NL8006225A - Catalytic cracking of metal-contg. heavy oils - by FCC process with controlled combustion in regenerator - Google Patents

Abstract

Cracking of feeds contg. 650 deg. F+ material with a Ramsbottom carbon value of at least 1% and a heavy metals content of at least 4 ppm (Ni equiv.) is carried out by passing a suspension of a cracking catalyst in the feed through a riser-type cracking zone at 900-1400 deg.F and 10-50 psia with a vapour residence time of 0.5-10 sec. to obtain a conversion per pass of 50-90% and a coke yield of 6-14 wt.% based on fresh feed. The amt. of coke deposited on the catalyst is 0.3-3 wt.%. The coke-contaminated catalyst is sepd. from the cracking prods., stripped to remove adsorbed hydrocarbons, and regenerated by burning off coke with an O2-contg. gas under conditions such that the coke content is reduced to 0.25 wt.% or less. The regenerated catalyst is then recycled to the cracking zone. The improvement comprises burning off at least the major amt. of coke in a regenerator in which the CO:CO2 molar ratio is maintained at 0.25 or more. In complete combustion in the regenerator helps to avoid overheating of the regenerated catalyst, thus preventing excessive heat transfer to the cracking zone (see also GB2063294).

Description

N.O. 29.566 4l · '- * · »1' +

Process for the Conversion of Carbon and Metal "Containing Oil."

Generally, gasoline and other liquid hydrocarbon fuels boil in the range of about 57 to about 345 ° 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 30 to 60% or more of the total volume of the oil consists of compounds boiling at temperatures above 34-5 ° C. Below are crudes, in which about 10% to about 30% or more of the total volume consists of compounds that have such a molecular weight that they will boil above 552 ° C or at least will not boil below 552 ° C at atmospheric pressure .

15 Because these are relatively abundant high-boiling.

crude oil components 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 into smaller molecules boiling in a suitable cooking range.

The cracking process, which is most widely used for this purpose, is known as Flow Catalytic Cracking (PCC). Although the PCC process has reached a very advanced state and many modified forms and variations have been developed, their unifying factor is that a vaporized hydrocarbon feed is cracked at an elevated temperature in contact with a cracking catalyst suspended in the feedstock. pen. After reaching the desired degree of molecular weight and boiling point decrease, the catalyst is separated from the desired products.

Natural state crude contains various products which tend to have quite unpleasant effects on PCC processes and only some of these difficult materials can be economically removed from the crude 8006225 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 sodium, potassium, etc.), sulfur , nitrogen and others. Certain materials, such as the relatively light metals, can be economically removed by desalination operations, which are part of the normal crude oil pre-treatment procedure for ECC. Other materials, such as coke precursors, asphalting and the like, tend to break down to coke during the cracking operation, which coke is deposited on the catalyst, impeding contact between the hydrocarbon feed and the catalyst and generally the strength or activity level is reduced. The heavy metals transfer almost quantitatively from the feed to the catalyst surface.

When the catalyst is repeatedly used for processing additional feed, which is usually the case 1, the heavy metals on the catalyst can accumulate to the point that they adversely affect the composition of the catalyst. and / or change the nature of its effect on supply. For example, vanadium tends to form fluxes with certain components of the commonly used ECC 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 4-0 carbon metal oil and is a particular challenge for 8006225 3 L · «the earth refining.

Generally, the coke-forming tendency or coke precursor content of an oil can be determined by determining the weight percent 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 Conradson carbon and the

Ramsbottom carbon tests, the latter of which is described in ASIM D524-76. In conventional RCC 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 different heavy metals do not have an equal catalyst poisoning activity, it is expedient to express the poisoning activity of an oil containing a given poisoning metal or metals as the amount of a single metal, 25 of which is determined to be a has equivalent poisoning activity. Therefore, the heavy metal content of an oil can be expressed by the following formula (formed after that of W.L. Nelson in Oil and Gas Journal of October 23, 1961, page 143)? wherein the content of each metal present is expressed in parts per million of such metal, as metal, on a weight basis, based on the weight of the feed:

Nickel equivalents = Ni + —g + τ * Γη +

According to conventional FCC practice, the content of heavy metals in the feed for FCC processing is controlled at a relatively low level, for example about 0.25 ppm nickel equivalents or less. The present invention relates to the processing of feeds which contain metals considerably above this value and which therefore have a substantially greater capacity for accumulation 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 has been a longstanding interest in the conversion of carbon metal oils to gasoline 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 uses "granular size" catalyst particles (much larger than the usual 50 FCC catalyst particle size) in a dense gravitational bed, instead of 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 effects 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 is 40 over the 25 years that have passed since 8006225 5

The holding residue process was first technically introduced, continuing with the difficult research of suitable modifications or alternatives to the PCC process, which would allow 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 treating the /γ / are oil feed to remove the metal therefrom prior to cracking, such as by water treatment, solvent extraction, and complexation with Priedel-Crafts catalysts, but these techniques are not justified as economically criticized. Another proposal uses a combination cracking process 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 controlled in relation to the equilibrium evaporation temperature at the bottom of the riser-type cracking unit used in the process. In yet another proposal, the feed is subjected to a careful prior hydrocracking treatment or v / attenuator before the feed is introduced into the cracking unit. It has also been proposed to contact a carbon metal oil, such as a induced crude oil, with warm taconite granules to produce gasoline. This is a small selection of the many proposals that have appeared in patent literature and technical reports.

Notwithstanding the great efforts and the fact that each of these proposals overcomes some of the difficulties involved, today's customary PCC practice is tacitly testimony 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 possible to largely avoid the problems of cooking precursors and heavy metals by sacrificing the liquid fuel yield, which would potentially be available from the highest boiling fractions. More particularly, in conventional FCC practice, as the feed, the fraction of crude oil is used which boils at about 34-3 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 34-3 ° 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 ECC 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, In particular, 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 same timely 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, increasing the total yield of gasoline and other liquid hydrocarbon fuels from a given amount of crude oil is becoming. 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. The present process is believed to be uniquely effective in treating the problem of treating such carbon-metal oils in an 8006225 / 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 343 ° C + portion thereof is characterized by a heavy metal content of at least about 4, preferably more than about 5, h most preferably at least about 5, 5 ppm nickel equi and 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 charged with hot conversion catalyst in a catalyst to feed weight ratio in the range of about 3 to about 18 and preferably 20 to 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 a dilute phase or stream for a predetermined residence time flow into the riser in the range of about 0.5 to about 10 seconds.

The reaction is conducted at a temperature from about 480 ° to about 760 ° C, measured at the reaction chamber outlet 35 under a total pressure of from about 70 to about 350 kPa under conditions sufficiently heavy to provide a per-pass conversion. 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 wt%, and preferably n n n fi 2 5 ö mark 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 with an oxygen-containing combustion carrier 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.

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 equivalent parts by weight of heavy metal, and a carbon residue after pyrolysis, greater than about 1%, greater than on-. has about 1.4% or greater than about 2% by weight. 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 for a replacement as required to compensate for normal losses and deactivation) to crack a carbon-metal feed under the above described conditions.

Heavy hydrocarbons that have not been cracked to gasoline on a first pass can be recycled with or without water treatment 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, a substantially one-time or single pass treatment (for example, less than about 15 vol.% kririg-loop based on the volume of fresh feed) 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 having a smaller impulse, 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 embodiment or other aspect of the invention, the converter feed contains 343 ° O + product which has not been treated with water and is characterized in part by the presence of at least about 5-5 wt. parts per million nickel equivalents of heavy metals. The converter feed is brought together not only with the above-mentioned cracking catalyst, but also with additional gaseous product, including steam, the resulting catalyst and feed slurry also containing gaseous product, the ratio of the partial pressure of the gaseous product added relative to that of the feed is in the range of about 0.25 to about 2.5. The residence time of the vapor is in the range of about 0.5 to about 3 seconds in the practice of this embodiment on this aspect of the invention. This preferred embodiment or aspect and that or that mentioned in the foregoing. the paragraph can be used in combination with each other or 35 separately.

The method as described above can be performed in conjunction with other preferred alternatives, refining treatments or more common conditions, some of which will be listed under heading 40 "Description of different and preferred embodiments".

Brief description 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 Different 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 allowing vacuum distillation if desired. and avoid other costly 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 20 hydrocarbon preparations which are asphalts or tars at ambient temperature, but which liquefy when heated 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 crude oils", which approximate the properties of reduced crudes, slate oil, tar sands extract, coal products liquid maing and dissolved carbon, atmospheric and vacuum-reduced crude oil, extracts and / or bottoms (raffinate) of deasphalting with solvent, aromatic lubricating oil refining extract, tar bottoms, heavy ground run 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, 8006225 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; however, it is 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 applied to 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 a prior vacuum distillation, thus resulting in capital investment and processing costs savings compared to conventional FCC processes, which require a vacuum distillation unit.

Table A provides a comparison between a conventional vacuum gas oil (T / G0), hitherto used at FCC, with various reduced crudes, which are a single example of the many reduced crudes that can be used in the present invention used.

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As can be seen from the table, the sulfur or higher boiling feeds are characterized by relatively lower API density values than the illustrative vacuum gas oil (VGO). Generally, those catalytic cracking process feeds with lower boiling temperatures and / or higher API densities are considered much better than feeds with higher boiling temperatures and / or 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 34-3 ° G , All cooking temperatures are based on standard atmospheric pressure conditions. Carbon metal oil, which is composed in whole or in part of a product boiling at and above about 34-3 ° C, designates such a product as a 34-3 ° C + product; and 34-3 ° C + product, which is part of or separated from an oil, which contains components boiling above and below 34-3 ° 0 may be referred to as a 34-3 ° 0 + fraction. However, the expressions "boiling above" and "34-3 ° 0 +" do not imply that all the product characterized by these expressions will have the boiling power. The carbon metal oils contemplated by the invention may contain a product which cannot boil under arbitrary conditions; for example, certain asphalts and asphaltenes can thermally crack during distillation, apparently without boiling. Therefore, when it is stated that the feed contains at least about 70% by volume of product which boils above about 343 ° C, it is to be understood that the 70% in question may contain some product which will not be at any temperature boil or volatilize. These non-boiling products, if present, can often, or for the most part, be concentrated in portions of the feed that do not boil below about 538 ° C, 552 ° C or higher. So when it is stated that at least about o η n 9 o ς 'le.

10%, more preferably about 15% and even more preferably at least about 20% (volume ° / o) of the 343 ° C + fraction will not boil below about 538 ° C or 552 ° C, it is to be understood that The whole or any portion of the product, which does not boil below about 538 ° C or 552 ° C, may or may not be volatile at and above the indicated temperatures.

Preferably, the intended feeds or at least the 343 ° C + product therein have a carbon residue after pyrolysis of at least about 2 or more. For example, the Ramsbottom carbon content can be in the 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 is noted that the illustrative VGÖ 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 crude oils reduced 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 hydrogen to carbon ratio in the range of from about 1.2 to about 1.9, and preferably from 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, at least 30 of which about 2 parts per million nickel (as metal, parts by 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 metal conditions have shown some reduction in the tendency to poison after repeated oxidations and reductions on the catalyst, and the literature describes criteria for establishing "effective metal" values. See, for example, the article by Cimbalo 5 et al. Entitled "Deposited Metals Poison PCC 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 the dehydrogenation, methanation and aromatic condensation activity of heavy metals collected on the cracking catalyst. usually not either.

It is known that about 0.2 to about 5 wt.% Of "sulfur" in the form of elemental sulfur and / or its compounds (however, reported as elemental sulfur by weight of feed) appears in PCC 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 decay. 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 SC ^ 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, 7, Cu and Pe in the sulfide form in the reactor.

These sulfides are much less active than the metals themselves 55 in promoting the dehydrogenation and coking reactions. As a result, it is acceptable to practice the invention with a carbon metal oil having at least about C3, acceptable above about 0.8%, and more acceptable at least about 1.5% by weight of sulfur 40 in the 343 ° C + fraction.

ft n 0 6 2 2 5

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 can temporarily neutralize these sites, 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-insoluble constituents, for example, at least about 0.5 w / w and more usually about 2% or more and even about 4% or more.

These can include, for example, asphaltenes 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 are in many cases bottoms 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 to which it is exposed, these metals can be. Interactions and reactions with the catalyst (including the catalyst support) which are not usually experienced in the processing of VGO under conventional FCC processing conditions. When the catalyst requirements and regeneration conditions so require, the necessary precautions will of course be taken 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 crude oil used for the preparation of the carbon-10 metal feed can be important if 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 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 343 ° C C boiling will not boil below about 552 ° C. The average composition of this 34-3 ° 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% 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 o λ noor I ö provided they do not act prevent the 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 from carbon metal oils that have not been subjected to any substantial cracking. Thus, for example, and preferably at least about 85%, more preferably at least about 90%, and most preferably virtually all carbon metal feed introduced in the present process is non-contacting oil been 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 catalyst to fresh feed weight ratio (feed not previously exposed to a cracking catalyst under cracking conditions) used in the process is in the range of about 3 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 near-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.

In 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 can vary widely. 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 545 ° C that this factory processes per average business day to liquid products boiling 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 ratio is in the range of about 2 to 5 · 10 While the present invention can be practiced in the range of about 2 to about 50 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 carry out 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 50 less per KDO of 159 liters per daily processing in the factory.

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 together with the withdrawal 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 8006225

dU

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, 10 additions may be used which are greater than the aforementioned; however, in the opposite circumstances, lower additions 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 substantial.

As a result, the process can be carried out with catalyst-bearing heavy metal accumulations, which have hitherto been considered quite impermissible in the conventional FCC-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. In particular, the accumulation can be in the range from about 4,000 to about 50,000 ppm and more particularly about 5,000 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 at and related to degenerate equilibrium catalyst. However, in the case where 8006225 21 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 3000 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 less than about 4 ppm contains nickel equivalents of heavy metals.

In any case, the equilibrium concentration of heavy metals in the circulating catalyst stock (including maintenance or variation if desired or required) can be controlled 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 active during an extended process run 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 preceding percentage is the volume percentage stan-0 Π Π 9 9 K.

standard feed, which is converted to gasoline with an end point of 221 ° C and lighter products at 482 ° C, a space velocity of 16 (weight space velocity, whsv) calculated on the basis of the catalyst dried at 593 ° C and 3C / 0 (catalyst to oil ratio) according to the preliminary ASTM 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 31.0 specific gravity at 15.6 ° C, g / cm ^ 0.8708

Eamsbottom 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 Σ factor 11.93 aniline point 182 20 bromine number 2.2 alkanes, vol. % 31.7 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 30% 351 50% 372 70% 390 90% 419.5 final boiling point 445.5 8006225 25

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 on the basis of the MAT activity, the preferred catalysts can be described based on their MAT activity "as introduced" into the process of the present invention, or based on their "as withdrawn" or equilibrium MAT activity in the process 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, which have been 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, but earning about 40% or more, and preferably about 60 ° / o or more preferred.

Any hydrocarbon cracking catalyst of the above conversion capacities can be used. A particularly preferred, preferred class of catalysts includes those catalysts which have 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.

40 Different types of catalyst are available within 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, semisynthetic or synthetic, alone or mixed with other products, which do not substantially impair the suitability of the catalyst provided that the resulting catalyst has the aforementioned activity and has pore structure. For example, if the catalyst is a mixture, it may 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 / lb, more preferably about 1 to about 40 yo, and most preferably about 5 to about 25 based on the total weight of the catalyst (on an anhydrous basis) of the zeolite, where in the remainder of the catalyst the porous refractory inorganic oxide is 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, 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, encompasses not only aluminosilicates, but also products in which aluminum 40 has been wholly or partly replaced, such as, for example, by 80 06 22 5 25 gallium and / or other metal atoms, and further includes product -ten 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 for replacing 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.

Examples of naturally occurring crystalline aluminosilicate zeolites that may be used or incorporated into the catalyst for the present invention include faujasite, mordenite, clinoptilot, chabazite, analyte, erionite, as well as levynite, dachiardite, paulingite, noselite , ferriorite, heulandite, scolccite, stibite, harmotome, phillipsite, brewsterite, flarite, datolite, gmelinite, caumnite, leucite, lazurite, 30 scaplite, mesolite, ptholite, nepheline, 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. Pat. No. 2,882,244, zeolite Y, U.S. Pat. No. 3,30,007, 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 0 6 2 2 5 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 2,995.4-23, Zeolite 0, U.S. Patent 5 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, Canadian 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. 3,140,24-9, 5,140,255, 3,94.4..482, and 4,157,151 are also suitable.

The crystalline faujasite-type aluminosilicate zeolites 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 size range commonly found in engineering 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. 50 even smaller crystallites. Crystalline zeolites exhibit 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. 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 deposition of coke in the gate specific surface and contamination by metal poisoning, will significantly increase the total zeolite specific surface Reduce. Therefore, "preferably, to minimize the effect of contamination and pore blocking, crystals larger than the normal size, as mentioned above, are not used 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, magnesia, and mixtures thereof and mixtures of such oxides with clays, as described, for example, in U.S. Pat. 3 * 034.948. For example, each of the zeolite-containing cracking catalysts for molecular sieve type streams can be selected which are suitable for preparing 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. Patent 3,944,482, wherein the catalyst contains 1-40 wt.% Of a rare earth exchanged zeolite, the remainder being a refractory metal oxide with a specified pore volume. §Ae ^ n / (feetPiffer 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 3 to about 160. more preferably about 40 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 activity of the catalyst, the coke burns 0 Ω Π 9 7 5 during a regeneration step, converting the coke into combustion gases containing carbon monoxide and / or carbon dioxide. Several products are known which, when incorporated into small amounts of cracking catalysts, 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 or 20% by weight of the catalyst, may be of any type which generally promotes carbon combustion under regeneration conditions. or may be somewhat selective with regard to completing the combustion of CO or / more preferably, for reasons explained in more detail below, some tendency to burn carbon to carbon monoxide rather than 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 zeo opnerate flavor AloO2 Si0o Oiao0 Feo0 TiO ~ m2 / g stop 2 3 _2 __2__2 AGZ-290 300 11.0 29.5 59, 0.40 0.11 o , $ 9 GEZ-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 FOC-90 240 8.0 44.0 52.0 0.65 0.65 1.1 HFZ 20 310 20.0 59.0 40.0 0.47 0.54 2.75 HEZ-55 210 19.0 59.0 35.2 0 .60 0.60 2.5 8006225 29

The AG2-290, GRZ-1, CCZ-220 and Super DX catalysts mentioned above are products of W.R. Grace and Co. F-87 and F0C-90 are products of Filtrol, while HFZ-20 and HEZ-55 are products of Engelhard / oloudry. 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 the catalyst sample and a standard product consisting of a high purity sodium X zeolite according to design No. 6 dated January 9, 1978 of the proposed ASTM 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 process of the present invention can be carried out with the above-described carbon-metal oil and catalyst as essentially the only products supplied 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 that 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 8006225 to a 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 vapors of feed and product 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 back to the more harmful elemental heavy metals. It is possible to take advantage of this situation 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 introduced into 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, catalyst or reaction zone to perform the aforementioned functions and others may vary if desired; however, this amount will preferably be sufficient to balance the heat balance of the process. For example, these products can be introduced into the reaction zone in a weight ratio with respect to the feed to about 0.4, preferably in the range from about 0.02 to about 0.4, more preferably 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 seems that the use of water tends to inhibit the reduction of catalyst-supported oxides, sulfites and sulfides 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 believed 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 be excess absorb heat from the catalyst. Preferably, the liquid or vaporous H 2 O contains less than about 100 ppm sodium and less than about 500 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 HgS dissolved therein, a number of additional advantages can be cultivated. The ecologically unattractive I ^ S does not need to be vented to the atmosphere, the recirculated water requires no further treatment to remove I ^ S30 and the H ^ S may help reduce coking of the catalyst by passivation of the heavy metals, ie by conversion thereof to the sulfide form, which has a less tendency than the free metals to increase the production of coke and hydrogen. In the reaction zone, the presence of water can dilute the carbon-metal oil vapors, reducing their partial pressure 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 such as: contributing to the atomization or dispersion of the feed Q Q Q Q £ 2 5 33; 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 the BCC literature. Addition of liquid water to the feed is discussed relatively little compared to the supply of steam directly in 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 heat is absorbed from the catalyst, from the feed, or from both, causes the water to be one. provides 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 liquid water may be accompanied by the addition of additives. ? 5 amounts of water as 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 , 5 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 low molecular weight compounds that allow or favor intermolecular hydrogen transfer; and compounds which 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, acting as diluents for reducing the feed partial pressure and / or as heat reducing agents for absorbing excess heat contained in the catalyst obtained from the regeneration step.

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 can be added or other functions can be performed 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 part 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 addition of catalyst, one or more points for the addition of additional product, one or more points for withdrawing products and one or more catalyst extraction points. The means for supplying the feed, catalyst and other product can vary from open pipes to refined nozzles or nozzles, with it being preferred to use means capable of breaking the liquid supply into fine droplets.

It is preferable that the reaction space, or at least 8006225, be more near vertical than horizontal and have 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 cm, 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, respectively, below about 0.052 g / cm 2 at the upstream (eg bottom) and downstream (eg top) ends of the riser.

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 "slippage" of catalyst may take place to some extent, particularly in certain vapor velocity ranges and some catalyst fillings, although it has been stated to be advisable, to use sufficiently low catalyst fillings to slip and limiting 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 substantially all of the evaporated cracked catalyst products. separates the downstream end of the riser. A preferred type of reactor incorporates ballistic separation of catalyst and products; that is, catalyst 5 is propelled in a direction defined by the riser and forced to continue its movement in the general direction thus established, while the products have to make an abrupt change of direction with a less impulse, resulting in an abrupt, 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 the downstream end receives the products. The discharge port communicates with a catalyst flow path, which extends to the conventional stripper and the regenerator, while the discharge port communicates with a product flow path, which is substantially or completely separated from the catalyst flow path, and leads to separators for separating the products from any relatively small portion of catalyst, which leads to an entrance to the product outlet opening. 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. Among these are feed, 50 catalyst and reaction temperatures, reaction and feed pressures, residence time and conversion levels, coke production and coke deposit on catalyst.

In conventional FCC operations with VGO, the feed is usually preheated, often to temperatures significantly higher than required to make the feed sufficiently flowable for pumping and for reactor feed. For example, preheating temperatures of about 370 ° C or 430 ° C have been reported. However, in the present process, as practiced today, it is preferable to limit the preheat of the feed so that the feed is able to adsorb a greater amount of heat from the catalyst, while the catalyst increases the feed to conversion temperature, at the same time minimizing the use of external fuels for heating 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 316 ° C, usually about 90 ° G to about 260 ° C, but higher preheating temperatures are not necessarily excluded.

The catalyst feed to the reactor can vary widely in temperature, for example from about 390 ° C to about 870 ° C, more preferably about 650 ° C to about 815 ° C, and more preferably about 705 ° C to about 760 ° C with about 720 ° C to about 74-6 ° C now being 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 760 ° 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 350 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) pressure 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 commonly about 0.4. to about 0.6, with the ratio of added gaseous product (which may include 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 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 just-described embodiments, 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 · 20 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 from about 0.5 to about 6 and from about 1 to about 4 seconds, with about 1.5 to about 3.0 seconds is now considered approximately 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.

8006225

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, the. 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 A and the most preferably about 1.2 to about 3, with about 1.2 to 2 now considered optimum.

In certain types of known FCC units, there is a riser which dissolves catalyst and product vapors together in an enlarged space, which is commonly considered to be a 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. A,066,533 and A,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 expediently considered when the vapor residence time in the riser and the vapor catalyst contact time are substantially equal for at least about 80%, more preferably at least about 90%, and most preferably at least about 95% by volume of the 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, one can avoid a tendency toward re-cracking and reduced selectivity.

8006225 41

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 greater. Preferably, the aforementioned conditions are maintained at sufficient levels to maintain the conversion levels in the range of about 60 to about 90%, and more preferably 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%. /O. The coke yield can be deposited more or less quantitatively on the catalyst. At the target catalyst to oil ratios, the resulting coke deposit may be greater than about 0.3, more usually greater than about 0.5, and often greater than about 1 weight percent coke, based on the anhydrous weight of regenerated catalyst.

Such a coke deposit can reach about 2 or about 3% or even higher.

Like the conventional ECC 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, but in some instances the present process may require somewhat more severe conditions than those commonly used. This may result, for example, from the use of a carbon-metal oil with components which do not volatilize under reactor conditions, the components themselves being 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. Such a stripping treatment may, for example, re-heat the catalyst, an extensive stripping treatment with steam, the use of gases with a temperature considered higher than normal for ECC / 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 B ^ S), hydrogen and other contents. For example, the stripper can be used at a temperature of about 555 ° C or 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 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 cracking 7GQ. 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

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.

In the regeneration of catalysts to very low carbon levels on regenerated catalyst, for example about 0.1% or less or about 0.05% or less, based on the weight of the regenerated catalyst, it is acceptable at least about the last 10 Burn 10 wt% or at least about the last 5 wt% coke (based on the total weight of the coke on the catalyst immediately prior to regeneration) in contact with combustion-producing gases containing excess oxygen. In this connection, it is contemplated that some selected portion of the coke, ranging from all coke to about the last 5 or 10% by weight, can be burned with excess oxygen. Note that excess oxygen means an amount in excess of the stoichiometric requirements for the combustion of all hydrogen, all carbon and any other combustible components present in the aforementioned selected portion of the coke immediately prior to regeneration . The gaseous products of combustion, which are conducted in the presence of excess oxygen, will in principle contain a significant amount of free oxygen. Such free oxygen, unless removed from the by-product gases or converted to another form by an apparatus or method other than regeneration, will usually manifest itself as free oxygen in the waste gas from the regenerator unit. In order to provide a sufficient driving force to complete the combustion of coke to low levels, when all or a portion of the coke is burned with excess oxygen, the amount of free oxygen will be noticeably not only noticeable, but substantial. say there will be a concentration of at least about 2 mole percent free oxygen in the total regeneration waste gas obtained in the total completed regeneration operation. While such a technique 40 is effective in achieving the desired low carbon 8006225 4-5 levels of matter 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 E 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 32841 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 regeneration of regenerated catalyst can significantly increase the level of exceed heat input, which in the riser is suitable for heating and evaporation of the feed and other products, for supplying the endothermic reaction heat for 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 be in the range of about 1160 to about 2795, more particularly about 1400 to about 2100, and more particularly about 1510 to about 1980 kJ / kg fresh feed. The aforementioned tra- 8 η n «? 9 njects refer to the combined heat, in kJ / kg fresh feed, which is transferred by the catalyst to the feed and reaction products (between the contact of the feed to 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, the heat has been 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 additives such as water, steam, naphtha and other hydrogen-producing compounds, waste gases and inert gases, or by radiation or other losses.

One combination of 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 some 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, increasing the amount of inert gas available in the regenerator for heat absorption and removal.

Another suitable and preferred technique for controlling or limiting the heat transferred to the fresh feed via recycled regenerated catalyst involves maintaining a specified ratio of the carbon dioxide and carbon monoxide formed in the regenerator, while such gases 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, wherein the aforementioned ratio is controlled as described below. Learn in particular is taught. at least the major portion, more preferably at least about 65 wt%, and even more preferably at least about 80 wt%, of the coke on the catalyst removed in a combustion zone, wherein the molar ratio of PO to CO is maintained at a level significantly below 5, for example, about 4 or less. When looking at the CO2 / CO ratio from the reverse viewpoint, it is preferred that the CO / CO2 molar ratio be at least about 0.25 and preferably at least about 0.3 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 CC to CO2, it has been proposed that the CO: CG2 molar ratio should be maintained at less than 0.2 when regenerating catalyst with high heavy metal accumulations from the processing of carbon-metal oils; see in this regard, for example, U.S. Patent 4,162,213. In the present invention, however, maximizing CO production while regenerating the catalyst is about 0.1% carbon or less, and preferably about 0.05 ° / ° carbon or less, an especially preferred embodiment of the present invention. In addition, according to a preferred method of practicing the invention, the whole nnfi 9 o ς sub-process of regeneration as a whole can be carried out to the aforementioned low carbon levels on regenerated oxygen deficient catalyst; more specifically, the total oxygen supplied to one or more regeneration stages may be the stoichiometric amount, and is preferably less than the stoichiometric amount that would be required to burn all hydrogen in the coke to ϋ, ρ and all carbon in burn the coke to CC ^. 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. Other 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 raises 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 transporting 40 spent catalyst to a first regeneration zone and feeding 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 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. Patent 2,938,739.

20 The multi-stage regeneration offers the possibility of combining low oxygen regeneration with the control of 00; CO2 molar ratio. For example, about 30% by weight or more, more preferably about 65 to about 95% by weight, and even more preferably about 80 to about 95% by weight, of the coke on the catalyst may be removed immediately prior to regeneration in one or more regenerative rapping, wherein the molar ratio CO: COP is controlled as described above. In combination with the foregoing, the last 5 wt% or more, or 10 wt # 30 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 step , 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 percent or less, or about 0.1 mol% or less, which is considerably less than the 2 mol% 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. before lowering the carbon content on the controlled 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 significantly less severe in the second zone than in the first zone (e.g., by at least about 5 * 5 and preferably at least about 11 ° C), that portion of the regeneration sequence, which involves the most severe conditions, performed 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% by weight with 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, when 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 carried out, for example, at relatively high temperatures, for example about 730 ° C to about 745 ° C using steam, 8006225 51 nitrogen or other inert gases as the stripping gas (the stripping gases). 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 in the practice 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 are theoretical as well as practical, while 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 performance. 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 increased products of gases and coke for a feed of 8006225 a given Ramsbottom carbon value . The addition of significant amounts of water 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 and residence times are chosen to reduce the ratio residence time of the catalyst in the reactor to the residence time of the catalyst in the regenerator will tend to be the ratio of the times during which the catalyst is, respectively, under reduction conditions and under oxidation conditions. 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 produced. 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 approximately optimal.

Careful carbon management can improve selectivity (the ability to maximize production of valuable products) and heat productivity. In general, the above-described metal control techniques also assist in carbon management. The suitability of water additive 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 8006225 53 factor in warn management. In accordance with prior HOC 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 may be expected, due to the weight of fresh feed added to the reaction zone. added.

Relatively high reactor temperatures are also favorable from the viewpoint of carbon management. Such relatively high temperatures result in complete spring vaporization of feed catalyst release product.

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 restriction of 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 fairly 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 (eg, pressure drop in the downstream equipment), the above-described advantages 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 within these ranges as low as possible.

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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 4,066,553 is the preferred type of equipment for carrying out 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 operation from a 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 can 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 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 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 the heat release in the regenerator. While heat removal from catalyst in or downstream of the regenerator by heat exchanger (including steam coils) has been proposed as q η after 9 9 k a heat release controlling agent, the techniques described above of multistage regeneration and control over the CO / CCh ratio (in either single or multistage regeneration) are considered more effective. The use of steam coils is considered partly 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 supply (which may have been heated in a feed pre-heater not shown) and water (if used) supplied by the supply line 9 »are supplied through the supply 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 slope portions, that is, at least 4 °, at least about 30 °. It is also known to provide risers that have downwardly flowing inclined or vertical sections as well as horizontal sections. 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, in which the feed and catalyst are introduced at an upper elevation and in which the feed and catalyst move under the influence of gravity 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 particles are discharged. This embodiment utilizes the so-called vented riser described in U.S. Pat. Nos. 4,066,553 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 4-0 with the catalyst particles are largely unable to follow the product vapors in the opening 22.

The vapors and those few particles that nevertheless 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 first stage cyclone separator, which is connected via a transfer line 17 to an optional second cyclone separator 25 · Separate the cyclone separators, either of the one-stage or multistage type from the products that withdraw 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, can be kept in suspension by agitation-causing nozzles 30 to which steam is supplied through the steam supply line 29. Spent catalyst, which 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 may 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 position. The air preheater 43 », although not usually used in heavy hydrocarbon processing according to the invention, can be used when starting up the unit with TGO; then, when the unit is switched to the carbon-metal supply, the preheating treatment can be aborted (or at least reduced). Additional fuel means can be provided for supplying fuel through the combustion air nozzles 48; however, this is usually not necessary since the carbon deposition on the catalyst 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. Although the 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 combustion device 58 through the catalyst recirculation circuit 55 and the heat control valve 56 in the combustion device. Part of the catalyst is entrained in the product gases, such as CO and / or generated by combustion of the carbon on the catalyst in the incinerator, and 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 nozzles; gas and / or steam 59 and through a baffle arrangement 40 54, the latter releasing regenerated 8006225 catalyst through outlet 69 to the. catalyst supply line 13 facilitates recycle for contact with fresh supply 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 62 and heat exchangers 60 and 63 When 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, which is connected to the steam boiler 67. Additional heat 15 are 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, it is preferred that the relative ratios of carbon monoxide and carbon dioxide are generated while the heat exchanged catalyst produces the combustion gases from the regeneration. An example of this technique is described in the preferred embodiment described in Fig. 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 in the feed line 82 acts as a feed preheater, whereby preheated feed material may be delivered to the bottom of the riser 91 reactor. Catalyst is delivered to the reactor through catalyst standpipe 86, the flow of the catalyst is controlled by a control valve 87 and suitable automatic control equipment (not shown), with which those skilled in the art of 4-0 designing and using riser type crackers 8 0 06 22 5 61 are known.

The riser 91 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 effective change. 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 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 with an outlet 110 below the top surface of the dense phase of the catalyst in the lower regeneration space 103 · 30. 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 inside the diffuser 111 along the central axis. Catalyst in 40 chamber 103 has access to the space within divider 8006225 device 111 between its walls and bayonet 113 ·

A small unsigned bayonet in the aforementioned space whirls up the catalyst and forces it upward to a horizontally disposed unsigned ring distribution device 3, where the open top end of the distribution device 111 opens to the chamber 103 · The rest of the air passing through the air supply line 113 can be heated in the air heater 117 (at least during start-up with VGQ) and is then fed into the line 118 of the aforementioned ring distribution. apparatus, which may include orifices, nozzles, or other apertures that generate an upward gas flow for fluidizing the partially regenerated catalyst in chamber 103.

The air introduced in the manner described above completes in regeneration 103 the regeneration of the partially regenerated catalyst received through the downcomer 107. The amount of air supplied is sufficient so that the air and / or the combustion gases obtained are still able to support combustion until it reaches the top of chamber 103. 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 contact the spent catalyst entering the transfer line for partial oxidation purposes. for spent 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 supporting carrier gas in the upper chamber 102. Supplementary air or other fluids may be introduced into, if desired the upper chamber 102 through the supply line 122, which discharges into or through gas distribution device 120.

Fully regenerated catalyst with less than 40 about 0.25% carbon, preferably less than about 8006225 63 0.1%, and more preferably less than about 0.05%, is withdrawn from the lower regenerator chamber 103 through a regenerated catalyst stripper 128, the outlet of which feeds the aforementioned catalyst standpipe 5 86. Thus, regenerated catalyst is returned to riser 91 for contact with additional fresh feed from feed line 82. Whatever heat is supplied to the recycled catalyst in regenerator 101, it is available for heat transfer with fresh feed into riser.

The distribution of the regenerator in upper and lower regeneration chambers 102 and 103 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 while obtaining a regenerated catalyst with low levels of residual coke for return to the reactor.

Due to the arrangement of the regenerator, the spent catalyst from the transfer line 97, with its high carbon loading, comes into contact with combustion-carrying gases in chamber 102, which have at least in part already been depleted of oxygen from the combustion of carbon. 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 113 and the branch line 114 may contain a relatively large amount of oxygen, the partially regenerated catalyst with which they come into contact in the lower regenerator chamber 103 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, here again the combustion temperature and the CO: QQ4 ratio in the lower regeneration chamber are quickly controlled. The 8006225 generation exhaust gases are removed from the upper regenerator chamber via the exhaust gas line 123, the control valve 124-, the fine catalyst particle trap 125 and the discharge 126.

The vapor products from the release canister 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 fractionator comprises a bottom discharge 133, a side discharge 134, and a flushing oil stripping device. 135 and a bottom drain stripper and drain line 136 connected to pump 137 to remove flushing 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 14-2 with a bottom discharge line 14-3 which opens into the pump 14-4 for discharging the gasoline product. Desirably, a portion of this product may be sent back to fractionator 132 through the recycle line 145, with flow 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 25. overhead product receiver discharges a stream consisting essentially of product with less than 5 carbon atoms, but contains some product with 5, 6 and 7 carbon atoms. If desired, the product with 5 more carbon atoms can be separated in this gas stream by compression, cooling and fractionation and recycled to the product receiver with a compressor, cooler and fractionator (not shown).

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.

Hitherto, commercial practice in some refineries has involved mixing relatively small amounts of 40 metal carbon metal oils with the vacuum gas oils, which are commonly used as feed for catalytic cracking of streams. It should be emphasized, however, that conventional practice has been aimed at limiting the amounts of carbon metal oil in such mixing requirement in order to provide a feed characterized by relatively low levels of nickel equivalents of heavy metals and by 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 at the relatively relatively high levels taught herein, such as, for example, when the amount of carbon metal oil varies from a predominant weight ratio to substantially all of the hydrocarbon cracking reagent in the feed.

Example IA - IS

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 (VGO) and reduced ruxve oils. 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 50 At a temperature in the range of about 523 - 527 ° C, the unit employed 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 1B will demonstrate that assuming that the vacuum gas oil in each mixture has been converted to the predetermined degree of 78 ie reduced crude oil present. in the lower part (about 40%) in the test of pre-40, image IA was converted to a degree of only about 44%.

8006225. While processing the mixture containing a greater amount of reduced crude oil (about 66%) indicated in Example ID, a conversion of 63% of the reduced crude oil was achieved. The increase in volume yield is also pointed out. Therefore, the invention can be practiced 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 is introduced into blends 10, compared to blends of considerably larger amounts of VGO and significantly smaller 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 percentage yield of liquid products at very suitable octane contents when the reduced crude is fed only compared to a mixture of reduced crude oil 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 8006225 by the corresponding text. After using the unit in accordance with this text and the conditions set forth in Table D, using regeneration in

two steps, the results were reported in Table D.

* 5 obtained.

Examples VII-X

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

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Claims (24)

5 I. provides a converter feed containing 34-3 C + product, which 34-3 ° C + product is characterized by a carbon residue after pyrolysis of at least about 1 and by containing at least about 4 parts per million of 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 flow reactor having 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 4-80 to about 760 ° C and under a pressure of about 70 to about 350 kPa sufficient to effect conversion per pass 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 ranging from about 0.3 to about 3% by weight, III. the catalyst separates from. the hydrocarbon stream generated by evaporated feed and cracking products obtained, IY. stripped adsorbed hydrocarbons from the separated catalyst, Y. the catalyst regenerates with oxygen containing the combustion support gas under conditions of time, temperature and atmosphere sufficient to reduce carbon on the catalyst to about 0.25 wt. .% or less, while gaseous combustion product gases are formed consisting of CO and / or CO2, and YI. recycle the regenerated catalyst to the reactor for contact with fresh feed. A method according to claim 1, characterized in that the 34-3 ° C + product is at least about 8006225 70% by volume of the feed and contains at least about 10% by volume product that will not boil below about 538 ° 0. 3. A method according to claim 1, characterized in that the carbon residue on the feed as a whole corresponds to a Ramsbottom carbon value of at least about 1%. A method according to claim 1, characterized in that the carbon residue of the feed as a whole corresponds to a Ramsbottom 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 15 (heavy metals), of which at least about 2 parts per million are nickel (as metal) by weight). 6. A method 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). The process according to claim 1, characterized in that additional catalyst is added to replace any catalyst that has been lost or withdrawn from the system, which additional catalyst has a microactivity of at least 60% by volume 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 of about 3000 wt. parts of ppm to about 70,000 parts by weight of nickel equivalents of heavy metal (heavy metals) measured in regenerating the equilibrium catalyst. . 9. Process according to claim 1, characterized in that a molecular sieve type zeolite catalyst containing at least about 5% by weight of sieve is used as the catalyst. 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 8006225 den 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. A method according to claim 1, characterized in that the partial or total pressure of the feed is in the range from about 20 to about 210 kPa. 13. A method according to claim 1, characterized in that the conversion is in the range from about 60 to about 90%. A method according to claim 1, characterized in that the conversion is in the range from about 70 to about 85%. Process according to claim 1, characterized in that the process is carried out in the presence zone in the reaction zone of additional gaseous and / or evaporable product in a weight ratio with respect to the feed in the range from about 0.02 to about 0, 4. Process according to claim 1, characterized in that the process is carried out without adding hydrogen to the cracking zone. 17. Process according to claim 1, characterized in that the process is carried out without prior hydrotreating of the feed. Process according to claim 1, characterized in that the process is carried out without prior removal of asphaltenes ... from the feed. 19. Process according to claim 1, characterized in that the process is carried out without prior removal of heavy metals from the feed. 20. Process according to claim 1, characterized in that the cracking reaction is carried out with a catalyst which has previously been used for cracking 35 © and carbon-metal feed under the conditions stated in claim 1. Method according to claim 1, characterized in that the total converter feed is cracked in one and the same conversion chamber. A method according to claim 1, characterized in that the converter feed is cracked in a substantially single pass manner. A method according to claim 22, characterized in that less than about 15% by volume of recycle 5 is present based on the volume of fresh feed. 24. Process according to claim 1, characterized in that at the end of the 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 abrupt change of direction resulting in an abrupt, almost instantaneous ballistic separation of products from catalyst. 25. Process according to claim 1, characterized in that a converter feed containing 343 ° C + product is used, which has not been hydrotreated and is characterized in part by the presence of at least about 51 parts per million. nickel equivalents of heavy metal (heavy metals), which converter feed is brought together with the cracking catalyst and with additional gaseous product, including steam, the resulting catalyst and feed slurry also comprising gaseous product, in which the partial pressure ratio of the added gaseous product with respect to that of the feed is in the range of about 0.25 "to about 2.5 and the vapor residence time of feed and products in the reactor is in the range of about 0.5 to about 3 seconds. 26. Process according to claim 1, characterized in that a converter feed containing 343 ° C + product is used, which has not been hydrotreated and is partly characterized by the presence of at least about 5 * 5 parts per million nickel equivalents of heavy metal (heavy metals), which converter feed is brought together with the cracking catalyst and with additional gaseous product, including steam, the resulting catalyst and feed slurry also containing gaseous product, in which the ratio of the partial pressure of the added gaseous product with respect to 40 that of the feed is in the range of about 0.25 8006225 to about 2.5, the vapor residence time of feed and products is in the range of about 0.5 to about 3 seconds and, at the end of the predetermined residence time, the catalyst is directed in a direction determined by the extended reaction chamber or an extension thereof, t while the smaller impulse products undergo an abrupt change of direction resulting in an abrupt, substantially instantaneous ballistic separation of products from catalyst. ****** 8006225