JPS61157581A - Catalytic cracking of paraffin charged stock material by zeolite beta - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for the catalytic cracking of heavy oil feedstocks using a zeolite beta-containing catalyst. The invention particularly relates to a process for the catalytic cracking of paraffinic feedstocks with catalysts of the type described above.

[Prior Art] Catalytic cracking of hydrocarbon oils using acidic cracking catalysts has been a well-established process for many years, and the process has been developed since the beginning of last year's Houdrif
low) type of fixed bed cracking equipment, and later thermophore catalytic cracking (moving bed catalytic cracking) (
TCC) equipment and fluidized bed catalytic cracking (FCC)
Many different types of catalytic cracking equipment are in use, including moving bed equipment such as catalytic cracking equipment. Among these devices, fluid catalytic cracking (1:” CC) devices are currently becoming the predominant type of device for catalytic cracking.

Moving fluidized bed operations and moving fluidized bed operations involve contacting the feedstock to the unit with a continuously circulating thermal cracking catalyst to effect the desired cracking reaction, and then separating the cracking products from the catalyst and discharging the catalyst. The catalyst is regenerated by oxidizing the coke that accumulates on top. 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 necessary to sustain the endothermic cracking reaction. The regenerated thermal catalyst is then recirculated into the reactor to once again contact the catalyst with the feedstock. In moving bed (TCC) operations, the catalyst is usually in the form of solid beads that fall by gravity through the reactor and regenerator, and in FCC operations, the catalyst is typically a free-flowing powder with a particle size of about 100 microns. It is.

Regardless of the equipment used, the catalyst used in catalytic cracking possesses acid functionality to promote 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 in the 1960's, and this type of catalyst is now widely used. Zeolites used in catalytic cracking can usually be characterized as large pore zeolites. This means that large polycyclic aromatic materials, which constitute a large fraction of the heavy oil charge to the catalytic cracking operation, must enter into the internal pore structure of the zeolite, which contains a large amount of acid sites on the zeolite. This is because it is essential. The large pore zeolites used in catalytic cracking operations incorporate mordenite and synthetic faujasite zeolites X and Y. Among the zeolites mentioned above, zeolite Y is particularly rare earth metal-exchanged zeolite Y (RE
Zeolite Y has now become the zeolite of choice due to its excellent stability towards hydrothermal decomposition when used in the form of the so-called ultrastable zeolite Y (USY) or the so-called ultrastable zeolite Y (USY).

[Problem to be Solved by the Invention] Although most of the feedstocks to catalytic cracking units contain large amounts of high-boiling aromatic components, some feedstocks, especially from Southeast Asian or Pacific sources, In particular, it contains a relatively large amount of waxy paraffins that are difficult to undergo catalytic cracking in the presence of aromatics. This type of charge is usually difficult to process in conventional catalytic cracking operations regardless of the type of catalyst used: when waxy gas oil derived from this type of crude oil is passed through the unit, the gasoline product tend to have relatively low octane numbers, and refractory paraffins tend to concentrate in the unconverted compartment, which has a very high pour point. To b)
9th penalty profit, 1 pu C, Chimata Chimata - and divination (not the 2nd room,
Furthermore, recycling of the unconverted fraction is of limited practical use due to the difficult-to-process nature of paraffins in this fraction.

Of course, the problems presented by the presence of waxy components in petroleum have been known for many years, and waxes have been extracted from various distillate segments, including middle distillates, including lubricating oils, heating oils and jet fuels, and gas oils. Various methods have been developed to remove components. Various hydrodewaxing processes have been developed to remove waxy components, and these processes selectively crack long-chain n-paraffins and slightly branched paraffins to produce low molecular weight compounds that can be removed by distillation. The above-mentioned paraffins are removed by manufacturing the product. In order to obtain the desired selectivity, the catalyst can normally only admit linear n-paraffins or slightly branched paraffins, but it is also possible to introduce more highly branched substances, naphthenes and aromatics. It is a medium pore size zeolite with an exclusive pore size.

This type of catalytic hydrodewaxing process is illustrated in U.S. Pat.
No. 868,113, No. 3,894,938, No. 4
, No. 4,181,598, No. 4,222,855, No. 4,229,282, and No. 4,247,388. However, ZSM-
Medium pore zeolites such as No. 5 are generally 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 into 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 large pore zeolites and used as catalytic cracking catalysts to improve the octane number of naphtha cracking products. Even when a medium pore zeolite is mixed with a conventional cracking catalyst in this way, the medium pore zeolite cannot effectively act as a cracking catalyst for a waxy charge. Therefore, problems remain when handling this type of feedstock.

Zeolite Beta is now a highly effective racking catalyst for highly paraffinic feedstocks, with Zeolite Beta providing increased yields of potentially alkylated materials and pour points for higher boiling cracked product fractions. (A
It has been found that it is possible to produce gasoline with improved octane number with a reduction in STM D-97).

SUMMARY OF THE INVENTION Accordingly, the present invention resides in a process for catalytic cracking of highly paraffinic hydrocarbon oils using a cracking catalyst containing zeolite beta.

The catalytic cracking process of the present invention is applicable to the catalytic cracking of highly paraffinic feedstocks, ie, feedstocks containing at least 20% by weight of paraffins. The process of the invention can be carried out in any conventional type of catalytic cracking apparatus, usually in the absence of added hydrogen in a moving gravity bed (TCC) apparatus or a fluidized bed catalytic cracking (FCC) apparatus. . FCC operations and TC
Since the C operation is well established, both are usually carried out in a reactor under slightly elevated pressure conditions and under heating.
There is no need to elaborate on their individual properties, other than to point out that this is an endothermic catalytic cracking process operated at temperatures above 50°C (below 1200°C), in which the catalyst is passed continuously in a sealed loop from the cracking reactor. is then sent to a regenerator to oxidatively remove the coke that has accumulated on the catalyst, restore the activity of the catalyst, and provide the heat necessary for endothermic cracking.

The oxidative regeneration operation can be carried out in a conventional bed type similar to the reaction bed, so that in TCC operation the regeneration operation is carried out in a moving gravity bed in which the catalyst particles move downwardly with the regeneration gas stream. In addition, in various FCC operations, the regeneration operation is usually carried out in a dense bed or a fluidized bed using a combination of a dense bed and a dilute phase moving bed, depending on the equipment used. A typical FCC operation is U.S. Patent No. 4,309,27.
No. 9, No. 4.309,280, No. 3,849.2
No. 91, No. 3,351,548, No. 3,271,
No. 418, No. 3,140,249, R1An
')Yumi 1-kai Kofue'++an Fuhetsugei Performance starts 3.14
No. 0,253, No. 2,906,703 and No. 2.
No. 902,432: Regeneration techniques applicable to FCC devices are disclosed in, for example, U.S. Pat.
, No. 050, No. 3,893,812 and No. 3.8.
No. 43,330. Reference is not made to the above specification for a detailed description of the above operations.

Generally, the catalytic cracking operations of the present invention can be carried out under conditions comparable to those used in existing operations, taking into account the capacity of the cracking equipment, the exact composition of the feedstock, and the type and distribution of the desired products. can. As is well known, some charges are catalytically cracked than others and require the use of higher temperatures.
For example, by maximizing the production of naphtha, or by maximizing the production of distillate, the product distribution can be changed.
ization will require other changes. Other changes in operating conditions are necessitated by the circulation rate and catalyst replenishment rate, which are a function of the system characteristics. The extent to which changes in these operating conditions affect the bioacid distribution obtained with a given device is known for that device.

The charging raw materials used in the present invention are highly paraffinic petroleum classification,
That is, a petroleum fraction containing at least 20% by weight of waxy components. The waxy component consists of n-baraffins and slightly branched paraffins with a small degree of short chain branching, such as monomethyl paraffins. In some cases, the petroleum fraction contains waxy components of at least 40% by weight or less, at least 60% by weight, and the ability of the catalyst of the present invention to actually treat highly paraffinic feedstocks may be reduced. can efficiently crack certain refined streams that are almost entirely paraffinic, such as wax, to produce more valuable products. Of course, the presence of a waxy component implies that the petroleum fraction has an initial boiling point recognized at a paraffinic molecular weight within the range that is waxy in nature. This usually means that the petroleum fraction is above the boiling point of the naphtha boiling range material, e.g.
It means having an initial boiling point of 90° C. or higher, and more usually an initial boiling point of about 300° C. (about 570° C. or lower). In most cases, the initial boiling point of the petroleum fraction is at least 345°C (below about 650°C). In most cases, the final boiling point is below 565°C (approximately 1050°C), but higher final boiling points may be encountered depending on the distillation equipment used before the cracking unit, and the final boiling point range is Large amounts of heavy fractions that are not substantially distilled may be removed. Therefore, normally the feedstock used in the present invention will have a boiling point within the range of 345-565°C (approximately 650-1050°C), but may also have boiling points in other boiling ranges, e.g.
Charges with boiling points between 0 and 500°C may also be encountered. Therefore, the feedstock can normally be characterized as gas oil, including vacuum distilled gas oil, and other highly paraffinic refined streams such as crude waxes can also be catalytically cracked using the catalyst of the present invention.

The feedstock usually contains varying amounts of aromatic components, usually polycyclic aromatics with alkyl side chains of varying lengths that can be removed during the cracking operation. However, the feedstock can also be highly paraffinic with a very low aromatics content, as for example in the rough waxes mentioned above.

Naphthenes can also be present in varying amounts, usually depending on the nature of the charge and the treatment of the charge prior to the catalytic cracking step. Typically, the feedstock does not contain unusually high amounts of aromatics.

The cracking operation is improved by subjecting the charge to various treatments prior to cracking to obtain a charge with improved cracking ability, but also product distribution or product properties. Hydrotreating the feedstock is a particularly useful ancillary treatment for removing heteroatom-containing impurities and saturating aromatics; hydrotreating removes heteroatom contaminants, especially Catalyst poisoning by nitrogen and sulfur is reduced, SO emissions from the unit are reduced, and the hydrogen content of the charge is increased to a level close to that of the product, resulting in improved product distribution and charge Resistance to cracking is improved.

The composition of two typical waxy gas oil charging feedstocks is as follows:
The compositions of the two hydrotreated charges are listed in Tables 3 and 4, and the compositions of the four crude wax charges are listed in Table 5. These charges can be used alone or in mixtures with other charges in the process according to the invention.

Table 1 Nominal boiling point range, 'C ('F) 345-540 (650
~1000) API specific gravity, 33.0 Hydrogen, weight % 13.6 Sulfur, weight % 0.07 Nitrogen, weight ppm 320 Basic nitrogen, weight ppm + a 160 CCRO, 04 Composition, weight % Paraffins 60 Naphthenes 23 Aromatics 17 Bromine number 0.8 KV, 100℃, cs 4.18 Pour point, ℃ (
Bottom) 46 (115) 951 true boiling point distillation, °C (
Lower) 510 (950) Table 2 API specific gravity 33.8 Pour point, °C (lower) 40 (105) Kinematic viscosity, 100 °C, as 3.0 Aniline point, °C (
95 (202,5>bromine number
1°, 7 refractive index, 70°C 1
．． 4538 Hydrogen, wt% 13.67 Sulfur, wt% 0.15 Nitrogen, ppm
180 Nickel, IIIITII 0.14
Vanadium, ppm theory 0.10 iron, ppm
2.0 copper, ppm
O, 1 or less Conradson carbon, weight% 0
,13 average molecule 1 313 Composition, weight % Paraffins 62.9 Mononaphthenes 1.6 Polynaphthenes 10.7 Aromatics 24.7 Initial boiling point 205 4015%
280 53710%
309 58930% 367
69350% 396 7457
0% 420 78990%
457 85595%
474 886 Final boiling point 485
905 Daiichi 1-jl Nominal boiling point range, °C (lower) 345-540 (650-1
000) API specific gravity 38.2 Hydrogen, wt% 14.65 Sulfur, wt% 0.02 Nitrogen, wt ppm 16 Pour point, °C (lower) 38 (100) KV, 10
0℃, cs 3.324 Nominal boiling point range, ℃ (lower) 343-455 (650-850) API specific gravity
31.0 Hydrogen, weight % 13.76 Sulfur, weight % 0.012 Nitrogen, weight ppm 34 Pour point, °C (lower) 32 (90) KV, 100
°C, as 4.139 Composition, weight % Paraffins 30 Naphthenes 42 No.-U Composition, weight % ABCD Paraffins 94.2 81.8 70.5 5
1.4 Mononaphthenes 2.6 11.0 6.3
16.5 Polynaphthenes 2.2 3.2 7
．． 9 9.9 Aromatics 1.0 4.0
15.3 22.2 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 that is described in U.S. Patent No. 3,308,069 and U.S. Reissue Patent No. 28,341; The method and properties of zeolite beta are described.

Zeolite Beta can be synthesized with a relatively high silica/alumina ratio, e.g. 100/1 or higher, and can be synthesized by heat treatment, including steam treatment, and acid extraction, and can also be used to create H-, M+, and H-sizes. A highly siliceous form of zeolite with a silica/alumina ratio of 100/1.1000/1.30000/1 or more from the lowest silica/alumina ratio at the time of synthesis of the zeolite by the method of island h,' can be manufactured. Although these forms of zeolite can be used in the process of the present invention, actual catalytic cracking requires catalysts possessing relatively high acidity and usually involves more acidic materials, with a silica/alumina ratio of 15/-150. /1 is preferred, and about 30
Very good results are obtained when using substances with a ratio of 71 to 70/1.

Since zeolite beta with such a silica/alumina ratio can be synthesized relatively easily, zeolite beta is used in a form in which the organic cations used in preparing zeolite beta are removed by subsequent calcination of the synthesized form. can do. For similar reasons, U.S. Pat.
11,770, it is usually not suitable to incorporate large amounts of alkali metal cations or alkaline earth metal cations into zeolites; This is to reduce the acidity of

However, if lower acidity is desired, higher silica/alkali metal cations or alkaline earth metal cations may be added to reduce acidity.
It is preferred to obtain relatively low acidity by using zeolites in the form of alumina ratios. This is because the higher the silica content of zeolite, the higher the resistance to hot water decomposition. Acid extraction is the preferred method of dealumination, which can be carried out by itself or in conjunction with pre-steaming; dealumination catalysts prepared in this way provide improved distillate (G/D > selectivity) was observed to have

The acid functionality of the zeolite at the time the zeolite is used as a fresh catalyst in an operation is usually about 0.1 or greater as determined by an alpha activity test, with preferred alpha activities ranging from 1 to 500 or more; More usually within the range of 5-100. The method for measuring alpha activity is described in U.S. Patent No. 4,016.
, No. 218 specification and Journal of Catalysis (
J, Catalysis) Volume 2 (1966), pages 278-287. However, the initial α
It should be remembered that activity is relatively easily reduced in industrial catalytic cracking equipment. This involves repeated passage of the catalyst through steam stripping legs to remove hydrocarbons entrapped in the catalyst.1. Also, during the regeneration operation, a large amount of water vapor is released by combustion of the hydrocarbon coke deposited on the zeolite.

Under these conditions, aluminum is removed from the zeolite's framework structure, reducing the zeolite's inherent acid functionality.

Zeolite beta can be synthesized with other trivalent crystalline framework atoms other than aluminum, for example to form borosilicates, boroaluminosilicates, gallosilicates or galloaluminosilicate structural isotypes.

These isotypes are considered to constitute the zeolite beta form and are referred to by the term zeolite specific/+JJ.
-J-Nino LA
,・It is used for substances with a certain crystal structure that possesses turns. Zeolites may be partially ion-exchanged with certain cations, including rare earth metals and metals from group iB of the periodic table, to improve hydrothermal stability.

Although zeolite beta is capable of promoting the desired cracking reaction on its own, zeolite beta is usually mixed with a sentencing or binder to resist the crushing forces and attrition encountered in industrial catalytic cracking equipment. Improves crush and abrasion resistance. Therefore, zeolites are usually mixed with clay or other binders such as silica, alumina or silica/alumina or other conventional binders. The binder provides physical strength to the catalyst particles and also provides density of the catalyst particles to control flow properties compatible with FCC equipment. Typically, the amount of zeolite in the catalyst particles ranges from 5 to 95% by weight, and from 10 to 6% by weight.
An amount of 0% by weight is preferred.

Although it can usually have some activity, the total acid function provided by the binder is the total catalytic activity measured by the alpha test. It is usually preferred that only small amounts of . This is because zeolites provide certain selective cracking properties that are desirable for paraffinic feedstocks.

Catalytic cracking, which is conventionally carried out in the absence of added hydrogen, does not require the presence of hydrogenation/dehydrogenation components as does hydrocracking, and the cracking catalyst of the present invention does not require such components. Nevertheless, metal components can be present for other purposes, in particular to promote the oxidation of carbon monoxide to carbon dioxide in the regenerator. The use of oxidation promoters to oxidize carbon monoxide to carbon dioxide in such regenerators is described in U.S. Pat. No. 4.47.
No. 3,658, No. 4,350,614, No. 4,1
No. 74,272, No. 4,159,239, No. 4,
No. 093,568, No. 4.072,600, No. 4
, 541,921, 4,435,282, 4,341,660, and 4,341,623. Typical oxidation promoters are noble metals,
Especially given that it is platinum and that an oxidation co-catalyst is usually present,
an amount of not more than 1000 ppm by weight, preferably 500 weight Jtp
May be present in amounts up to about 100 pp by weight
m is a typical maximum value. In certain cases, 0
, 1 ppm by weight are sufficient, and amounts of 0.1 to 100 ppm by weight are by no means uncommon. The oxidation promoter can be present on the catalyst or as a separate component.

Other zeolites in addition to zeolite beta can be present in the catalyst. If other zeolites such as ZSM-5 are included in the catalyst for the purpose of improving the octane number, e.g. U.S. Pat. No. 3,769,202;
No. 3, No. 3,894,931, No. 3.894,9
No. 33 and No. 3,894,934, those zeolites contain a sublime amount of zeolite beta, usually e.g. 50% by weight of the amount of zeolite beta, typically zeolite beta. No. 4,309, which describes the use of medium pore zeolites in cracking catalysts for the purpose of improving octane numbers, although they can be used in amounts from about 10% to about 30% by weight of
For example, as described in No. 279, from 0.1 to
Even small amounts of zeolite, such as 0.5% by weight, can be used.

When the catalyst is used in a moving bed operation, the catalyst is typically 1 mm thick.
It can be shaped into bill, extrudate or oil drop spheres with an equivalent particle diameter of ~6 mm, preferably about 2 m+* (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 can generally be used in particle sizes of usually 10 to 300 microns, typically about 100 microns.

As mentioned above, the catalytic cracking operation is an endothermic operation carried out under high temperature conditions, and the heat required for the operation oxidizes the carbon (coke) that accumulates on the catalyst during cracking in the catalytic cracking operation cycle. supplied by The catalyst that has undergone the regeneration operation thus serves as a medium for transferring the heat produced in the regenerator to the endothermic cracking operation.

As mentioned above, each individual cracking device has its own specific operating characteristics that determine the exact conditions under which the device is used. However, the operating conditions are usually heated, typically above about 550°C (below about 1200°C) or about 760°C (although Shibaji is characterized by even higher temperatures).
Temperatures above 1400° C.) are only occasionally encountered. This is because such temperatures tend to cause sintering of the catalyst and are near metallurgical limits in most equipment. In riser-type cracking equipment, the above-mentioned temperatures are the temperatures typically occurring at the top of the riser. As mentioned above, the pressure is usually just above atmospheric pressure - typically up to about 1000 kPa (about 130 psiH), more usually about 500 psiH.
The pressure is up to kPa (absolute pressure) (approximately 58 psig). The catalyst/oil weight ratio is usually in the range 0.1 to 10, more usually 0.2 to 5, and the conversion rate, i.e. the rate at which the charge is converted to lower boiling products, is an important operating parameter. and usually at least 50% by weight. Therefore, in gas oil at 345° C. (about 650° C. or below), at least 50% by weight of the feedstock is converted into the boiling point category below 345° C. (about 650° C. below). Usually the conversion is 50-80% by weight or more, 9
Up to 0% by weight. However, it may be necessary to limit conversion due to downstream equipment limitations, particularly 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 conventional alkylation equipment. is a desirable product because of its production, but the rectification equipment connected to the cracking equipment may not be large enough to handle the large quantities of light olefins.

When using zeolide beta, zeolite beta shows itself to be a stable racking catalyst;
It has good hydrothermal stability, especially in dealumination forms with high silica/alumina ratios, and is associated with industrial applications where the catalyst is circulated through a steam stripping zone and subjected to steam at elevated temperatures during regeneration. It has good potential for use in love-king equipment. Additionally, zeolite beta has a remarkable ability to crack paraffins before aromatics, and n-paraffins are cracked before isoparaffins. Zeolite Y, on the other hand, is selective for naphthenes and aromatics and, as a result, highly paraffinic feedstocks are believed to be less susceptible to cracking in cracking operations using Zeolite Y. Zeolite Beta can successfully convert highly paraffinic feedstocks to lower boiling point products, but when large amounts of aromatics are present and the paraffin content is correspondingly low, the U.S. patent application It is desirable to use catalyst mixtures containing zeolite beta and faujasite type zeolites, such as those described in US Pat. No. 775,189. Note that the above-mentioned specification describes a method using a mixed cracking catalyst which is a mixture of zeolite beta and faujasite type zeolite.

By preferentially cracking the waxy paraffins in the feedstock, zeolite beta efficiently dewaxes the feedstock, thereby reducing the unconverted fraction, e.g.
(approximately below 650) lowers the pour point of the section. Therefore, the cracking process of the present invention can be used for non-hydrocracked gas oil dewaxing in environmental routes where aromatic products are acceptable. At high conversions, typically 60% or 70% by weight, there is a decrease in the pour point of the converted fraction, indicating selectivity for the conversion of high molecular weight components.

Zeolite Beta has a distillate selectivity comparable to that of dealuminated zeolite Y with an equivalent silica/alumina ratio, but the removal of waxy paraffinic components from zeolite increases as the paraffin content of the feedstock increases. was observed to become progressively more effective.

Dewaxing the unconverted section can extend the final boiling point of the distillate, which is limited by the pour point. For example, for the dewaxing effect of the catalyst, the light fuel oil (LFO) category is
It can be extended to a range of 5° C.+ (approximately 650 degrees Celsius), thereby increasing the size of the LFO reservoir.

Similarly, lowering the pour point of the 345° C.+ (below 650+) category can expand the final boiling point category of heavy categories, such as heavy fuel oil (HFO).

Another specific advantage of Zeolite Beta is that Zeolite Beta is a gasoline boiling range product [C9-165°C (C
The aim is to improve the octane range of A330 (lower). Cracking of highly paraffinic feedstocks over zeolite Beta results in an improvement in octane number (R10) of at least 2, but usually between 3 and 5, compared to cracking over conventional cracking catalysts based on zeolite Y. It will be done.

○ ＾ l'l L trs -4-)z ts -nohiro / D 4 convex S J+ More pronounced: Zeolite Beta produces more alkylates with a higher C</C3 ratio than Zeolite Y.

These features contribute to higher alkylate yields and alkylate quality to further improve gasoline yields. Although naphtha octane quality and alkylate octane quality remain relatively constant as conversion rates change, as higher conversion levels are increased, conventionally a small increase in the octane number occurs.

The present invention will be further explained with reference to Examples (hereinafter simply referred to as "examples" unless otherwise specified).

Examples 1-424 compare the performance of two different cracking catalysts on two different feedstocks. One catalyst was a conventional catalyst based on zeolite Y, and the other catalyst was based on zeolite beta.

A conventional catalyst is the balanced Duravide 9A (D u
rabead 9 A) (trade name), a moving bed catalytic cracking catalyst taken from a moving refinery. Duravibead 9A was in bead form containing 12% by weight of conventional REV zeolite in a silica/alumina binder.

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

The two catalysts were then tested for catalytic cracking of two different gas oil charges with the properties listed in Table 6 below.

No.-U API specific gravity 23.7 32.9 Pour point, °C (lower) 35 (95) 4
0 (105) Aniline point, °C (lower) 71 (
160) 94(202) Sulfur, wt%
0.51 0.15 Nitrogen, weight ppm
1600 20G nickel, weight ppm
O,530,14 vanadium, weight ppm
O,240,10 average molecular weight 35
7 320 paraffins, weight% 16.4
62.2 Naphthenes, weight% 37.8
13.6 Aromatics, wt% 45.8
24.2 As is clear from Table 6 above, gas oil B is significantly more paraffinic than gas oil A.

Each catalyst was loaded into a laboratory-scale fixed-bed cracking apparatus capable of simulating moving-bed cracking;
It was used to crack the seed diesel fuel charge material.

The conditions used and the results obtained are shown in Tables 7 and 8 below.
Record in the table.

-7t% Catalyst Zeotite Beta Zeotite Y temperature, °C (bottom)
496 (925) 498 (925) Catalyst/Oil (g Zeotito Beta) 0.38 0
．． 36 Experimental time (minutes) 10 1
0 conversion rate, volume % 5353 C5+ gasoline, volume % 41.6 44.
7 Total class 04, volume% 8.8 6.
5 Dry gas, weight% 5.4 4.6
Coke, weight % 3.4 3.6 Octane number (Rho) 91. F 91
．． IC1=, volume% 4. F 2
・6C4=, volume% 5.2 2
．． 5iC4, volume% 2.9
3.1 alkylate, volume % 18.6
8.5 Alkylate (R10) 94.1
93.6 Gasoline + Alkylate J [%
58.2 53.2 Gasoline + alkylene octane number (R10) 92.4 91.
5 No. 8 Table 23.3 22.5 HFO 1% by volume 345°C+(850'F+) 16.7
17.5 LFO pour point, °C (lower) -4 (25)
2 (35) HFO pour point, °C (lower) 35 (95)
46 (115) As shown in Figures 7 and 8, Zeolite Beta offers only marginal advantages over conventional Zeolite Y when using a relatively non-paraffinic charge such as Gas Oil A. . Although the octane number of the gasoline produced is about the same, cracking with zeolite beta produces a 0.9 higher gasoline+alkylate octane number and 5% more gasoline+alkylate by volume. These advantages are greatly increased when the feedstock is highly paraffinic. As shown in Figure 8, cracking of paraffinic gas oil B with zeolite beta produces a large amount of gasoline + alkylate (75.0 vol. % in Example 3, 64.0 vol. % in Example 4), and even more The improvement in pour point of the heavy sections is significant.

Somewhat surprisingly, the octane number of the gasoline and alkylate fraction produced by cracking with Zeolite Beta is 91.9, which is higher than the gasoline+alkylate fraction produced by catalytic cracking with Zeolite Y. That is, Zeolite Beta not only produces more gasoline than operations using commercially available Zeolite Y-based catalysts, but also produces gasoline with a higher octane number.

In Examples 5-13, two different catalysts were tested on three different waxy gas oils with high paraffin content.

The first catalyst extracts zeolite Y with acid, then the temperature is 650℃.
(below 1200) and 24 hours in 100% steam at atmospheric pressure
A dealuminated zeolite Y catalyst prepared by time steam treatment.

The final steamed zeolite had a silica/alumina ratio of 226/1.

The second catalyst was a calcined zeolite beta catalyst (silica/alumina ratio of 30/1) which was steam-treated in the same manner as described above to increase the silica/alumina ratio to approximately 228/1.

A small-scale concentration reactor was used as described below. The small-scale concentration reactor was cracked for 10 minutes, purged with helium for 5 minutes, then 40% oxygen:60%
It was operated in a cycle with nitrogen to complete the oxidative regeneration and a final 1 minute helium purge. The catalyst is pure zeolite (US standard) crushed to 60-80 mesh (American standard).
50 cc) and 30 cc of acid-washed quartz chips [80-120 mesh (American standard), Vycor (trade name)] were used in a mixed form. Comparative experiments to demonstrate the extent of thermal cracking were carried out using 80 cc crushed Piker quartz chips; the reaction temperature in each case was 510 °C (below 950 °C);
Space velocity (LH5V) was varied from 1.5 to 12 h-1.

Product was collected over 10 cycles; mass balance was greater than 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 listed in Table 9 below.

1st fire-j1 C1 weight% 85.65 85.82
81.50N1% by weight 12.13 1
2.67 13.280, weight% 0.
3O N, weight% 0.09 0.01 0.
01S, weight% 2.15 0.22
0.03 Ash content, wt% 0.01 N i, ppm
O, 5 car 0.01 book IV, ppm
O,50,5 car IOCR0,
44 Pour point, "C324357 lower 90 110 1
35 distillation, weight % 215°C - (420 below -) 0 0 0
215-345℃ (420-650 below) 0 7
．． 20 2.09345~455℃(650~850
Bottom) 54.02 60.85 58.99455~5
80℃ (850~1075 lower >34.73 28.33
36.26580℃ ÷ (10〕5 below +)
11.25 3.62 2.66P/
N/A composition, weight % Paraffins 31 52 81 Aromatics 49 15 10 Naphthenes
20 33 9* represents the following.

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

Chopsticks - 1dan - table WHSV 10.2
9.9 4.5215℃ conversion rate
45.42 20.49 3.603
45℃ conversion rate 72.86 3
6.08 13.13c, +c21.54 0
．． 74 1.10C3+C47,583,100,
10 Cs 215℃ 36.
33 16.65 1.53215~345
℃ 23.85 1
2.68 9.41345-455℃ 5
4.02 18.83 41.84 5
7.90455-580℃ 34.73
5.64 16.98 22.20580
℃+ 11.25 2.67
5.10 6.80 Coke
3.56 2.93 0.99
Distillate selectivity 32.70 3
5.10 71.700/D
1.52 1.32 0.26
Pour point, 'C32131313 lower 90 55 55
55 Note: After acid cleaning, the silica/alumina ratio is 250.
/1゜fruit-upper table WHSV 9.6
10.5 5.0215℃ conversion rate
65.02 29.92 1.2
3345℃ conversion rate 82.10
52.14 6.08c, +c22.23
0.66 0.13C3+C, 17,468,97 c, -215℃ 45.3
3 20.29 0.16215~345℃
7.20 14.48 25
．． 00 11.61345-455℃ 6
0.85 10.17 32.04
67.98455-580℃ 28.33
3.90 9.47 19.175
80℃+3.62 2.
53 2.90 coke
3.89 0.67 0.94 Distillate selectivity 9.55 36.80 7
2.50G/D
6.23 1.14 0.04 pour point, ℃4
3 33 27 43 bottom
110 92 80 110 Note: After acid cleaning, the silica/alumina ratio was 250/1°.
↓Sujin raw material Zeotito Y Beta
Chisso WHS V
13.0 10
．． 2 5.0215℃ conversion rate
69.00 69.15 2.34345
°C conversion rate 77.30 78.
17 4.08c, +c,
o, st
1.72 0.18C, +C, 11,452
5,45C, -215℃
54.67 41.98
0.42215~345℃ 2.0
9 8.77 7.68
3.74345-455℃
58.99 15.27
12.92 5F, 49455-580℃
38.26 6.27
6.21 36.29580℃+
2.66
0.69 2.18 0.12
Coke 0.00 2.07
1.80 1.74 Distillate selectivity
8.82 7.30 41.40G/D

8.18 7.51 0.25 Pour point, “C57541849 Lower 135 130 65
120 Note: After acid cleaning, the silica/alumina ratio is 25.
0/1° A comparison of Tables 10 to 12 shows that the dewaxing activity of zeolite beta is related to the paraffin content of the feedstock. HVGO-C with relatively low wax content (31%
For paraffins), there is no improvement in the pour point at 345° C. by thermal cracking, cracking on a zeolite Y catalyst, or cracking on a zeolite beta catalyst. 345 °C + pour point for the products obtained using Zeolite Y catalyst and Zeolite Beta when the paraffin content of the charge increases (paraffin content 52% for HVGO-D and 81% for HVGO-E) There is a difference. Although the distillate selectivity for the two zeolites is similar, the lower pour point allows for an extension of the distillate final boiling point above 345°C, achieving a higher distillate oil selectivity with Zeolite Beta. Selectivity increases.

LL Previously [i] A steam-treated zeolite beta catalyst was used with other waxy charges. The catalyst was used for cracking as in Examples 5-13.

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

Table 13 API specific gravity 33,4 Pour point, °C (lower) 40 (105) 1 (V
,40℃,cs
9.55I(V, 100℃, as
2.74CCRO,05 Aniline point, °C (lower) 92.5 (198,5
0) C5 weight% 86.10N1 weight%
13.76S, weight%
0.13N, weight pp 140 Simulated distillation, weight % 215℃-1,46 215-345℃ 29.40 345-455℃ 61.71 455-540℃ 7.43 540℃+ O P/N/A, Weight % Paraffins 56.8 Naphthenes 14.8 Aromatics 29.4 The results of cracking the mixed phase charge at two different severities are reported in Table 14 below. Pour point is 315℃
This is about the (600 lower +) category.

Catalyst Zeolite beta Zeolite beta temperature, °C (bottom)
445 (835) 505 (941) Zeolite/oil weight ratio 0.49 0.88 Catalyst/oil weight ratio 0.49 0.88345℃-
Conversion rate, weight % 54.1 79.5 Pour point,
215℃ ÷,℃ (lower) 21 (70) 10
(50) Pour point, 345°C +, °C down) 29 (85
) 1B (65) shows that the high boiling point fraction is efficiently dewaxed and the pour point is lowered with higher conversion.

mヱ19 HVGO-D was heated at 500"C over a REY cracking (12% REV on silica-alumina) catalyst in a fixed bed and a steam-treated zeolite beta cracking catalyst prepared in a manner similar to Examples 5-13. cracked at LFO [230-365°C (45o-69o)
Bottom)] Distillate yield and cetane index were determined for the individual catalysts at two different conversions. The results are listed in Table 15 below.

LFO 345℃-Yield Cetane (L Ml Kanjin JL-1 Jurugi 11-1
6 REY 50.1 25.5
45.817 REY 57.6 2
1.1 41.418 Zeotito Beta
52.3 21.3 43.1
19 Zeolite Beta 55.5
The distillate from the 22.3 42.3 zeolite beta catalyst is of similar cetane quality to the distillate from REV.

Claims (1)

[Claims] 1. Producing a cracking product separated from the catalyst by contacting a hydrocarbon oil having an initial boiling point of 200° C. or higher with a circulating thermal cracking catalyst in the absence of added hydrogen; A process for the catalytic cracking of hydrocarbon oils with an initial boiling point of 200° C. or higher, which comprises continuously regenerating the catalyst on a circular operation basis by oxidatively removing the carbon deposited on the cracking catalyst during the cracking process.
A method for catalytic cracking of hydrocarbon oils having an initial boiling point of 200° C. or higher, characterized in that the charged raw material contains at least 20% by weight of paraffins, and the cracking catalyst contains zeolite beta. 2. The method according to claim 1, wherein the raw material to be charged boils in the range of 300 to 500°C. 3. The method according to claim 1 or 2, wherein the feedstock contains at least 40% by weight of paraffinic components. 4. A process according to any one of claims 1 to 3, wherein the feedstock contains at least 60% by weight of paraffinic components. 5. The method according to any one of claims 1 to 4, wherein the catalyst contains 5 to 95% by weight of zeolite beta. 6. Zeolite Beta has a silica/alumina ratio of 15/1~
150/1. A method according to any one of claims 1 to 5. 7. The method according to any one of claims 1 to 6, wherein the zeolite beta has an alpha activity of 1 to 500. 8. The method according to any one of claims 1 to 7, wherein the catalytic cracking operation is a fluid catalytic cracking operation. 9. A method according to any one of claims 1 to 7, wherein the catalytic cracking operation is a moving gravity bed catalytic cracking operation. 10. The method of any one of claims 1 to 9, wherein 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 or more by weight. 12. The method 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. 13. The method of 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. Claims 1 to 1 in which the conversion rate to a product with a lower boiling point than the charged raw material is at least 50% by weight.
The method described in any one of items 4 to 4. 16. The conversion rate to a product with a boiling point lower than that of the charged raw material is 50.
16. A method according to any one of claims 1 to 15, wherein the amount is 90% by weight. 17. The process according to any one of claims 1 to 16, wherein the feedstock has an initial boiling point of at least 345°C. 18. Contacting a hydrocarbon oil with an initial boiling point of 200°C or higher with a circulating thermal cracking catalyst in the absence of added hydrogen to produce cracking products separated from the catalyst and deposited on the cracking catalyst during cracking. In a process for catalytic cracking of hydrocarbon oils with an initial boiling point of 200° C. or higher, which comprises continuously regenerating the catalyst on a cyclic operation basis by oxidative removal of the carbon produced, at least 40% by weight of paraffins. 1. A method for catalytic cracking of hydrocarbon oils having an initial boiling point of 200° C. or higher, characterized in that a charge containing a zeolite beta is brought into contact with a catalyst containing zeolite beta to produce a product with a lower pour point. 19. The method of claim 18, wherein the feedstock contains at least 60% paraffins. 20. The method according to claim 18, wherein the cracking catalyst does not contain more than 1000 ppm by weight of metal components. 21. The cracking catalyst is 0.1 to 10 as a metal component.
21. The method of claim 20, containing 0.00 ppm by weight of carbon monoxide oxidation cocatalyst. 22. Contacting a hydrocarbon oil with an initial boiling point of 200° C. or higher with a circulating thermal cracking catalyst in the absence of added hydrogen to produce cracking products separated from the catalyst and applying the mixture onto the cracking catalyst during cracking. In a process for the catalytic cracking of hydrocarbon oils with an initial boiling point above 200° C., which comprises continuously regenerating the catalyst on a cyclic operation basis by oxidative removal of deposited carbon, at least 40% by weight of paraffin A process for the catalytic cracking of hydrocarbon oils having an initial boiling point of 200° C. or higher, characterized in that a charge containing a zeolite beta is contacted with a cracking catalyst containing zeolite beta to produce a gasoline boiling range product with improved octane number. . 23. The method of claim 22, wherein the feedstock contains at least 60% by weight of paraffins. 24. The method according to claim 22, wherein the cracking catalyst does not contain more than 1000 ppm by weight of metal components. 25, the cracking catalyst is 0.1 to 10 as a metal component
25. The method of claim 24 containing 0.00 ppm by weight of carbon monoxide oxidation cocatalyst.