JPH0412754B2 - - Google Patents

Description

Claim 1 A method for catalytically cracking a portion of residual oil having a component boiling above 565°C (1050°C) of heavy oil, in which a portion of this residual oil is catalytically cracked using an ultra-stable Houjasite genus supported in a matrix. A process for catalytic cracking of residual oils, characterized in that contact is carried out at a temperature of at least 510°C (950°C) with a catalyst containing from 10% to 80% by weight of crystalline zeolites to obtain a gasoline boiling range product. . 2. The method of claim 1, wherein a portion of the residual oil contains metal organic compounds that boil above about 552°C (1025°). 3 The catalyst is at least ultrastable crystalline zeolite.
A method according to claim 1, containing 20% by weight. 4 Decomposition of a portion of the residual oil at temperatures between 510 °C and 760 °C during the residence time of the hydrocarbons in contact with the catalyst particles for less than 5 seconds.
9. The method of claim 1, wherein the process is achieved at a temperature within the range of 950°C to 1400°C and a regenerator temperature of at least about 732°C (1350°C). 5. The process of claim 1, wherein the products of the cracking operation include light cycle oil, gasoline boiling range material, and gaseous components readily convertible to gasoline boiling range components. 6. A portion of the residual oil containing metal-organic compounds boiling above 552°C (1025〓) is brought into contact with a catalyst, and the catalyst is deactivated by the precipitated carbonaceous material,
Furthermore, the precipitated carbonaceous substances are at least treated with oxygen.
removed by combustion at a temperature of 732°C (1350°),
2. A process as claimed in claim 1, in which a regenerated catalyst having a residual carbon content of less than 0.25% by weight is obtained and the thus regenerated catalyst is recycled to a cracking process. 7. The method of claim 1, wherein the ultrastable zeolite has a unit cell size of less than about 24.65 Å. 8. Achieving the removal of precipitated carbonaceous substances by at least one operation in a dense fluidized catalyst bed regeneration tower,
The method according to claim 6. 9. Removal of precipitated carbonaceous substances is achieved through multiple sequentially arranged dense fluidized catalyst bed regeneration operations;
The method according to claim 6. 10. The method of claim 6, wherein the removal of precipitated carbonaceous materials is achieved by a combination of a dense liquid catalyst bed regeneration operation and a dispersed catalyst phase regeneration operation. 11 Ultrastable crystalline zeolites have less than 1% by weight of alkali metal ions, a unit cell size of less than 24.65 Å, and a silica to alumina molar ratio within the range of 3.5 to about Contact with the catalyst is accomplished in a confined suspension across the reaction zone at a temperature at least equal to the pseudocritical temperature, obtaining a hydrocarbon residence time of less than 5 seconds, and converting the vaporous hydrocarbon conversion product into a carbon-based Claim 1 wherein the catalyst particles containing precipitates are recovered from the catalyst particles passing through the reaction zone.
The method described in section. 12 Ultra-stable Houjasite zeolites distributed in matrix materials selected from kaolin clay-silicon oxide bond materials, silica-alumina, clays, silica, alumina, high surface area amorphous materials generating active decomposition sites, and mixtures thereof. The method according to claim 1, wherein the method comprises: 13. The catalyst consists of an ultrastable haujasite crystalline zeolite in an amount ranging from 30 to 50% by weight;
The method according to claim 12. 14. The method of claim 12, wherein the ultrastable crystalline zeolite component of the catalyst is produced under conditions to obtain a high surface area material, a silica/alumina ratio of at least 3, and a unit cell size of less than 24.65 Å. . 15. Decomposition of a portion of the crude oil residue was sufficiently enhanced to substantially simultaneously vaporize a portion of the fill residue oil while contacting the hot catalyst particles under atomization conditions in a time period of less than 3 seconds. 13. The method of claim 12, which is achieved at temperature. 16. The process of claim 15, wherein the temperature of the catalyst is at least equal to the pseudocritical temperature of the feed and a portion of the residual oil consists of metal-organic components boiling above 552°C (1025°C). 17 The elevated temperature of the catalyst achieved by combustion of carbonaceous precipitates from residual oil conversion is 732 °C depending on the feed Conradson carbon content.
17. The method of claim 16, wherein the catalyst regeneration temperature is increased within the range of 1350 to 1600 degrees Celsius. 18 The atomized diluted substance is atomized together with a portion of the residual oil consisting of one or more substances selected from steam, light usually gaseous hydrocarbons consisting of _CO2 , _C3 -substances. 16. The method according to claim 15, wherein the method is used using an atomizing nozzle. 19. The method of claim 12, wherein a portion of the residual oil comprises high-boiling Conradson carbon producing materials and metal contaminants. 20 Part of the residual oil was decomposed at approximately 510℃ (950℃).
13. The method of claim 12, wherein the process is carried out at a temperature in the range from 1400 DEG C. to 760 DEG C. and at a feed rate equal to or higher than the hypocritical temperature. 21 A process for catalytically cracking a residual oil consisting of vacuum bottom oil, in which the residual oil is treated with about 30 to 50 ultrastable Houjasite crystalline zeolites dispersed in a matrix material of clay and silica binder to create active cracking sites. % by weight, and the decomposition is carried out in the reaction zone of the riser for about 0.5 to 3 seconds at the pseudocritical temperature of the residual oil;
A method for catalytic cracking of residual oil consisting of vacuum bottom oil, characterized in that a catalytic cracking product containing gasoline and a light cycle oil consisting of two-membered rings is separated from catalyst particles containing carbon-based precipitates. 22. The process of claim 21, wherein the separated catalyst containing carbonaceous precipitates is regenerated in the direction of catalyst flow in a continuous separated catalyst regeneration zone of increasing temperature. 23. The method of claim 22, wherein the residual carbon content on the catalyst is removed to less than 0.25% by weight by continuous catalyst regeneration steps. 24. The method of claim 21, wherein the zeolite has less than 0.5% by weight Na ₂ O and a higher surface area than rare earth-exchanged haujasite crystalline zeolites. 25. The method of claim 1, wherein the ultrastable Houjasite crystalline zeolite contains at least one element selected from the group consisting of Cr, Mo, and W. 26. The method of claim 1, wherein the ultrastable Houjasite crystalline zeolite contains at least one element selected from the group consisting of magnesium and calcium. 27. The method of claim 1, wherein the ultrastable Houjasite crystalline zeolite contains at least one element selected from the group consisting of Group IVA and Group VA metals. BACKGROUND OF THE INVENTION Fluid catalytic cracking has undergone many changes since its inception in the early 1940's. One of the recent process advances in fluid catalytic cracking has stimulated numerous process design improvements.
This was the emergence of the use of zeolite catalysts. However, until recently the feedstock has remained largely unchanged, consisting mostly of atmospheric distillation residues and vacuum gas oil. However, with the industrial economic necessity of processing low-quality crude oil and the need to maintain high gasoline yields at the same time, low-quality feedstock
Being able to convert using the FCCU method is now an extremely important issue. The present invention improves the processing boiling range of crude oil feedstocks, including substantially all of the atmospheric distillation residues, vacuum gas oil residues, or portions thereof, to This can be done in a selective manner as fully discussed below, such that the atomized and vaporized mixture is converted at relatively high temperatures using the ultrastable crystalline zeolite catalyst demonstrated herein. catalytic cracking of crude oil feedstocks. U.S. Pat. No. 4,287,048 demonstrates a particularly ultrastable "Y" type crystalline zeolite and a process for its production as follows. "Stabilized" or ultrastable Y-type zeolites are well known. This Y-type zeolite is described, for example, in US Pat. No. 3,293,192 and US Pat.
McDaniel) and P.K. Maher (PK
Maher) publication “Society of
Chemical Engineering (London) Monograph Molecular Thieves (Society of
Chemical Engineering (London) Monograph
Molecular Sieves), p. 186 (1968), in which case the teaching of these publications is included for reference only. In general:
"Ultrastable" means highly resistant to collapse of crystallinity due to high temperatures and steam treatments and an R ₂ O content of less than 4% by weight, preferably less than 1% by weight (where R is Na , K or all other alkali metal ions) and are characterized by a unit cell size of less than 24.5 Å and a molar ratio of silica to alumina in the range of 3.5 to 7 or more. . The ultrastable form of Y-type zeolite is obtained primarily by substantial reduction of alkali metal ions and reduction of unit cell size. Ultrastable zeolites are evidenced by both small unit cells in the crystal structure and low alkali metal content. As is generally known, the ultra-stable form of Y-type zeolite is made by combining Y-type zeolite with ammonium salts, such as ammonium nitrate, until the alkali metal content of Y-type zeolite is reduced to less than 4% by weight. It can be obtained by sequential base exchange with an aqueous solution of Furthermore, base-exchanged zeolite has a temperature of about 537.8℃ (1000〓) to about 815.6℃
Baked at a temperature of (1500) for several hours,
cooled, then again base exchanged successively with aqueous solutions of ammonium salts until the alkali metal content is reduced to less than 1% by weight, then washed and again between about 537.8°C (1000〓) and about 815.6°C (1500〓). ) to yield ultrastable zeolite Y. The successive ion exchange and heat treatments lead to a substantial reduction in the alkali metal content of the original zeolite and to shrinkage of the unit cells, which leads to the superior stability of the resulting Y-type zeolite. It is certain. The particle size of the zeolite is usually in the range 0.1-10μ, in particular in the range 0.5-3μ. Suitable amounts of ultrastable Y-type zeolite in catalysts according to the invention range from about 10% to about 80% by weight of the total catalyst.
% by weight, preferably from about 30% to about 50%. DISCLOSURE OF THE INVENTION Vapor distillation bottom oil, vacuum gas oil + residue, residual oil, reduced vapor distillation residue oil
crude oils), as well as topped crude oils,
Consisting of rock oil, coal liquefied oil products and tar sands oil products, all of which have a temperature of approximately 537.8°C.
(1000〓) or a catalytic cracking or catalytic conversion heavy oil feed rate having components boiling at a temperature higher than about 565.6°C (1050〓), the selective flow of the composition demonstrated herein is Optimal catalytic conversion of the oil feed into a highly vaporized and atomized catalytic stage using catalyst particles. The heat required to substantially completely vaporize and atomize all of the high boiling oil feed is at least about 732.2°C (about 1350°C), which is completed in the absence of substantial loss of hot water to the catalyst. ), preferably by operating a relatively high regeneration tower temperature above about 760.0°C (about 1400°C). Conventional zeolite cracking catalysts consisting of relatively large amounts of one or more rare earth-exchanged haujasite zeolites are susceptible to significant hydrothermal deactivation under regeneration conditions at temperatures above about 760.0°C (about 1400°C). can be,
and is required to remove relatively large amounts of hydrocarbonaceous materials precipitated during the residual oil cracking operation. Commercial experience with catalytic cracking heavy oil feedstocks and catalytic cracking light oil feedstocks has observed that poor feedstock quality tends to significantly increase the regenerator temperature to high levels. . (For purposes of this discussion, heavy oil feedstock and light oil feed rates are assumed to include high boiling residual oils with high Conradson process carbon content in the feed). Additionally, the regeneration tower temperatures typically used in conventional gas oil cracking, such as the provision of steam coils in the regeneration tower, external contact coolers, and/or other equipment used by some operators. The selectivity of the hydrogen conversion reaction is limited by
Undesirable large amounts of coke and “cycle oil”
It is observed that it is turned to produce a liquid product called . Cycle oils are liquid products consisting of large amounts of fused ring aromatic compounds. Fused ring aromatic compounds are 2-, 3-, 4-, and mostly 6-membered carbocycles. Light cycle oil (LCO)
Cycle oils consisting primarily of two-membered rings, referred to as hydrocarbons, are commercially available as middle distillates. Cycle oils consisting primarily of three-membered rings and a large number of fused rings, such as those found in some heavy cycle oils and especially slurry oils, have low commercial value and are usually marketed only as bunker heavy oils. There is. On the other hand, it has been observed that in commercial catalytic cracking of heavy feedstocks consisting of residual oils, if the tendency of the regenerator temperature to rise to high levels is not restricted, undesirable reactions to the above selectivity do not occur. be done. That is, at high regenerator temperatures and temperatures generally higher than those used commercially for gas oil cracking, higher than about 732.2°C (1350°C), coke production is lower than that observed in conventional gas oil cracking. The production amount is equal to or lower than that, and there are difficulties in producing fused ring aromatic compounds larger than two-membered rings. In the search for suitable catalysts for converting high-boiling residual oils, contrary to many ideas in the prior art, for example Davison Chemical Co.
High surface area crystalline zeolites, such as the ultra-stable crystalline zeolite commercially identified as Z-14US by Chemical Co. Despite the catalytic activity, it is observed that the zeolite conversion catalyst is highly stable and effective at the high regeneration temperatures required in the process. Furthermore, and importantly, pursuing the process concept according to the present invention, the high surface area ultrastable crystalline zeolite contributes to significant reduction in the precipitation of hydrocarbonaceous materials and improves the yield of light cycle oil products. improves the cost of heavy cycle oils and generally improves gasoline composition and gasoline formation at comparable new feed conversion levels than would be achieved using conventional rare earth-exchanged zeolites such as CREY. It is observed that a selectivity of component-enriched products occurs. Furthermore, commercially available highly active zeolitic catalysts consisting of rare earth-exchanged zeolites are observed to suffer from various surface area reductions. This reduction in surface area is believed to be due to hydrothermal instability under conditions of the preferred unit mode of operation. If the surface area is progressively reduced, the product selectivity is also increased, leading to increased production of heavy cycle oils, especially cycle oils with ring structures larger than two-membered rings, H ₂ ,
It is directed to the production of increased gases consisting of C ₁ and C ₂ and in particular to the production of atmospherically distilled gasoline. The external surface, such as that provided by the high surface area ultrastable zeolites, can be readily utilized to carry out the now substantial molecular weight reduction of the high molecular weight components in the slurry oil to the desired low molecular weight components. It has been found to be extremely effective in obtaining active decomposition sites. The hydrothermal stability of the ultrastable crystalline zeolite catalyst obtained as demonstrated and briefly discussed herein is similar to the hydrothermal stability of rare earth-exchanged "Y"-type haujasite, called CREY. and is used to form catalyst particles on a cracked hydrocarbon feed. The ultrastable zeolite-containing catalyst maintains a significantly higher surface area of the equilibrium catalyst at high regeneration temperatures than that obtained with CREY catalysts. A matrix or substrate having a relatively high amorphous surface area that creates active decomposition sites is
It can be used with ultrastable zeolites in place of inert matrix materials in catalytic reactions and contributes to the cracking of high boiling cycle oil components obtained in atmospheric distillation residue oil cracking operations. However, unlike cracking using amorphous cracking catalysts, the ultrastable hydrogen form of the zeolites discussed here can be used to achieve the desired cracking or cracking of high molecular weight hydrocarbon components with substantial reduction in coke and gas production. Perform the conversion. This difference observed in product selectivity when ultrastable crystalline zeolites are used in place of CRAY for atmospheric distillation residue oil cracking is unexpected and in line with previously expected results. I couldn't do it. Therefore, approximately 551.7℃ (1025〓)
Decomposition of high-boiling residual oils consisting of metal-organic components boiling at temperatures higher than that described herein uses an ultrastable form of crystalline zeolite in the catalyst composition resulting in a high surface area particle composition. It is effective in several important ways that have been identified. Therefore, at least two basic operating conditions are required to adequately crack a high boiling range feedstock consisting of a high Conradson carbon resid oil and to obtain the desired product selectivity. It is concluded that: 1. High regeneration temperature means high catalyst temperature at the oil catalyst contact point. 2. A high surface area catalyst that can maintain a much higher surface area than can be obtained with CREY-containing catalysts under conditions of high regeneration temperatures, greater than about 760.0°C (1400°C). Catalyst compositions that have been found to satisfy the above operating conditions and are suitable for specifically converting high-boiling residual oil-containing feedstocks include ultrastable crystalline zeolites such as those described herein. It is a catalyst consisting of This particular crystalline zeolite, sieve or crystalline aluminosilicate is called in industry an ultrastable sieve or crystalline zeolite. Compared to the catalyst state containing rare earth-exchanged zeolite (CREY), the catalyst containing ultrastable sieves has a relatively lower activity but a similar high surface area of the catalyst as measured in the fresh catalyst state. It is. This catalyst is
They are described in various patent specifications briefly cited herein. Catalysts containing ultra-stable zeolites have been discussed in publications for their application in cracking operations starting from conventional desulfurized gas oils, but are characterized by low relative activity and relatively high cost compared to rare earth-containing zeolites. Therefore, it was not accepted industrially. However, when applied to residual oil decomposition work,
It has been found that ultrastable zeolite catalysts obtain and produce significant improvements in cracking selectivity over the state of highly active rare earth-exchanged zeolite-containing catalysts, thereby making them superior catalysts. This is illustrated in the commercial results presented in Table
In this table, the decomposition data represents a comparison of the performance of ultrastable sieve-containing catalysts and rare earth-exchanged zeolite-containing catalysts. The figure is a graph showing the shrinkage of the ultrastable crystalline zeolite obtained during calcination under various temperature conditions. This shrinkage is observed to be substantially less than that obtained when CREY catalyst compositions were exposed to similar conditions. DETAILED DESCRIPTION OF THE INVENTION: One type of zeolite-containing catalyst that is particularly suitable for use in the residual oil conversion process according to the present invention is the ultrastable zeolite-containing catalyst originally identified commercially as Z-14US. Composed of crystalline zeolite. The production of ultrastable crystalline zeolites discussed above is described in U.S. Pat. No. 4,287,048 and U.S. Pat.
3,293,192 (1966) and 3,402,966, which publications are hereby incorporated by reference. The reference materials proven above and the ultrastable sieves or crystalline zeolites described in the US patent specification are characterized by a significant reduction (1-1.5%) in the unit cell size of the starting sodium zeolite. This shrinkage is caused by the extraction of aluminum cations from the crystalline zeolite during the manufacturing process. This is included in Figure 17 and with it on page 320 of the book entitled "Zeolite Chemistry and Catalysis" by McDaniel and Maher. The drawings showed that it was genuine. In this figure, the shading corresponds to the unit cell shrinkage of ultrastable zeolites of various silica to alumina ratios. To be an ultrastable crystalline zeolite component of the catalyst suitable for use in the process of the invention, the zeolite should have a SiO ₂ /Al ₂ O ₃ ratio greater than 3 and a unit cell size or lattice constant of Less than 24.65 Å.
In a detailed embodiment, the ultrastable zeolite is
It will have a SiO ₂ /Al ₂ O ₃ ratio of at least 5 with a unit cell size of about 24.5 Å or less.
High sodium content of zeolites, matrix components and residual oil feeds are known to deactivate the cracking catalyst of the zeolite crystal structure relatively quickly, thus reducing the sodium content of these materials and especially of the finished zeolite. It is important to reduce the sodium content to at least 1% by weight or less. Various techniques for achieving this low sodium content are discussed in publications. Residual Na ₂ O on the zeolite structure is
Preferably it is lower than 0.5% by weight. As stated in the patent specifications cited above and incorporated by reference, other cations include:
It can be loaded into the ultrastable zeolite by ion exchange methods well known in the art. As is known and understood by those skilled in the art, ultrastable zeolites useful in the present invention include all such cationically modified zeolites, such as those from substantially all groups of the Periodic Table except Group IA. Zeolites containing cations by exchange can be included. In particular, certain advantages can be obtained by incorporating specific cations. For example, ion exchange with rare earth elements, ie, those with atomic numbers 57-71, can increase the activity and enhance or increase the stability of ultrastable zeolites. Similarly, incorporating elements from the magnesium and/or chromium group (Cr, Mo and W)
May be useful in accelerating sintering. Magnesium and calcium can be advantageously formulated as _SOx scavengers, metals from groups IVA and VA.
It can be useful for passivating metals such as nickel. In general, ultrastable zeolites useful in the practice of the present invention may include substantially any metal or combination of metals without departing from the spirit of the invention and its applicability to the invention.
For example, it can be modified by replacing it with an exclusion example of a group IA element, such as Na. The level of decomposition activity of ultrastable crystalline zeolites is lower than that of rare earth-exchanged zeolites, such as CREY. Therefore, a significantly more ultrastable zeolite than CREY is required to form catalyst particles of comparable activity. This high loading has heretofore been considered inappropriate for use in low regenerator temperature hydrocarbon conversion operations. Currently, it has been reported that the highly active FCC catalyst is contained in a range of 15 to 40% based on the rare earth Y-type zeolite. For conventional rare earth zeolite catalysts used in FCC units, gas oil processing and generally lower than about 760.0℃ (1400〓), usually about
For operation at regenerator temperatures maintained below or above 732.2°C (1350°C), ultrastable crystalline zeolite catalysts consisting of 60-160% ultrastable zeolite for the same activity level can be used. required to use. Apparently, the catalyst could never contain more than 100% of all components. Such high zeolite content catalyst particles are used by catalyst suppliers and catalyst manufacturers to obtain such catalyst compositions with suitable physical friction resistance or hardness properties for use in circulating fluid catalytic cracking systems. raises difficult questions. Approximately 732.2℃ required for high temperature conversion of residual oil
At relatively high regenerator temperatures in the range of (1350〓) to about 871.1°C (1600〓), the ultrastable crystalline zeolite catalyst obtained as described above can be compared to the rare earth Y sieve (CREY)-containing catalyst. found to produce an equilibrium activity equal to or greater than the equilibrium activity;
and results in high equilibrium surface area and liquid product selectivity without producing undesired coke as demonstrated herein. Also, approximately 732.2℃
(1350〓) or higher, characterized by a regenerated catalyst temperature at least equal to the tentative critical temperature of the high-boiling oil feed-catalyst suspension mixture temperature in the oil feed. It has been found that heavy or high boiling polycyclic components can be readily heat exchanged and catalytically exchanged to lower boiling desired products by high surface area ultrastable zeolite catalysts in current catalytic cracking equipment. . Commercial testing of the ultrastable hydrogen-type crystalline zeolite-containing catalyst demonstrated herein yields the data shown in Table 1. Play tower about 760.0
For this work, which operates above ℃ (1400〓),
Ultrastable zeolite-containing catalysts actually outperform CREY catalysts. That is, low coke yields are observed and there is a substantial reduction in heavy cycle oil yield and its gravity. Special light cycle oils and gasoline are available in liquid form at the cost of coke and heavy cycle oils.
Produced together with C ₃ and all factors resulting in significantly increased yields and economic benefits.

【table】

[Table] The reduction in heavy cycle oil products and increase in light cycle oil products obtained as evidenced above is due to the fact that rare earth exchanged crystalline zeolite (CREY)
This was surprisingly unexpected when comparing the results obtained with catalysts containing . Both forms of zeolite catalyst were supported by relatively inert matrix materials. An increase in the equilibrium surface area indicates that substantially zeolite is present in an equilibrium catalyst consisting of a catalyst containing ultrastable hydrogen-type zeolite.

Table: The large surface area of ultrastable zeolites is clearly significantly more effective in obtaining sensitive degradation sites of activity to produce the molecular weight reduction experienced in slurry oils. Unlike cracking using amorphous cracking catalysts, ultrastable hydrogen zeolites are observed to carry out this cracking with little or low coke and gas production. The data provided in the table show that the equilibrium activities of two types of catalysts, ultrastable zeolites and rare earth exchanged zeolites, are approximately
After exposure to a regenerator temperature of 760.0℃ (approximately 1400〓),
It is clearly shown that even though the CREY catalyst starts at 3-4 times the activity of the ultrastable zeolite catalyst, it is exactly the same in terms of activity. It is expected that the benefits obtained by using ultrastable catalysts at ever higher regenerator temperatures will be even greater. The following description follows from the above observations in connection with the fluid catalytic cracking of residual oils using ultrastable crystalline zeolite catalysts. 1 A high catalyst temperature at the oil catalyst contact point relative to a high regenerator temperature is required to more completely vaporize the high boiling residual oil feedstock. 2 Lack of adequate evaporation and atomization of the feed promotes slight cracking selectivity, i.e. high coke production, high cycle oil production, especially in cyclic structures larger than two-membered rings. Rich cycle oil, high gas production and low gasoline production are encouraged. The poor performance attributable to improper evaporation of the feed is believed to be due to "coke blocking" of active catalyst locations by a portion of the feed that does not evaporate. 3 If the residual oil content of the feedstock increases, the high temperature of the catalyst at the oil contact point (relative to high regenerator temperature) can reduce almost all of the feed if undesirable cracking selectivities can be avoided. must be able to rise to a high optimal level to promote effective evaporation. 4 Utilization of catalysts containing rare earth-exchanged zeolites is not compatible with high temperature regeneration despite their inherent relatively high initial activity due to rapid surface area breakdown and rapid loss of activity in high temperature regeneration environments. do not. 5 Catalysts containing ultrastable sieves or crystalline zeolites decompose residual oils at acceptable catalytic activity levels at the desired high temperature conditions despite their relatively low fresh catalytic activity and still provide the desired high surface area. Compatible with commercial degradation methods when retained. This high surface area is balanced by the desired cracking selectivity, i.e., high yields of gasoline and gasoline-forming components, increased cycle oils with two-membered rings produced at the cost of cycle oils with multi-membered rings. yields together with substantially lower coke production and reduced gas production. Ultrastable zeolites can be supported by any one of a variety of number of support materials or matrices. For example, matrices other than inert kaolin-clay silicon oxide binder combinations can be used to house or include the ultrastable hydrogen-exchanged crystalline zeolite. actually,
All known state of the art or conventional catalyst matrix materials can be used. Such materials may include synthetic silica-alumina, clay, silica or alumina binders or combinations thereof. Preferably, the finished catalyst contains more than 20% by weight and less than 80% by weight of ultrastable hydrogen-type crystalline zeolite as demonstrated herein. However, according to the present invention, the ultra-stable crystalline "Y" which is preferably used for cracking high-boiling residual oils
Zeolite-type catalysts can be used in conjunction with metal capture materials or metal suction materials to accumulate metals. Preferably, the finished catalyst contains more than 20% by weight or less than 80% by weight of the ultrastable hydrogen-form crystalline zeolite demonstrated herein. Conradson High-boiling hydrocarbons of catalytic cracking or catalytic conversion processes consisting of carbon-producing materials use catalytic temperature conditions obtained with a thermally regenerated catalyst at least equal to the tentative critical temperature of the feed. This results in the highest catalytic conversion at high evaporation-atomization conditions during contact with the high surface area zeolite-containing catalyst specifically defined herein. The catalyst regeneration temperature therefore limits the residual oil feed rate during the combustion of the precipitated carbonaceous material, even though the ultrastable zeolite catalyst composition used in the conversion process according to the invention contributes to a reduction in coke production. Approximately 732.2℃ (1350〓) when the Conradson method carbon value increases
will increase higher than that. Therefore, when process vacuum gas oil consists of a portion of crude oil residue,
As carbonaceous precipitates increase in relation to feed Conradson carbon content, experience regeneration temperatures as high as about 871.1°C or higher than about 732.2°C (1350°C) or higher. I can do it. The catalytic conversion operation according to the invention is carried out in a riser contacting zone such that the residence time of the hydrocarbons in contact with the catalyst particles can be limited to within the range of 0.5 to 5 seconds, usually within the range of 1 to 3 seconds. Preferably, it is one of relatively short vaporized hydrocarbon contact with a special catalyst composition consisting of 20-80% by weight of ultrastable crystalline zeolite as the dispersed catalyst phase. This dispersed catalyst phase-vaporized hydrocarbon contact can be met with practical measurements by using an atomized diluent material in conjunction with a high boiling hydrocarbon feed. Suitable diluting substances for this purpose are those that reduce the high-boiling feed partial pressure and combine light, conventional gaseous hydrocarbons consisting of steam, CO ₂ , C ₃ -substances or combinations thereof with the hot catalyst particles. The hydrocarbon feed is included in such an amount as to achieve the desired atomization-evaporation dispersion contact. Atomization of the feed can be effected substantially by using suitable atomization nozzles. Therefore, the operating parameters to achieve an optimized contact between the feed and the catalyst particles are: Excess feed flow velocities of about 3.0 m/sec (10 ft/sec) are also included to achieve feed atomization spray with or without the use of diluent material across the cross section. The operating parameters identified above promote relatively homogeneous mixing within the feed evaporation section of the riser reactor in a minimum amount of time and thus preferably provide thermal catalyst particles to the atomized charge feed. It is also directed to improving rapid heat transfer from and preventing localization of the improved catalyst-to-oil ratio that contributes to a dense catalyst bed phase. That is, the operating conditions and practices are selected to ensure relatively dilute phase suspension contact between the catalyst particles and the atomized oil feed for evaporative conversion transfer through the riser conversion zone. be done. Such dilute catalyst phase operations result in catalyst particle concentrations within the range of about 32 to about 160 kg/m ³ (2 to 10 lb/ft ³ ), preferably in excess of about 80 kg/m ³ (about 5 lb/ft ³ ). Include without. The catalytic hydrocarbon feed suspension formed as obtained above exits the riser contacting zone at a sufficiently elevated temperature to maximize the recovery of vaporized hydrocarbon material separately from the catalyst particles. Approximately 5 before draining
Passed through the riser contact zone with a hydrocarbon contact time of less than seconds. In a particularly detailed aspect, the present invention provides materials for producing vacuum gas oils containing high-boiling Conradson process carbon, preferably with hydrocarbon residence times in the range of 0.5 to about 5 seconds, usually not exceeding about 3 seconds. is directed to the catalytic conversion of high-boiling residual oils, characterized by the use of a special ultrastable crystalline zeolite-containing catalyst at a temperature equal to or above the feed pseudocritical temperature in the riser contacting zone. ing. Therefore, if the final boiling point of the hydrocarbon feed or its Conradson carbon content increases, the catalyst regeneration temperature will also generally increase in response to the increased precipitated carbonaceous material removed by combustion, and the The inventive concept will contribute to high temperature regeneration and feed conversion. However, as discussed above, the use of ultrastable zeolite catalysts results in lower coke yields than those obtained with rare earth type zeolite catalysts, and therefore as discussed herein. contributes in some way to the advantages of the method concept according to the invention. Depending on the feed hydrocarbon to be converted, its boiling range and the factors contributing to the Conradson carbon content, a hydrocarbon conversion operation can be performed at approximately 510.0°C (950°C).
〓) to approximately 760.0℃ (approximately 1400〓) or at a temperature equal to or higher than the tentative critical temperature of the feed rate, from approximately atmospheric pressure to approximately 7Kg/cm ² (gauge pressure) (approximately 100 psig) up to but generally about 3.5
This can be done by using a reactor pressure not exceeding Kg/cm ² (gauge pressure) (approximately 50 psig). The riser pipe disassembly work according to the present invention was carried out on July 15, 1980.
It can be used in conjunction with the catalyst regeneration device described in co-pending application No. 169,086, filed in Japan, the contents of which are incorporated herein by reference. It is the apparatus and working concept described in the above application, except that the method of implementation is specifically modified by using an ultrastable crystalline zeolite-containing catalyst as obtained herein. It can be used with significant advantage in protecting the active electrical properties of ultrastable crystalline zeolite catalysts, especially when the residual coke on the ultrastable zeolite catalyst is reduced to less than about 0.25% by weight. can. Having generally described the methods and concepts according to the invention and a detailed discussion of the embodiments supporting them, the invention is thereby unduly limited except as defined by the following claims. It's not a thing.