JPH0649869B2 - Catalytic cracking method for paraffinic raw materials with zeolite beta - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for catalytically cracking heavy oil charging raw materials using a zeolite beta-containing catalyst. The invention particularly relates to a process for catalytic cracking of paraffinic feeds with a catalyst of the type described above.

[Prior Art] A catalytic cracking method for hydrocarbon oils using an acidic cracking catalyst is a well-established method for many years, and the method is a fixed bed cracking apparatus of the food reflow type of the previous year, and Many different types of catalytic cracking equipment have been used, including moving bed equipment such as the Thermophore catalytic cracking (moving bed catalytic cracking) (TCC) equipment and the fluidized bed catalytic cracking (FCC) equipment. Among these devices, fluid catalytic cracking (FCC) devices are now becoming the predominant type of devices for catalytic cracking. In moving gravity bed and moving fluid bed operations, the charge to the unit is contacted with a continuously circulating thermal cracking catalyst to effect the desired cracking reaction, then the cracking products are separated from the catalyst, Regenerates the catalyst by oxidizing the coke that accumulates on it. The oxidative regeneration operation in this process serves the purpose of removing coke that deactivates the catalyst and returning the temperature of the catalyst to the temperature required to maintain the endothermic cracking reaction. The regenerated hot catalyst is then recirculated to the reactor to recontact the catalyst with the charge. Moving floor (T
In CC) operation, the catalyst is usually in the form of solid beads that fall by gravity through the reactor and regenerator, and in FCC operation, the catalyst is usually a flowable powder with a particle size of about 100 microns.

Regardless of the equipment used, the catalyst used for catalytic cracking possesses acid functionality to accelerate the resulting cracking reaction. Initially, acid functionality was provided by amorphous catalysts such as alumina, silica-alumina or various acidic clays. Significant improvements in catalytic cracking processes were provided by the introduction of crystalline zeolite cracking catalysts of the 1960's, and this type of catalyst is now widely used. Zeolites used for catalytic cracking can usually be characterized as open pore zeolites. It is essential that large poly-dry aromatic substances that make up a large fraction of the heavy oil charge feedstock into the catalytic cracking operation have to be introduced into the internal pore structure of the zeolite containing a large amount of acid sites on the zeolite. This is because. The open pore zeolites used in the catalytic cracking operation include mordenite, and synthetic faujasite zeolites X and Y. Among the above-mentioned zeolites, zeolite Y is especially rare earth metal exchanged zeolite Y (RE
Y) or the so-called ultrastable zeolite Y (USY) has now become the zeolite of choice because of its excellent stability against hydrothermal decomposition when used in the form of Y.

[Problems to be Solved by the Invention] Although most of the charging materials for the catalytic cracking equipment contain a large amount of high-boiling aromatic components, some charging materials especially from Southeast Asian or Pacific sources are In particular, it contains a relatively large amount of waxy paraffins which are relatively hard to undergo catalytic cracking in the presence of aromatics. This type of feedstock is usually difficult to process in a conventional catalytic cracking operation regardless of the type of contact used: when a waxy gas oil derived from this type of crude oil is passed through the unit, a gasoline product. Tends to have a relatively low octane number, and difficult-to-treat paraffins tend to be concentrated in the unconverted fraction, which has a very high pour point and is therefore a mixed component in fuel oil. Is not suitable for use as. Furthermore, recycling of the unconverted section is of limited practicality because this section has the intractable nature of paraffins.

Of course, the problems presented by the presence of waxy constituents in petroleum have been known for many years and include waxy matter from various distillate fractions, including middle distillates including lubricating oils, heating oils and jet fuels, and gas oils. Various methods have been developed for removing components. Various hydrodewaxing processes have been developed to remove waxy components, and these processes have low molecular weights that can selectively crack long chain n-paraffins and slightly branched paraffins to be removed by distillation. The above-mentioned paraffins are removed by producing a product. In order to obtain the desired selectivity, the catalyst can usually only admit linear n-paraffins or slightly branched paraffins, but more highly branched substances, naphthenes and aromatics. It is a medium pore size zeolite with pore sizes to exclude. Catalytic hydrodewaxing processes of this kind are described, for example, in US Pat.
3,668,113, 3,894,938, 4,176,050, 4,181,598, 4,222,855, 4,229,282 and 4,247,388. But,
Medium pore zeolites such as ZSM-5, which are very effective as dewaxing catalysts in the hydrotreating processes described above using relatively light feeds, are usually not suitable for use as cracking catalysts. This is because the pores of medium pore zeolites are too small to allow large polycyclic aromatics to enter the internal pore structure of the cracking zeolite. Therefore, medium pore zeolites cannot be used for catalytic cracking, although medium pore zeolites can be mixed with atmospheric pore zeolites to be used as catalytic cracking catalysts to improve the octane number of naphtha cracking products, Thus, even when the medium pore zeolite is mixed with a conventional cracking catalyst, the medium pore zeolite cannot effectively act as a cracking catalyst for the waxy feed. Therefore, problems with handling this type of feedstock remain.

Zeolite Beta is now a very effective cracking catalyst for high paraffinic feedstocks, which increases the yield of potentially alkylateable substances and the pour point of the higher boiling cracking product fraction. (A
It has been found that it is possible to produce gasoline with an improved octane number with a decrease in STM D-97).

[Means for Solving the Problems] Accordingly, the present invention resides in a catalytic cracking method for high paraffinic hydrocarbon oils using a zeolite beta-containing cracking catalyst.

The catalytic cracking method of the present invention is applicable to the catalytic cracking of high paraffinic feeds, ie feeds containing at least 20% by weight paraffins. The process of the present invention can be carried out in any conventional type catalytic cracking unit, usually in a moving gravity bed (TCC) unit or a fluidized bed catalytic cracking (FCC) unit in the absence of added hydrogen. Since FCC operation and TCC operation are well established, both of them are usually heated at about 550 ° C in a reactor under a condition of slightly pressurized pressure under heating.
It is not necessary to elaborate on their individual properties, other than to point out that they are endothermic contact cracking processes operated at temperatures above (1200 ° F). The catalyst is continuously sent from the cracking reactor through a closed loop to a regenerator to oxidatively remove the coke accumulated on the catalyst to restore the activity of the catalyst and supply the heat required for endothermic cracking. . The oxidative regeneration operation can be carried out in a bed of the same type as the reaction bed, so that in the TCC operation the regeneration operation is carried out in a moving gravity bed in which the catalyst particles move downwards countercurrently with the regeneration gas stream. In various FCC operations, the regeneration operation is usually performed in a dense bed or a fluidized bed in which a dense bed and a dilute phase moving bed are used in combination depending on the equipment used. A typical FCC operation is US Special Bureau No. 4,309,279.
No. 4, No. 4,309,280, No. 3,849,291, No. 3,351,54
No. 8, No. 3,271,418, No. 3,140,249, No. 3,140,2
No. 51, No. 3,140,252, No. 3,140,253, No. 2,90
No. 6,703 and 2,902,432 are disclosed:
Regeneration techniques applicable to FCC devices include, for example, US Pat.
No. 898,050, No. 3,893,812 and No. 3,843,330. See the above specification for a detailed description of the above operations.

Generally, the catalytic cracking operation of the present invention will be carried out under conditions comparable to those used in existing operations, paying attention to the capabilities of the cracking equipment, the exact composition of the feedstock, and the desired product type and distribution. it can. As is well known, some feedstocks are less susceptible to catalytic cracking than other feedstocks, requiring the use of higher temperatures,
Changes in product distribution may require other changes, for example by maximizing naphtha production or maximizing distillate production. Other changes in operating conditions are required due to the circulation rate and catalyst replenishment rate that are characteristic of the equipment. The extent to which these changes in operating conditions affect the product distribution obtained in a given device is known for that device.

Charge Material The charge material used in the present invention is a highly paraffinic petroleum product,
That is, a petroleum category containing at least 20% by weight of a waxy component. The waxy component consists of n-paraffins and slightly branched paraffins with a small degree of short chain branching, such as monomethyl paraffins. In some cases, the petroleum fraction contains at least 40 wt% or even at least 60 wt% waxy components, and the ability of the catalysts of the present invention to actually treat highly paraffinic feedstocks is similar to crude wax. Certain refined streams, which are almost all paraffinic, can be efficiently cracked to produce more valuable products. The presence of waxy components, of course, implies that the petroleum fraction actually has an initial boiling point found at paraffinic molecular weights within the waxy range. This is usually because the petroleum segment is above the boiling point of the naphtha boiling range material, for example about 200 ° C (about 390
It means having an initial boiling point of ≧ ° F) or more usually more than about 300 ° C (about 570 ° F). In most cases, the petroleum fraction has an initial boiling point of at least 345 ° C (about 650 ° F). In most cases, the final boiling point will be below 565 ° C (about 1050 ° F), but higher final boiling points may be encountered depending on the distillation equipment used before the cracking equipment, and the final boiling point fraction is substantially It may contain a large amount of heavy fraction that is not top distilled. Therefore, the charging raw material usually used in the present invention is 3
It has a boiling point in the range of 45 to 565 ° C (650 to 1050 ° F), but has another boiling point range, for example, 300 to 5
Charges with a boiling point of 00 ° C may also be encountered. Therefore, the feedstock can usually be characterized as a gas oil, including vacuum distilled gas oil, and other highly paraffinic refinery streams such as crude wax can also be catalytically cracked using the catalyst of the present invention.

The charge usually contains various amounts of aromatic components, usually polycyclic aromatics with alkyl side chains of various lengths which can be removed during the cracking operation. However, the charge can also be highly paraffinic with a very low aromatics content, as in the crude waxes described above.
Naphthenes can also be present in varying amounts, depending on the nature of the feedstock and the treatment of the feedstock prior to the catalytic cracking step. Usually, the feedstock does not contain unusually high amounts of aromatics.

The cracking operation can be improved or the product distribution or product characteristics can be improved by subjecting the charge to various treatments prior to cracking to obtain a charge with improved cracking capabilities. Hydrogenation of the feedstock is an adjunct treatment that is particularly useful for removing heteroatom-containing impurities and saturating aromatics; hydrogenation provides heteroatom contaminants, especially nitrogen. And catalyst poisoning by sulfur is reduced, and SOx from the equipment
Emissions are reduced and the hydrogen content of the feed is increased to a level close to that of the product to improve product distribution and feed crackability.

The composition of two typical waxy light oil feedstocks is shown in the first section below.
The compositions of the two hydrotreated feeds are listed in Tables 3 and 4, and the compositions of the four crude wax feeds are listed in Table 5 and Table 2. These feeds can be used in the process according to the invention either alone or in a mixture with other feeds.

Cracking Catalyst The cracking catalyst used in the present invention contains zeolite beta as an essential cracking component of the catalyst. Zeolite beta is a known zeolite described in U.S. Pat.No. 3,308,069 and U.S. Reissue Pat.No. 28,341, which include zeolite beta,
Methods for preparing zeolite beta and properties of zeolite beta are described.

Zeolite beta can be synthesized at relatively high silica / alumina ratios, eg 100/1 or higher, and it is also possible to achieve higher ratios by heat treatment including steaming and acid extraction. From the lowest silica / alumina ratio at the time of
Highly siliceous forms of zeolites with silica / alumina ratios of up to 1000/1, 30000/1 or higher can be produced. Although these forms of zeolite can be used in the process of the present invention, the actual catalytic cracking requires a catalyst possessing a relatively high acidity, usually contains more acidic materials, and has a silica / alumina ratio of about 15 / -15.
Materials with 0/1 are preferred, about 30/1 to 70/1
Very good results are obtained when using materials with a ratio of. Zeolite beta with this silica / alumina ratio is relatively easy to synthesize, so zeolite beta is used in a form in which the organic cation used in the preparation of zeolite beta is removed by subsequent calcination of the synthesized form. can do. For similar reasons, it is usually not preferred to incorporate large amounts of alkali metal or alkaline earth metal cations into the zeolite as described in US Pat. No. 4,411,770. This is because alkali metal cations or alkaline earth metal cations usually reduce the acidity of the zeolite. However, if a lower acidity is desired, it is possible to use a zeolite in the form of a higher silica / alumina ratio rather than adding alkali metal cations or alkaline earth metal cations to reduce acidity. It is preferred to obtain a low acidity. This is because the higher the silica content of the zeolite, the higher the resistance to hot water decomposition. Acid extraction is the preferred method of dealumination, which may be carried out on its own or in combination with pre-steaming; the dealumination catalyst produced by this method has improved distillate (G / D) selectivity. It was observed to have sex.

The acid functionality of the zeolite at the time the zeolite is used as a fresh catalyst in the operation is usually about 0.1 or greater as determined by the α activity test, with suitable α activities ranging from 1 to 500 or more, More usually within the range of 5-100. A method for measuring α activity is described in US Pat. No. 4,016,218.
Issue and Journal of Catalysis (J. Catalog
lysis) Vol. VI (1966), pp. 278-287. However, remember that the initial α activity is relatively easily reduced in industrial catalytic cracking equipment. This is because the catalyst repeatedly passes through the steam stripping legs to remove the hydrocarbons contained in the catalyst,
Also, in the regeneration operation, a large amount of water vapor is released by the combustion of hydrocarbonaceous coke deposited on zeolite. Under these conditions, aluminum is removed from the zeolite framework structure to reduce the zeolite's inherent acid functionality.

Zeolite beta can be synthesized with other trivalent crystal skeleton atoms other than aluminum and can form, for example, borosilicates, boroaluminosilicates, gallosilicates or galloaluminosilicate structural isotypes. These these isotypes are considered to constitute the zeolite beta form, and the term zeolite beta is used for materials with a certain crystal structure that possess the characteristic X-ray powder analysis pattern of zeolite beta. Zeolites may be partially ion exchanged with certain cations including rare earth metals and metals of Group IB of the Periodic Table to improve hydrothermal stability.

Although zeolite beta can promote the desired cracking reaction by itself, zeolite beta is usually mixed with a matrix or binder to resist the crushing forces and attrition encountered in industrial catalytic cracking equipment. To improve crush resistance and abrasion resistance. Therefore, the zeolites are usually mixed with other base materials such as clay or silica, alumina or silica / alumina or other conventional binders. The binder imparts physical strength to the catalyst particles and also imparts a density of catalyst particles for controlling the fluidity that is compatible with the FCC unit. Usually, the amount of zeolite in the catalyst particles is in the range of 5 to 95% by weight,
Amounts of 0% by weight are preferred.

Although some commonly used binders may themselves have significant catalytic activity, it is usually preferred that the total acid functionality provided by the binder be only a small amount of the total catalytic activity as measured by the alpha test. . This is because the zeolites provide the particular selective cracking properties desired for paraffinic feeds.

Catalytic cracking, which is usually carried out in the absence of added hydrogen, does not require the presence of hydrogenation / dehydrogenation components as is the case for hydrocracking, and the cracking catalysts of the present invention do not require the components described above. Nevertheless, metal components may be present for other purposes, especially to promote the oxidation of carbon monoxide to carbon dioxide in the regenerator. The use of an oxidation co-catalyst to oxidize carbon monoxide to carbon dioxide in such a regenerator is described in U.S. Pat.
No. 8, No. 4,350,614, No. 4,174,272, No. 4,159,2
No. 39, No. 4,093,568, No. 4,072,600, No. 4,541,
921, 4,435,282, 4,341,660 and 4,3
No. 41,623. A typical oxidation co-catalyst is a noble metal, especially platinum, and if an oxidation co-catalyst is usually present, an amount of 1000 ppm by weight or less, preferably 500.
It can be present in an amount of up to ppm by weight, about 100 p
pm is the typical maximum. In certain cases,
Very small amounts of cocatalyst reduced to 0.1 ppm by weight are sufficient, amounts of 0.1 to 100 ppm by weight are not uncommon. The oxidation cocatalyst can be present on the catalyst or as a separate component.

In addition to zeolite beta, other zeolites can be present in the catalyst. When other zeolites such as ZSM-5 are included in the catalyst for the purpose of improving the octane number, for example, U.S. Pat. Nos. 3,769,202, 3,758,403, 3,894,93.
No. 1,3,894,933 and 3,894,934, those zeolites have an amount of less than or equal to the amount of zeolite beta, usually for example 50% by weight of the amount of zeolite beta, typically zeolite beta. Can be used in an amount of from about 10% to about 30% by weight of U.S. Pat. No. 4,309,300, which describes the use of medium pore zeolites in cracking catalysts for the purpose of improving octane number.
No. 279 as described, for example, 0.1 to
It is even possible to use a small amount of zeolite, such as 0.5% by weight.

When the catalyst is used in a moving bed operation, the catalyst is usually about 1 mm
It can be formed into pills, extrudates or oil drop spheres having an equivalent particle diameter of 6 mm, preferably about 2 mm (1/32 to 1/4 inch, preferably about 1/8 inch). When the catalyst is intended for use in a fluid catalytic cracking process, the catalyst is usually 10-300 microns, typically a first
A particle size of 00 microns can generally be used.

Operating conditions As mentioned above, the catalytic cracking operation is an endothermic operation performed under high temperature conditions, and the heat required for the operation is due to the oxidation of carbon (coke) accumulated on the catalyst during the cracking of the catalytic cracking operation cycle. Supplied.
Thus, the overall operation, including the regeneration operation, is operated in a thermal equilibrium mode and the regenerated catalyst acts as a medium for transferring the heat produced in the regenerator to the endothermic cracking operation. As mentioned above, each cracking device has its own specific operating characteristics which determine the exact conditions used for the device. However, operating conditions are usually about warming conditions, typically about 550 ° C. (about 1200 ° F.) or higher, or shibashi, which is characterized by higher temperatures, but about 76 ° C.
We rarely encounter temperatures above 0 ° C (about 1400 ° F). This is because such temperatures tend to result in sintering of the catalyst, which is near metallurgical limits in most equipment. In a riser-type cracking device, the temperatures mentioned above are the temperatures typically performed at the top of the riser. As mentioned above, the pressure is usually just above atmospheric pressure, typically up to about 1000 kPa (absolute) (about 130 psig), more usually up to about 500 kPa (absolute) (about 58 psig). . The catalyst / oil weight ratio is usually in the range of 0.1 to 10, more usually 0.2 to 5.

The conversion, ie the rate of conversion of the feed to lower boiling products, is an important operating parameter, usually at least 50% by weight. Therefore, 345 ° C + (about 650 °
In the light oil of F), at least 50% by weight of the feedstock can be converted to the boiling point range below 345 ° C (about 650 ° F). Usually, the conversion is 50-80% by weight or more,
Up to 90% by weight. However, it may be necessary to limit the conversion rate due to downstream equipment limitations, especially distillation capacity limitations. One feature of the process of the present invention using a highly paraffinic charge and a zeolite beta cracking catalyst is that large amounts of light olefins are produced and these olefins are converted to high octane naphtha in a conventional alkylator. Although the rectification unit connected to the cracking unit may not be large enough to handle large amounts of light olefins, it is a desirable product because it can.

Operational characteristics When using zeolite beta, zeolite beta itself shows that it has a stable cracking catalyst,
It has good hydrothermal stability, especially in the dealuminated form with a high silica / alumina ratio, in connection with which the catalyst circulates through the steam stripping zone and receives steam at high temperatures during regeneration. Has good potential for use in various cracking equipment. Moreover, zeolite beta has a remarkable ability to crack paraffins before aromatics, and n-paraffins are cracked before isoparaffins. In contrast, zeolite Y is selective for naphthenes and aromatics, and as a result, highly paraffinic feedstocks are believed to be less susceptible to cracking in zeolite Y cracking operations. Zeolite beta can successfully convert highly paraffinic feeds to lower boiling products, but when there is a large amount of aromatics and correspondingly low paraffin content,
It is desirable to use a catalyst mixture containing zeolite beta and a Faujacio type zeolite as described in US Pat. No. 775,189. In addition,
The above specification describes a process using a mixed cracking catalyst which is a mixture of zeolite beta and faujasite type zeolite.

By preferentially cracking waxy paraffins in the feed, zeolite beta effectively dewaxes the feed, resulting in an unconverted fraction, eg 345 ° C.
(Approx. 650 ° F) Decrease the pour point of the section. Therefore, the cracking process of the present invention can be used for nonhydrocracked gas oil dewaxing in environmental routes where aromatic products are acceptable. At high conversions, such as typically 60% or 70% by weight, there is a reduction in the pour point of the converted fraction, indicating selectivity for conversion of high molecular weight components.
Zeolite beta has a distillate selectivity comparable to that of dealuminated zeolite Y with the same silica / alumina ratio, but as beta content of the feedstock increases, zeolite beta flows in the unconverted section. It was observed that the removal of waxy paraffin components gradually became more effective as indicated by the dots.

Dewaxing of the unconverted fraction can broaden the final boiling point of the distillate, which is limited by the pour point. For example, due to the dewaxing effect of the catalyst, the light fuel oil (LFO) segment is 345 ° C +
It can be extended to the (about 650 ° F +) range, which can extend the size of the LFO reservoir. Similarly, lowering the pour point in the 345 ° C + (650 ° F +) segment can extend the heavy segment, eg, the final boiling point segment of heavy fuel oil (HFO).

Another particular advantage of zeolite beta is that it is a gasoline boiling range product [approximately C ₅ -165 ° C. (C ₅ −
330 ° F)] octane range.
An improvement in octane number (R + O) of at least 2, usually 3 to 5, is obtained by cracking of highly paraffinic feedstocks on zeolite beta compared to cracking on conventional cracking catalysts based on zeolite Y. An octane number (R + O) of 90 or more can be achieved. Furthermore, the improvement is more pronounced when considering the contribution of octane number from the alkylate fraction: Zeolite Beta produces higher amounts of alkylate with a higher C ₄ / C ₃ ratio than Zeolite Y. These features contribute to higher alkylate yield and alkylate quality to further improve gasoline yield. The octane quality of naphtha and the octane quality of alkylate are relatively constant as the conversion rate changes, but at higher conversion levels than normal, the octane number increases slightly as before.

Hereinafter, the present invention will be further described with reference to Examples (hereinafter, simply referred to as "examples" unless otherwise specified).

Examples 1-4 (Examples 2 and 4 are proportional) Examples 1-4 compare the performance of two different cracking catalysts on two different feeds. One of the catalysts was a conventional catalyst composed mainly of zeolite Y, and the other catalyst was composed mainly of zeolite beta.

Conventional catalyst is equilibrated Durabead 9A (Durabe
It is a sample of ad9A) (trade name) and is a moving bed catalytic cracking catalyst taken out from a moving refinery. Durabead 9A is a conventional RE in silica / alumina binder.
It was in the form of beads containing 12% by weight of Y zeolite.

Zeolite beta catalyst is 50 wt% zeolite beta
It was extruded with a mixture of (zeolite beta silica / alumina ratio 40/1, α-activity 400 in hydrogen form) and 50% by weight of α-alumina form. The catalyst was dried and calcined in nitrogen at 540 ° C (1000 ° F) for 3 hours,
It was then calcined in air at 540 ° C (1000 ° F) for 3 hours. The sodium content in the catalyst was 495 ppm. The zeolite beta catalyst was then steamed in 100% steam at a temperature of 700 ° C. (1290 ° F.) and atmospheric pressure to an α activity of 6.

The above two catalysts were then tested for catalytic cracking of two different gas oil feedstocks with the properties set forth in Table 6 below.

As is clear from Table 6 above, gas oil B is significantly more paraffinic than gas oil A.

Each of the catalysts was loaded into a laboratory scale fixed bed cracking device capable of simulating moving bed cracking, and 2
Used to crack seed gas oil feedstock.
The conditions used and the results obtained are shown in Tables 7 and 8 below.
Described in the table.

As shown in FIGS. 7 and 8, when using a relatively non-paraffinic feedstock such as gas oil A, zeolite beta provides only an advantage over conventional zeolite Y. The gasoline produced has almost the same octane number, but cracking with zeolite beta is less than 0.
9 high gasoline + alkylate octane number and 5% by volume
It produces a lot of gasoline + alkylate. These advantages are significantly increased when the feedstock is highly paraffinic. As shown in FIG. 8, cracking of paraffinic gas oil B with zeolite beta produces a large amount of gasoline + alkylate (75.0% by volume in Example 3 and 64.0% by volume in Example 4). In addition, the improvement of pour points in the heavier sections is significant.

Somewhat surprisingly, the octane number of gasoline and alkylate fractions produced by cracking with zeolite Beta is octane number of gasoline + alkylate produced by catalytic cracking with zeolite Y (R + O) 8
It is 91.9, which is considerably higher than 8.3. That is, Zeolite Beta not only produces a greater amount of gasoline than operations using commercially available zeolite Y-based catalysts, but also produces gasoline with a higher octane number.

Examples 5 to 13 (comparative examples except Examples 6, 9 and 12) In Examples 5 to 13, two different catalysts were tested on three different high paraffin content waxy gas oils.

The first catalyst acid-extracts zeolite Y, then the temperature is 650 ° C.
24 in 100% steam (1200 ° F) and atmospheric pressure
It is a dealuminated zeolite Y catalyst prepared by steaming for a period of time. The final steamed zeolite had a silica / alumina ratio of 226/1.

The second catalyst was a catalyst obtained by steam-treating a calcined zeolite beta catalyst (silica / alumina ratio 30/1) in the same manner as described above and increasing the silica / alumina ratio to about 228/1.

The catalysts described above were used in fluidized bed cracking of the three gas oils described below using a small scale dense bed reactor. The small scale dense bed reactor was operated in a cycle with 10 minutes cracking, 5 minutes helium purge, then 40% oxygen: 60% nitrogen to complete oxidative regeneration, and finally 1 minute helium purge. It was Catalyst is 60-80 mesh
(American standard) Pure zeolite (50cc) crushed and acid washed quartz chips [80-120 mesh (American standard), 30cc of Vycor (trade name)] were used in a mixed form. . A comparative experiment to show the extent of thermal cracking was performed using 80 cc of ground biker quartz chips. The reaction temperature in each case is 510
℃ (950 ° F), space velocity (LHSV) is 1.5 ~
It was changed to 12 hours- ¹ .

The product was collected over 10 cycles; the mass balance was above 95% in all cases. All products were analyzed by gas chromatography.

The properties of the three heavy vacuum gas oils (HVGO) used in this example are set forth in Table 9 below.

The results are shown in Tables 10 to 12. The pour points listed are in the 345 ° C + (650 ° F +) range.

A comparison of Tables 10-12 shows that the dewaxing activity of zeolite beta is related to the paraffin content of the feed. For relatively low wax content HVGO-C (31% paraffins), there is no improvement in pour point of 345 ° C + section due to thermal cracking, cracking on zeolite Y catalyst or cracking on zeolite beta.
When the paraffin content of the charging raw material is increased (paraffin content HVGO-D: 52%, HVGO-E: 81%
%), There is a difference in 345 ° C. + pour point for products obtained using Zeolite Y catalyst and Zeolite Beta. The distillate selectivity for the two zeolites is similar, but the distillate final boiling point above 345 ° C can be increased by lowering the pour point, and the distillate achieved by zeolite beta is achieved. Selectivity is increased.

Examples 14-15 Steamed zeolite beta catalyst was used with other waxy feeds. The catalyst was prepared by the same method as in Examples 5-13 and used for cracking by the same operation as in Examples 5-13.

The properties of the mixed phase charge used are listed in Table 13 below.

The results of cracking the mixed phase charge at two different severity levels are set forth in Table 14 below. Pour point is 315 ° C
This is for the (600 ° F +) category.

It shows that the high boiling point fraction is efficiently dewaxed and the pour point is lowered at a higher conversion rate.

Examples 16-19 HVGO-D on REY cracking (12% REY on silica-alumina) catalyst in fixed bed and steam treated zeolite beta cracking catalyst prepared in a similar manner to Examples 5-13 at 500 ° C (925 ° C). Cracked in F). LFO [230-365 ° C (450-690 ° F)]
Distillate yield and cetane index were measured at two different conversions for each catalyst. The results are listed in Table 15 below.

The distillate from the zeolite beta catalyst is similar in cetane quality to the distillate from REY.

Claims (25)

[Claims] 1. A cracking product separated from the catalyst is produced by contacting with a thermal cracking catalyst which is circulated in the absence of hydrogen with the addition of a hydrocarbon oil having an initial boiling point above 200 ° C. and cracking during cracking. In a catalytic cracking method for hydrocarbon oil having an initial boiling point of 200 ° C. or higher, which comprises continuously regenerating the catalyst on the basis of a circulation operation by oxidatively removing carbon deposited on the catalyst. A method for catalytically cracking a hydrocarbon oil having an initial boiling point of 200 ° C. or higher, wherein the cracking catalyst contains zeolite beta in an amount of at least 20% by weight. 2. The method according to claim 1, wherein the charging raw material boils in the range of 300 to 500 ° C. 3. Claim 1 or 2 in which the feedstock contains at least 40% by weight of paraffinic constituents.
Method described in section. 4. A process as claimed in any one of claims 1 to 3, in which the feedstock contains at least 60% by weight of paraffinic constituents. 5. The process according to claim 1, wherein the catalyst contains 5-95% by weight of zeolite beta. 6. The zeolite beta has a silica / alumina ratio of 1.
A method according to any one of claims 1 to 5 having claims 5/1 to 150/1. 7. The zeolite beta according to claim 1, which has an α activity of 1 to 500.
The method described in the section. 8. A method according to claim 1, wherein the contact cracking operation is a fluidized contact cracking operation. 9. A method according to claim 1, wherein the contact cracking operation is a moving gravity floor contact cracking operation. 10. A process according to any one of claims 1 to 9 in which the zeolite beta is the sole zeolite cracking component in the catalyst. 11. The method according to any one of claims 1 to 10, wherein the cracking catalyst does not contain a metal component of 1000 ppm by weight or more. 12. The cracking catalyst according to any one of claims 1 to 11, wherein the cracking catalyst contains 0.1 to 1000 ppm by weight of a metal component as a carbon monoxide oxidation promoter.
The method described in the section. 13. A method according to claim 12 wherein the oxidation promoter is present in an amount of 0.1 to 100 ppm by weight. 14. The method according to claim 12 or 13, wherein the oxidation promoter is platinum. 15. A process as claimed in any one of claims 1 to 14 in which the conversion to products having a lower boiling point than the feed is at least 50% by weight. 16. The method according to claim 1, wherein the conversion rate to a product having a boiling point lower than that of the charging raw material is 50 to 90% by weight. 17. The method according to claim 1, wherein the charging raw material has an initial boiling point of at least 345 ° C. 18. A hydrocarbon oil having an initial boiling point of 200 ° C. or higher is contacted with a circulating thermal cracking catalyst in the absence of added hydrogen to produce a cracking product separated from the catalyst and the cracking catalyst during cracking. At least 40% by weight in a catalytic cracking process for hydrocarbon oils having an initial boiling point of 200 ° C. or higher, which consists of continuously regenerating the catalyst on the basis of a circulation operation by oxidatively removing the carbon deposited on it. 200 to produce a lower pour point product by contacting a zeolite beta containing catalyst with a feedstock containing paraffins of 200
Contact cracking method for hydrocarbon oils with initial boiling point above ℃. 19. A method according to claim 18 wherein the feedstock contains at least 60% paraffins. 20. The method according to claim 18, wherein the cracking catalyst does not contain a metal component of 1000 ppm by weight or more. 21. A cracking catalyst having a metal component of 0.1.
21. A method according to claim 20 which contains from 1 to 1000 ppm by weight of carbon monoxide cocatalyst. 22. A cracking product separated from the catalyst is produced by contacting with a thermal cracking catalyst circulating in the absence of hydrogen with the addition of a hydrocarbon oil having an initial boiling point above 200 ° C. and cracking during cracking. 200 ° C consisting of continuously regenerating the catalyst on a cyclical basis by oxidatively removing the carbon deposited on the catalyst
In the catalytic cracking method for hydrocarbon oils having the above initial boiling points, a feedstock containing at least 40% by weight of paraffins is contacted with a zeolite beta-containing cracking catalyst to produce a gasoline boiling range product with an improved octane number. A method for catalytically cracking a hydrocarbon oil having an initial boiling point of 200 ° C. or higher. 23. The method of claim 22 wherein the charge comprises at least 60% by weight paraffins. 24. The method according to claim 22, wherein the cracking catalyst does not contain a metal component of 1000 ppm by weight or more. 25. The cracking catalyst has a metal content of 0.1.
25. The method according to claim 24, containing 1 to 1000 ppm by weight of carbon monoxide oxidation promoter.