheating treatment may be aborted (or at least reduced) Additional fuel means may be provided for the supply of fuel through the combustion air nozzles 48, however this is usually not necessary mainly 'since' the carbon deposit on the catalyst 10 provides more than enough fuel to maintain the required temperature in the regeneration section. Regenerated catalyst, most of the carbon of which has been burned, exits the combustion device through an upper outlet 50 and cross pipe 51 to a second chamber 52, where it is deflected into the lower part of the chamber by a baffle 53. use of the two-stage regeneration is contemplated and preferred, in this particular embodiment, the secondary chamber 52 primary was operated as a separation chamber, although it can be used to remove additional carbon to about 0.1% or less at the final regeneration steps.

The catalyst is moved from the secondary chamber 52 in three different directions. A portion of the catalyst can be recycled to the incinerator 38 through the recirculation catalyst 55 and heat control valve 56 in the incinerator. Part of the catalyst is entrained in the product gases, such as CO and / or CO 2 generated by combustion of the carbon on the catalyst in the incinerator, and the entrained fine catalyst particles go up in chamber 52 to two sets of primary and secondary cyclones, generally indicated by 57 and 58, which separate these fine catalyst particles from the product gases. Catalyst collected in cyclones 57 and 58 and discharged through their downcomers is directed to the bottom of chamber 52, where the catalyst is kept in suspension by inert gas and / or steam nozzles 59 and baffle arrangement 40 54, the latter facilitates the release of regenerated 8006227 60 catalyst through the outlet 69 to the catalyst feed line 15, thereby recycling it for contact with fresh feed at fork 12, as previously described.

Combustion product gases generated by regeneration of the catalyst and separated from entrained fine catalyst particles by sets 57 and 58 of primary and secondary cyclones in chamber 52 are exhausted through the discharge lines 61 and 52 and heat exchangers. Boots 60 and 65. Since such gases contain significant amounts of CO, they can be sent via the gas supply line 64 to an optional furnace 65 in which the CO is burned to heat a heating coil 66 connected to the steam boiler 67. Additional heat 15 can be supplied to the contents of the boilers by secondary line 68, which circulates fluid from the boiler 67 to the heat exchangers 60 and 63 and back to the boiler. This is, of course, only an example of many possible regeneration arrangements that can be used. The amount of heat returned from the regenerator to the riser via regenerated catalyst can be controlled in any of the ways described above; however, the present invention controls the relative ratios of carbon monoxide and carbon dioxide generated while the catalyst is heat exchangeable with the combustion gases from the regeneration. This same technique is also included in the preferred embodiment described in Figure 2.

In Fig. 2, reference number 80 identifies a supply control valve in the supply line 82. Supply line 83 (if used) introduces liquid water into the supply.

The heat exchanger 81 in the feed line 82 acts as a feed preheater, whereby preheated feed material can be delivered to the bottom of the riser 91 reactor. Catalyst is delivered to the reactor through catalyst standpipe 86, with flow of the catalyst controlled by a control valve 87 and suitable automatic control equipment (not shown), which are known to those skilled in the art of designing and using riser 8006227 k type crackers.

The riser pipe 9Ί may optionally contain a provision for the injection of water, steam and, if desired, other gaseous and / or evaporable material for the purpose described above. The reactor is equipped with a release chamber 92 similar to the release chamber 19 of the reactor shown in Figure 1, and the embodiment of Figure 2 therefore includes means for directing product vapors for a sudden and target change. 10 separation of the catalyst as in the previous embodiment. The catalyst exits the clearing space 92 through the stripper 94 which operates in a similar manner to the stripper 32 of FIG. 1. Spent catalyst exits from stripper 94 to regenerator 101 through a spent catalyst transfer line 97 with a gate valve. to control the flow.

The regenerator 101 is divided into an upper space 102 and a lower space 103 by a separator panel 104-20 between the upper and lower ends of the regenerator.

The spent catalyst from transfer line 97 enters the upper space 102 in which the catalyst is partially regenerated. A funnel-like collection device 106 with an obliquely cut top edge receives partially regenerated catalyst from the top surface of the dense phase of the catalyst in the top space 102 and delivers it through a downcomer 107 not an outlet 110 below the top surface of the dense phase of the catalyst in the lower regeneration space 103.

Instead of the internal catalyst downcomer 107, an external downcomer can be used. Valve members in such an external downcomer can control the catalyst residence time and flow rate in and between the upper and lower spaces.

Air is supplied to the regenerator through an air supply line 113. Part of the air passes through a branched supply line 114 to bayonet 115 which extends upwardly into the interior of the diffuser 111 along the central axis. Catalyst in 40 chamber 103 has access to the space within the divider 8 0 06 22 7 62 device 111 between its walls and the bayonet 11.5

A small unsigned bayonet in the aforementioned space whirls up the catalyst and forces it upward to a horizontally disposed unsigned ring distribution device, where the open top end of the distribution device 111 opens to chamber 105. The rest of the air, which passes through the air supply line 115, can be heated in the air heater 117 (at least during the stepping up with VGO) and is then placed in the slate. Inlet 118 of the aforementioned ring distribution device, which may include openings, nozzles, or other openings that generate an upward gas flow to fluidize the partially regenerated catalyst in chamber 105.

The air introduced in the manner described above completes in regeneration 105 the regeneration of the partially regenerated catalyst received through the downcomer 107. The amount of air that is supplied is sufficient so that the air and / or the resulting combustion gases are still able to support combustion until reaching the upper end of chamber 105. The aforementioned downcomer 107 extends through a widened opening in panel 104, to which is attached a gas distribution device 120, which is concentric with and surrounds the downcomer. Via the gas distribution device 120, the combustion support gases, which are now partially freed from the combustion support gas, are introduced into the upper regenerator chamber 102, where they come into contact with the 50 entering spent catalyst from the transfer line for spent oxidation purposes. Catalyst 97 · Opened probes 121 or other suitable means in the gas distribution device 102 contribute to achieving an even distribution of the partially relieved combustion support 55 carrier gas in the upper chamber 102. Supplementary air or other fluids may be introduced into the upper chamber 102 through the supply line 122, which discharges into or through gas distribution device 120.

Fully regenerated catalyst with less than about 40% Q, 25% carbon, preferably less than about 0.190%, and more preferably less than about 0.05%, is withdrawn from the lower regenerator chamber 105 through a regenerated catalyst stripping device 128, the outlet of which feeds the aforementioned catalyst standpipe 86. Therefore, regenerated catalyst is returned to riser 91 for contact with additional fresh feed from the feed line 82. Whatever heat is supplied to the recycled catalyst in the regenerator 101 is daze. Is..available, yoor · .Wiam1 »averdraclit / -; -. .

10 with the fresh supply in the riser.

The distribution of the regenerator in upper and lower regeneration chambers 102 and 105 not only compensates for variations in the regenerator residence time of the catalyst, but is also unique in helping to limit the amount of regeneration heat imparted to the fresh feed, while a regenerated catalyst is obtained with low levels of residual coke for return to the reactor.

Because of the arrangement of the regenerator, the damaged catalyst from the transfer line 97, with its high carbon loading, in chamber 102 comes into contact with the combustion-bearing gases, which are at least partly already depleted of oxygen by the combustion of carbon from partially regenerated catalyst in the lower regenerating chamber 102. This makes it possible to control both combustion and the amount of carbon dioxide generated in the upper regenerating chamber 102. Although the air or other regenerating gas supplied by the air supply line 115 and the branch line 114 may contain a relatively large amount of oxygen, the partially regenerated catalyst with which they contact in the lower regenerator chamber 105 is already part of the carbon removed. The high concentration of oxygen and the temperature of the partially regenerated catalyst work together to quickly remove the residual carbon in the catalyst, thereby obtaining a clean regenerated catalyst with a minimum of heat release. Therefore, the combustion temperature and the CO: CO2 ratio in the lower regeneration chamber are again quickly adjusted here. The regeneration 80 06 22 7 64 generation exhaust gases are removed from the upper regenerator chamber via the exhaust gas line 123, the control valve 124, the trap for fine catalyst particles 125 and the exhaust 126.

The vapor products from the release chamber 92 can be processed in any suitable manner, such as, for example, by removal through the vapor discharge pipe 131 to the feed of the fractionator 132. This fractionation direction comprises a bottom discharge 133, a side discharge 134. a rinse oil stripper 135 and a bottom drain stripper and drain line 136 connected to pump 137 to remove rinse oil. The overhead product from the stripper 135 is brought through the top return line 138 from the stripper to the fractionator 132.

The main top discharge line 139 of the fractionator is connected to the overhead product receiver 142 with a bottom discharge line 143 terminating in the pump 144 to discharge the gasoline product. Desirably, a portion of this product may be sent back to fractionator 132 through the recirculation line 145, the flow of which is controlled by the control valve 146. The overhead product receiver also includes a water receiver 147 and a water discharge line 148. The gas outlet 150 of the The overhead product receiver draws off a stream consisting essentially of product having less than 5 carbon atoms, but. contains some product with 5, 6 and 7 carbon atoms. If desired, the product with 5 and more carbon atoms in this gas stream can be separated by compression, cooling and fractionation and recycled to the product receiver with a compressor, cooler and fractionator ( not signed).

Examples

The following examples are given for illustrative purposes only and not to limit the invention. Data on the catalysts used are provided in Table B.

So far, commercial practice in some refineries has involved mixing relatively small amounts of carbon metal oils with the vacuum gas oils, which are commonly used as a feed for catalytic cracking of streams. It is to be emphasized, however, that conventional practice has been aimed at limiting the amounts of carbon metal oil in such mixing requirement to provide a feed characterized by relatively low nickel equivalent contents of. heavy metals and due to relatively low levels of carbon residue after pyrolysis. Quite unexpectedly, however, it has been found that the conversion level of the carbon-metal oils is greater when such oils are used in sufficient amounts such that the nickel equivalents of heavy metals and the carbon residue are relatively high learned levels, such as, for example, when the amount of carbon metal oil varies from a major weight ratio to substantially all of the hydrocarbon cracking reagent in the feed.

Example IA ID

In these examples, the unit is used as indicated substantially in Fig. 1 and as described in the following text. Examples 1A-1C illustrate the embodiment with mixtures containing different relative amounts of vacuum gas oils (VGÖ) and reduced crudes. Examples IC and ID compare the embodiment with a mixture against an embodiment with 100% reduced crude oil. For analysis of the vacuum gas oils and the reduced crudes, see Table C.

For operating conditions and the summary and results, see Table D.

Comparison of the Results of Examples 1A and 13 At a temperature in the range of about 523 - 527 ° C, the unit used herein is known to produce a conversion level of about 76% when used with equivalent catalyst on VGO similar to the vacuum gas oils as illustrated in Table C. A comparison of the data of Examples 1A and 13 will show that assuming the vacuum gas oil in each mixture has been converted to the predetermined degree of 78%, the reduced crude contained in the lower portion (about 40%) in the Example 40 test IA was converted to a degree of only about 44%, 8006227 at ÖÖ while processing the mixture, which greater amount of reduced crude oil "contains (about 66%) indicated in Example ID, a conversion of 63% of the reduced crude oil was achieved. Also, the increase in volume yield is pointed out. The invention is carried out to produce a fairly high conversion of the reduced crude oil and / or a fairly high volume yield at very suitable octane contents when the reduced crude oil is mixed. , compared to blends with significantly greater amounts of VGO and significantly less amounts of reduced crude oil.

Comparison of the results of the example IC and ID A comparison of the data of example IC and ID 15 will show that when the VGO in the mixture of example IC is assumed to have been converted at the predetermined degree of 78%, then the reduced crude was converted to a degree of only about 58% when it constitutes about 42% of the feed, while it was converted to a degree of about 64% when it represented 100% of the feed. The increase in volume percentage yield is again pointed out. Therefore, the invention can be practiced in such a way as to provide a fairly high conversion of reduced crude oil and / or increased volume percent yield. liquid products at very suitable octane contents when the reduced crude is fed only as compared to a mixture of reduced crude with VGO.

Examples II and III

Using the reduced crude oil of Example ID indicated in Table C, a unit constructed in accordance with Figure 1 was used in accordance with the portion of the text with respect to Figure 1 and in accordance with the conditions. as set forth in Table D, whereby the results indicated in Table D were obtained.

Examples IV-VI

These examples were performed with a unit 40 constructed in accordance with the teachings of Fig. 2 and 8006227 & the corresponding text. After using the unit in accordance with this text and the conditions set forth in Table D, using two stage regeneration, the results reported in Table D 5 were obtained.

Examples VII-X

These examples were performed in a semi-technical unit using a feed, catalyst "1"; and operating conditions as indicated in the table of bubbles A, B and D. Figures 3-5 of the drawings show the yield in percent by volume of (3) olefins, (4) saturated products and olefins and (5) gasoline, respectively, against the volume percent conversion obtained using the feeds and catalysts of Examples VII-X repeated at different levels.

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8006227

Claims (36)

Process for the economical conversion of carbon-metal oils to lighter products, characterized in that: 5 I. provides a converter feed containing 34-3uC + product, which 343 ° C + product is characterized by a carbon residue after pyrolysis of at least about 1 and in that it contains at least about 4 parts per million nickel - equivalents of heavy metal (heavy metals), 10 II. converts the converter feed with cracking catalyst to form a stream containing a slurry of the catalyst in the feed and pass the resulting stream through a progressive stroning reactor with an elongated reaction chamber which is at least is partially vertical or inclined for a predetermined vapor residence time in the riser in the range of about 0.5 to about 10 seconds at a temperature of about 480 to about 760 ° C and under a pressure of about 70 to about 350 kPa, which is sufficient to effect conversion per passage in the range of about 50% to about 90%, while coke is generated in amounts in the range of about 6 to about 14% by weight based on fresh feed and coke is deposited on the catalyst in amounts in the range of from about 0.3 to about 300 weight percent, III. separates the catalyst from the resulting cracking products, TV. strips adsorbed hydrocarbons from the separated catalyst, 30 V. The catalyst regenerates by burning the coke in at least one regeneration zone with oxygen containing the combustion supporting gas under conditions of time, temperature and atmosphere sufficient to regenerate the carbon on the catalyst to about 0.25 wt. ./o or less, while gaseous combustion product gases are formed, containing CO and / or CO2, and in which at least the major weight part of the coke is burned in one of the regeneration zones, wherein the CO: CO2 molar ratio is maintained at a level 40 of at least about 0.25, and 8006227 m 71. recycled the regenerated catalyst to the reactor for contact with fresh feed. 2. Process according to claim 1, characterized in that the 343 ° C + product is at least about 70% by volume of the feed and contains at least about 10% by volume product, which will not boil below about 538 ° C. 3. Process according to claim 1, characterized in that the carbon residue on the feed as a whole. . ,. .. corresponds to. an Eamsbottom carbon value. of at least about 1%, Method according to claim 1, characterized in that the carbon residue of the feed as a whole corresponds to an Eamsbottom carbon value in the range from about 2 to about 12. Method according to claim 1, characterized in that the feed as a whole contains at least about 4 parts per million nickel equivalents of heavy metal (heavy metals), of which at least about 2 parts per million are nickel (as metal weight part). 6. A process according to claim 1, characterized in that the feed as a whole contains at least about 5 parts per million nickel equivalents of heavy metal (heavy metals). 7. Process according to claim 1, characterized in that additional catalyst is added to replace catalyst that has been lost or withdrawn from the system, which additional catalyst has a microactivity of at least 60 vol. % and any catalyst withdrawn from the system has a microactivity of at least about 20% by volume. 8. Process according to claim 1, characterized in that there is an accumulation of heavy metals on the catalyst in the range from about 3000 parts by weight to about 70,000 parts by weight of nickel eivival of heavy metal (heavy metals) measured in regenerated equilibrium catalyst. 9. Process according to claim 1, characterized in that a zeolite catalyst of the molecular sieve type, which contains at least about 5% by weight of sieve, is used as the catalyst. 8006227 * é 10. A method according to claim 1, characterized in that the predetermined residence time in the feed riser and product vapors is about 3 seconds or less. Process according to claim 1, characterized in that the temperature in the reactor is maintained in the range from about 530 to about 650 ° C. The method of claim 1, with the. ... k. and me. r.k ,. that the partial or total pressure of the feed is in the range of about 20 to about 210 kPa. The method according to claim 1, characterized in that the conversion is in the range from about 60 to about 90%. 14. A method according to claim 1, characterized in that the conversion is in the range from about 70 to about 85%. 15 ·. Process according to claim 1, characterized in that the process is carried out in the presence of additional gaseous and / or evaporable product in the reaction zone in a weight ratio with respect to the feed in the range from about 0.02 to about 0.4. 16. Process according to claim 1, characterized in that the process is carried out without addition of hydrogen to the cracking zone. Process according to claim 1, characterized in that the process is carried out without prior hydrotreating of the feed. 18. Process according to claim 1, characterized in that the process is carried out without prior removal of asphaltenes from the feed. Process according to claim 1, characterized in that the process is carried out without prior removal of heavy metals from the feed. Process according to claim 1, characterized in that the cracking reaction is carried out with a catalyst previously used for cracking a carbon-metal feed under the conditions stated in claim 1. 21. Process according to claim 1, characterized in that the total converter feed is cracked in one and the same conversion chamber. 22. A method according to claim 1, characterized in that the converter feed is cracked in a substantially single pass manner. 2J. Process according to claim 22, characterized in that less than about 15% by volume of the cycle is present "relative to the volume of fresh feed. - Process according to claim 1r - with - h e- t-5 is characterized in that the converter feed is combined with liquid water in a weight ratio with respect to the feed in the range of from about 0.04 to about 0.15 and in which a stream is formed, which is a mixture of the feed, the catalyst and steam from the evaporation of the liquid water, which is passed through the reactor for the conversion of the feed. 25. Process according to claim 24, characterized in that a weight ratio of liquid water to converter feed of about 0.04 to about 0.1 is used. The process according to claim 24, characterized in that a liquid water to converter feed weight ratio of from about 0.05 to about 0.1 is used. The process according to claim 24, characterized in that the water is brought together with the converter feed at or prior to contacting the converter feed with the cracking catalyst. The process according to claim 24, characterized in that the water is brought together with the converter feed before contacting the converter feed with the cracking catalyst. 29. Process according to claim 1, characterized in that, at the end of the predetermined residence time, the catalyst is propelled in a direction defined by the extended reaction chamber or an extension thereof, while the products are subject to an abrupt change of direction drops below-40, resulting in an abrupt, almost instantaneous ballistic separation of products from catalyst. 30. Process according to claim 1, characterized in that the converter feed is combined with liquid water in a weight ratio with respect to the feed in the range from about 0.04 to about 0.15 and wherein a flow is which contains a mixture of the feed, the catalyst and steam from the evaporation of the liquid water and is flowed through the reactor for the conversion of fresh feed, and wherein at the end of the above said predetermined residence time, the catalyst is propelled in a direction determined by the extended reaction chamber or an extension thereof, while the products with a smaller impulse undergo an abrupt change of direction, resulting in an abrupt, almost instantaneous ballistic separation of products from catalyst. 31. Process according to claim 30, characterized in that the regeneration is carried out at a temperature in the range from about 540 ° C to about 815 ° C. The process according to claim 30, characterized in that the regeneration is carried out at a temperature in the range from about 690 ° C to about 25 775 ° C. The process according to claim 30, characterized in that the catalyst is regenerated to a carbon content of about 0.1% or less. 34. Process according to claim 30, characterized in that the catalyst is regenerated to a carbon content of about 0.05% or less. A method according to claim 30, characterized in that the combustion conditions are controlled to limit the presence of any excess oxygen in the total waste gas obtained from the total completed regeneration treatment to about 0, 2 mol% or less. 36. Process according to claim 30, characterized in that the combustion conditions are re-adjusted to limit the possible presence of an excess of oxygen in the total waste gas, which is obtained from the total, completed regeneration. treatment to about 0.1 mol% or less. 37. Process according to claim 30, characterized in that the regeneration is carried out by passing the catalyst successively through a plurality of regeneration zones and wherein about 65 ° / o to about 95% of the coke present on the catalyst immediately prior to regeneration is removed with control of the CO: CO2 molar ratio to a level of at least about 0.25. 38. Process according to claim 30, characterized in that the regeneration is carried out by passing the catalyst successively through a plurality of regeneration zones and wherein about 80% to 95 ° / o of the coke present on the catalyst immediately before regeneration is removed with control of the CO: CO2 molar ratio at a level of at least about 0.3% which catalyst has been regenerated to a carbon content on the catalyst of about 0.05% by weight or less. ****** 8006227