NL8520238A - METHOD AND APPARATUS FOR CRACKING RESTOLIES - Google Patents

Description

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Process and apparatus for cracking residual oils In the prior art, residual oils are referred to as residues, reduced crude, bottom fractions from atmospheric distillation, capped crude, vacuum residues or simply as heavy oils. It is also known that such high boiling parts of crude oil contain very stubborn components, such as polycyclic aromatics and asphaltenes, the catalytic cracking of which produces high yield gasoline plus lower and higher boiling hydrocarbon fractions, due to the deposition of large amounts coke on the catalyst. In addition, metal impurities in the heavy fractions of crude oil comprising vanadium, nickel, copper, iron, etc. are deposited on the and / or pores of the catalyst thereby further poisoning and / or deactivating the spent catalyst. In fact, the prior art view that the effect of the coking tendencies of the heavy oil fractions with the effect of the heavy metals is so predominant that the resulting yields are unacceptable in terms of industrial operations.

In view of the problems recognized in the prior art in the processing of heavy oil and its bottom fractions containing such impurities, it has previously been proposed to effect a separation of materials comprising the residual or heaviest fractions or a prior effect conversion of the heaviest and undesirable components. To achieve the desired separation, the prior art uses various methods such as vacuum distillation, liquid extraction, hydrogenation or certain thermal cracking processes for the separation or control of contamination. Adsorption of undesirable components, in particular metal components, on particulate material with no or little cracking activity has also been used. Thermal cracking, such as delayed coking and liquid coking, as well as visbreaking, have also been used to refine heavy residual oil; however, the molded products boiling above 250 ° C do not appear to be a particularly good raw material; are for fluid catalytic cracking due to the resulting high concentrations of polycyclic aromatics.

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Residual oil with relatively high boiling fractions of crude oil, which residual oil is obtained as bottom fractions from atmospheric distillation and / or vacuum distillation, is therefore referred to by the oil industry as 85 2 02.3 8 Λ.

i 2 considered an emergency supply because the oil contains large amounts of constituents that are generally believed to be coking properties; : has shelves and contains heavy metals. For example, a residual oil may contain a carbon residue of more than 0.6% by weight and, according to industry opinion, it contributes to the production of coke in high added content in a cracking treatment and causes it with the ; high metal contents rapidly deactivate the cracking catalyst resulting in unprofitable yields. Therefore, there is a tendency in the prior art to exclude these materials from the raw materials for fluidized cracking.

For the purpose of the invention, residual oil may include materials boiling from 205 ° C to the crude oil end point, above 980 ° C. The materials with this wide boiling range can be light gas oil boiling from about 205 to 425 ° C, medium gas oil boiling from about 315 to 455 ° C, heavy gas oil boiling from about 315 to 650 ° C and the components above 650 ° C to the end point of crude oil include, including carbon-forming components such as polycyclic aromatics, asphaltenes and metal impurities as well as total crudes. Separately prepared base materials, such as those prepared with hydrogen extraction liquid extraction, may also be included as feed to the process.

The invention

The invention relates to the simultaneous conversion of both the high-boiling and the low-boiling components of residual oils by 25; high selectivity for petrol and light components and with a j; low coking. The problems of the past associated with the high regenerator and catalyst temperatures are largely obviated by the principles of the process according to the invention. Namely, according to the invention, high regeneration temperatures are achieved ; ; 30 hours for the catalyst are promoted and these high temperatures: the catalyst is utilized to provide the desired cracking reactions at a; high conversion and high selectivity for gasoline and gasoline convertible products to be carried out in one operation without excessive coking. Fluid catalytic cracking is successfully applied to starting materials obtained by distillation, liquid extraction and hydrogenation, into distillation areas where immediate evaporation by a hot regenerated catalyst is possible. Cracking of the high-boiling residual hydrocarbon components had less results than desired, which is largely due to the fact that the testers

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significant limitations were bound and did not come to the conclusion that success is only possible if almost immediate and complete

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atomization / evaporation is effected at the first contact of the heavy oil with the very hot catalyst particles at a temperature above the pseudo-critical temperature of the supplied residual oil. This means that as the boiling range of a gas oil by addition; of residues increases, the catalyst temperature must also be raised. The prior art not only lacked insight and thus knowledge of these facts, but also deliberately prevented the necessary high catalyst temperature from being achieved in the process in connection with two factors: 1) metallurgical limits of the regeneration equipment, (2) thermal stability of the catalyst.

Currently available fluidized cracking techniques seem to agree that the practical maximum regeneration temperature and hence the regenerated catalyst temperature should be limited to the range of about 705 ° C to 760 ° C, even if temperatures up to 815 and 870 ° C are often mentioned. In fact, the temperature restriction of 705-760 ° C necessarily limits the oil supplied to the catalytic cracking plants to distilled, liquid-extracted and hydrogenated gas oil separated from boiling residues above 550 ° C in order to achieve the desired conversion rates.

The present invention relates to the provision of an arrangement of devices or equipment and of methods of application, which, among other things, enable the temperature of the regeneration of the catalyst to be raised to at least 980 ° C without the thermal activity of the catalyst being unnecessarily thermal. harm is done.

The invention also encompasses a range of equipment or equipment that can withstand the severe temperature treatments contained in the invention.

Thus, for example, the undistilled crude oil boiling from about 205 ° C or higher to the crude oil end point, such as from capped crudes, can be cracked under conditions where high conversions of the oil supplied: to lower boiling substances including gasoline and lighter hydrocarbons are achieved with gasoline yields comparable to that of the prior art gas oil cracking including comparable coking. The need for costly cleaning of 40 raw materials or preparation techniques and equipment in the form of des-g K 9 A 9 'Tl <β

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thus, elimination, liquid extraction, hydrogenation or various thermal processes are omitted.

The products obtained by the method according to the invention are made of; similar to those resulting from the more common fluidized catalytic cracking of relatively clean gas oil. That is, Cg's and lighter gases, C3 and C4 olefins and alkanes, gasoline boiling from C5's up to 220 ° C and cracked light and heavy recycle oils are obtained. The cracked recycle oils or gas oil known as light and heavy recycled oil or decanted oil thus obtained are of such a quality that they can be hydrogenated and sold as low sulfur fuel oil, moderately hydrogenated and sent to the fluidized plant catalytic cracking can be recycled for more complete conversion to gasoline or, preferably, part or all of it can be hydrocracked to gasoline boiling range components.

Hydrocracking of the cracked recycle oil obtained according to the description to form gasoline, coupled with alkylation of the catalytic C31s and C41s, results in gasoline yields per barrel of 200 ° C plus crude oil residue brought into the catalytic cracker from up to 125 percent plus 3 to 4 percent propane. Such total processing is energetically balanced or even accompanied by a net yield of fuel oil and steam for other applications. The energy balance takes into account what is necessary for capping the crude oil.

! Very important for the successful cracking of residual oil is that there is as close as possible evaporation contact between the particles of the fluidized catalyst and the supplied heavy oil. That is, effecting almost complete evaporation or atomization of, in particular, the high molecular weight constituents of the supplied oil when they come into contact with the hot catalyst particles, benefits the conversion operation. It is important that the high-boiling residual part of the oil together with the lower-boiling; gas oil portion is almost completely evaporated on contact with the hot 35; regenerated catalyst at a temperature above the pseudo-critical temperature of the supplied oil, because only a more finely divided evaporation of the supplied components can result in a larger portion of the feed being more fully cracked into gasoline-yielding components. What does not evaporate remains almost un-converted, resulting in significant amounts of catalytic recirculating oil and / or is adsorbed on the surface of the hot catalyst and is gradually converted, especially in coke, accompanied by a loss of gasoline yield and a rapid decrease in the activity of the catalyst. To achieve the most desired conversion, the mixing temperature between the feed oil and the catalyst should be lysator to be at least equal to and preferably higher than: the pseudo-critical temperature of the residual oil supplied but again; not so high that unwanted cracking occurs.

The preheating temperature of the fed oil, the temperature of the hot regenerated catalyst particles, the cracking activity of the catalyst, the volume of diluent injected into the feed such as steam, the time during which the hydrocarbon vapor remains in contact with the catalyst and the process pressure are important process variables that are easily accessible to the oil refiner and that allow him to set the reaction conditions that are not | be necessary to set almost complete evaporation of the feed and thereby achieve a very selective conversion to gasoline and lighter hydrocarbons in combination with the production of heavier recycle oil of a quality suitable for hydrogenation or hydrocracking to additional material in the gasoline boiling range.

Another desirable process parameter is to provide a riser cross-sectional equilibrium temperature almost simultaneously with well-designed and arranged feed nozzles. An output velocity of the feed in the range of from 3 to 400 meters per second and preferably from 90 to 150 or more meters per second is particularly desirable, the feed nozzle being arranged relative to the riser cross section that at least circles of equal surface area of the cross section of the riser are sprayed.

Each feed nozzle may or may not be provided with a steam jacket if necessary to limit possible coking of the feed hydrocarbon through the nozzle tube. A significant one; amount of diluent, up to about 7 weight percent steam or other the appropriate diluent is also injected into the residual oil supplied to lower its equilibrium evaporation temperature and to achieve the best attainable atomization of oil with a particular nozzle. The dilution of the supplied oil with steam or other means of the bar usually ranges from 1 to 15% by weight.

The above factors determining the contact and mixing between the atomized oil and the fluidized catalyst 8520238 6 particles are to ensure that the mixture is accelerated through the evaporation zone of the riser relatively uniformly and in a minimal time frame and thus little or no catalyst is entrained, the heat transfer from the hot catalyst to the atomized; 5 heavy oil is accelerated. Also, locally increased catalyst to oil ratios characteristic of a densified catalyst phase are avoided. That is, the conditions become; selected for dilute phase contact between catalyst and feed oil in the evaporator portion of the riser and portions located thereafter opposite the locally dense phase contact conditions within the riser.

A reduced heavy crude typically contains 10 to 12 percent hydrogen in the molecular structure. The lighter fractions are usually richer in hydrogen than the heavier fractions. Generally, the larger molecular structures are considered to be low hydrogen. The lighter, hydrogen-rich fractions are thermally relatively stable but are relatively easily catalytically cracked with special catalyst compositions such as zeolite-containing catalysts. The heavier, high molecular weight, low hydrogen fractions are considered to be thermally unstable and readily thermally cracked on contact with solids at temperatures ranging from 500 to 980 ° C. The immediate and complete evaporation of the heavier fractions discussed above promotes simultaneous thermocracking of the high molecular weight components including some asphaltenes, ultimately converting a larger portion of the total residual oil successfully and in high yield in gasoline and recycle oil with little coke and gas formation. Nearly instantaneous, complete atomization / evaporation of the heavy residual oil components upon contact with the fluidized catalyst particles by a sufficiently high catalyst temperature, a low partial hydrocarbon pressure and the use of an oil-atomizing injection system allows for dense phase cracking and thus promotes the desired thermocracking of some of the large asphaltene-like structures to form low boiling recycle oil at the expense of coke production. If the above is not achieved, the "coke seal" phenomenon occurs. Thereby, heavy hydrogen-depleted molecules are deposited and clog the pores that provide access to the active cracking surfaces of the catalyst, making the catalyst relatively ineffective to effect high conversion for a long time. of the heavy oil into desired products from the light and / or heavy components of the feed.

In the design and use of an installation of the type contemplated and described in this invention, an essential consideration is: 5 for operation that the temperature of regeneration of the fluidized catalyst must not be limited by carbon combustion, at least to about 980 ° C. The factors associated with the supply oil preheating temperature, riser temperature, hydrocarbon partial pressure and method of injecting and spreading the oil are important but are all subject to practical limitations and once optimized each should be taken into account with the temperature of the catalyst regenerator to be unlimited with respect to carbon combustion so that the temperature may rise to a level required for a given heavy oil composition to provide the desired immediate contact by atomization or evaporation with the catalyst catalyst particles to promote catalytic cracking and, at the same time, thermal cracking of the large, less stable molecular structures in the fed oil.

Table A illustrates the effect on gasoline yield and | ; coke when a given residue is removed from atmospheric distillation cracked without restriction to the regeneration temperature in comparison; cracking with the regenerator temperature controlled! limited. These operations are compared to the cracking of a gas 25 oil obtained from the same crude oil after vacuum reduction to provide; removal of asphaltic constituents whereby the obtained gas oil is cracked under prior art conditions.

Table A shows that when the temperature of the regenerator or the catalyst is limited, the gasoline yield in the cracking of a 30 'residue decreases significantly and the coke yield increases almost proportionately. It should also be noted that residues can be cracked: to higher gasoline yields and with coke quantities formed as are obtained with a conventional gas oil as the starting material.

Table B illustrates again the same factors and contains gas oil cracking data compared to those where 10 resp. 20 volume percent vacuum residue is added. From this overview it appears that the presence of residues under optimal conditions leads to higher total conversions, higher gasoline yields and equal or 40 slightly lower coke yields than with conventional gas cracking 8520238 8 .....

oil.

Table A

5 Effect of restriction of regeneration temperature and comparison of bottom fractions of atmospheric distillation with raw material consisting only of gas oil

Atmospheric: 10 bottom fractions Only gas oil regenerator temp: high low conventional gasoline yield full 67.7 63.5 61.5 coke weight%: 5.3 8.0 6.1 15

Table B

Cracking gas oil according to current technique as opposed to cracking 20 residue

Mild conversion

Gas oil + Gas oil +! _ Gas oil 10% residue 20% residue_ 25 conversion vol.% 66.0 71.0 79.0 petrol yield vol.% 59.8 61.8 66.1: coke weight% 3.0 3.6 5.6

Optimal conversion conversion vol.% 76.5 77 79.5 30; gasoline yield vol.% 61.5 67.4 67.7 weight% 6.1 4.3 5.3

Analysis of the products obtained in the cracking of complete bottoms of atmospheric distillation compared to that of only gas oil from the same crude oil reveals some other interesting properties: (1) The liquid products formed have, on average, a higher hydrogen content .

40 (2) The research octane rating of the gasoline is significantly higher.

8520238 9 (3) The engine octane rating of the gasolines is clearly higher, resulting in a much improved value for (R + M) / 2 which is important for the production of unleaded petrol.

(4) The cracked gas oil products commonly referred to as light and heavy recycle oil and decanted oil are clearly richer in dual and triple condensed aromatics than in four, five and six fold condensed aromatics. The high concentration of naphthalenes, anthracenes and phenanthrenes in the cracking products makes them attractive starting materials for hydrocracking into petrol.

(5) The coke produced under optimal conditions has a very low hydrogen content. Hydrogen concentrations in the range of 3-6 wt% are found as opposed to 8-10 wt% in gas oil cracking operations of the prior art. The lower hydrogen content of the coke produced can only be explained by the fact that the process conditions employed promote the polymerization of polycyclic hydrocarbons present on the catalyst surface, releasing significant amounts of hydrogen for hydrogen transfer reactions leading to the observed higher hydrogen content of the liquid product. -ten. This phenomenon is not observed in the cracking of gas oil according to the current technique. These reactions are exothermic and largely compensate for the endothermic primary cracking reaction. As a result, the total reaction heat can be reduced by 40 to 50 percent. This contributes to slower turnover rates for the catalyst and, consequently, to lower cooking production. The lower hydrogen content in the coke is also important when regeneration of the catalyst is performed according to the method of the invention; thing.

A strong siliceous catalyst comprising alumina or magnesia with or without a catalytically active crystalline! aluminosilicate or crystalline zeolite and having a fluidisable particle size, preferably in the range of from about 20 to about 1200 microns, can be significantly measured in cracking activity and in amounts. language impurities accumulated during the cracking operation vary. If the accumulation of the metals on the catalyst makes it impossible to maintain a desired conversion level, consideration is given to using a continuous or semi-continuous catalyst change and removal of contaminated catalyst to maintain the desired cracking activity in addition to regeneration of the catalyst. catalyst. The catalyst stock can also be almost completely or partially replaced if necessary at reversal conditions, after a long service life or due to a change in the feed composition most convenient for the process to achieve the desired raw material conversion. .

Metal poisoning has long been known as an important one! obstacle to cracking residues. However, it has been found that metal contaminants at a high regenerator temperature can be significantly deactivated and the negative effects can be significantly reduced if the amount of coke on the recycled catalyst remains below about 0.05 percent by weight. It appears that about 5 percent conversion is lost at about 0.1 weight percent coke on the regenerated catalyst in addition to the expected coke deactivation due to the metal contamination. However, in cracking reduced crude oil of the invention, metals such as nickel, vanadium and iron have some beneficial properties, such as activating or accelerating the dehydrogenation ring, the hydrogen transfer reaction, and promoting the combustion of carbon monoxide in the regenerator, resulting in less coke is deposited on the regenerated catalyst without the need for an external activator. On the other hand, sodium and all other alkali metals are still considered serious impurities, especially for a zeolite-containing catalyst. It has been found that desalting the oil feed is a more economical approach to a solution to the sodium problem than using "soda sink" traps. At the ; desalting the feed well, the amount of sodium therein can be kept well below 1 ppm.

30 Regeneration of the Catalyst

To achieve the desired high catalyst temperatures required for the successful cracking of oil containing oil residues, special regeneration techniques and specially designed and applied equipment or process equipment are required. The high temperature cracking technique of the invention promotes the deposition of relatively high concentrations of coke or hydrocarbonaceous material on the catalyst when it comes into contact with the supplied oil. The concentrations are usually not below 1 percent and in some cases above 2 percent by weight. However, it is desirable that the catalyst be regenerated to a carbon content of less than 0.10 wt%, I52023f 11 .............

preferably from less than 0.05 and most preferably up to about 0.02 weight percent. The regeneration techniques and equipment used in the prior art cracking are not suitable for achieving the vigorous regeneration of the catalyst; 5 required for cracking residual oil for the following reasons: (1) The large amounts of coke that may be deposited on the catalyst are promoted by low catalyst turnover rates, i.e. by low catalyst / oil ratio - 10 things. The combination of low catalyst / oil ratios and high carbon contents automatically leads to high regeneration temperatures, which are above normal limits for the stainless steel used in prior art regenerators, in the design of cyclone systems and extraction systems is used for catalysts, etc. Also, the temperatures are above the conventional temperature limits of the currently used energy recovery systems of about 760 ° C.

(2) The highly active catalysts currently used in catalytic cracking do not have a thermally stable structure at the high regeneration temperatures according to the invention, if this hard regeneration is carried out in one step or even if it is carried out in several steps in a single barrel. Two very basic factors influence the stability of the catalyst during regeneration. With the increasing amounts of coke on the spent catalyst, ever higher temperatures on the catalyst particles develop when the coke is burned in a single vessel, even when multi-step regeneration is performed in the same vessel. These high surface temperatures themselves make the catalyst I30 ineffective. In addition, the catalyst deactivates rapidly at high temperatures when the steam generated from coke combustion from molecular hydrogen attached thereto can remain in contact with the catalyst when the catalyst reaches its highest temperature.

In a particular embodiment of the invention, regeneration of the spent catalyst in a two-barrel system is carried out with a two-stage catalyst flow system designed and utilized to overcome the catalyst generation problems of the prior art. With the regeneration 40 of the catalyst of the invention, a coke content on the recovered catalyst of preferably less than 0.02 weight percent is obtained without undesirably exceeding metallurgical constraints or the thermal stability of the catalyst.

The catalytic cracking process of the invention relates to the cracking of high-boiling hydrocarbons commonly referred to as residual oil and having an initial boiling point of at least 205 ° C; these hydrocarbons are obtained from crude oil, waste; oil and tar sands, upon cracking, supply gasoline and lower and higher carbon-10 known hydrocarbon components. The residual oil feed is mixed in the reaction zone of a riser with a highly active cracking catalyst recovered from a regeneration region at a temperature preferably above the pseudo-critical temperature of the feed.

The hydrocarbons are mixed with the hot regenerated catalyst at a temperature above about 205 ° C; is at least equal to the pseudo-critical temperature of the feed: under conditions under which a highly atomized and generally vaporous suspension of hydrocarbon and catalyst is formed.

A slurry separator located at the riser outlet separates about 70 to 90% of the catalyst from the vaporous material. A particular feature of a particular slurry separator used is that high vapor surface velocities are possible therein during the separation of catalyst particles in the separation vessel before the vapor enters the reactor cyclones for further separation of entrained catalyst particles. The hydrocarbons leaving the reactor cyclones are subsequently separated in a fractionation column. The spent catalyst particles recovered from the riser cracker are stripped at a temperature of about 480 to about 600 ° C and contain de-carbonating carbonaceous residue at a level of from 1.0 to about 2.5 weight percent or more coke. The stripped catalyst is passed to a first dense catalyst bed in a first limited temperature catalyst regeneration zone which is kept below 815 and usually below 760 ° C. The combustion of hydrocarbonaceous material to be carried out in this first stage of low temperature catalyst regeneration is effected at a relatively mild temperature sufficient to contain all the hydrogen present in the hydrocarbonaceous deposits and about 10 to 80% of the total amount of carbon therein. to burn. The regenerator temperature is limited to the range of 620 to 815 ° C and preferably to a temperature of

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13 does not exceed the hydrothermal stability of the catalyst or the metallurgical limits of a conventional low temperature regeneration. The flue gases that are rich in carbon monoxide are collected from the first stage regenerator and are usually sent to a carbon monoxide boiler to generate steam through a more complete combustion of the carbon monoxide present. The gases may optionally before going to the carbon monoxide boiler through a blower for energy recovery. The mild regeneration of the catalyst serves to prevent local overheating of the catalyst in the presence of the catalyst. limit steam generated during combustion of hydrogen such as; that steam generated does not reach a temperature at which it activates; catalytic hydrothermally important. From the first regenerator, a partially regenerated catalyst with limited temperature and containing a further carbon residue free of hydrogen is recovered. The hydrogen-free and residual carbon-containing catalyst is passed through a separate regenerator of unlimited higher temperature where the residual carbon is almost completely burned to carbon dioxide at a high temperature in the range of 750 to 980 ° C in a moisture-free atmosphere.

This second separate stage in which the catalyst is regenerated at a high temperature serves to limit the amount of catalyst and its residence time at the high temperature while achieving a carbon burn rate such that the residual carbon content on the regenerated hot catalyst particles is less than 25 0. .05 wt.% And preferably is less than 0.02 wt.%.

Traditionally designed catalyst regenerators used in the prior art fluid catalytic cracking process contain various internal components which are essential. are for the successful execution of the process. This includes 1930s cyclones, usually consisting of several stages and designed to limit process losses to catalyst, catalyst return lines (diplegs) from the cyclones to the catalyst bed, and various support devices for the above facilities, and further a hopper or the like facility plus associated tubes -35 to allow catalyst collection and disposal and recycling back to cracking process. In the prior art systems, these necessary features are of a metal construction, usually of stainless steel, and are exposed directly to the combustion temperatures of the regenerator. It is the presence of these metal parts in the combustion zone of the regulates 5 9 0 9 λ ft 'Ö &. ·. V fcn & · & 14 generation that limits or maintains the maximum temperature that can be reached or maintained during catalyst regeneration. The upper limit is generally 760 to 815 ° C.

In the second separate high temperature catalyst regeneration phase of the invention, the problems associated with the above limitations are solved by having all metals in; directions such as cyclones, diplegs, discharge hopper, sheath and support system; be placed outside the combustion zone and in fact outside the entire regenerator 1 itself. The regenerator vessel, which is free from all of the above-mentioned internal components in the combustion zone for the catalyst, is lined with refractory material as are all connecting lines, external cyclones and diplegs. The design of such a regenerator combination is considered to be a significant improvement over the prior art. Regenerated catalyst of a desired high temperature is withdrawn from a relatively dense fluidized catalyst bed in the second stage regenerator via a conduit located outside the regeneration vessel. The catalyst is then first introduced into a stripping zone and then sent to the riser reactor at the above-mentioned desired high evaporation temperature and in an amount sufficient to evaporate the residual hydrocarbons supplied according to the working techniques of the invention. Hot flue gases from the second regenerator are sent to external cyclones to recover entrained catalyst particles, further used to recover waste heat and then fed to an expansion turbine or vented into the atmosphere. Since the cyclones of the second regeneration stage with the highest temperature are placed externally, a number of further measures are mentioned in addition to those already mentioned. : long-term benefits achieved. Once the cyclone separators have been moved from the interior of the catalyst regenerator 30 to the outside thereof, it is helpful to increase the cross-section and / or length of the cyclone separator and improve the separation efficiency so that a single cyclone separator can be used ! instead of the two-step separation and yet an improved separation efficiency is achieved. This is partly obtained: 35! using a straight cylindrical tube or flue pipe, or a tube with a bent portion inside it outside the cyclone which generally coincides with the curvature of the cyclone wall and is tangentially connected to the cyclone. This curved flue pipe causes a centrifugal movement of the hot flue gas and catalyst-40 slurry resulting in a concentration of entrained PKAA 4 * 7 filyloo 15 particles and improved cyclone separation efficiency between gases and solids allowing for significant changes in the design of the cylone. In addition, a very important factor in favor of the use of an external cyclone is that the total length of the cyclone can be increased because it no longer needs to fit into the refractory lined regenerative vessel with limited dimensions and space and the separation efficiency of the cyclone can be significantly improved. The combined effect of the above-described flue pipe and the cyclone is that an external single-stage cyclone can be made equivalent of a series-connected internal two-stage cyclone separation system. Externally placed refractory lined cyclones can be made of carbon steel even when used with a regenerator operating at temperatures between 760 and 980 ° C. In addition, the external cyclones, when used in conjunction with the process, can be monitored with an infrared camera and repaired relatively easily before being replaced when the plant is out of use or the process is switched over.

The residual oil cracking process according to the invention becomes an important one; A breakthrough in the fluidized catalytic cracking art incorporating relatively clean gas oil, which allows more efficient conversion of the feedstock boiling residues above 540 ° C and, most importantly, the necessary and desired high catalyst temperatures can be achieved at the same time process conditions which are not significantly more harmful to the catalyst used in the process than in the conventional fluidized catalytic cracking of gas oil. The desired final high temperature regeneration of the catalyst of the present invention is required to achieve the near instant atomization or evaporation of the heavy residual oil feed components through the catalyst thereby increasing a greater proportion of the bottom fractions of a barrel of crude oil, shale oil etc. or any other high molecular weight liquid hydrocarbonaceous material is converted to lower boiling substances including gasoline. This is considered an important step forward in the oil refining industry and reduces the "free world countries" dependence on imported crude oil. The process according to the method allows the processing of less good crude oil, which can be obtained more cheaply.

Further advantages of the residual cracking process according to the invention relate to a limitation of the energy consumption S5? Flv.ïf, '\ ·? .5 V <V, i * 16 in the total processing of the entire barrel of crude oil and limitation of both air and water pollution. Some of these savings are achieved through vacuum distillation units, asphalt extraction units and in some cases various thermal processes such as; 5 delayed coking and thermal viscosity reduction no longer need to be used. These and other prior art processes would normally be used for further processing of the atmospheric residues.

Typical energy savings in a crude oil unit by shutting down a vacuum unit are about 0.6 to 1.0 volume percent on the crude oil charge. The air and water pollution often associated with the above-mentioned saved processes is also avoided.

A further important advantage of residual oil cracking according to the invention lies in obtaining a percentage of sulfur removal of about 60 to 70 percent without significant separate hydrogenation treatments. The HgS formed in cracking can be removed by washing with amine from vaporous hydrocarbons and fed to a claus unit to recover elemental sulfur and sell it as such, as opposed to the release of significant amounts in the form of SO £ in the regeneration combustion processes.

Those skilled in the art will recognize that the conversion of residual hydrocarbons can be accomplished in a number of different equipment arrangements 25: 1, which preferably include a crack zone in a riser; equipped with a multiple feed for hydrocarbons; reaching an intimate contact with the fluidized catalyst particles and a desired short contact time in a contact region of the riser located in front of a separation zone which may or may not be a 30 °. can contain relatively shallow dense, fluidized catalyst bed.

: Separation of hydrocarbon products from the riser; catalytic converter can be mechanically adjusted or by the state of the art known and suitable arrangements for this purpose. In all of these hydrocarbon conversion arrangements, however, regeneration of the catalyst used is the most effective in use; of the sequential regeneration techniques of the invention. The regeneration concepts and process techniques particularly proposed and described in the invention are therefore used with significant advantage in any catalytic cracking operation.

Fig. 40 1 is a vertical projection diagram of a two-stage 8520238 17 catalyst regeneration arrangement adjacent to and in combination with a hydrocarbon conversion riser arrangement. A limited and cylindrical size recovery and collection zone around the riser effluent comprises a first catalyst vapor separator protruding horizontally from an riser reactor outlet and adjacent to a cyclone separator; delivery device placed in the upper part of the collection vessel.

Fig. 2 is a vertical projection diagram of a side by side 10; a catalytic cracking and regenerating arrangement of the catalyst comprising a superimposed two-stage catalyst regenerator which is provided with relatively large cyclone separators outside the vessel in which the second stage of the high temperature catalyst regeneration takes place.

FIG. 3 is a horizontal sectional view of the arrangement of a raw separator at the riser ports of FIGS. 1 and 2.

Fig. 4 is a more detailed sketch of the lower portion of the hydrocarbon conversion zone of the riser of FIGS. 1 and 2, particularly depicting the inlet for the feed oil with multiple nozzles.

Fig. 5 is a graphical representation of the conversion being monitored! reaches for two different systems of residual oil atomization. System 2 uses a more atomized oil than in System 1.

Fig. 6 is a vertical projection diagram of the bottom portion of a cracking zone in a riser with a regenerated catalyst feed line, a fluidizing gas supply line and a nozzle arrangement whereby a highly atomized feed oil is formed in the riser at a relatively high speed. Discussion of Special Embodiments In the process diagrams discussed below, equipment is provided for catalytic cracking of residual oil at relatively high temperatures to gasoline to hydrocarbon boiling range materials that can be easily converted to gasoline boiling and fuel oil components. . Regeneration of the there-35; in particular, the cracking catalyst used takes place in a two-step regeneration operation of the catalyst, in which limited temperatures are maintained in a first separate regeneration zone, especially to remove hydrogen deposited by hydrocarbon products from the cracking operation. Carbon monoxide formation is not particularly limited in the first regeneration zone, and deactivation of the catalyst, Eg% A, 7 tf byc ü L ö b 18 tor as a result of the combustion of hydrogen-formed steam is desired. kept low. Thereafter, hydrogen-free residual carbon is removed from the partially regenerated catalyst in a second, separate, relatively dense, fluidized catalyst system at a higher temperature and sufficiently high oxygen concentration to limit the formation of significant amounts of carbon monoxide or steam by effecting combustion of residual carbon deposited on the catalyst. The temperature of the regeneration in this second stage can become sufficiently high to achieve a desired oil contact temperature. Generally, the temperature range of the regenerated catalyst is between about 760 and 980 ° C.

The flue gas from the regeneration of the second phase is therefore almost or completely free of carbon monoxide. Since the second phase regeneration flue gas is rich in carbon dioxide, that C02 rich gas may or may not be used thereafter for steam generation, catalyst stripping between process steps and other applications as desired. The thus regenerated catalyst comprising a residual carbon on the catalyst concentration of less than 0.20 percent by weight and preferably less than 0.05 percent by weight is included in the cracking; i 20 process returned.

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Those skilled in the art will appreciate that the process scheme of the invention minimizes deactivation of the catalyst by high temperature steam and is an energy-saving measure, which is included herein. time of energy restrictions is particularly desirable. This means that the i25; two-stage regeneration according to the invention, the requirements with regard to the air blower are limited compared to a one-stage regeneration! ; while coke is more completely removed and the catalyst particles up to! heated to a desired high temperature. The limited regeneration of the first phase at a relatively low temperature is not limited as regards the formation of carbon monoxide in which steam is usually formed and the regeneration of the second phase in a higher temperature takes place in the absence of steam formed in which only a residual part is left; the total carbon originally deposited on the catalyst is removed. These energy-saving process conditions are of major economic benefit to the cracking operation in that a smaller carbon monoxide boiler for producing steam used in the process can be used to process the volume of flue gas obtained in the first regeneration step. The flue gas obtained at a much higher temperature from the separate second regeneration step in which no appreciable combustion-stimulating amount is obtained. 85 2 0 23 8

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When carbon monoxide is present, it can be cooled in a suitable device or heat exchanger to form even more steam.

The residual oil processing arrangement according to the invention further provides important energy savings in that by introducing a residual oil into the cracking operation of atmospheric distillation of a crude oil, energy-intensive vacuum distillation and asphalting, delayed coking and other forms of feed preparation which are important amounts of energy are avoided. The steam generated by the carbon monoxide-rich flue gas as indicated above and / or obtained from the process, generally gaseous hydrocarbons, can be used with the oil feed as a diluent to improve the atomization of the feed upon contact with the hot regenerated catalyst.

The hot catalyst particles obtained according to the invention and introduced into the cracking operation may have a desired higher temperature than normally achieved in a one-stage, low temperature regeneration of the prior art. In addition, this is obtained without damage from steam and / or hydrothermal damage to the hotter catalyst. In addition, the regeneration sequence of the invention economically releases more heat for the desired evaporation and endothermic catalytic conversion of the residual hydrocarbons. Further energy saving advantages are achieved by processing a residual oil containing crude oil components difficult to process above 550 ° C into more desirable lower boiling products including products in the boiling range of gasoline and precursors of gasoline by deleting associated ; high energy consuming operations such as vacuum distillation, propane asphalting, viscosity reduction, delayed coking, hydrogen enrichment of the feed and combinations thereof as hitherto | used in oil refining.

The process combinations according to the invention have taken into account: maintaining the desired equilibrium catalyst in the; system by replacing catalyst circulated in the system with 35 lower metal catalyst particles obtained, for example, as a fresh catalyst or as an equilibrium catalyst from other cracking operations of a clean raw material. Thus, part of the low temperature first regeneration step or the higher temperature second regeneration step or both as normal catalyst loss or catalyst particles separated by special extraction can be replaced by fresh catalyst particles with a suitable high | cracking activity and with lower levels of deposited metal contaminants.

The process concepts of the invention are useful for designing basic systems and are adaptable to many different refining operations currently in use that involve a single regeneration operation in combination with a hydrocarbon conversion such as riser cracking or dense cracking fluidized bed. In all of these operations, the regeneration temperature should be limited to a low temperature first phase and a separate high temperature second phase in order to achieve the advantages of the invention, particularly with regard to; saving energy and avoiding hydrothermal damage in; high temperature to the cracking catalyst in the presence of steam formed.

It is readily apparent that with the principles of the step-by-step catalyst regeneration of the invention, a significant improvement can be achieved in any hydrocarbon conversion process, regardless of whether the hydrocarbons introduced in the cracking process include asphaltic constituents and barely processable or metal impurities. lots of coke producing vulma; material that does not contain significant amounts of metal impurities and / or asphaltenes. However, the benefits of the process innovations of the invention improve significantly as side treatment 125 of the crude hydrocarbon charge to remove these materials is limited.

Furthermore, those skilled in the art will appreciate that existing limited temperature catalytic cracking and regeneration equipment can be modernized so that the high-temperature operations of the invention can be performed with minimal capital expenditure and rebuild time, whether or not for example, to modernize a vertical regenerator arrangement with a single-stage reactor, a horizontal regenerator arrangement with a single-stage reactor or one of the more modern installations with a hydrocarbon conversion zone 35 in the riser reactor in combination with a closed catalyst bed in open connection with a catalyst regenerator located at the top of the riser.

For example, when considering FIG. 1, spent catalyst particles recovered from a hydrocarbon waste oil conversion operation 40 and hydrocarbonaceous hydrocarbons are disclosed therein; Deposits included passed through line 1 into a first densely fluidized catalyst bed 3 into regeneration vessel 5. Regeneration vessel 5 herein is a relatively low temperature regeneration vessel whose i; temperature is kept below about 800 ° C and the oxygen concentration supplied by regenerator gas through line 7 and distributor 9 is limited to the desired regeneration temperature during combustion, in particular of hydrogen and hydrocarbonaceous deposits associated with hydrocarbon residues from residual oil cracking to keep. The combustion in this first regeneration step occurs under conditions that steam and a carbon monoxide-rich regeneration flue gas are generated. The flue gas thus formed is passed through cyclone separators, which are represented by gauges 11 and 13, to separate entrained catalyst particles therefrom before the gas is discharged via line 15. The catalyst thus separated from the carbon monoxide-rich flue gases by the cyclones is passed through suitable dip pipes to the catalyst bed; returned. For regeneration vessel 5, the regeneration conditions are chosen so that the carbon removal catalyst is only partially regenerated leaving sufficient residual carbon on the catalyst to achieve higher temperatures for the catalyst particles than 760 or 815 ° C upon complete removal. by combustion with excess oxygen-containing regeneration gas.

In the arrangement of Figure 1, the first stage of catalyst regeneration accomplished in vessel 5 is a relatively low temperature operation which is preferably limited to about 760 or 815 ° C and produces a carbon monoxide-rich flue gas. Partially regenerated catalyst which no longer contains a significant amount of hydrogen giving rise to steam formation is led via discharge pipe 17 from the catalyst bed of the first regeneration step to the adjacent separation zone or vessel 19. A downflowing, relatively dense fluidized mass of partially regenerated catalyst is passed through vessel 19 countercurrent with aeration and stripping gas fed via line 21. The aeration gas is preferably a gas that is relatively inert, at least as regards the deactivation of the partially regenerated catalyst, and is preferably a gas which transfers the moisture-formed components with the catalyst to a second regeneration step at a temperature above 815 ° C C significantly limited. Suitable aeration gas-40s for use in zone 19 include carbon dioxide, virtually moisture-free flue gas, nitrogen, ft! K ^ A Ά 'Έ tk ö v / * f / Λ Η' -? Ana Ana ïs * ftnaïst '22 dry air and combinations thereof.

The partially regenerated catalyst is passed out of vessel 19 through standpipe 23 which connects to the catalyst line 25 and riser pipe 27. A gas such as air, nitrogen, carbon dioxide or a mixture thereof can be added through the gas supply lines 29 and 31 to transport the catalyst. At the entrance 29 in the pipe bend between the pipes 23 and 25 and further on in the transport pipe, different gas supply pipes can also be arranged to promote the transport of the catalyst. A regeneration gas such as air or an oxygen-enriched gas stream is added through line 31 to the partially regenerated catalyst in riser 27. Tube 27 opens into a catalyst bed 33 held in the lower portion of a relatively large diameter regeneration zone or vessel. Down in catalyst bed 33, additional regeneration gas such as air is introduced through line 37 which connects to an air distributor adapted to the high process temperatures.

In the regeneration of the second stage carried out in regenerator 35, the temperature is in the range of 760 to 980 ° C and 20 higher than that of the first regeneration stage to allow almost complete removal of residual carbon not removed in the first stage to accomplish. Regenerator vessel 35 is a refractory lined vessel that has virtually no surface metal internals or cyclones so that the desired high temperature regeneration can take place. In this high temperature operation, residual carbon on the catalyst is preferably limited to less than 0.05 percent by weight and a high temperature flue gas stream of carbon dioxide is recovered by external cyclone separators. Preferably, relatively large one-stage cyclone separators 30 are used with refractory lined drums. An external gas-filled portion 39 is provided with all-round arms on which cyclone separators are suspended or arranged as shown in the drawing by the arms 41 and 43 which are connected to the cyclones 45 and 47. On the other hand, the cyclone arrangement of fig. .2 35 discussed below in regenerator 35 are used. The catalyst thus separated from flue gas at elevated temperatures up to 980 ° C is recycled via the applied compounds. A high temperature carbon dioxide rich flue gas is separately withdrawn from each cyclone separator for further use if desired or as a 40 combined hot flue gas stream 49 which, in a non-illustrated infi K ft x $

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23 can be generated in the direction of steam. Those skilled in the art will recognize that more than one cyclone separator can be used simultaneously and that the number of cyclones in succession is determined by the size of each and of the arrangement used.

The catalyst regenerated in the second regeneration step and heated by burning residual carbon to a concentration below 0.10 wt.% And preferably below 0.05 wt.% Carbon to a temperature above that of the first regeneration step is removed from bed 33 discharged via line 51 to adjacent vessel 53. The withdrawn catalyst is preferably aerated with a moisture-free, or at least substantially moisture-free, gas which is supplied via line 55 into the adjacent catalyst collection zone or vessel 53. The aeration gas is then led via line 57 to the upper part of vessel 35. The hot regenerated catalyst having a temperature above 15760 ° C is passed out of zone 53 via standpipe 59 comprising a flow control valve 61. The hot catalyst then passes through transport line 63 to the lower portion 65 of a riser 67 which serves as a hydrocarbon conversion zone. Aeration gas or ascending gas, such as light hydrocarbons recovered from a further distillation process apparatus for light distillation ends or other suitable fluidized gaseous material not shown in the process, is introduced into the riser via line 69 below the catalyst inlet.

Of particular interest in hydrocarbon conversion is that the low residual carbon hot catalyst is forced upward and mixed in the riser with various hydrocarbon streams flowing through different insertion nozzles into the refractory lined portion of the riser wall. supplied. More particularly, the riser wall is provided with a widened wall portion 73 through which the various horizontally spread feed nozzles protrude inwards and upwards. A diluent gas such as steam, light hydrocarbons or a mixture thereof is added to the residual oil to obtain a better atomized dispersion thereof and a vaporization with the fluidized hot catalyst particles. The riser section adjacent the outlets of the feed oil nozzles is preferably widened into a larger diameter riser vessel through which the evaporated oil and catalyst slurry is passed. In order to further promote the desired mixing and the almost instantaneous evaporation of the imported residual oil components, a number of small feed streams for atomized oil are mixed with the upflowing catalyst. The carbonaceous hydrocarbon material comprising cracked products mixed with suspended catalyst particles flows up through the riser 67 and is discharged through the slurry separator at the top of the riser. Various prior art measures can be used for this purpose. The first slurry separator referred to as a crude separator at the end of the hydrocarbon conversion zone in the riser is depicted as an outwardly widening protruding portion of the riser in the form of butterfly wings in conjunction with relatively large openings in the wall of the riser near its closed top end. That is, the coarse separator at the top of the riser from the side and viewed from above resembles a butterfly-shaped device. The protrusions are open at the bottom in connection to the vessel 87 around it for venting hydrocarbon vapor largely separated from the catalyst particles. The sides 77, FIG. 3, are dense nearly vertical bulkheads, and the ends 79 adjacent to the wall of vessel 87 are dense, nearly vertical curved! bulkheads. The top end of each protrusion is closed with a sloping roof 81 so that as little as possible of catalyst particles and coke particles settling on it remains thereon. The slope of the roof bulkhead is preferably at least equal to the angle of repose of the used catalyst and preferably greater to prevent the catalyst from remaining on the roof. Other arrangements known in the art to achieve high vapor discharge rates can be used for the first separation of the hydrocarbon vapor catalyst slurry exiting the top of the riser.

In practice, the vaporous materials comprising hydrocarbons and diluents mixed with suspended catalyst are passed through the openings 75 in the riser and expanded into both protruding chambers A and B to reduce the speed of the mixture, changing direction of the ingredients of the slurry and concentration of the catalyst particles separated from the vaporous material along the vertical curved outer wall 79 of each protruding chamber. The catalyst particles thus concentrated or separated fall down the wall and are collected as an annular catalyst bed 83 below which comprises a catalyst stripping zone. The vaporous material separated from the catalyst particles flows down through the open bottom of each protruding chamber adjacent to the riser wall and from there flows up into one or 40 more cyclone separators represented by separator 85 in an 852 023 8 25 upper portion of vessel 87. Hydrocarbon vapors, diluent and gaseous stripping material separated from the catalyst are passed through line 89 to product recovery plants (not shown). Catalyst separated in one or more cyclones j i 5 is led via connections to catalyst bed 83. Strip gas such as steam is led to bed 83 via line 91. Stripped hydrocarbons go with the produced hydrocarbon vapors from the crude separator and enter the cyclone separator arrangement. The: stripped catalyst containing hydrocarbonaceous cracking product 10; of residual oil and metal impurities is discharged through line 93 with valve 95 therein and then passed through line 1 to the first regeneration stage.

Fig. 2 shows an apparatus arrangement that deviates from the arrangement of Fig. 1 in that the individual regeneration vessels 2 and 4 are stacked one above the other on the same axis, with regenerator 4 having the highest temperature being the uppermost vessel. Furthermore, the hot flue gas; From regenerator 4 discharged through refractory lined pipes 6 and 8 which are arranged in T-shape with a large cyclone separator in open connection therewith and suspended from the horizontal arms 8 of the T-shaped pipe. In this equipment arrangement, the multi-feed 14 hydrocarbon conversion riser reactor 12 and crude slurry separator 16 correspond to the same features as in FIG. However, this system or other arrangements are adapted to be used in combination with one, two or more large cyclone separators 18 in the upper portion of the catalyst collection vessel 20 adjacent to the riser exit port inside or outside collection vessel 20. Also an arrangement corresponding to that shown for the top of the regenerator 4 of the apparatus may be used.

In the device arrangement of Fig. 2, hot regenerated cheese is a catalyst with a temperature above 760 ° C, which temperature is at least equal to the pseudo-critical temperature of the residual oil supplied, is placed at the bottom of riser 12 where it is mixed with riser gas or aeration gas which is fed through line 24 to obtain ; 35 went from an upflowing slurry. The thus aerated or slurried catalyst is then contacted with several streams of atomized oil through various inlet nozzles 14. In a particular embodiment, there are six horizontally spaced nozzles, see FIG. 4, which are shown in the manner shown. at the 40 widened portion of the riser through the wall of the riser ste-%? L U L O ö 26 ken. With the oil supply, steam or other diluent can be injected to obtain good atomization as discussed above.

A suspension of vaporous hydrocarbons and catalyst; 5 rises through riser 12 and is introduced into the roughly separating protrusions 16 as discussed in FIG. The hydrocarbon vapors separated from the catalyst particles are passed through one or more cyclone separators 18 to further recover catalyst, and then the hydrocarbonaceous vaporous material 10 is passed via line 26 to a fractionator not shown.

The catalyst separated using facilities 16 and cyclone 18 is collected as a catalyst bed in the bottom portion of vessel 20. At the bottom of the bed, a stripping gas such as steam is introduced through line 28. The stripped catalyst is passed through line 30 with valve 72 to a catalyst bed 32 which is regenerated in vessel 2. A regeneration gas such as air is supplied at the bottom of bed 32 through a feed pipe 34 which has connection with air distribution ring 36. Regeneration zone 21 is maintained as a regenerator 20 with a relatively low temperature below 815 ° C and with selected conditions such that part of the deposited carbon and all hydrogen are removed from the hydrocarbonaceous material deposited upon cracking. In this operation, a carbon monoxide-rich flue gas is formed which is separated from entrained small catalyst particles by one or more cyclones, such as cyclones 38 and 40, connected in parallel or in series with another cyclone. The carbon monoxide-rich flue gases are recovered from the separation cyclones via line 42 to be used as discussed herein.

Partially regenerated catalyst is discharged from the lower portion of bed 32 and up through riser 44 into the lower portion of a dense fluid catalyst bed 46 in a bottom. a separate regenerator with an upper interface 48 is guided. Regeneration gas, such as air or oxygen-enriched gas, is passed into bed 46 through line 50 which communicates with air distribution ring 52. Regeneration vessel 4 is a refractory lined vessel without metal appendages as discussed above so that the temperature is not limited by metal parts and to a higher temperature, such as above 815 ° C to 980 ° C, or to the temperature required for full carbon dust combustion can increase. In this catalyst regeneration environment, the residual carbon remaining on the catalyst after the first 852 0 2 3 8 ..... 27 I temperature-limited regeneration is released.

I: I.

completely removed at the unlimited temperature of this second stage. Therefore, in regenerator 4, the temperature is not particularly limited to a maximum level, except by the amount of carbon 5 to be removed, and sufficient oxygen is supplied to produce carbon dioxide-rich flue gases that no longer contain combustion-promoting amounts of carbon monoxide. The carbon dioxide-rich flue gas thus formed is led with some entrained catalyst material from the dense flowing catalyst bed 46 to a more dilute catalyst phase above from which the flue gas passes through lines 6 and 8; which communicate with more than one cyclone 10 is discarded.

; Line 8 is bent straight or horizontally and is tangentially connected to cyclone 10. The curvature of line 8 preferably partially corresponds to the curvature of the cyclone wall so that in line 8 before entering the cyclone separator a first centrifugal separation; of entrained catalyst particles is created. With this ; Arrangement, high efficiency catalyst particles are separated from the hot flue gases and the efficiency of the cyclone separators can be further improved by extending the cone bottom of the cyclone. Catalyst particles thus separated are passed through the refractory-coated compound 56 to catalyst bed 46 in the high temperature regenerator. Carbon dioxide-rich flue gases without combustion supporting amounts of carbon monoxide are passed from cyclone 10 through line 58 to be used as described herein. Irrigated in zone or vessel 4 at a temperature of up to 980 ° C Opened catalyst particles are led via refractory lined line 60 to vessel 62 and then through line 64 with valve 66 I: 1 to line 22 which connects to the riser reactor 12 discussed above. The bond is supplied with a distribution ring in vessel 62, aeration gas is supplied.

The gaseous material withdrawn from top of vessel 62 via line 70 is passed to the upper portion of vessel 4.

The device arrangement of Figure 2 is a compact side-by-side system arranged in pressure balance to achieve the desired circulation of catalyst particles and the particular desired process conditions discussed here. The operation of the system is improved by using spherical catalyst particles of less than 200 µm and with an average particle size selectable from the range of 50 to 120 µm. Account has been taken of the modification of the system of fig. 2 by adding extra

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28 cyclones on vessel 20 with openings there at the top of the exit of the conversion zone in the riser. The external cyclone separators can also be arranged in a similar manner to that shown for the lines 6 and 8 and cyclone 10 of regenerator: 5 4 and can be connected to a vertical shortened vessel 20 and used in place of internal cyclone 18. Thus separated Catalyst particles can be recycled through appropriate tubing connections connecting to the collected particle bed at the bottom of vessel 20 and contacted with the stripping gas supplied via line 28.

In FIG. 4, a device arrangement is shown in more detail which is useful for separately feeding hot regenerated catalyst and residual oil raw material into the bottom riser section 65 of FIG. 1 or riser 12 of FIG. 2. The residual oil is fed through a series of straight or curved tubes 71. The tubes can be provided with a tubular jacket forming an annular zone for delivering steam if desired. In the arrangement of Figure 4, at a previously indicated elevated temperature that is above the pseudo-critical temperature of the residual oil feed, hot catalyst is passed through refractory line 63 to a bottom portion 65 of the hydrocarbon conversion riser 67, each of which is refractory. lined lined. Aeration gas or fluidizing gas for the catalyst is passed via line 69 to a gas distributor at the bottom of the riser. At the bottom of the riser, a hot slurry of the catalyst and propellant gas is formed which is then passed through the riser to its widened portion to be contacted there; with the residual oil introduced via the various supply tubes 71. The oil introduced via 71 I is mixed with a diluent such as steam or light hydrocarbons entering through line 109 and significantly limiting the partial pressure of the introduced hydrocarbons. Additional added steam for the oil supply nozzle is supplied through steam inlet 111 in a ring formed around pipe 71. A series of such sheathed nozzles are horizontally spaced and release oil into the cross section of the riser; preferably there are six such nozzles which effect the high temperature contact between fluidized catalyst particles and oil with; in view of the almost instantaneous evaporation / atomization of the supplied residual oil. The disposed nozzles release oil into a widened section of the riser after passing through section 73 40 which has been considered as a semi-tubular section in PK O A o 7 Ö V L y L 5 y 29 in an arrangement! the riser wall filled with refractory material. The nozzles are arranged so that the oil enters a straight portion of the riser so that the atomization / evaporation contact with the upwardly flowing suspended catalyst particles in the riser is further intensified. The series of oil feed tubes are preferably arranged in a circle spaced from the riser wall within the enlarged diameter of the riser to achieve the desired mixing of oil with the hot catalyst particles to allow almost instant evaporation of the supplied residual oil. It is recognized that various devices used in the art, including atomizing nozzles, may also be used to more fully atomize the residual oil supplied for more intensive evaporative contact with the hot catalyst particles at a temperature of at least 760 ° C and within the range from 815 to 980 ° C. j

The cracking of residual oil according to the invention is based on the recovery process. generating the catalyst at a very high temperature, whereby a catalyst with a very low residual carbon content is obtained at a temperature above the pseudo-critical temperature of the supplied residual oil, whereby an almost instantaneous evaporation of the supplied residual oil is obtained. Another important aspect of the combined operation is to maintain the activity of the catalyst by replacing part of the metal-contaminated catalyst with fresher catalyst and effecting initial regeneration of the catalyst under limited temperature conditions. thereby minimizing deactivation of catalyst particles by steam during regeneration. The cracking operation of the invention is essentially a treatment of the hydrocarbons all at once since there is no recycle or circulation of oil hydrocarbons in the cracking operation. On the other hand, light, normally gaseous hydrocarbons, process-generated steam and carbon dioxide can be recycled into the process and used for the above-described purposes. Furthermore, it is possible to alkylate shaped and suitable olefinic components in unsealed, downstream equipment and hydrocracked shaped hydrocarbons boiling above the boiling point of gasoline to produce additional gasoline and / or light oil. The hydrocarbon product boiling above gasoline can be hydrogenated to remove sulfur and nitrogen to form acceptable fuel oil material.

40 The concepts of cracking regeneration discussed above

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In particular, 8% 30 catalysts are used to provide a high degree of productivity in the catalytic conversion of high-boiling hydrocarbons, especially residual oils, in the production of crackers; to obtain gasoline, gasoline precursors and catalytic recycle oils.

The process concepts discussed below are more particularly aimed at obtaining a high degree of product selectivity in the cracking operations discussed above by paying more attention to another process variable. This other process-10 variable mainly has to do with obtaining a nebulization of the heavy oil and with the injection system more suitable for the intended purpose.

In this process concept, it is particularly desirable to obtain near instant evaporation and heat and catalyst conversion of atomized oil droplets upon contact of a finely atomized oil with fluidized catalyst particles. The velocity of the hydrocarbon vapor and catalyst slurry increases as it flows up through the riser, thereby obtaining a low catalyst concentration in the slurry within the range of 16 to 160 kg per m3 and usually not above about 80 kg per m3 . The faster the evaporation and conversion of the oil thus takes place, the less there is a pressure drop next to the supply of atomized oil and upon contact with upward flowing catalyst particles in the reactor tube.

25: It should be noted that when performing the present method

the product selectivity of the residual oil conversion by thermal and catalytic means can be varied considerably depending on the degree of atomization of the heavy oil which is contacted with the hot catalyst particles to evaporate the feed oil. In particular, an important process variable relates to the use of a suitable atomizing nozzle which achieves a high degree of atomization and contact of the residual oil at a relatively high speed with the upflowing hot catalyst particles suitable for this purpose. The thermal and catalytic conversion of the evaporated oil to the desired products thus takes place in a very short period of time, at the same time lowering the temperature of the suspension formed as discussed here. In this preferred process environment, a highly atomized oil is introduced into the riser cracking zone at a rate above 90 meters per second to 400 meters per second and in a fan-shaped pattern p & o r * y G

by £ yOe \ 31 from about 10 to 15 degrees in the vertical direction and about 90 to! 120 or more degrees in a generally horizontal direction on the cross section of the riser. This contributes to more intensive contact in an upflowing fluidized slurry of finely divided hot catalyst particles with an initial particle concentration ranging from about 160 to about 560 kg / m 3. This rate of formed slurry decays almost immediately and a slurry of an upflowing hydrogen vapor vapor and a dispersed catalyst particle phase forms. The rate at which this occurs minimizes the pressure drop in the formation of a slurry of product vapors and catalyst which is withdrawn from the riser reactor at a rate within the range of about 18 to 36 m / s. The catalyst concentration of the slurry formed can be varied considerably if desired to optimize the conversion of the supplied hydrocarbons. The concentration of catalyst in the slurry can be less than 80 kg / m3 and even only 16 to 32 kg / m3 at the riser outlet.

When near instantaneous evaporation of oil droplets is obtained as discussed here, the thermal and catalytic conversion thereof occurs in a short vertical space of the riser reactor in a very short period of time. This may be associated with a slight pressure drop in a vertical section of the riser above where the oil is fed to about 1.50 but no more than about 3 meters from there. The temperature of the slurry formed quickly decays or is reduced to a level between about 500 and 540 or 565 ° C as measured below or at the riser outlet. In effecting immediate evaporation of the atomized oil, up to about 50 percent thermal conversion of the oil occurs in addition to catalytic conversion thereof to form gasoline, gasoline precursors and high yield circulating oils. The cracking reaction combination turns out! occur in the riser in a very short period of time in the range of from 0.5 to about 2.5 seconds and the desired almost complete conversion with optimum yields of gasoline products is believed to occur between about 0.5 and about 1 or 1.5 seconds-35. High yields of gasoline and light recycle oil are obtained when the riser reactor above the entry point of the atomized oil experiences a slight pressure drop and when the contact between hydrocarbon vapors in the riser and suspended catalyst particles is limited to less than 1.5 seconds.

40 In developing the concepts of the residual oil conversion zo & R on 9 x ft 32 as set forth herein, it further appears that the atomization of the oil to a droplet size corresponding to or smaller than the particle size of the used fluidized catalyst and setting it up; of an average particle size of between about 20 and about 150 micrometers also contribute to achieving rapid evaporation of the supplied residual oil at a relatively high rate whereby a suspension under low pressure drop is formed in the riser reactor which then passes through the riser as described above .

In the graphical representation of Fig. 5, a comparison is made between the conversion achieved with a first residual oil atomization system and a second system. System 2 includes the nozzle arrangement of Fig. 6 and provides a much higher degree of supply atomization than System 1. Fig. 5 speaks for itself and clearly shows a significant improvement in catalytic conversion between the first and second. misting system on even though it is on both! : there is the same degree of thermal conversion. System 1 of Fig. 5 includes less than the desired atomization of residual oil supply and results in limited catalytic conversion to desired gasoline products and thus lower product selectivity than desired, although a thermal conversion of at least about 50% is achieved. This observation is compared to the result of a second oil feed atomization nozzle system in which a stronger atomization of the oil is obtained and its droplet size corresponds to the particle size of the catalyst. This gives a more fully vaporized oil feed which is intensively and immediately mixed with sufficiently suspended high temperature catalyst particles to form a suspension of a highly dispersed phase thereof; to shape. Figure 5 shows graphically that both process systems achieve the same thermal conversion but have different overall product selectivity. The second atomization system of Figure 6I gives a higher overall conversion due to the improved catalytic conversion of the atomized oil. That is, when the activity of the catalyst is related to the surface area of the catalyst multiplied by the catalyst-oil ratio, the second atomization system of Figure 6 consistently gives higher rates of conversion with the more atomized oil, as shown in the graph. In this conversion of highly atomized and evaporated residual oil hydrocarbons, it is preferable that the average surface area of the catalyst is kept at a level of at least 40 m 2 / g by continuous or intermediate replacement with catalyst particles having a larger © R o ft n · > * λ ΰ £ ύ ö 33 ..- ................

specific surface area and preferably the catalyst surface is maintained at a higher level up to about 80 or 120 m2 / g depending on the desired hydrocarbon conversion and the economic aspects of the catalyst replacement.

5 The exact mechanism by which an improved residual oil conversion, product selectivity and yield are achieved by the above-described system 2 versus system 1 cannot be fully established, but it can be noted that a highly atomized oil which is generally horizontal The cross section of the riser through the nozzle of FIG. 6 is apparently causing a very rapid evaporation of the fine oil droplets causing intensive vapor contact with the hot flowing catalyst particles at a temperature equal to or greater than the pseudo-critical temperature of the atomized residual oil.

Thus, it appears that in relatively drastic environments where residual oil and catalyst contact of system 2 occurs, highly atomized oil droplets that are the same size or smaller than an average catalyst particle size of about 100 µm and are thus uniformly dispersed at the pseudo-critical temperature of the feed can be almost completely evaporated in a fraction of a second or even converted almost completely thermally and catalytically. It is clear that such process conditions in which a highly atomized oil comes into contact with catalyst particles as described above have a decisive improvement in the conversion and selectivity of the product obtained.

In the catalytic cracking process described herein, the phenomenon of cleavage of asphalt into desired molecular size reduction to aromatics of up to 3 rings is a new and useful concept in the prior art. This process concept is particularly related to obtaining a high temperature thermal conversion or reduction of the asphalt component. This requires an elevated catalyst temperature above the normally used temperature achievable by the regeneration technique discussed here which produces the desired molecule size reduction of asphalt.

In this new process for catalytic cracking of residual oil, it is considered essential for successful processing that there is an almost instantaneous reduction of the asphalt components and the struk-40; this takes place, largely at the point of the oil injection, in a very short period of time, which is no more than a fraction of a second and anticipating or occurring simultaneously with the catalytic cracking of atomized gas oil components. Decreasing the asphalt component of the oil feed naturally enriches the gas oil portion of the feed with aromatic ingredients including di- and tri-cyclic aromatics and large ring compounds, but preferably without significant amounts of 4- and 5-ring aromatics.

The driving force for the cleavage or molecular reduction of asphalt is essentially thermodynamic or kinetic and the limiting factor 10 is related to the heat transfer rate from the hot catalyst particles to the asphalt molecule. The desired heat transfer rate increases exponentially with the reduction of the particle or droplet size of the injected oil mist. Therefore, when super-hot catalyst particles come into contact with super-atomized oil, the desired cleavage of the asphalt molecule into high yield mono-, di- and tricyclic aromatics is obtained, without condensation of polyaromatic rings as observed in coking processes in which a higher cooking production occurs. In this asphalt split, the time frame within which the split takes place must be sufficiently short so that the structure of the cracking catalyst does not become; masked by coke contents such that normal conversion of the lighter gas oil component of the feed is too limited.

Thus, an important function of the catalyst to oil: 25 ratio, in addition to splitting asphalt, is to maintain a mixing temperature high enough to maintain the normal endothermic catalytic conversion of the gas oil components of the gas oil components crackable below 540 ° C. residual oil to take place. In this regard, it will be recognized that a low turnover rate of an extremely hot catalyst or low temperature catalyst particles does not achieve this desired conversion; will achieve as effective as a higher turnover rate of catalyst particles of sufficiently high temperature giving the desired high catalyst-oil ratio.

It is noted that there is a catalyst temperature that is most suitable and desirable for effecting the desired conversion of a residual oil raw material with a given asphalt content. This is indicated by and is identifiable with the pseudo-critical tem-; temperature of the residual oil. In addition, the conversion temperature must be increased as the percentage of asphalt in the feed increases in order to achieve the desired rapid or immediate evaporation of the heavy oil in the presence of hot catalyst particles to achieve the desired product selectivity. and low coke yields are achieved In this regard, the desired catalyst temperature occurs almost automatically in the above-described special two-stage regeneration 5 when the asphalt content of the oil bank increases and when the temperature of the second stage catalyst regenerator for burning carbon deposits is not limited. is so because the coke content of the spent catalyst increases with a higher asphalt content in the feed.

This higher coke content of the catalyst, when the catalyst is regenerated, causes a higher temperature of the regenerated catalyst. Regeneration of catalyst particles with higher coke contents than normal is important to protect the activity of the catalyst.

The process combination indicated herein relies on rapid splitting of the asphalt components at high temperature into a highly atomized residual oil supply, as discussed above, which, with recovery and disposal, leads to higher yields of gasoline and light recycle oil. The cleavage, in particular of the asphalt component of the residual oil, provides significant amounts of di- and tricyclic aromatics and further some higher boiling polycyclic compounds. These components which do not generally convert by catalytic cracking react to hydrocrackings in the form of hydrogenated products with fewer rings in favor of mono- and dicyclic compounds which contribute to the formation of gasoline and / or few other distillates with high cetane number. Furthermore, the hydrogenated higher boiling product of hydrocracking is a hydrogen donor for the residual oil when returned to the catalytic cracking treatment.

The process for catalytic cracking of residual oil and catalyst regeneration discussed here is an important breakthrough in catalytic cracking technology that addresses metallurgical limitations; the regeneration equipment and the temperatures reached in it! economically bypasses. This involves a molecular reduction; from asphalt which contributes to a further improved yield: to gasoline and to light fuel oil, especially when the process is coupled to hydrogenation operations such as hydrocracking of polycyclic components in the recycle oil product of the catalytic cracking step. The process combination described here adapts to changes in the properties of the starting material. Another important aspect is the finding that no unusually complicated instrumental EO O ï P

V

36 whether control systems are necessary to maintain smooth and stable operation.

The rate at which a residual oil is converted to gasoline, lower and higher boiling hydrocarbons by a high temperature catalyst as described above is further increased when more attention is paid to the following process parameters. For example, when the above-described riser cracking system of FIG. 2 is adapted so that the feed nozzle arrangement of FIG. 6 for preparing and fan-injecting highly atomized residual oil droplets into the high velocity upflowing suspension of hot fluidized catalyst particles may be incorporated therein. significantly improved conversion can be obtained. In this operation, it is desirable that the upflowing catalyst slurry has a concentration in the range of at least 160 to about 560 or more kg of catalyst particles per m 3 to effect rapid and intensive contact with the highly atomized oil supplied.

The improved conversion to the residual oil riser of the present invention relies to a significant extent on the supply of a highly atomized residual oil to catalyst particles having an average particle size in the range of about 20 to 150 µm or less, at a relatively high speed, for example not more than about 120 / un and having an area in the range of 40 to 120 m3 / g. Catalyst particles with an average particle size in the range of from about 60 to about 120 µm are especially 25; der eligible. The size of the atomized oil droplets may be equal to or smaller than the average particle size of the catalyst. However, it is preferred that the atomized supplied oil give a droplet size corresponding to the particle size distribution of the catalyst or less than the average particle size.

A very important aspect of a successful cracking of residual oil in a riser is related to the attainment of a rapid: thermal cracking of in particular asphaltenes, and a catalytic cracking of crackable vaporous components and with the rapid attainment; temperature reduction of the slurry which significantly reduces thermal degradation of products in the form of high coke yields. To give a clearer picture of the improved conversion of residual oil into a riser according to the invention, the following table has been compiled.

y &, v L * 3 t? 37 ......

Table 1

Evaporation time for atomized reduced crude oil 1 5 Droplet size Evaporation time (microns) (milliseconds) 300 85 | 200 40 100 9; 10 50 3 20 2 10 1 j This table shows that a reduced crude oil or residual oil atomized to a droplet size of 100 µm or less, as is particularly desired here, has a very short evaporation time of 9 milliseconds or less when the oil is in contact; comes with catalyst particles with a temperature at least equal to the pseudo-critical temperature of the supplied oil.

The concepts discussed herein for catalyst regeneration and riser cracking to process residual oil and reduced crude oil relate to obtaining one; high degree of desired product selectivity at the expense of coke production and less desirable gaseous material.

25 From the above discussion it clearly shows that on

the moment of injection of atomized oil and contact with a suspension of high temperature catalyst particles, all follow-up reactions and interactions in a very short period of time from milliseconds to about 1 second but less than about 2 seconds occur depending on the process parameters such as temperature, atomization of the feed, activity of the catalyst expressed in useful surface area and contact time. Furthermore, all of these conditions change as the reactor riser passes in a manner that contributes to the final desired products including gasoline, recycle oil, and an amount of coke, the process taking place in heat-equalization. What should especially be avoided appears to be a prolonged contact of cracking products, including di- and tricyclic aromatics, with the hot catalyst, as this threatens degradation of products and increases coking. A very fast temperature-40 1 aging after evaporation and cracking of the supply which occurs unintentionally p ff B

> 38 for 2 seconds and preferably within about 1 second appears to be important for optimizing the yield of gasoline and recycled oil products. This is achieved in particular when the concepts of the improved riser operation 5 set forth above are employed. A rapid temperature drop to within the range of 510 to about 565 ° C is desired.

The preferred process concepts discussed above are accompanied by a rapid molecular expansion of vaporous cracking products at the initially prevailing high temperature which automatically contributes in a fraction of a second to a significant increase in the speed of the slurry formed along with acceleration of the catalyst particles is achieved. When residual oil cracking is carried out according to the indicated process concepts, an unfavorable radial distribution of the slurry suspension in the riser is minimized and thus clumping of the catalyst and other local concentrations of catalyst particles along the riser wall contributing to an undesirably high ratio. from catalyst to oil avoided.

The rapid evaporation and conversion of residual oil at a relatively high speed as discussed herein appears to be associated with a very small pressure drop in the riser within a limited area of less than about 3 m vertical above the inlet nozzles. ; long.

; This low pressure drop condition proves to be the opposite of what is found with poor mixing of feed oil and catalyst in the first portions of a riser to 1m 50 or 3m; from the beginning. Thus, it is clear that a high degree of atomization of the feed oil is an important process parameter, as is its distribution along the cross-section of the riser in a pattern which provides an immediate intensive evaporation contact with catalyst particles. progresses for its conversion as indicated herein. A fan-shaped pattern of 10 or 15 degrees in the vertical direction at about 80 to 150 degrees in a direction perpendicular to it appears to give a very intensive contact.

: 35 The introduction of atomized oil at a high speed of about 150 m / s, more or less as taken into consideration herein, does not appear to be harmful to the process. Namely, it has been determined that an inlet velocity of atomized oil at the outlet of the nozzle of 400 m / s at a distance of 2.5 cm from it has already dropped to about 200 m / s and at a distance of 5 cm from the tip of the nozzle 8520238 * 39 to only 105 m / s. At a distance of 15 cm, the speed decreased to j 40 m / s. According to the method of the invention, the cracking of a residual oil in the riser takes place in a very short period of time of about 2.5 or no more than about 1.5 seconds, depending on the type of residual oil and the temperature caused by the catalyst when the feed oil is preheated to less than 425 ° C and more usually below 260 or 315 ° C.

In the arrangement of Fig. 6, the lower section 82 of the riser is smaller in diameter than the upper section 80 and both are connected by the transition section 84. Fluidized catalyst particles are introduced via tube 86 into the lower narrow section of the riser brought. Below the catalyst inlet 86, fluid conduit gas is introduced into the riser through conduit 88 connected to a manifold within the riser. Line 90 provided with valve 92 allows the catalyst to be drained from the bottom of the riser. The fluidizing gas supplied to line 88 may consist of gaseous catalytic cracking products from which gasoline precursors have been separated, and steam may also be used instead. A low-quality fluidized gaseous material such as naphtha can be used singly or in admixture with recycled gaseous hydrocarbons as a fluidized transition medium to effect a gradual change of direction in the flow of hot catalyst particles as a slurry at the top of the riser to the nozzle inlet. in the widened riser section. Connections for instruments can be placed in the riser; wall and more particularly above the transition portion 84 for determining pressure drop and temperature of the operating system.

i

The feed nozzle includes cylinder 94 with a limited grooved opening 96 in a cylindrical heat dispersing jacket 98. The insert the end piece protrudes through the riser wall just above the transition portion of the riser, directed upward at a desired angle. It has been found that j! an angle of about 30 degrees in this particular embodiment; is peaceful. The feed oil is introduced into the atomizing portion of the nozzle with or without a gaseous diluent such as steam, light hydrocarbons or other suitable substances to reduce the partial pressure and / or the viscosity of the oil introduced through line 100 which communicates is positioned with opening 102 so that the heavy oil entering through the opening lands on a flat surface of surface 104 and causes droplets to form there which are passed through a line Ü R (tpw ^ £, li L © * 40 ...... .......

106 and limited opening 108 with high velocity gaseous material flowing in are further reduced to finer droplets. The nebulized; heavy oil of the desired droplet size corresponding to the particle size of the fluidized catalyst as indicated above and is formed outside the riser reactor, passes at high speed through the cylinder portion of the nozzle system and is fed therethrough through grooved opening 96. A single groove opening can be used to form a fan-shaped pattern of atomized oil droplets in the riser. For example, there may also be two grooves arranged at an angle of 90 degrees to each other. It is preferred that two or more such nozzle systems are equally spaced horizontally along the riser. For example, there may be 3, 4 or more such nozzle systems. It is also possible to vertically arrange two or more of the discussed nozzle arrangements in a limited vertical part of the riser reactor above the transition part, so that a part with very turbulent intensive contact between the highly atomized oil and the upwardly flowing catalyst particles. at the desired high temperature which is at least equal to the pseudo-critical temperature of the oil is obtained.

It is also possible to arrange the arrangement of oil supply nozzles as discussed in an upper portion of the riser reactor wall no more than about 3 m below the riser outlet so that the product vapor from the thermal and catalytic cracking upon exit from the top of the riser can be quickly separated from the catalyst.

Now that the many implementation concepts which contribute to the new combined method according to the invention for improving the quality of heavy oil such as residual oil, reduced crude oil, drained crude oil and the like have been discussed and special examples have been described in connection therewith. it is understood that no restrictions should be imposed therefrom, except as indicated in the following claims.

i 85.2 02 3 8

Claims (31)

1. Process for converting residual oil with flutdized catalyst eggs, which process comprises: | (A) passing an upflowing slurry of fluidized catalyst particles at elevated temperature through a reactor zone in a riser; (b) atomizing a convertible residual oil feed to a droplet size corresponding to the particle size of the catalyst particles in the upflowing slurry; (c) supplying the atomized residual oil at a velocity of more than 90 m / s contacting the upflowing slurry of catalyst eggs; (d) maintaining the contact temperature between the catalyst particles and the atomized residual oil feed slurry at a sufficient level to provide up to 50% thermal conversion of the atomized supplied oil and catalytic conversion thereof in an order of magnitude greater than that with a less atomized supplied oil is available to obtain; and | (E) separating the suspended vaporous products from; step (d) of the catalyst eggs in a time frame of less than 2 seconds. j 1 1 'C O N C L' Ü $ I Ë S i The method of claim 1, wherein the feed rate of the atomized oil is within the range of 90 to 400 m / s. The method of claim 1, wherein the feed rate of the atomized oil is about 150 m / s. The method of claim 1, wherein the mixing speed at the contact between atomized oil and upflowing catalyst slurry limits the pressure drop in the riser beyond the contact point to no more than about 0.2 kg / cm 2. The method of claim 1, wherein the pressure drop 3 m beyond the nebulizing oil feed point is no more than 0.07 kg / cm 2. A method according to claim 1, wherein the atomized residual oil contains 35%. a droplet size corresponding to a catalyst particle size: selected from the range of 20 to 150 µm as the average particle size is introduced into the riser conversion zones as a number of discrete fan-shaped droplet dispersions coming into intensive contact with upflowing fluidized catalyst-40 particles at a temperature sufficiently above the pseudo-critical temperature of the oil supply to thermally crack asphalten toes. i I The method of claim 1, wherein the average particle size of the catalyst is selected from. the range from 60 to 120 µm and the droplet size of the atomized oil is equal to or less than 120 µm. The method of claim 1, wherein the supply oil is atomized in at least two consecutive steps outside the riser cracking region and the atomized droplets are then passed through a limited elongated enclosed zone communicating with a groove supply opening in the end of those zones, which opening is generally horizontal in the cross-section of the riser to be fed therein. 9. A method according to claim 8, wherein the atomized oil is supplied at high speed in a fan-shaped droplet pattern which generally slopes upwards in the riser. The method of claim 1, wherein thermal and catalytic conversion of the atomized residual oil occurs over a period of time within the range of 0.5 to 1.5 seconds. The method of claim 1, wherein from the suspension into the! riser, separated catalyst, hydrocarbonaceous deposits which are carried out in two successive stages of catalyst regeneration! removed, the first stage being sufficiently in temperature; limited to produce a carbon monoxide-rich flue gas and minimize hydrothermal degradation by steam generated and the second stage of catalyst regeneration has a temperature sufficiently above that of the first stage to produce carbon dioxide-rich flue gases in the presence of a sufficient excess of acid - i! dust-containing gas to almost completely remove carbon on the catalyst in an atmosphere of unlimited temperature so that catalyst particles are produced at a temperature equal to or | is higher than the pseudo-critical temperature of the residual oil supply. 12. Process according to claim 11, wherein the regeneration operation of the catalyst takes place in a stacked arrangement next to the riser arrangement and the riser in a higher part thereof has a larger diameter than in a lower part. above the entrance for the atomized oil. The process according to claim 1, wherein the atomized residual oil is contacted with catalyst particles having a surface area of 40 in the range of from 40 to 100 m 2 / g under conditions which are sufficient to convert them thereto. according to the top curve of fig. 5. The method of claim 1, wherein the atomization of the residual oil into small drops and the temperature of a slurry formed with hot catalyst particles are sufficient to thermally split above 570 ° C boiling and asphalt and asphaltenes oil components into mono- , di- and tri-cyclic aromatic compounds which can be upgraded by hydrogenation and / or hydrocracking. : 10 The method of claim 1, wherein the residual oil is atomized to a drop size of 100 µm or less and the high temperature evaporation is such that it is completed within a second. 16. The method of claim 1, wherein thermal and catalytic conversion of the highly atomized residual oil with suspended hot catalyst is complete within a second and the temperature of the vaporous product slurry formed is reduced to the range of about 500 ° C to about 565 ° C. A process according to claim 1, wherein the conversion temperature is increased as the asphalt content of the feed oil increases and the catalyst regeneration takes place at a temperature which satisfies the pseudo-critical conversion temperature of the residual oil. 18. A process for converting a residual portion of crude oil with high temperature fluidized catalyst particles which process comprises: (a) flowing a suspension of high temperature fluidized catalyst particles through a conversion zone in a riser; (B) atomizing a convertible residual oil feed to a droplet size corresponding to or smaller than the hot slurried catalyst particles in the range of 20 to 200 µm; (c) supplying the atomized residual oil of step (b) at a speed in the range of 90 to 400 m / s and contacting it with the upflowing slurry of hot catalyst particles initially at a temperature at least equal to the pseudo-critical temperature of the residual oil; (d) providing an initially sufficiently high temperature of the contact between the catalyst particles and the atomized residual oil 8 5 2 0 2 3 8% * to reduce the asphalt components in the residual oil and up to 50% thermal conversion of the atomized obtaining oil and causing catalytic conversion of oil vapors formed in the upflowing slurry to lower the temperature of the slurry 5, and (e) separating vaporous hydrocarbonaceous conversion products of step (d) from catalyst particles after rising tube area has been completed in less than about 2 seconds. : 10 The method of claim 18, wherein the feed rate of the residual oil into the catalyst slurry is about 150 m / s. The method of claim 18, wherein the rate of contact between the supplied atomized oil and the catalyst slurry limits the pressure drop in the riser to no more than 0.2 kg / cm 2. The method of claim 18, wherein the pressure drop at about 3. beyond the inlet point of the atomized oil is no more than about 0.07 kg / cm 2. 22. The process of claim 18, wherein the residual oil is introduced into the riser conversion zone in the form of a plurality of separate fan-shaped droplet dispersions over the riser zone i for intensive contact with upflowing fluidized catalyst particles at a temperature sufficiently above the pseudo The critical temperature of the supplied oil is that asphaltenes in the oil are thermally cracked. The process of claim 18, wherein the average particle size of the catalyst is within the range of 20 to 120 µm and the residual oil is atomized into droplets of 100 µm or less in diameter. 24. A method according to claim 18, wherein atomization of the supplied oil takes place outside the crack zone of the riser and the atomized oil droplets formed then through an elongated enclosed zone connecting to a narrow elongated cross-sectional opening at the end thereof which is horizontally in the cross section of the riser is located. The method of claim 24, wherein the atomized oil is supplied from the elongated orifice at a speed above 90 m / s in a horizontal fan-shaped droplet pattern generally tilted upwardly in the riser. 26. The process of claim 18 wherein thermal and catalytic conversion of the nebulized residual oil with the suspended catalyst 8520238 * V / κ * '45 ..... riser fully occurs within a time frame within the range from 0.5 to 1.5 seconds. 27. The process of claim 18 wherein the catalyst separated from the hydrocarbon products comprising hydrocarbonaceous deposits is passed through two successive catalyst regeneration steps j, the first stage being limited in combustion temperature to form a carbon monoxide-rich flue gas. wherein hydrothermal degradation of the catalyst in the presence of steam generated is minimized and combustion of the second catalyst regeneration step 10 is promoted sufficiently to form high temperature carbon dioxide-rich flue gases comprising oxygen with carbon almost completely removed on the catalyst to form catalyst particles with a temperature at least equal to the | pseudo-critical temperature of the residual oil supply. , 15 ; The method of claim 18, wherein the catalyst particles 1 have an area within the range of 40 to 100 m 2 / g and the temperature conditions are sufficient to obtain an oil feed conversion corresponding to the top curve of Fig. 5. 29. The method of claim 18, wherein the atomization of the residual oil to small droplets of less than 100 µm and the temperature of the suspension of atomized oil and catalyst are sufficient to obtain a split of above 570 ° in one part. C-boiling constituents comprising asphalt and asphaltenes to form mono-, di- and tri-cyclic aromatic components in the hydrocarbon product. j 1 I The process of claim 18, wherein thermal and catalytic reaction of the highly atomized residual oil with the catalyst slurry lowers the temperature of the vapor and catalyst slurry formed in the riser to within the range of about 500 ° C to about 565 ° C. The method of claim 18, wherein the conversion temperature is increased as the asphalt content of the residual oil is higher and regeneration of the catalyst is completed at a temperature satisfying the pseudo-critical conversion temperature of the residual oil with the higher asphalt content. p * 5 9 n 9 t 0