DE2248826A1 - CATALYTIC HIGH TEMPERATURE CRACKING WITH CRYSTALLINE ZEOLITE CATALYSTS WITH LOW COCK FORMATION - Google Patents

Description

Catalytic high temperature cracking with crystalline zeolite catalysts of low coke formation

The invention "relates to catalytic cracking of hydrocarbon oils using finely-divided ones Catalyst particles suspended in the gaseous hydrocarbon material serving as the reaction material. In particular, "the invention relates to catalytic cracking of selected hydrocarbon oils or fractions thereof with suspended catalyst particles of high activity and selectivity under selected conditions for the production of gasoline and to improve the thermal equilibrium of the company. In particular, the invention relates to a method for grazing, which is intended to achieve maximum utilization of a low coke type crystalline zeolite cracking catalyst in ascending reactors of lower

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To give contact time at elevated cracking temperatures.

The role of catalytic cracking in fluidized bed and moving bed systems is current Level well known in the art. Catalytic cracking operations have been used until recent years forced a silica-alumina cracking catalyst which, according to today's standard values, is considerably less active and, in particular, considerably less selective for performing catalytic cracking the hydrocarbon feed to form the gasoline product is. This created considerable difficulties in the previous systems in achieving high yields of the conversion products without excessive formation of carbon-containing impurities.

The current evolution of the catalytic cracking operations deals with such systems, which more active and more selective cracking catalysts, for example use those containing crystalline zeolites to carry out the conversion. The cracking technology with crystalline Zeolites therefore necessarily requires far more sophisticated cracking systems than they have been in the prior art Technique known or developed to take full advantage of the conversion properties of the catalyst. Numerous previous systems and those in favor of using highly active crystalline zeolite cracking catalysts were converted, resulted in an ineffective operation and caused an unfavorable catalyst regeneration, excessive circulation unconverted feed and generally ineffective utilization of the catalyst composition or catalyst mass .

The present invention is concerned with an improved order of the conversion steps in which more effective the properties of a crystalline zeolite

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crack catalyst of high activity and high selectivity can be used.

According to the invention, there is the conversion process of hydrocarbons in products from the gasoline boiling range in that

(a) a first hydrocarbon feed with finely divided, regenerated catalyst particles. under education a suspension with a temperature of at least

5 ^ 0 ° C is combined,

(b) this suspension through an elongated confined first conversion zone under such rate conditions that a hydrocarbon residence time in the range
from 1 to 12 seconds result, is guided, *

(c) the suspension after passing through the conversion zone for the recovery of the vaporous hydrocarbon material, separated from the finely divided catalyst particles is separated from a relatively high temperature,

(d) the separated, finely divided catalyst particles with freshly regenerated catalyst particles of high temperature and a second, more temperature resistant hydrocarbon feed than the first hydrocarbon feed to form a second suspension
to be united

(e) the second suspension through a second at an elevated temperature of at least about 510 ° C (950 ° F)
elongated conversion zone is conducted under speed conditions such that a hydrocarbon residence time in the range of 2 to 15 seconds results,

(f) the second suspension after passing through the second conversion zone into a hydrocarbon vapor phase and a catalyst phase of reduced activity
is separated,

(g) the separated catalyst phase from reduced

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Activity is stripped off and

(h) "ihdestetiB part regenerated abge st mature part catalyst at Ainet x 3) eap © temperature in the range of 540 ° C to 760 ° C (iÖOQ ^ö £ to 1400 ° F) ffiit by combustion of the carbonaceous material to an oxygen-containing Eegeneriergas of will »'■

The method according to the invention .tAttsft <ü «-fei * advantages:

(a) A highly selective crystalline catalyst with low coke formation can wtlt be exploited.

(b) The hydrocarbon feedstock and With regard to the previous systems "when using the same catalyst used to be reduced by lower coke formation *

(c) A more efficient cracking of the Kohlfenwafeseretoff fractions of low molecular weight and liohereta Molecular weight can be reached *

(d) The treatment of the feed fractions of high molecular weight and / or heavy can in an ascending reactor of kürtet at higher or lower and a higher ratio of catalyst £ U oil er are sufficient than they are in the treatment of compounds of lower molecular weight iiii ti »» th ascending »reactor can be applied»

(e) The highly active catalyst of low Koksbilöuhg can be more selective for converting hydrocarbon feedstocks at temperatures in the range from 480 to 650 ° C (900 to 1200 ° F) when using a Catalyst Cl residence time less than 15 seconds and with a ratio of catalyst ευ oil up to

to 25! 1 set?: T will »

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(f) The conversion selectivity of the catalyst can in the treatment sequence through the use of a diluting, gaseous material for atomization and / or Evaporation of the hydrocarbon feed either partially or completely, leaving relatively fine droplets in intimate contact with the suspended catalyst fines', and to achieve the desired Reduction of the hydrocarbon partial pressure, so that the catalytic conversion of the same in the system is brought to an optimum, increased

(g) The one to the regenerator from at least the second Catalyst returned to the ascending reactor is more suitable, by the greater part of the endothermic heat of reaction requirements of the double ascent conversion system to deliver.

In the method according to the invention, the contact time varies between catalyst and hydrocarbon according to the hydrocarbon feed fed to the selective cracking operation. In general is the cracking procedure effected in a reaction zone with a dispersed catalyst phase on orders of magnitude Amount from just a few seconds to around 15 seconds limited and in most cases the contact time is limited depending on the composition of the hydrocarbon feed for a period of time ranging from 4 x to Limited to 12 seconds. On the basis of the invention, there is thus a sequence of a catalyst cascade, which the use of crack temperatures in the range from 480 to 6 ^ 0 ° C with a number of different ratios from catalyst to oil and different contact times, as specified here in detail, allowed.

The treatment principle according to the invention requires a limited contact time ζfor a suspension

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a highly active catalyst and the hydrocarbon feed before the suspension is discharged into a suitable separating device. A separating device particularly suitable for this purpose consists of one or more Cyclone separators at the outlet end of the transfer line reactors, which is used to separate the catalyst particles and the hydrocarbon material without substantial cooling after discharge from the transmission line cracking zone. Through the application of a few small cyclones in series, the separation time is reduced, even if such small cyclones are of limitation subject to some mixing of oil and catalyst.

If the cracking operation with dispersed catalyst phase at high temperature conditions in the range of 480 to 650 ° C and a short contact time of less than 15 seconds, as stated here, results a way of working with a low catalyst load, which is economically attractive and which allows the formation of a favors superior quality of the product in improved quantity. .

TJm obtained from the method described here Increasing product quality through product distribution or selectivity becomes a relatively high-boiling feed virgin hydrocarbon material to a first ascending reactor with freshly regenerated catalyst for a limited dwell time resulted in it. A hydrocarbon material with relatively high coke formation, for example coker gas oil and recycle hydrocarbons from the cracking operation are fed to a second ascending reactor in contact with a catalyst mixture which is made of the catalyst used in the first reactor and periodically regenerated catalyst. A diluent flow

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'2248I2S

medium how wet ode3? Dry cycle gas or water vapor can be used in one or both reactors to reduce the hydrocarbon partial pressure 2; U and / or to control the contact time by increasing the overall velocity of the vapors and the coke particles in the reactor of the hydrocarbon feed in relatively fine droplets which will self-distribute more uniformly in intimate contact with the fine catalyst particles. Gaseous diluents which can be used in the treatment combination according to the invention with varying degrees of success further include light, gaseous hydrocarbons, which are known as dry gas (C-, and lighter hydrocarbons) or wet gaseous hydrocarbon _{streams such as those containing G y +} and (^ -hydrocarbons.

Flexibility of operation to obtain the desired values of the "conversions on a pre-pass basis" may be obtained can be achieved by using one or more a suitably spaced hydrocarbon coating * - Kung inlet nozzles along the length of the ascending Reactor in which fresh or virgin feed material is treated. In this embodiment a preheated dilution material with the hot, freshly regenerated catalyst is formed combined in a suitable suspension at high temperature, which is brought to flow through the ascending or restricted reaction zone to the point of the inlet of the hydrocarbon feed to be converted "The con- ' Hydrogen feed is mixed with the flowing high temperature suspension and "during the run." through the remaining part of the Reaktlöiiszone up to Suspension separator, for example one or more

Cyclone separators. It is important » (less suspension practically immediately after bucket Ts, t © M.st» te »dwell time is separated so that a is avoided Reduction and hindered settling is avoided, as these separation processes involve a .iotte after cracking in a more dilute one. While it is true that the suspension of the suspension may have a certain effect, such processes are particularly -too. avoid. Therefore it will

that the ßucj> ension in the ascending zone in a ho cia towards aaas Cyclone separation device is applied so that it is separated Catalyst with a relatively high heat content

application specified here can be recovered

In one embodiment of the invention lysator coming from the ascending reactor, in which fresh or virgin feed is treated, has been separated,

which of relatively high temperature, which ^ AQ ¹⁵ C.

(1000 ° F) is subject to a limited gear without significantly reducing the temperature of the catalytic converter. The catalyst that a small amount of remained! carbonaceous material due to the property ©! » If the catalyst contains low coke formation at the higher temperatures used, it is then mixed with a freshly regenerated catalyst in sufficient quantity to form a catalyst mixture of increased which is sufficient for the conversion of the coke in the second ascending reaction given here. The one increasing through the second. !! reactor

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is conducted under cracking conversion conditions suspension discharged into a suitable separation device, which is arranged so that a rapid separation of the catalyst particles caused by the hydrocarbon vapors. The hydrocarbon vapors of the first and the second Ascending reaction zones are recovered and passed to a suitable extraction device. The one from the Second suspension separated catalyst is stripped and then in one or more regeneration stages, which sufficient to remove the deposited carbonaceous material from the catalyst by separating it regenerated, so that the catalyst is heated to an elevated temperature, which is used to carry out the catalytic Conversion reactions is suitable.

In another embodiment, the separated different rising reactors the catalyst is provided as a dense fluidized bed of catalyst in a vessel or hopper, the _/ gen by a baffle plate which extends upwardly from the vessel base and with catalyst Strömungswe as slots or passages is , so that by adjusting the level of the catalyst bed on each side of the baffle plate, the catalyst is caused to flow through the slots to the catalyst bed with a lower pressure applied. This variation in the basic arrangement of the catalyst flow provides further flexibility in the method of actuating the system.

Another embodiment of the invention is concerned with the collection of the separated catalyst from all of the ascending reactors in a single sealed Fluidized bed of the catalyst wherein the catalyst particles are mixed with a suitable stripping gas and stripped of the hydrocarbon vapors. at

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this special embodiment measures have been taken around the stripped catalyst to one or more To lead stages of regeneration. In addition, facilities for withdrawing the catalyst particles are either from the upper or lower part of this catalyst bed for mixing with fresh, regenerated catalyst and use in the second ascending reactor as described above.

The essential crystalline aluminosilicate cracking catalyst mass of low coke formation can be combined with a metal oxide, which the regeneration of the Catalyst increased by converting CO into COo, which the available heat recovery from the system is improved by the catalyst. The cracking catalyst mass can also of low coke formation with a catalyst of the ZSM-5 type, which also has properties of the low Has coke formation, either as a homogeneous mixture of particles or as separate and discrete particles in the system combined so that the amount of one material introduced into the system differs from that introduced into the system Amount of other material may be different. In a special embodiment, the composition comes a metal oxide such as chromium oxide with ZSM-5 type catalyst particles as such a mass is likely contain less coke than the crystalline aluminosilicate catalyst particles of low coke formation, and the use of this composition in combination with the crystalline aluminosilicate of lower Coke formation into consideration. Under the cracking temperature conditions used, especially in the ascending reactor with fresh feed, the during the Cracking stage formed olefinic constituents with the formation of aromatics, in particular by the catalyst from

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2241826

ZSH-5 type cyclized. The ZSM-5 type catalyst. can with the zeolite catalyst of low coke formation in amounts ranging from about 10 to about 90% _r usually in the range of about 40 to about 80% are pooled. The zeolite ZSK-5 is described in British Patent 1,161,974.

The catalyst regeneration processes which can be used according to the invention are those which enable the hydrogen-hydrocarbon material or the carbon residue material to be removed from the catalyst particles, for example by incineration in the presence of an oxygen-containing gas or air, the catalyst to an elevated temperature in the. In the range of about 590 to about 760 ° C (1100 to 1400 ° J ¹ ). It is important to the operation of the invention that the catalyst be stable at the elevated temperatures indicated above in order to provide the greater proportion of the heat required in the catalytic cracking or conversion steps discussed above. Catalyst generation temperatures above 650 ° C and up to 760 ° C (1200 to 1400 ° F) are therefore contemplated. The catalyst regeneration processes to be considered for use with the cracking stage according to the invention comprise ascending or transfer line regeneration zones either alone or in combination with regeneration processes in a dense fluidized bed catalyst bed through which the catalyst is suspended as a suspension in oxygen-containing regeneration gases under conditions that a maximum retention of the generating. Heat in the catalytic converter is guaranteed to move. One·. Combination of generation zones with dispersed catalyst phase alone or in combination with a working method in a dense fluidized bed - catalyst bed can

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ORIOtHAL.

be applied, being in the arrangement catalyst and move regeneration gases so that the desired removal of the carbonaceous deposit is achieved. An order of ascending order is considered to apply dispersed catalyst phase operations through which the catalyst is sequentially as a suspension in the Rsgeneriergas under regeneration temperature conditions moved, the amount of regeneration gas, for example air, fed to each reactor is controlled or limited in such a way that the temperatures occurring during the regeneration of the catalyst be limited. The regeneration temperatures can also be converted into carbon monoxide by combining a metal oxide with the catalyst as mentioned above and by increasing the amount of coke or coal-containing material deposited on the catalyst during the cracking stage before it is passed to the regeneration stage is increased v / ground. Since air is a common regeneration gas, the variation in the amount of carbon-containing gas is important Material on the catalyst leading to the regenerator is most effective for temperature control. at In a further embodiment, one or more ascending regenerators can be used in conjunction with eiiMwr Regen «- with a denser bed of catalyst, how it got through a dense fluidized bed catalyst bed is formed, or by countercurrent flow of the catalyst downwards the regeneration zone and countercurrent of the upward flowing Regeneration gas can be applied. With these arrangements hits the denser catalyst suspension when it meets Moved downwards through the system, a steadily increasing concentration of the oxygen-rich regeneration gas. In these systems and arrangements the control tone is used it is preferred, also for economic reasons, that the

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set equipment is of such a size that the Catalyst use of the system is kept to a minimum, with the formation of a technically attractive Operational arrangement tolerates.

It follows from the above discussions that a considerably greater utilization of the available heat is achieved in the cracking procedure described and that more than such a combination of ascending Reactors with a conventional catalyst regeneration system can be used. The arrangement described here is particularly attractive for treating the same or a combination of hydrocarbon feedstocks, d. H. heavy gas oil, light gas oil, recycled oil, straight run gasoline or naphtha, and any combination applies on their own reaction parameters and maintains them, for example temperature, space velocity, reaction time and catalyst / oil ratio. The arrangement is also for multiple pass hydrocarbon feed to be converted attractive to increase gasoline product yields.

In the cracking operation described herein, temperatures are preferably on a high order in the range of about 540 up to about 700 or 760 ° C. However, it is contemplated that a lower temperature may be used in some specific applications under certain circumstances. In general, the temperature will not be below 480 ° C (900 ° I ¹ ). Working pressures can range from about atmospheric pressure to a few atmospheres depending on the system used. Generally, the pressure will be chosen within a range of from about 1.05 to about 1.5 or 5> 2 atmospheres (15 psig, to 50 or ^^ psig). The operating room velocities are relatively high and are chosen so that contact

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times of catalyst with oil in the virgin feed cracking stage in the range from about 1 second to about 12 seconds, and usually in the range from 4 to 8 seconds result. The contact times used in the recycle cracking stage are in the range of about 2 to 15 seconds and can be a few seconds longer than used in the Virgin feed cracking stage. on the other hand is that applied in & r's conversion of virgin loading Ratio of catalyst to oil in the range from about 4 to about 10: 1 and in the range from about 6 to 25: in the conversion of recycle and coke feed material.

The zeolites used in the low coke catalysts are those with pore sizes in the range from 6 to 15 α units, preferably the X zeolite or Zeolite Y- The zeolites, of the type ZSM-5 »those in combination can be used with the relatively large-pored zeolites in the new cracking process according to the invention, should have a relatively medium pore size. The catalysts used in the new process according to the invention of the ZSM-5 type are thus likely to allow entry of normal aliphatic compounds and slightly branched aliphatic compounds, especially monomethyl-substituted ones Connections in their inner pore structure allow, however, all connections that at least contain a quaternary carbon atom or a molecular measurement equal to or significantly larger than one have a quaternary carbon atom, exclude. Farther aromatic compounds can have side chains similar to the normal aliphatic compounds mentioned above indicated slightly branched aliphatic compounds have side chains, which are in the inner pore structure of the present catalysts occur. A Complete Discussion of the Pore Properties of Zeolite

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ZSM-5 is given in Belgian patent 765,682. Process for the production "of catalytic masses ZSM-5 "act with rare earth exchanged zeolite" Y. Are in Dutch patent publication 71-137 ^ 0. The term "ZSM-5" also refers to the zeolite ZSM-8, which is included in the Dutch patent publication 70-14807 described later.

In a special embodiment, the new catalyst compositions according to the invention consist of a physical mixture of at least two different cracking components, one of which consists of an aluminosilicate with a pore size greater than about 72 units. In a Ausführuiigsform a Geniisch the liatalyEatorteilchen is used, each, particles containing only one of two types of zeolites. For example, a mixture of spray-dried particles consisting of crystals of the ZSIl-5> type in a matrix and particles containing paujasite crystals in a matrix can be added as a supplement to the cracking unit. On the other hand, the catalyst components can be pelletized, cast, shaped, spray-dried or otherwise vexformed into pieces of the desired size and shape, such as rods, spheres, pellets and the like.

The .composition of the aluminum silicate with the Inorganic oxide can be obtained by various methods in which the aluminum silicates on a Particle size less than 40 microns, preferably less than 10 microns, and intimately mixed with an inorganic oxide, the latter being im water-containing state, for example in the form of a hydrosol, hydrogel, moist, gelatinous precipitate or is present in the dried state or as a mixture thereof.

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_ 16 -

Thus, the finely divided aluminum silicates can be used directly with a silica-containing gel, which by hydrolysis of a basic solution of an alkali silicate with a Acid such as hydrochloric acid, sulfuric acid, acetic acid and the like., Can be mixed. Mixing the three Components can be effected in any desired manner, for example in a ball mill or other types of Mills. The aluminum silicates can also be in a hydrosol are dispersed, which occurs when an alkali silicate is reacted with an acidic or alkaline coagulating agent was obtained. The hydrosol is then left to settle into a mass to form a hydrogel, which is then dried and broken into pieces of the desired shape or by conventional spray drying processes is dried or through a nozzle into an oil bath or another suspension medium immiscible with water is dispersed so that spherical bead particles of the catalyst are obtained, as in U.S. Patent 2 384-94-6 indicated. That way obtained kiesisäurehaltige aluminum silicate gel is from Washed free soluble salts and then dried and / or, if desired, calcined.

In the same way, the aluminum silicates can be mixed with an aluminum-containing oxide. Such Gels and hydrous oxides are known in the art and can, for example, by adding ammonium hydroxide, Ammonium carbonate and the like to a salt of aluminum such as aluminum chloride, aluminum sulfate, aluminum nitrate and the like, in an amount sufficient to form the aluminum hydroxide, which then is converted into aluminum oxide after drying. The aluminum-containing oxide can be added to the aluminum silicate while the latter is in the form of a hydrosol,

3 0 9 8 1 5/1 1 1 p

Hydrogel or a moist gelatinous precipitate or hydrous oxide or in the dried state is present.

The catalytic, inorganic oxide matrix can also consist of a multiple gel, which consists of a predominant amount of silica together with one or more metals or oxides thereof from groups IB, II, ΊΙΙ, IV, V, VI, VII or VIII of the periodic table. Particular preference is given to multiple gels of silica with metal oxides of groups IIA, III and IVa of the periodic table, in particular those in which the metal oxide consists of a rare earth metal oxide, magnesium oxide, aluminum oxide, zirconium oxide, titanium oxide, beryllium oxide, thoroxide or combinations thereof. The preparation of multiple gels is known and generally comprises either separate precipitation or common precipitation processes, in which a suitable salt of the metal oxide is added to an alkali silicate and an acid or. Base, as necessary, is added to precipitate the corresponding oxide. The silica content of the silica-containing gel matrix under consideration here is generally in the range from 55 to 100% by weight, while the metal oxide content is in the range from 0 to 4-5 % .

The catalyst product can be heated in water vapor or other atmospheres such as air near the temperatures considered for conversion, but can also be heated to operating temperatures initially during use in the conversion process. Generally, the catalyst is dried between about 65 and 315 ° C (150 ° F to 600 ° 1) and then can be in air, water vapor, nitrogen, helium, exhaust gas or other gases not harmful to the catalyst product at temperatures in the range of about , 260 to

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8? 0 ° C (500 to 1600 ° F) for periods in the range of Calcined for 1 to 4-8 hours or more. Of course the aluminum silicate can also be calcined before being incorporated into the inorganic oxide gel. ■ Of course, the aluminum silicate or the aluminum silicates do not need to be incorporated into the matrix an ion exchange, but can in this way also during and / or after the incorporation to be dealt with in the matrix. Preferably the zeolite exchanged metal and calcined and then receives a second exchange with a metal or a Hydrogen precursor.

It has further been found in accordance with the invention that catalysts with improved selectivity and other beneficial properties for gas oil cracking are obtained when the catalyst product is subjected to a mild steaming treatment at elevated temperatures of 825 to 870 ° C (800 to 1600 ° F) and is preferably carried out at temperatures of about 540 to 815 ° C (1000 to 1500 ° F). The treatment can be carried out in an atmosphere of 100 % steam or in an atmosphere of water vapor and air or a gas which is not harmful to the aluminum silicate. The steam treatment obviously results in favorable properties of the aluminum silicate masses and it can be carried out before, after or instead of the calcining treatment.

The particle size of each type of zeolite that forms the catalyst system is not particularly critical, however, should be less than 100 microns and particle sizes within a range of less than 0.1 to 10 microns are preferred. It should also be pointed out that each individual component of the catalyst system does not have to be of the same particle size.

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The specific ratio of one component to the other component in the catalyst system is likewise not particularly critical and can vary within an extremely wide range. However, it was found that for most purposes the weight ratio of aluminum silicate of ^ZSM-5-f IYP to the aluminum silicate of larger pore size, with which it is vermis.cht, within the range of 0.05: 1 "up to 10: 1 and preferably from 1: 3 up to 2: 1, and even more preferably from 1: 2 to 1: 1.

It is preferred that a limited amount of alkali cations be associated with the aluminum silicates since the The presence of alkali metals has a tendency to suppress or limit the catalytic properties shows whose activity as general Hegel assumes with an increased content of alkali catalysts. That's why it will it is preferred that the aluminum silicates not exceed 0.25 equivalents per g-atom of aluminum and preferably not more contain more than 0.15 equivalents of alkali cations per g atom of aluminum.

In terms of using the aluminum silicate of great Metal cations connected to pores are the general order of preference first in cations of trivalent ones Metals to which cations of divalent metals adjoin, while cations of monovalent metals are at least preferred. Of the trivalent metal cations, the most preferred cations are rare ones Earth metals either individually or as a mixture of the rare earth metal cations. ·

Furthermore, it is particularly preferred that at least some proton or proton precursors with the aluminum silicate are connected. It is also preferred that the two aluminum silicates have an atomic ratio of SiIi-

3 0 9 8 1 B / 1 1 1 9

cium to aluminum of at least 1.25 »preferably 1.8 and even cheaper to have at least 2.0.

In the process according to the invention, the cracking catalyst has a particle size such that it can be guided in a vortex flow through the risers, catalyst separators, scrapers, transfer lines and regenerator. The particle size is generally between 10 and 100 microns in diameter, preferably 40 to 80 microns. A particle size of about 60 microns
Diameter is considered optimal.

Low coke crystalline aluminosilicate cracking catalysts of the type with particular benefit can be used within the scope of the invention, will be more specific with reference to the following table and the accompanying table Figures 1 and 2 explained as examples. The table gives the chemical properties of the various Cracking catalysts containing crystalline zeolites with different selectivity properties and in particular Coking properties again.

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CJ ("ar ': Chemical properties of Tabel ^J Al ₀ O 1.84 - shows Zeolite cracking catalysts of the X-Y type. ⁴ T- - Calcined 3 hours Pores ./649 ⁰ C / Mitt Q ~ '" ~ Z "! τ— S ^ ebart ■ crystalline 0.96 shows Incandescent 13-15 air volume ler CD / ^ Chemical analysis, wt.% 2.5 Na ₀ O ZrO ₀ SO ,, loss _t , 2 12-14 Upper cm 5 / s Pack - By CD S ^-1 O ₀ ^ C- C. surfaces density, mes ^ 2.9 area, Q, 93 g / cm3 ser cn 13.8 2.8 m ² / g 0.89 micron _x ; 14.0 , 12 15.4 415 0.67 0.47 77 , 18.0 3 ^ 6 0.05 442 0.79 0.46 C. % ο "Ήξυ 84.4 14.0 2.5 0.04 328 0.58 0.56 co [U /, -X-Jj. 05.0 31.0 0.87 0.12 2.0 <0 486 0.69 Ξ. IC-20? Έ HY ■ 77.4 32.6 1.67 0.05 280 0.66 0.63 79 - * "· 1 υ / '- χνϋΧ 85.5 35.0 1.00 0.09 269 0.58 0.55 70 , ^ _ <2% HEX 66.0 29.3 0.66 0.04 • 270 0.52 • H 12- ": 4% HEX 64.6 36.8 2.30 0.07 0 329 0.55 0.58 - ■ " ΛΤ-F 2ΞΥ (2) 25.7 2.20 0.46 203 0.57 0.65 71 i τ ί ^ 'j HE "" " 66.6 33.0 2.01 0.22 295 0.55 0.61 65 'J ₁ O HEX 60.5 33.2 ■ 1.18 0.04 , 18 14 227 0.64 L. 6.7% Η3Χ 73.5 31.7 2.06 0.11 260 0.68 0.64 Q: 5% KEY 64.0 15.2 0.0 0.05 0.38 4-5% EEY 65.7 45.5 - 0.14 0.46 C. ('- ■ / - —— · - (τ, 67.5 43.8 - 0.07 169 0.72 0.79 51 Γ ) ⁸² 'a 14.0 } By difference on a 100% basis 0.62 ο 10% HEY 26.7 ") The Kristallini did 0.77 561 0.37 0.54 53 H 5% HEY 53Λ 35.9 ) The crystallinity 0.05 ο 0.68 Q b > 1Οτί HEY 84.8 13th 0.09 325 0.92 0.80 Z 20% Y 71, '1 25th 0.68 450 0.58 70 Γ " U - 61.6 0.02 340 Type 0.50 • (ι - 87 0.03 N>
IO (2 75 a material from the X- (3 20% shift to OO a sieve OO

Figure 1 shows a graph of coke on charge versus conversion after thermal Treatment of the specified catalyst compositions.

Figure 2 is an illustration of coke on the charge versus the conversion after steaming the specified catalyst mass.

Fig. 3 shows schematically an arrangement of the process stages, a double ascending operation for the catalytic conversion of the hydrocarbon reactants and interconnecting catalyst transfer means for conveying the catalyst particles to the regenerator and from the regenerator to the ascending conversion operations.

FIG. 4 shows schematically a modified embodiment of FIG. 3> where the double ascending catalyst-Samrael funnel through a vertical baffle plate is separated, the one with catalyst flow passages for the passage of the catalyst in each direction is equipped by the vertical baffle plate.

Fig. 5 shows schematically a further certification of Fig. 3, which is a common fluidized bed of the Catalyst withdrawn from each riser and each catalyst extraction device above the stripping section for supplying the catalyst for the second ascending reactor.

To achieve the in Figs. 1 and. The operating conditions applied to the values plotted in 2 are indicated on the figures. The hydrocarbon feed used to achieve these values was a Hid-Continent Long Cut Gas Oil (WCMCGO). Ec follows from these figures that the; Catalyst "C" specifically indicated by the curve, which is to be regarded as a catalyst with low coconut formation *, brought a further ^{lower cocure rate at any given conversion level (} '' than others

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BATH

Catalyst masses both after steam treatment and after thermal treatment. A close check of the values shows that some of the catalyst masses are far higher coke formers after the thermal treatment. The thermal treated catalyst is said to be a freshly-made catalyst reproduce. The steamed catalyst mass is intended to reproduce a catalytic converter which is in equilibrium and which is in a technical operation. It it can be observed in particular that the catalyst compositions I, H, B and P are practically a straight line on FIG and are examples of catalysts with higher coke formation than those found for catalyst C ■ which is represented by the curve on the figure. The above observation is also made with respect to the one in Pig. 2 plotted values. This results in directly from this information, such as the coke on the charge with the conversion and with different catalyst compositions varies. According to the arrangement of the Pig. 3 is a hydrocarbon feed, for example a virgin batch, fresh batch, or fractions thereof, into the treatment facility passed through line 2 to furnace 4-, wherein the feed is at the desired elevated temperature within the range from etx ^ a 150 to 425 ° C (300 to 800 ° P) or higher. The preheating of the hydrocarbon feed can be carried out in the presence or absence of one suitable diluting, gaseous material, as indicated above, in such amounts that the desired Reduction of the hydrocarbon partial pressure is effected. The diluent used can be steam, dry hydrocarbon gases or a gaseous one Material, which contains (^ + - hydrocarbons and especially C, - + - hydrocarbons. The amount of

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The diluent employed will of course vary with the type and boiling range of the fresh feed used and will be used in a lesser amount if, for example, a low molecular weight hydrocarbon feed as distinguished from a virgin feed having a boiling point of up to about 540 or 650 ° C ( 1000 ° F or 1200 ° P). The preheated feed with the combined diluent is at the desired elevated temperature in line 6 with the freshly regenerated catalyst withdrawn from the regenerator through attached standpipe 8 to form a suspension with a catalyst to oil ratio within the range of 4 (F 900) and united to 10/1, at a temperature of at least about 480 C, preferably at a temperature in the range of ^ AO C up to about 650 ° C (1000 ° F to 1200 ° F). The temperature chosen to achieve the riser conversion will of course depend on the specific product desired on a given hydrocarbon feedstock. For example, a product containing significant amounts of olefins and / or isobutane can be obtained with very little coke formation, especially when high temperatures are used and the crystalline zeolite cracking catalyst of low coke formation, e.g. Catalyst C described above, alone or in combination is used with a ZSM-5 type catalyst. Working conditions are used which generally maximize the yield of a product in the gasoline boiling range. Under certain conditions it may be beneficial to form significant amounts of olefins suitable for use in alkylation reactions to form a gasoline boiling range product, in which case the low coke catalyst C alone in the absence of catalyst particles of the ZSM-5 -Type ver

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is turned. In any case, the suspension formed in the manner described above is caused to move through the ascending vessel 10 at such a speed that there is a dwell time therein within a range of 1 to 12 seconds, preferably limited to a range of 4 to 8 seconds , results. Thus, if a very short residence time in the riser is desired, for example in the range of 1 to 4 seconds, it is possible to use a gaseous diluent material to form a suspension with the freshly regenerated catalyst, this suspension being allowed to flow through the The initial portion of the ascending reactor is brought before the hydrocarbon reactant material is brought into contact therewith in the downstream portion of the reactor. Thus, the riser for the fresh charge can have a plurality of spaced apart hydrocarbon charge inlets 7 ¹ and 7 "along the length to thereby vary the residence time during which the hydrocarbon reactants are in contact with the catalyst suspension in the ascending In any case, the hydrocarbon feed in the riser is converted for a certain residence time before it is separated from the suspended catalyst by the feed into the funnel 14-, wherein the separation is carried out by one or more cyclone separators, which are in the Funnel 14. It is preferred that the separation of the suspension is terminated from the beginning in one or more cyclone separators which are installed inside or outside the catalyst saramel funnel in order to prevent undesired, prolonged cracking Avoid, so the Su Spension in the dilute catalyst phase of a funnel is not sufficient to the invention

30981 5/1119

22Λ8826

to get desired separation. It is also important to the method and principles of the invention that the recovered from the suspension discharged from the riser vessel at its highest temperature separated catalyst so that the available heat of the catalyst is used to the maximum benefit discussed above can be. Quenching of the suspension or the separated catalyst must therefore be avoided.

In the arrangement of FIG. 3, that is from the ascending vessel the suspension discharged from the fresh charge is separated, for example, by the cyclone separator 11, wherein the separated hydrocarbons are fed to a collecting chamber 12 in the upper part of the catalyst funnel 14. The collected hydrocarbon vapors are passed from chamber 12 through line 16 to a suitable fractionator (not shown), which is of the conventional type.

The catalyst separated from the suspension is removed from the cyclone through an outlet 18 into the dense fluidized bed the catalyst particles 20 passed below. A stripping gas, such as water vapor, viird at a increased stripping temperature to the lower part of the catalyst bed 20 is introduced through line 22 so that it flows upward therein without significant cooling thereof and the entrained vaporous hydrocarbons are removed from the hot catalyst particles. Facilities are available to the stripped hydrocarbons and the stripping gas for example by a separate To carry out cyclone separation before the stripped gaseous material is passed into the collection chamber 12. All entrained catalyst fines that are separated in this cyclone separator become your catalyst bed by a suitably attached immersion limb

30981 5/1119

returned. A practically vertical baffle 24 is provided in the funnel and extends upwardly from the bottom thereof to keep the catalyst separate from the riser 10 as a separate bed of catalyst collected in the lower part of the funnel. The upper part of the funnel and the area above the dense phase of the separated catalyst bed can be in open communication with one another. The catalyst recovered as catalyst bed 20, which is at a relatively high temperature which is not significantly below the riser vent plug temperature, also contains a relatively small amount of deposited carbonaceous material thereon and, as a result, has a considerable amount of activity remaining and for further use , as indicated here, available heat. The catalyst in bed 20 is therefore withdrawn from the lower part thereof through standpipe 26. The catalyst withdrawn through the standpipe 26 is mixed with hot, freshly regenerated catalyst withdrawn from the regenerator 50 through the standpipe 28. The amount of freshly regenerated catalyst combined with the partially consumed catalyst varies as a function of the temperature of the partially consumed catalyst and the temperature selected for converting the hydrocarbon feed in the second riser vessel. Thus, the temperature of the catalyst mixture depends on the conversion temperature desired in the second ascending reactor, which is generally above about 480 ° C (900 ° E ¹ ) for the treatment of heavy feedstocks such as recycle hydrocarbons, coker gas oils and / or high feedstocks Molecular weight is either alone or in admixture with one another. In any case, there is the hot catalyst mixture, the partly used catalyst and freshly regenerated catalyst

30981 S / 1 1 1 9

22A8826

contains, at a temperature sufficient to provide a greater proportion of the endothermic heat requirements of the recycle conversion riser. In some cases
the amount of the regenerated catalyst combined with the partially consumed catalyst is sufficient to
a substantial part, if not all of the
Providing endothermic heat loss from the partially spent catalyst and this supplemental heat in combination with the hydrocarbon feed preheat is sufficient to effect the elevated temperature conversion desired in the second riser reactor, referred to herein as the recycle riser reactor. Thus, the second riser reactor contains an agitated suspension of the
Catalyst hydrocarbon feed and a diluent gaseous material having a temperature within the range of about 510 to about 565 ° 0 (950 ° F
to 1050 ° F) and a catalyst / oil ratio in the range
from 6 to 25/1 · The suspension will move through the
second ascending reactor for a certain residence time within the range of 2 to 15 seconds. It is also possible, as discussed above with regard to the riser vessel for the fresh charge, to use a gaseous diluent material to convey the mixed catalyst phase through the initial part of the recycle riser reactor, so that a
Higher molecular weight hydrocarbon feed
may be introduced therein in a downstream part of the riser, for example through inlets 37 's 37 "and 37'" to give contact times of about 2 seconds and higher. Thus, the majority of the
Hydrocarbon feed inlets extending the length
of the recycle ascending vessel are attached at a distance,
achieving very low. Hydrocarbon residence

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times in it. Generally, the residence time is the hydrocarbon / Ka talysator-Sirspensi on in the Eecycle ascending vessel within a range of 2 to 15 seconds selected, with dwell times of 4 seconds or more at higher catalyst to oil ratios are generally preferred. It follows from this that the transformation a light gas oil fraction for a longer period of time when used in the conversion of a heavy gas oil fraction. -

In the specific arrangement of FIG. 3, the eecycle charge is introduced through line 32 to furnace 34- wherein it is at an elevated cracking temperature either in the presence or absence of a diluent gaseous material is heated. The amount of the gaseous diluting material used depends, as above,

Depending on the hydrocarbon feed used and the extent to which it is desired to lower the partial pressure of the hydrocarbon feed to be converted. In any event, the cracking of an Eecycle hydrocarbon feed is increased by relatively low hydrocarbon partial pressures and sufficient amounts of diluent must be used to maximize this effect. The feed, preheated to an elevated temperature and combined with the catalyst mixture in the manner previously described, is then passed through the eecycle riser reactor 36 at a temperature within the range of about 480 to about 650 ° C (900 ° F to 1200 ° F). guided. In the suspension, a conversion of the hydrocarbon feed is achieved during the passage through the ascending reactor before it is discharged into the funnel 14, which the GycloniJepari; toreirichtung contains, or by direct delivery into a cyclone-iieparator 3 &, <^ ^{er a} > n end of the ascending vessel

3 0 9 015/1119

is attached and inside the funnel 14- "is located,

is separated. The suspension in the ascending vessel 36 is according to a specific example in the cyclone separator separated into a hydrocarbon vapor phase and a catalyst particle phase. The hydrocarbon vapors will collected in the chamber 12 and from there to a fractionation device (not shown) out. The separated catalyst is passed through a suitable immersion limb passed into a dense fluidized bed catalyst bed 40 The dense fluidized bed of the catalyst particles 40 is carried through by the entrained hydrocarbon vapors Steam or another suitable wiping medium stripped, which is introduced to the lower part of the bed through line 42. The stripped catalyst that containing the deposited carbonaceous material is removed through a standpipe 44 and used for catalyst regeneration guided.

According to the arrangement according to FIG. 3, the catalytic converter in the standpipe 44 with a regeneration gas, for example air or another suitable oxygen-containing regeneration gas mixture, which is introduced through line 46, combined to form a suspension which then through the ascending regenerator 48 for delivery in the upper dispersed phase of the regeneration vessel 50 out will. This ascending regenerator can also dispense into the upper part or the intermediate part of the cause dense bed of the catalyst in the regenerator. The catalyst in the ascending regenerator 48 receives a partial regeneration herein and is exemplified after separated from the release into the dilute phase, for example by settling, and becomes part of the tight bed of the under the catalytic converter · It is important that all formed in the catalyst phases and the breakdowns available amounts of heat can be obtained. The lying

0 9 815/1119

ORIGINAL INSPECTED

generating gas, such as air, or a gaseous gas supplemented with oxygen Material is introduced into the bottom or lower portion of the catalyst bed 52 through inlet means 56. The gaseous products of the combustion or the »exhaust gases are circulated through one or more catalytic converters. Running separators (not shown) passed in the upper part of the regenerator, in which the entrained catalyst fines be separated from the exhaust gas before the exhaust gases from the top of the regenerator through line 54 removed.

Figures 4 and 5 differ from that above 3 mainly in the arrangement of the catalyst funnel or the design the housing of the cyclone separators at the discharge of each riser and use a cascade-like one Conveying the catalyst particles separated from each ascending vessel effluent to the catalyst particles removed therefrom separate catalyst streams.

In particular, FIG. 4 differs from FIG. 3 in that a vertical baffle plate 24 similar to that shown in Fig. J is attached and a catalyst flow through slots 60. With this arrangement there is a transport of the catalysts between the those discharged from the ascending vessel 10 and that Catalyst bed 20 forming and that of the riser vessel 36 discharged and forming the catalyst bed 40, so that a further control of the ratio of catalyst results in oil, which is particularly desired in the ascending vessel 36 will. For example, in an operation where higher temperatures of the catalyst fed to the regenerator may be desired, a flow of the fresh Charge riser 10 discharged catalyst to flow out of bed 20 through the slots in the vertical Subdivision and unification with the stronger

15/1119

contaminated catalyst in bed 40 from the riser 36 was delivered and then to the regenerator was caused. Of course, the reverse flow of the catalyst can be made through the slots 60 by changing the upper bed level of the catalyst bed 40, which was discharged from the riser vessel 36 on above the upper bed level of the catalyst 20 on the other side of the baffle plate 24, that of the riser 10 was released. This latter catalyst flow is used in cases' ■■■ where a high Ratio of catalyst to oil in the ascending vessel 36 in addition to increasing the amount of carbonaceous material on that possibly fed to the hegeneration zone Catalyst is desired.

According to the arrangement shown in FIG. 4, the is off the catalyst withdrawn from the standpipe 26 is normally combined with the freshly regenerated catalyst and that on this catalyst mixture formed in this way is stored in the ascending vessel 36 in the same way as with regard to FIG. 3 and 4 dealt with, inserted. Furthermore, the catalyst withdrawn through the standpipe 44 is sent to the generator in FIG in the same way as dealt with with regard to Fig. 3 ^ d 4, guided. The variation of the operation of FIG. 4 with respect to that of FIG. 3 lies mainly in the fact that a Catalyst flow between the separated catalyst beds 20 and 40 is achieved in the desired manner.

FIG. 5 further illustrates a further variation of the principle of FIG. 4 in that that of each Raising vesselG deployed catalyst as a common, dense fluidized bed of the catalyst is accumulated, which the lower part of it by a stripping gas stripped within a relatively limited Abctreifo.bschnittes with alternately stacked impact

309815/1119

disks, so that there is intimate contact between the catalyst particles and the stripping medium caused.

In the. Arrangement of the E ¹ Ig. 5, the catalyst is withdrawn through a standpipe 44 for transport to the regenerator in the manner outlined above. In this arrangement, the catalyst vent standpipe 26 extends upwardly in the dense fluidized bed of the catalyst particles to a catalyst vent cone 62 mounted above the relatively confined catalyst stripping section. The stripping steam is introduced to the lower part of the catalyst bed and causes a significant stripping of the catalyst in the upper part of the bed before it enters the vent cone 62. In this arrangement, it is contemplated to add a hydrocarbon material such as recycle oil, slurry oil or other high molecular weight hydrocarbon material for partial transfer at a location practically between the vent cone and an upper portion of the catalyst stripping section. In this embodiment, additional carbonaceous material for heat equalization purposes is deposited on the catalyst prior to its return to the regenerator.

The arrangement of the B ¹ Ig. 5 can be further modified by withdrawing all of the catalyst below the stripping gas inlet, regardless of whether it is returned directly to the reactor, for example via the standpipe 44, or to the riser vessel J6 as a mixture of the catalyst particles with freshly regenerated catalyst. The amount of carbonaceous material deposited on the catalyst can be varied considerably.

In a further embodiment, the funnel 14

309818/1119

. 5 are used i ⁿ a manner similar to an elutriator FIG wherein catalyst particles are of reduced density due to the carbonaceous Abscheidüngen to accumulate in an upper portion of the dense fluidized catalyst bed, while the denser catalyst particles due to the small amount of carbonaceous Deposits are accumulated in a lower part of the dense fluidized bed catalyst bed. Thus, the denser catalyst is withdrawn from the lower part of the catalyst bed for passage to the riser vessel 36 in a mixture with freshly regenerated catalyst and catalyst particles containing a higher amount of carbonaceous material are withdrawn from an upper part of the catalyst bed for return to Am regenerator by for example, a suitable extension of the vent standpipe 44 is attached.

309815/1119

Claims (1)

Claims 1. Process for the conversion of hydrocarbons in products from the gasoline boiling range, characterized in that (a) a first hydrocarbon feed with finely divided regenerated catalyst particles to form a suspension with a temperature of at least 5 ^ 0 ° C (1000 ° P) is united, (b) this suspension through an elongated confined first conversion zone under velocity conditions, which give a hydrocarbon residence time in the range from 1 to 12 seconds, is performed, (c) this suspension after passing through the conversion zone to recover the vaporous hydrocarbon materials separated from the finely-divided catalyst particles is separated from a relatively high temperature, (d) the separated, finely divided catalyst particles with freshly regenerated catalyst particles from high temperature and a second hydrocarbon feed that is more temperature resistant than the first hydrocarbon feed Loading is combined to form a second suspension. (e) the second suspension at an elevated temperature of at least about 510 ° C (950 ° P) through a second elongate one Conversion zone under rate conditions that have a hydrocarbon residence time in the range of 2 to 15 seconds result, is performed, (f) the second suspension after passing through the second conversion zone separated into a hydrocarbon vapor phase and a catalyst phase of reduced activity will, (g) the separated catalyst phase from reduced Activity is stripped off, 309815/1 1 1 9 (h) and at least a portion of the stripped catalyst at a temperature in the range of 5 ^ 0 ° C to 760 ° C (1000 ° F to 1400 ° P) by burning the carbonaceous material with an oxygenated regeneration gas is regenerated. 2. The method according to claim 1, characterized in that the first hydrocarbon feed is a fraction of low molecular weight and a high molecular weight fraction as the second hydrocarbon feed is used. 3- The method according to claim 1 or 2, characterized in that that the first hydrocarbon feed is a Virgen gas oil and the second hydrocarbon feed one or more of the hydrocarbon materials coker gas oil, Recycle oil and residue inks can be used. 4. The method according to claim 1 to 3, characterized in that as finely divided catalyst particles a crystalline zeolite cracking catalyst of low coke formation is used. 5. Method according to claim 1 to 4-, characterized in that that as finely divided catalyst particles a mixture of a crystalline zeolite cracking catalyst of high activity and a ZSM-5 type conversion catalyst is used. 6. The method according to claim 5, characterized in that a catalyst mixture which contains \ * less than 50 % of the conversion catalyst of the ZSM-5 type is used. 7- method according to claim 1 to 6, characterized in that that a sufficient amount of the regenerated catalyst separated from the first conversion zone combined catalyst is used to produce a catalyst mixture with a temperature within the 309815/1119 Range of about 510 to about 595 ° G (950 ° F to 110O ⁰ F). . . 8. The method according to claim 1 to 7> characterized in that in the second conversion zone a larger Catalyst to oil ratio is applied than it is applied in the first conversion sz one. 9. The method according to claim 1 to 8, characterized in that that a gaseous diluent material along with the hydrocarbon feedstocks for each Conversion zone is applied. 10. The method according to claim 1 to 9j, characterized in that that part of the from the first conversion zone separated catalyst is combined with the catalyst separated off from the second conversion zone and then is performed for catalyst regeneration. 11.- The method according to claim 1 to 10, characterized in that part of the from the second conversion zone separated catalyst is returned to this and a further separated part to the catalyst regeneration to be led. 12. The method according to claim 1 to 11, characterized in that the discharged from each conversion zone Catalyst in a common fluidized bed of the catalyst particles is performed and receives a stripping of a stripping gas, with a portion of the stripped catalyst for catalyst regeneration and another part of the stripped catalyst with the freshly regenerated Catalyst is combined and fed to the inlet of the second conversion zone. 15. The method according to claim 1 to 12, characterized in that that of the stripping operation of the second conversion zone recovered contaminated catalyst is regenerated in stages, with at least one stage in one 3 0 9 815/1119 Regeneration operation in a dense fluidized bed consists. 14. The method according to claim 1 to 13, characterized thereby draws that the regeneration of the catalyst in at least one Regenerxerarbeitsgang in dispersed phase at the outlet adjacent to the upper interface of a dense fluidized bed of the catalyst to be regenerated is performed. 15 · The method according to claim 1 to 14, characterized in that a gaseous dilution material for formation a suspension in an initial portion of the second conversion zone, including the second hydrocarbon feed is added in a downstream part thereof. 16. The method according to claim 1 to 15, characterized in that that a gaseous diluent material to form a suspension with the freshly regenerated catalyst particles in an initial part of the first university conversion zone and used to flow upward therethrough and the first hydrocarbon feed downstream of the flowing suspension is added. 17 · The method according to claim 1 to 16, characterized in that that preheating of the first and second hydrocarbon feeds is used so that a portion of the conversion heat requirements in each conversion zone is provided. 18. The method according to claim 1 to 17 »characterized in that that all of the catalyst discharged from the first conversion zone to the second conversion zone to be led. 19 · Process for the production of gasoline, characterized in that this in connection with the Mg. 3 »^ 5 of the drawings is used. 309815/1119