DE1645773A1 - Process for the selective production of hydrocarbons in the gasoline boiling range - Google Patents

Description

Process for the selective production of hydrocarbons in the gasoline boiling range

The invention relates to a method for the catalytic hydrocracking of petroleum hydrocarbons for the production of fuel oils and in particular a Hydrocracking process, in which hydrocarbons without excessive Gas formation can be hydrocracked until it is completely used up.

Γη Recently, there has been an increasing tendency to use hydrocracking processes for production of fuel oils, especially gasoline. Hydrocracking has found particular application for the conversion of relatively resilient feedstocks that contain heavy aromatic hydrocarbons or other polycyclic Contain hydrocarbons, too low-boiling

0098207 1.47 & -

Products, e.g. gasoline, without excessive gas and coke formation. It has been suggested to use a catalyst to use which comprises a hydrogenation component on a cracking carrier; the latter can either consist of an amorphous material, e.g. silicon dioxide-aluminum oxide, or a zeolite carrier «If used a catalyst with an amorphous base material, it is necessary to feed the hydrocarbon to a pretreatment to undergo. to remove practically all organic nitrogen compounds from it. When the pre-treatment stage is not carried out, the organic nitrogen compounds cause a sweeping effect Degradation of the amorphous supported catalyst under hydrocracking conditions and causing rapid catalyst deactivation after himself. When this occurs, the implementation of more frequent generations and / or the application undesirable conditions which adversely affect the catalyst selectivity, or both are necessary in order to maintain the desired conversions in hydrocracking. Furthermore, the catalysts show with amorphous support, usually lower activity than the zeolite catalysts and they age faster (lower Stability) than the zeolite catalysts.

Zeolite-supported catalysts, on the other hand, show comparatively no increased cracking activity for them so resistant portions of the charge and lower Quality deterioration when exposed to organic

Nitrogen compounds compared to the amorphous supported catalysts. Furthermore, zeolite-supported catalysts show an improved selectivity compared to the amorphous supported catalysts in that less light hydrocarbons, such as butane, are produced. It is these properties of the zeolite supported catalysts that have encouraged their increased use in Hydrokraek processes. However, the zeolite-supported catalysts have the disadvantage of exhibiting a poor ability to crack polycyclic hydrocarbons having a relatively high molecular weight as compared with the amorphous supported catalysts. This is likely due to intra-particle diffusion limitations due to the relatively small pore sizes of the zeolites. This disadvantage limits the use of a zeolite-type catalyst when cracking to exhaustion is sought o Sub cracking to exhaustion is one. Procedure for practically complete. Conversion of the oils Jrischbeschickiing to desired products in this JFalle 'fuel such as gasoline to understand ^ under favorable selectivity conditions by recycling the unconverted effluent from the hydrocracking is substantially completely converted to this _s. When zeolite catalysts are used to hydrocrack feedstocks containing resilient hydrocarbons under normal hydrocracking conditions, the specific gravity of the non-

009820/1416

converted recycle material from the hydrocracking stage during the operating period of the hydrocracking system continuously ■■ as the material contains increasing amounts of resilient polycyclic hydrocarbons. In many The specific gravity of the hydrocracked will drop The return discharge is even greater than the specific gravity the incoming pretreated hydrocarbon feed. Dm the return outflows of progressively worse To hydrocrack quality, it becomes necessary to apply increasingly severe conditions, e.g. elevated temperatures. But if relatively severe hydrocracking conditions are used to induce cracking of the recycle effluent, there is generally a loss of yield in fuel oil product a «This loss of yield is based on secondary cracking reactions of the deeper the boiling portion of the hydrocarbon feed Formation of excessive amounts of undesirable gaseous Products. Furthermore, the zeolite catalysts tend to under-conditions increased operating severity to be clogged by coke-like substances, resulting in a loss of Catalyst activity leads. The way out of a previous separation of the majority of the resilient polycyclic hydrocarbons from the feed, for example by fractionation, is particularly disadvantageous / since this either leads to a corresponding loss of yield or a corresponding increase in the required.

09820/1476

Lead feed to achieve corresponding yields

's .

would.

If an amorphous supported catalyst is used in hydrocracking, the hydrocarbon feed should be less than about 100 ropes-per-million organic nitrogen, and preferably less ^; than about 10 parts-per-million organic nitrogen. When using a zeolite-supported catalyst for hydrocracking, the hydrocarbon feed should contain less than about 500 parts-per-million organic nitrogen, and preferably less than about 50 parts-per-million organic nitrogen, depending on the feedstock. Organic nitrogen compounds can be removed from the hydrocracking feed in a number of ways, the preferred method being hydrofining to convert the nitrogen compounds to ammonia. If a zeolite catalyst is used in the hydrocracking stage, the ammonia formed can either be removed from the hydrocracking feed, then achieving relatively low catalyst aging rates, or it can be left in the hydrocracking feed, resulting in savings by eliminating intermediate stages of feed compression and heating . The ammonia can be left in the feed in limited amounts when using zeolite catalysts since the zeolite catalysts create one in the presence of ammonia

retain a considerable proportion of their activity, while catalysts with amorphous support retain their activity not in the presence of ammonia, so that increasingly severe hydrocracking conditions are required. The application of increasingly severe hydrocracking conditions too poor product selectivity.

The hydrofine pretreatment is carried out by removing the nitrogenous hydrocarbon feed brings into contact with hydrogen in the presence of a hydrogenation catalyst. The hydrofining conditions are generally relatively mild and are adjusted to allow denitration and desulfurization is brought about while hydrocracking reactions so low as possible, hydrocracking reactions must be kept as low as possible during the hydrofining stage, since the catalyst by such reactions heavily deactivated and the selectivity of the catalyst is adversely affected. This either makes an increased Hydrofining capacity or frequent regenerations of the Hydrogenation catalyst required. With an integrated Hydrof unification hydrocracking process in which the hydrogenating fine liquid effluent fed into the Hydrokfackstufe it is desirable to adjust the hydrofining capacity according to Limiting aspects of economical operation and frequent regeneration of the hydrogenation catalyst avoid to keep downtime as low as possible to keep. The normally used hydrogenation

catalyst comprises a hydrogenation component with no backing material or on an absorption carrier that has little or has no cracking activity. In the case of the hydrogenation component, it can a metal of group VIb or group VIII of the periodic table, their oxides, their sulfides or mixtures be about it. Typical of such hydrogenation components

* are nickel oxide, cobalt oxide, cobalt sulfide-molybdenum sulfide, Kickelsulfide-tungsten sulfide and the like. Suitable carriers or Absorbent carriers include heat-resistant inorganic ones Oxides such as aluminum oxide, clays such as bauxite, zirconium oxide, titanium oxide, etc. The hydrogenation component is usually on the base material in amounts of about 5 - 4-0% by weight, based on the weight of the wearer "present."

It is an object of the invention to provide an improved hydrocracking process, in particular a hydrocracking process in which a hydrocarbon feed is largely or entirely in selective mode is converted into desired products, with low catalyst aging rates at the same time.

The invention provides a catalytic hydrocracking process in which the hydrocarbon feed to the point of being used up with the formation of fuel oils, in particular Gasoline being cracked. Part of the hydrocarbon be feed is converted in the presence of a zeolite-based hydrocracking catalyst, while the remainder the hydrocarbon feed in the presence of a Hydrocracking catalyst is converted with amorphous support.

00ÖÖ2Ö / U7ß

Such conversion conditions are maintained, that the zeolite catalyst is preferably hydrocracking of compounds with a molecular size that is sufficiently small to allow entry and exit through to enable the pore of the zeolite. The compounds of smaller molecular size are mainly in the lower-boiling ones Proportions of hydrocarbon feed. Furthermore, such conversion conditions are brought about- "

^ leads that the catalyst with "amorphous support primarily brings about hydrocracking of those compounds which have too large a molecular size to allow entry into the zeolite pores In addition, such conversion conditions are maintained '; that the catalyst selectivity for the production of products in the gasoline boiling range in the procedure according to the invention is significantly better than the selectivity for ...: formation of products in the gasoline boiling range, which can be achieved _: if either an amorphous carrier hydrocracking catalyst or a zeolite base hydrocracking catalyst is used alone. For this purpose, in the process according to the invention, the amorphous catalyst and the zeolite catalyst are arranged in separate reactors or in the same reactor, in separate beds ie a ■■ - ,. stepping. Hydrocarbon feed with a relatively low organic nitrogen content can be in the.

0 0 9 8 2 0/1476 ........

first hydrocracking zone with either the catalyst amorphous support or with the zeolite catalyst .in contact to be brought. In any case, the one from the last one Hydrocracking zone obtained fraction which is above the desired Products boiling, returned to the catalyst with amorphous support for reaction.

In the method according to the invention, a high boiling hydrocarbon feed if required hydrated refined to their organic content Nitrogen to less than about 500 parts-per-million too decrease when first using a zeolite-based catalyst is brought into contact, and on less than about 100 parts-per-million decrease when first in contact with an amorphous carrier catalyst is brought. Via effluent from the hydrofining stage passed into a separator to remove ammonia and hydrogen sulfide from the hydrocarbon feed to be hydrocracked to separate. The feed received from the separator, hydrocracking is done with a hydrocracking catalyst with zeolite base and with a hydrocracking catalyst with amorphous carrier, which are in separate zones, in contact brought. Such hydrocracking conditions are maintained that the catalyst with zeolite carrier, the pore size of which is about 6 to about 15 Angstrom units, primarily those hydrocracked compounds which enter the pores of the zeolite relatively easily can, while the amorphous carrier catalyst is

0098207147 «

lent those compounds "which can not penetrate relatively easily into the pores of the zeolite. In the second hydrocracking zone, a conversion of the products generated in the first hydrocracking zone in the gasoline boiling range is kept as low as possible (400 ⁰ F) boiling products separated off below about 204 ⁰ C from the effluent of the first hydrocracking zone and passes the boiling above about 204- ⁰ C (4-0O ⁰ P) portion of the effluent to the second hydrocracking zone, or by the .. does not separate. effluent to the first hydrocracking zone and holds the conversion and the temperature in the second hydrocracking zone within certain limits. in each case, however, ■ is the effluent from the second hydrocracking zone for the production of gasoline boiling range below about 204- ⁰ O (400 ⁰ F) boiling products and a fraction boiling above about 204- ⁰ C (400 ⁰ F). The above about 204 ° C (400 ⁰ F) boiling fraction or part thereof recovered from the second hydrocracking zone is cracked to exhaustion by recycling to the zone containing the amorphous supported catalyst. If the gasoline boiling products are not separated from the first hydrocracking zone effluent, the first hydrocracking zone effluent can be cooled prior to its introduction into the second hydrocracking zone to provide the desired conversion and temperature control in that zone. When the hydroge

009820/1476

cracked effluent from both Hydrokrackζoneη zur.Gewinnung is separated from products in the gasoline sector the fraction boiling above the gasoline boiling range is passed into the second hydrocracking zone. The one above the Gasoline range boiling fraction of the effluent from the The second hydrocracking zone is recycled to the hydrocracking zone containing the amorphous supported catalyst. The amount of gasoline produced is at a maximum brought by all parts of the effluent that boil above the gasoline range ^ for conversion to the catalyst be recycled with amorphous carrier.

It has been found that by using both a zeolite-supported hydrocracking catalyst and an amorphous-supported hydrocracking catalyst, in combination with each other, - substantial process improvements over a process using either one Achieved hydrocracking catalyst with zeolite carrier or a hydrocracking catalyst with amorphous carrier alone. will. Surprisingly, it has been found that when using Both types of hydrocracking catalysts in a hydrocracking process produce high gasoline boiling products Yields with improved selectivity towards Gasoline products are produced while catalyst aging rates are small Total amount of hydrocarbon feed converted, including their resistant parts, i.e. polycyclic Connections, with simultaneously lower

009820/1416

constriction of gas with boiling points around CL and below, than is produced in a procedure using one of the catalysts alone. The procedure according to the Invention therefore has considerable practical application Advantages due, among other things, to the fact that less hydrocarbon feed is used to produce given Quantities of products in the gasoline boiling range are required, compared to a procedure using either type of catalyst alone. Farther becomes the desired in the method according to the invention Degree of conversion of the hydrocarbon feed with less production of gaseous products obtained compared with a method in which one of the types of catalyst is used alone. Furthermore, in the method according to the invention to the desired extent of conversion, achieved at the same time lower catalyst aging rates compared to a process in which one of the catalyst types is used alone. There are these three factors in combination, namely high yields, good selectivity and low catalyst aging rates, those for the practical application of a hydrocracking process are of particular importance. Bas method according to the invention is characterized by these technical advantages, even when using relatively unfavorable hydrocarbons einsatsmaterialle & j which are resistant to hydrogen deficiency Contain hydrocarbon compounds «-. '. ".-.-. - .. ~

In this document, the term "conversion" denotes the amount of material used in Volume percent of the initial charge that was used once Passage is converted to products boiling below about 204 C (400 F).

The amorphous supported hydrocracking catalyst, referred to herein, comprises one or more hydrogenation components in combination with a cracking component in the form of an amorphous support material having pores greater than about 20 angstrom units, preferably between about 30 and about 200 angstrom units most preferably between about 4-0 and about 100 Jigstrom units. The hydrogenation components that can be used include the metals of Groups VIb and VIII of the Periodic Table, as well as their oxides, their sulfides, and mixtures thereof. The Group VIb metals that can be used include chromium, molybdenum and tungsten; the Group VIII metals that can be used include iron, nickel, cobalt, the platinum group metals and the palladium group metals. Preferred hydrogenation components are Mckel tungsten sulfide, Mckel sulfide, cobalt molybdenum sulfide, platinum and palladium. The useful amorphous cracking components include the oxides of metals of groups Ha; HIa and IVb of the periodic table, as well as silicon dioxide, or mixtures thereof * Examples of amorphous crackers that can be used are: silicon dioxide-aluminum oxide silicon dioxide-zirconium oxide _? Silica-magnesia, silica, Alumlniumoxyd n 'like.

In the case of the cracking components used in the form of the amorphous The carrier is materials with an activity index above about 20 and preferably above about 35? measured after the "Cat-A" test according to Alexander and Shimp ', National Petroleum Hews, 36, p. R-537 (August 2, 1944).

The hydrogenation metal component of the amorphous catalyst makes about 0.1 to about 25 weight percent based on that ^ Weight of the amorphous crack carrier, from. Im! "All of precious metals, such as platinum or palladium, are preferably about 0.1-6% by weight and particularly preferably about 0.2-2% by weight, based on the weight of the amorphous cracking support. In the case of a hydrogenation metal component other than one Preference is given to using about 6-18% by weight of noble metal based on the weight of the amorphous cracking support. The hydria component can be incorporated into the amorphous carrier through impregnation, joint precipitation on the surface of the Carrier, mixing or other known methods. A preferred hydrocracking catalyst with amorphous carrier includes nickel sulfide and tungsten sulfide in Quantities of 6-18 wt .- # of the metals nickel and tungsten an amorphous silica-alumina carrier containing 60-90% by weight silica and having an activity index greater than about 40. *

The zeolite hydrocracking catalysts used in the present invention comprise one or more hydrogenation components in combination with a crystalline aluminosilicate zeolite base material, that exhibits cracking activity. To the

0090-20 / 1471

- 15-- ■■ "■ - ..:

hydrogenation components which can be used in connection with the zeolite carrier belong to the metals of groups VIb and VIII des Periodic table and their oxides or sulfides, or mixtures of which * belong to the group VIb metals that can be used Chromium, molybdenum and 7folfram, while the usable metals Group VIII iron, Hickel, EoTaLt, the platinum group metals and the palladium group metaires. The preferred hydrogenation components are Hickel ^ tungsten, Eobalt molybdenum, Platinum and palladium. The zeolite cracking component acts it is a crystalline aluminosilicate structure with pores of uniform dimensions, those of aluminum oxide and silicon dioxide tetrahedra * Numerous crystalline aluminosilicates are currently available, each of which has its own distinctive pore size openings. In the context of the invention, it is useful to have a crystalline aluminosilicate with pore size openings between use about 6 and about 15 angstrom units. According to the invention Crystalline aluminosilicates used are characterized by a low sodium or alkali metal content of less than about 5% by weight »preferably less than about 2% by weight, calculated as alkali metal oxide and based on the Weight of crystalline aluminosilicate.

The zeolites used can consist of naturally occurring or synthetic zeolites mitej? Derive application of known base exchange methods. % of the zeolites that can be base-exchanged for use in the process according to the Erfiatong include naturally occurring SecIItb / a

such as faujasite, mordenite, ghabazite, stllbit, .IPerrionite, "heulandite, Dachiaridite and erionite, as well as synthetic "zeolites, such as zeolites X, X, B, L and T. These synthetic zeolites are described in US Pat. No. 3,140,252. The aforementioned zeolites are mixed with a medium containing metal ions contains, which are exchangeable for sodium or alkali metal ions, in a manner according to US Patents 3 140 24-9 and 3 140 2 ^ 3 base-exchanged, - by one

™ High Activity Selective Cracking Catalyst.

Metallic cations which can be exchanged for the alkali metal ions in the zeolite in order to improve its cracking activity are those of groups Ib to VIII of the periodic table, as well as the rare earths. Furthermore, the alkali metal can be obtained from the zeolite. be removed by base exchange with a hydrogen-containing cation, e.g. ammonium ions, in order to convert the zeolite in the hydrogen form. obtain. Furthermore, the zeolite can be base-exchanged in such a way that the alkali metal cations are replaced by a mixture of the above metal cations or a mixture of the above _; Metallkatiönen can be replaced with a hydrogen-containing ion. Those zeolites which contain rare earth metal cations, rare earth metal cations and hydrogen or Niokelkationen, - since such zeolites have high cracking activity and good selectivity are preferred. In any case, the alkali metal _{content of the zeolite 4,} calculated as alkali metal oxide, should be below about 5 wt .-? Έ and preferably below about 2 wt .- #, based on the weight of the zeolite,

1845773

to achieve the desired cracking activity and selectivity obtain.

The hydrogenation metal component of the zeolite catalyst is present in amounts from about 0.1 to about 25 weight percent on the weight of the zeolitic cracking support, depending on the hydrogenation metal used;

Noble metals, such as platinum or palladium, are preferably used in amounts of about 0.1-6% by weight, particularly preferably about 0.2-2% by weight, based on the weight of the supported zeolite catalyst. In the case of a hydrogenation metal component other than a noble metal, this is preferably used in an amount of about 6-18% by weight, based on the weight of the supported zeolite catalyst. The hydrogenation component can be introduced into the supported zeolite catalyst by ion exchange, impregnation or physical mixing or by other known methods. Preferred zeolite catalysts include hydrogenation components such as nickel sulfide and tungsten sulfide mixtures _? in amounts between about 5 and about 15% by weight of the metals nickel and tungsten, platinum in amounts of about 0.1-5% by weight, in combination with rare earths or hydrogen-containing zeolite Y or zeolite X.,

In the Kohlenwasserstoffbeschickungsn that the invention may be used in the method according to, is goloh © distillates in the range between about 204 ° and about 593 ⁰ GC ^ OO - boil 1100 ° F), or "m Hückstandsfraktionen that essentially free of ash and

009120/1478

Asphalt components are. Usable hydrocarbon feeds include heavy virgin vacuum gas oils, coker gas oils, catalytic cracking gas oils, heavy aromatic oils Extracts such as those obtained by furfural extraction of high-boiling hydrocarbons, e.g. propane deasphalt raffia inate, light, medium and heavy gas oils, or mixtures thereof. . :. -

^ In one embodiment of the invention, a

Hydrocarbon feed, which is preceded by induction a low organic nitrogen content has been treated in a first hydrocracking stage with a = Supported zeolite catalyst and hydrocracked in a second hydrocracking stage with an amorphous supported catalyst. The hydrocarbon The charge for the first stage hydrocracking should be less than about 500 parts-per-million organic nitrogen preferably less than about 30 parts-per-million. When using the catalyst with a zeolite carrier

P in the first hydrocracking stage will have various advantages of processing achieved. Supported zeolite catalysts are not so badly damaged by organic nitrogen compounds, like catalysts with amorphous supports. Accordingly, the conditions under which the feed is pretreated is, preferably by hydrofinishing to convert organic Nitrogen compounds in ammonia can be relatively mild. This in turn reduces the required operational sharpness the hydrofinishing stage, as the last traces these nitrogen compounds are difficult to remove.

Me lower required operating severity in the hydrofining stage reduces catalyst aging rates and leads to a significant technical advantage; otherwise must the fed feed have significantly lower concentrations of organic nitrogen compared to Zeolite catalysts to achieve satisfactory catalyst aging

guaranteeing rates of return. Furthermore, if the hydrocarbon feed is brought into contact with the zeolite catalyst in the first hydrocracking stage, the polycyclic aromatic compounds are more saturated at this stage. If these polycyclic compounds then in the second hydrocracking stage with the catalyst with ^ amorphous Carriers become hydrocracked is prone to coke formation due to their increased hydrogen content s- lower, '■ "

In the hydrofining stage, which precedes the first hydrocracking stage, the hydrocarbon feed brought into contact with a hydrogenation catalyst under relatively mild conditions in the presence of hydrogen to give organic nitrogen compounds Convert ammonia and organic sulfur compounds to hydrogen sulfide. It is desirable in the hydrofine ■ grade the nitrogen compounds while keeping them as low as possible Causing undesirable Hydrokraekreactions to convert in order to reduce in this way a feedstock To form nitrogen content of the specified type.

The degree of conversion in each of the hydrocracking stages depends in part on whether the below about 2OA- ⁰ O (400 ⁰ S ¹ )

".- .. - 20 '- ■■■'.

boiling products of the gasoline sector from the discharge of the first hydrocracking zone prior to introduction "of the material into the second hydrocracking zone. If a separation of the outflow from the first hydrocracking zone the conversion in each hydrocracking zone is between about 40 and about 80 #, preferably between about 50 and about 70%, based on single pass and the corresponding Feeds to each of the hydrocracking zones.

The embodiment W, is brought about in which no separation of lower boiling hydrocarbons between the hydrocracking zones is explained in more detail below.

A conversion of the incoming feed to ^{products boiling below 204 0} C (40O ⁰ F) of less than about 40 % results in a loss of product yield per unit time due to excessive amounts of recycled material, while conversions above about 80 % lead to excessive overcracking from feedstock to coke and gaseous pro-

^ Dukten "leads in the first Hydrokrackstofe following 'conditions are maintained: a temperature in the range between about 232 ° and about 482 ⁰ O (450-900 ⁰ F), preferably between about 288 ° and about 399 ⁰ C (550- 750 ⁰ F); a total pressure in the range of between about 35 and about 350 atmospheres (500 to 5000 psig) _f preferably between about 70 and about 210 atmospheres (1000 psig) i an hourly flow rate of the liquid between about 0.1 and about 10 y / h / V _$ preferably between about 1 and about 5 V / h / Vj a hydrogen circulation rate between about 178 and about 35 ^ 0 standard m- / w ,

preferably between about 534 and about 1425 storms / m. The effluent from the first hydrocracking stage is passed into a separating device, for example a separator, in which components that are liquid under normal conditions are separated from components that are gaseous under ITormal conditions and contain hydrogen, hydrogen sulfide and gaseous hydrocarbons under normal conditions. A hydrogen-rich gas is recovered from the gaseous effluent and returned to the first hydrocracking zone. The liquid from the separation stage is further separated into ^{products of the gasoline range boiling below about 204 0} G (400 F) and a liquid boiling above the desired gasoline boiling range Liquid boiling the desired range of gasoline is then fed to a second hydrocracking stage.:.

In the second stage hydrocracking reactor, an amorphous carrier catalyst is used as discussed above. In the second hydrocracking stage, the following conditions are maintained, a temperature between about 260 ° and 454 ° 0 (500-85O ⁰ F), preferably between about 288 ° and 399 ⁰ C (550 - 75O ⁰ F); a total pressure between about 35 and about 210 atmospheres (500-3000 psig), preferably between about 70 and about 140 atmospheres (1000-2000 psi-g); A maximum of about 0.1 and about 10 V / h / Y and a torsion between about 0.5 and about Z a hydrogen flow rate of about 89 %, about VBi and preferably swisoliea about 534 and 6tw &"1425 Stmvm%

- ■■ -. ■■ · - 22 -

The effluent from the second hydrocracking stage becomes a separation stage supplied in order to obtain the desired products in the gasoline boiling range. The effluent from the second hydrocracking stage, which boils above the product in the gasoline boiling range, is separated and to the inlet of the second hydrocracking stage returned. The recycle stream is mixed with the incoming pretreated feed from the second stage hydrocracking and cracked there to the point of being used up. Furthermore, a hydrogen-rich gas is obtained from the separation stage and added recycled to the second hydrocracking zone, in the process according to According to the invention, it is preferred to have a common separation stage for the outflow from the first and the outflow from the second To use hydrocracking, as this produces considerable economic advantages. When using the common separation stage becomes part of the hydrogen-rich Gas that is recovered from this is returned to the first hydrocracking stage, while the Eest to the second Hydrocracking stage is recycled. ,

In another embodiment within the scope of the invention, an amorphous supported hydrocracking catalyst is used in the first hydrocracking zone and a zeolite supported hydrocracking catalyst is used in the second hydrocracking stage. This embodiment is suitable when heavy hydrocarbon feedstocks are processed, which have an initial boiling point above about 42? ° G (800 ⁰ F). The above about 2O4 ° 0 (400 ⁰ F) '* boiling effluent odelr proportion DAYON from the first Eydrokrackstufe that the amorphous catalyst © Rthälfc, - is ia that the

006820 / $ 147

Second hydrocracking stage containing zeolite catalyst passed. The boiling above about 204- ⁰ C (4-0O ⁰ F) fraction of the effluent from the second hydrocracking stage is returned to the first Hydrokrackstuf e. In this embodiment, technical advantages over the use of one of the hydrocracking catalysts alone are achieved in particular in that the feed can be cracked to products in the gasoline boiling range under conditions of improved selectivity and relatively low catalyst aging rates. However, when an amorphous catalyst is used in the first stage hydrocracking, the results are not as favorable as those described above in some respects. Embodiments of the process in which the zeolite catalyst is used in the first hydrocracking stage. These issues relate to the need to control process variables within more limited ranges in order to achieve the desired yields, catalyst selectivity, and catalyst aging rates. Thus, if an amorphous supported catalyst is used in the first hydrocracking stage, the incoming feed must have significantly lower concentrations of organic nitrogen compared to zeolite catalysts in order to ensure satisfactory catalyst aging rates. This in turn requires that the preceding hydrofinishing stage be carried out with increased operational severity in order to convert these organic compounds to ammonia, and increases the likelihood of a more rapid quality change.

tion of the hydrogenation catalyst.

Furthermore, if the catalyst with amorphous ! Cointer is used in the first and not in the second hydrocracking stage, increases the tendency for coke to form on the catalyst. This is because the polycyclic portions of the feed Are deficient in hydrogen and are therefore good coke precursors. Accordingly, there is a larger amount of hydrogen required at this stage to reduce coke formation. On the other hand, if the pretreated charge is first treated with the When zeolite is hydrocracked, the polycyclic bonds become generally not cracked at this stage, but more saturated. These more saturated polycyclic compounds when brought into contact with the amorphous catalyst in the second stage hydrocracking, have an essential less tendency to form coke. This leads to less Hydrogen to regulate or prevent catalyst coking necessary is.·

Furthermore it is »if the catalyst with

amorphous "carrier is used in the first-n hydrocracking stage, technically lind economically not expedient, a common Separation stage to be used for both hydrocracking stages «This is based on the difficulty of the rope of the discharge of the first HydxOteack level, the one above the desired gasoline range "boils from the effluent of the second hydrocracking stage, the one above of the desired gasoline range boils in a common To cede separation stage »so that special and expensive facilities would be required. As explained above, would be

the separation necessary because the higher-boiling effluent from the Hydrocracking stage containing the amorphous catalyst in Contact with the zeolite catalyst is brought while the higher boiling effluent from the hydrocracking stage, which the Contains zeolite catalyst to react with the catalyst amorphous carrier is returned. .

Even if a procedure is to be carried out in which the effluent from the first hydrocracking stage is not separated for the recovery of products in the gasoline boiling area, it is less favorable to use the amorphous catalyst instead of the zeolite catalyst in the first hydrocracking stage. This is due to the fact that zeolite catalysts have a higher activity for cracking the lower-boiling hydrocarbons than the catalysts with amorphous support. If the zeolite is used in the second stage without removing the products of the gasoline boiling range as the effluent from the first stage, the level of cracking of the products of the benzene boiling range produced with the amorphous catalyst is increased due to the larger amounts of these products, - "the look in the feed to the two © olitiikatalysatö3 are" Blas © ^ rhoate · concentration of erwünschtem'Produkt in-.d@r Besehielsung gu second Stuf @ _s - clie the Zeolithkatalysat @ ^i> "contains ,, requires an E © gelu & g -unä Eoatroll® der Bsaktiöa & conditions within sharp Cb? © nS5isn _s xm elm Übarkrackuag li @ s © r An «so gsriag wifs possible su haltsn ^,. '.' ■: ■

Even if a procedure in which the amorphous catalyst is used in the first hydrocracking stage and a zeolite catalyst in the second hydrocracking stage is less favorable than the preferred embodiment discussed above, this procedure, too, has significant advantages over a process that does one who uses catalysts alone. In any case, this procedure allows hydrocracking until the feed is used up to products in the gasoline boiling range with improved selectivity to gasoline and relatively low catalyst aging rates compared to a process using one of the catalysts alone. When using the amorphous catalyst in the first hydrocracking stage, the feed contains less than about 100 Ropes-per-million organic nitrogen and preferably less than 10 ropes-per-ffiillion organic nitrogen. The effluent from a Hydrofeinungsstufe is preferably passed into a iErenneinrichtung in which containing a gaseous under UormalbedingOngen component containing ammonia and hydrogen sulfide is 9 is separated from AEEN liquid under Hormalbedingungen Ingredients * The liquid components are from day Irish means to the Hydrokraekung first stage _s the Amorphous carrier catalyst contains _{s passed a} . The um-. Waadlung in each Hydrokrackgon. © is between about 40 "and about 80 % n voraugaw © iii ©. smiseiiea about- §0 uwd about '70 % _$ on eggamaLig © 3s Bureiigang; xmä dt © © ntspi? ® © h®

feet? each HydrokrackaoTi ©, ^ fhaltex ^ SI®

in the first hydrocracking stage, which the. amorphous catalyst

ο contains, are as follows: A temperature of between about 260 and about ■ 4-54- ⁰ C (500 - 850 ° F) and preferably between about 288 ° and about 399 ° C (550 - 75O ⁰ P); Total pressure between about 35 and about 210 atmospheres (500-3000 psig) and preferably between about 70 and 14-0 atmospheres (1000-2000 psig)} space velocity between about 0.1 and about 10 V / hr / V, preferably between about 0 , 5 and about 2 V / h / V; Hydrogen circulation rate between about 89 and about. 3560 StmVm ^ (500. - 20,000 SOi ¹ ZB), preferably between about 534 · -and about 14-25 .Stnr / nr (3000 "to 8000 SOF / B). The third outflow from the first hydrocracking stage is preferably passed into a separating device, in which the under normal conditions gaseous portion of the outflow is separated from the portion of the outflow that is liquid under formal conditions. The normally gaseous portion of the outflow contains a predominant proportion of hydrogen and also low-boiling gaseous hydrocarbons. The gaseous portion of the outflow becomes a hydrogen-rich G- he receives efi. and recycled for use in the hydrocracking reactions.

The liquid outflow from the separation device is passed into a second hydrocracking stage * which contains a hydrocracking catalyst with zeolite carrier * The following conditions are maintained ; A Semperatur swischen about 232 ° and about ⁰ 4-82 G (4-50 - 90O ⁰ F) ₈ is preferably between about 288 ° and about 399 ⁰ O (550 -750 ⁰ F); a total pressure between about 35 and about 350 atü (50Ό - 5000 psig), preferably between

Q0S2O /

see about? 0 and about 210 atmospheres (1000-3000 psig); a haul speed between about 0.1 and about 10 V / h / V, preferably between about 1 and about 5 V / h / V. » a hydrogen circulation rate between about 178 and about 3560 Stnr / m (1000 to 20,000 SGF / B), preferably between about 534 and about 1425 - Stv? / v? (3000-8000 SCF / B). The effluent from the second hydrocracking stage is then passed to a separation stage in which the desired gasoline products from gaseous products and a

P heavy liquid effluent to be separated. The heavy one liquid effluent from the separation stage becomes the first hydrocracking stage recycled to practically completely convert the recycle material to desired gasoline products. In In this way, the incoming charge is practically completely with the production of predominantly gasoline and no fuel ■ - "■ -. <.. - - ■■" "" ■

conversion of an excessive amount of gaseous hydrocarbons.

As mentioned above, eira? Execution

In accordance with the invention, the effluent from the first hydrocracking zone is not used for etite removal. Lower boiling hydrocarbons are separated before they are introduced into the second hydrocarbons. If no separation is effected between the zones, the conversion to below 204 ⁰ C (4-00 ⁰ F) boiling products in each is:? Zone unterhäb about 40% retained "so that the overall conversion is for both zones is between about 40 and about 80%, preferably between about 50 and about? 0% _Λ based on single passage, and the feed to the first hydrocracking zone. Some hydrocracking in the first hydro;

d.O 9 i 20/14

Lower-boiling hydrocarbons produced in the cracking stage, for example gasoline, are kept at a minimum value in the second hydrocracking stage by regulating the temperature conditions in this stage. This embodiment has the advantage of eliminating the product separation stage or reducing the capacity of a product separation device between the hydrocracking stages. However, the temperature conditions in the second hydrocracking zone must be controlled more precisely than "in a procedure in which the products of the gasoline boiling range are separated from the effluent of the first hydrocracking stage, because the hydrocracking is an exothermic reaction, that obtained from the first hydrocracking stage "Effluent" must be cooled prior to its introduction into the second hydrocracking stage. The process according to the invention in this embodiment can be carried out either in a common reactor with separate hydrocracking beds through which the hydrocarbon feed to be cracked is passed in succession, or in separate reactors. When using iron separate catalyst beds in a single iteaktoj? the temperature control becomes particularly important, since it is very difficult to change the pressure and the temperature of the bed to control the conversion iii the beds. Usually "are used in the Ausführungsf ona using a einsigen Reaktors.drei .to five separate beds © In this Attsfutaaageform Bird the Einsatgsäterial preferably dureh Hydro £ e ± nusg- ₉ .vm orgaaissli © and organische'Schwsfelverbia & Ungen in -.. Of iro3? Bt © h @ iid

/1

and reduce the organic nitrogen content to less than about 200IeUe-Oe-MiIIiOn. The effluent from the final hydrocracking stage is fractionated to produce fractions including a fraction in the gasoline boiling range and a higher boiling fraction which. passes over about 204 ⁰ O (400 ⁰ F) to win. The higher boiling fraction from the separator then becomes the

- the cracking stage containing the amorphous catalyst, recycled. . ■,. If the products are not separated in the gasoline boiling range from the effluent of the first hydrocracking stage, the following conditions are in the Hydrokrackstuf e, containing the catalyst with an amorphous carrier, eitelten maintained: a temperature between about 260 ° and about 454 ° G (500-650 ⁰ F and preferably between about 288 ° and about 399 ° C (550 - 75O ⁰ F) \ a total pressure of between about 35 and about 210 atmospheres (500 - 3,000 psig), preferably between about 0 and about 140 atm (1000?

ψ , up to 2000 psig); an hourly tree flow rate of the liquid between about 0.1 and about 10 Y / h / V, preferably between about 0.5 and about 2 Y / h / Vj and a hydrogen circulation rate -between about 89 and about 35δΟ Star / m (500 to 20,000 SCF / B), preferably between about 534 and about 1425 StmVm ⁵ (3000-8000 SOF / B). '

The conditions in the Hydrokrackstuf e _f containing the ZeoXithkatalysator are as follows? A temperature between about 232 ° and about 482 ⁰ O (450-900 ⁰ S ¹⁾ _s preferably between about 288 ° and about 399 ° 0 (550-750 ⁰ F) j an overall

-009820/1476

pressure between about 35 and about 350 atii (500-5000 psig), preferably from about 0 to about 210 atii (1000-3000 psig); an hourly space velocity of the liquid between about 0.1 and about 1.0 V / h / V, preferably between about 1 and about 5 V / h / V; eäe hydrogen circulation rate between about 1? 8 and about 3560 StmVm (1000-20.00p SGF / B), preferably between about 354 and about 1425 Stmvia (300O _- - 8000 SOF / B).

In the method according to the invention it is provided ^{to produce gasoline products which boil in the range between about C 1} and about 204 0 G (400 ⁰ F). The desired end point of a gasoline product can change depending on the conditions in the reforming stage to which the products in the gasoline boiling range produced according to the invention can be fed. Thus, in the method according to the invention, the desired end point can be between about 149 ° C (300 ⁰ I ') and about 204 ⁰ C "(400 ⁰ I), usually between about 182 ° and about 199 ⁰ G (360-39O ⁰⁾ The fraction of the effluent from the final hydrocracking stage which has an end point above the desired gasoline product can be recycled to further hydrocracking. It is also within the scope of the invention to remove hydrocarbon fractions boiling above the gasoline storage from the product of the final hydrocracking stage separator! νατΛ to win * So a nozzle fuel oil fraction in the boiling range of about 204 ° to about 288 ⁰ O (400 - 55O ⁰ I) for further processing or a fuel or heating oil can be obtained

1M5773

according to the W & Erfindurig eT 'about 2 (A ⁰ C (4OQ ^ lX to bring about the generation of -products ■ in the gasoline to a maximum value.

"The attached Figure 1 shows a simplified Form the process flow to be used if the zeolite catalyst be used in the first hydrocracking stage and the amorphous catalyst in the intermediate separation stage is provided.

According to FIG. 1, fresh feedstock is introduced into a hydrofiner 1 through a line 2 and there brought into contact with a hydrogenation-dehydrogenation catalyst and hydrogen gas. The feedstock is subjected to ¹ 1 mild Hydrofeinungsbedingungen in the Hydrofeinez to cracking reactions to be kept as low as possible and simultaneously convert nitrogen compounds to ammonia and sulfur compounds to hydrogen sulfide. The hydrotreated effluent is withdrawn from the hydrofiner 1 through a line 3 and introduced into a separating device 4, for example a separator. In the separation device 4- the normally gaseous components are separated from the normally liquid components; of the hydrated effluent separated. The separated gaseous components are withdrawn from the separating device 4 through a line 5. A = Part of the separated gas is removed by a line 6 out of the system, while fresh hydrogen is introduced through a conduit into the hydraulic Feiner 1, to desired concentrations of hydrogen to maintain and Will Continue pure ¹

009820/1478

- 35 -, ■ '■ ■ "

tendency to build up hydrogen sulfide and ammonia: to prevent. The liquid portion of the hydrofine outflow is withdrawn from the separator 4- through a line 8 and as Feeding into a first hydrocracking stage 9 introduced «

The first hydrocracking stage 9 contains the zeolite-supported catalyst described above. The loading the first hydrocracking stage is there with the zeolite catalyst and hydrogen under conditions to cause conversion and recovery of products in the gasoline boiling range brought into contact. The effluent from the first stage hydrocracking is withdrawn through a line 10 and into a separator 11 led. In the separator 11 is the Outflow of the first hydrocracking stage with the outflow of the second hydrocracking obtained in the manner described below

stage mixed. In the separation device 11 this mixture is then in a normally gaseous component and a normally liquid component separated. The gaseous Component is removed from the separator 11 through a line 12 and divided, with a portion through Lines 13 and 14 to the first hydrocracking stage 9 and a Part through lines 16 and 17 to the second stage hydrocracking 15 can be returned. The gaseous component from the Separation device 11 consists mainly of gaseous Hydrocarbons in the 0 ^ boiling range and below and off Hydrogen and it can contain small amounts of ammonia and hydrogen sulfide. The liquid portion of the hydrocracking effluents is from the separating device 11 by a

Line 18 removed and sent to a distillation tower 19. The liquid portion of the hydrocracked discharge

consists mainly of hydrocarbons in the boiling range

from C _c and above. In the distillation tower 19, the 5

gasoline products boiling below about 199 ° (390 F) are separated from the hydrocracked effluent and withdrawn from distillation tower 19 through line 20. The portion of the hydrocracked effluent that ^{boils above about 199 ° C (39O 0} F) is withdrawn from the distillation tower 19 through a line 21 and sent to the second hydrocracking stage 15.

In the second hydrocracking stage 15, the liquid portion of the hydrocracked effluent becomes the unconverted. Feeding from the first hydrocracking stage 9 and not in turn ·. Converted recycle material comprises, ie, components which have not previously been converted in both the first and second hydrocracking stages 9 and 15, respectively, contacted with an amorphous supported hydrocracking catalyst and hydrogen to obtain products in the gasoline boiling range. The hydrocracked effluent from the second hydrocracking stage 15 is passed through a line 22 into the separation device 11. In the separator 11, the effluent from the second hydrocracking stage is separated into a gaseous component and a liquid component, as described above. Fresh hydrogen :? is fed to the first hydrocracking stage 9 and the second hydrocracking stage 15 through lines 23 and 24, respectively. ^

The invention is illustrated below by way of examples

009820 / 141S

Welter verjanseb; aulicht, but she is not on this special one Implementation form restricted.

Example 1 .. · ..: -

This example; -shows that- at sEMfe "^ fe & weaÄng 'of a ^; ]% j & pierkc ^ xmenfce jarnfweissrntfen Zecfe ^^ sstors to h ^ ärukraekung a ve3 ^ altnisiiiali9 mtKoäisiBiäiemä a cliuktirut a sclilenilertüe in case of transformations of the project lKefcfii3ar.s ^ iroiiis with f ortsciirei-bender .time? " is constantly increasing.

It was impregnated with liicfcel-WQlfram Sea.tener-earth-zeolite-X-Hydrokraclcfcatalysator in the following ends Way manufactured "

There were 8.59 ^ g (18v9 pounds) of a partially with rare earth exchanged 'zeolite X with a solution of Ί40 g mixed rare earth chlorides. 6HoO i- ⁿ -2 640 ml of water and the mixture for 1 hour at 82 ° C (180 ° ^) erhitist. The resulting mixture was filtered, discarding the liquid portion and recovering the solids. The above treatment was repeated with the solids recovered from the filtration step. The resulting solids were then washed with water until chloride free. The chloride free solids contained 0.6 wt% sodium. The solids were then at 121 ^° C. for 16 hours

F) dried and then 1 hour at? 60 ° C (1400 ° F) calcined, wherein zeolite X exchanged with rare earths was obtained in the form of a powder. This powder was made with

009820/1476

an aqueous solution of AOHaonium hydroxide and tungstic acid containing 17.5% by weight of tungsten mixed to impregnate tungsten in the powder in an amount of 10% by weight based on the weight of the resulting powder. The resulting mixture was dried for 16 hours at 121 ° 0 (250 ^° E), wherein an impregnated tungsten with rare earth zeolite X was incurred in powder form. The powder impregnated with tungsten was then treated with an aqueous

^ Solution of nickel nitrate containing 14.5% by weight of nickel mixed so that impregnation of the powder with 4% by weight of nickel, based on the weight of the resulting powder, was brought about. The resulting mixture then became 16 hours at 121 ° G (25O ⁰ F), to obtain an impregnated with nickel and tungsten, rare earth X powder was obtained · The resulting powder was mixed with 2 wt .-% stearic acid and pellets of 3.2 χ 3 »2 mm (1/8 inch by 1/8 inch) pressed. The pellets were calcined by

fc they slowly at first in an atmosphere of 98 vol .-% nitrogen and 2 vol .-% air at 4-54 ⁰ G (85O ⁰ F) and then in air at 100 J6iger 538 ⁰ C (100O ⁰ F) for a total were heated for 3 hours.

The above catalyst was used for the hydrocracking of a pretreated hydrocarbon feed which was obtained by mixing 20.4% by volume of light coker gas oil, 12.4% by volume of heavy coke gas oil, 19-3% by volume of light gas oil from one Cracking process with catalytic heat transfer medium (KKJ) and 4-7 * 9 VoI, -% of an area of

003820/1476

heavy gas oil from a cracking process with catalytic heat transfer medium (TOO) and secondary extract, obtained by IFurfurol extraction of heavy cycle material from a process with catalytic heat transfer medium (TOO). The Hydrokraekbeschickung obtained by Hydrofeinung the above feedstock _v over a pre-treatment catalyst in the presence of hydrogen under mild conditions at a lemperatur of 388 ⁰ O (730 ⁰ F), a total pressure of about 14-0 atm (2000 psig) at an hourly space velocity of the liquid of 1 V / h / V and a hydrogen circulation rate of about 1335 StmVnr ⁵ (7500 SCF / B). The raw batch and the hydrofine batch had the following properties:

008 120 / $ 141

- 58 -

Table I.

raw.

Specific weight

⁰ API
Aniline number, "

Sulfur, leile
million

Nitrogen, parts-ge-million

Hydrogen, weight J6

Distillation, ⁰ O ( ⁰ I)
Start of boiling

5%
%
%
%
%
%
%

%

34
#
End point
Recovery, %

0.941 19.0 131.4

1100

710

10.69

198 (388) 259 (498) 276 (528) 501 (575) 525 (614) 546 (655) 364 (688) 376 (710) 390 (755) 405 (761) 428 (802) 444 (852) 95.0

hydrofined

0.871
30.9
163.3

47.3

1.2
12.68

175 (347) 241 (465) 257 (494) 278 (532) 295 (562) 311 (591) 325 (617) 341 (646) 358 (676) 378 (712) 400 (751) 419 (786) 95.0

O0fl «20 / U7i

The hydrofined feed specified above was hydrocracked under the conditions given in Table II, the results also given in Table II were obtained. The discharge from the Hydrocracker was fractionally distilled to below

about 195 ° C (380 ⁰ F) to gain boiling fractions. The above

about 193 ° 0 (380 ⁰ F) boiling fraction was recycled to the inlet of the ÄTdrokrackers to bring about a hydrocracking until the complete exhaustion.

009820/1476

Table II

OD ΙΌ O

Operating time, days

conditions

Total pressure, kg / cm (psi)

Temperature, G

4.0

6.3

8.3

11.2

13.3

ptrical loading-return loading)

Hp circulation, & tm? / V?

(SGF / B)

Conversion, Vo1 .-% Hp consumption, Stnr / m (SOF / B)

116 116 116 116 116 116 (1650) (1650) (1650) (1650) (1650) (1650) 299 300 304.5 309 309 309.5 (570) (572) (580) (588) (588) (589) 0.6-0.4 0.6-0.4 0.6-0.4 0.6-0.4 0.6-0.4 0.6-0.4 1425 1425 1425 14-25 1425 1425 (8000) (8000) (8000) (8000) (8000) (8000) 99.9 99.5 98.0 91.8 100.0 94.4 177 148 159 146 191 208 (997) (833) (896) (823) (1072). (1169)

Table II continued .

Table II (continued) Product distribution

Ο., Gew.-Jb Gjp, wt .- $ 6

LG. ,, Vol.-9

ο iC, -, Vol.-9

% 52-82 ⁰ C (125-180),% by volume

^ 82-193 ° G (180-380), vol-?

ί 193 ° G (380), Vol.-96

_m total

Selectivities _T vol .-%

C ₄ -I93 ° C (380 ⁰ F) G ₅ -I93 ° G (38O ⁰ F) 52-193 ° O (380 ⁰ F) 82-193 ° G (180-380 ⁰ F)

0.03 0.01 0.02 0.01 0.01 - 0.07 0.11 0.07 0.08 0.15 - 1.27 1.35 1.51 1.52 2.39 2.95 9.2 10.0 10.6 10.8 15.1 22.3 3.1 3.2 3Λ 3.4 5.0 6.1 11.1 11.6 11.6 11.8 16.4 19.7 1.3 1.3 1.1 1.2 1.8 1.9 13.2 9.6 14.0 12.3 11.7 7.2 82.4 84.3 79.6 71.9 69.9 61.8 0.1 0.5 2.0 8.2 5.1 120.4 120.5 122.3 119.9 119.9 124.6 120.3 120.6 122.7 121.3 119.9 126.0 108.0 ■ 107.3 108.4 105.9 99.8 95.9 95, -6 94.5 95.5 91.7 81.6 • 73.1 82.4 84.7 81.2 78.3 69.9 65.4

Samples of the recycle stream were periodically taken during the reaction and checked for specific gravity (APi density) examined. The results are in the accompanying

2 reproduced as curve 2.

As can be seen from Table II, the yield of products in the gasoline boiling range decreased considerably in a short period of time, while the amount of products boiling _{below C 1}

^w gaseous components increased considerably. This means an undesirable loss of catalyst selectivity in a short operating time · For example, the selectivity took the catalyst for conversion of the entering feed to G _5-193 ° C (380 ⁰ F) naphtha of 108 vol .-% after 2.8 days of operation at 95 , 9 Vol .- # after 13.3 days of operation. During the corresponding period of time, the selectivity for the formation of products in the boiling range of O ^ and below increased from 11.7% by volume to 30.1% by volume. The fc selectivities are calculated in Table II and the following examples by measuring the percentage by volume of the fraction formed, based on the effluent, by converting it into percentage by volume. This calculation gives the amount of particular fraction obtained as a percentage of the total converted product. Still took

the specific weight of the return flow (decrease <* sr API density), so that it was itself higher than that of the entering. pretreated Hydrokraek feed. This shows a Accumulation of resistant components in the back

009820/1476

lead current due to poor capability of the catalytic converter to crack these materials. On the other hand, if this resistant materials under increasingly sharp ones Conditions were hydrocracked, resulted in a considerable, Licher loss of product selectivity.

Example 2

* - This example shows that when a trailing current

hydrocracking from the hydrocracking treatment described in Example 1 with a catalyst with an amorphous carrier instead of a catalyst with a zeolite carrier, an improved product distribution and conversion can be achieved. after the hydrocracking process was in operation for about 80 days. Approximately equal parts of the withdrawn recycle stream were hydrocracked separately in a single pass, one part with an amorphous supported catalyst and the other part over that described in Example 1. Zeolite-supported catalyst \ the withdrawn recycle stream had the following properties:

009820/1476

16,5773 _ 44 -

Table III 0.906 204- (400) specific weight 24.6 263 (506) Density ⁰ API 40 294- (560) Sulfur, parts-per-million 5 355 (671) Nitrogen, parts-ge-million Distillation (by gas chromatography) 386 (727) Onset of boiling, ⁰ C ( ⁰ P) 467 (872) 5% 494 (923) 10 % 95 30 % 50 % 70 % 90 % Recovery, %

The amorphous supported catalyst used was nickel sulfide on silica-alumina.

Table IV shows a comparison of the results obtained using the two catalysts.

0 09820 / 1A 7 6

Table IV conditions

Total pressure, kg / cm (psi)

Temperature, C (S ¹ )

LHSV

! ^ - circulation, stm ⁵ / m ⁵ (SCF / B)

Conversion to products below 199 ⁰ O (39O ⁰ B ¹ ), vol -96

H ₂ consumption, Stm ⁵ / m ⁵ (SGF / B)

Product distribution
C ₁ -C ₅ ,% by weight

Zeolite

(15OO) (558)

1.0 (7500)

44.0 (13OO)

other C ^, - hydrocarbons _{, Vol.iC 5} , Vol.-96

other C ^ hydrocarbons, vol. 52 - 82 ⁰ C (125 - 180 ⁰ F), vol .-% 82 - 199 ⁰ C (180 - 39O ⁰ F), vol. -96 199 - 343 ⁰ C (390 - 65O ⁰ F), vol .-% 34-3 ⁰ C (650 ⁰ F) , vol. 56 selectivity, vol .-% (82 - 199 ° C; 180 - 39O ⁰ F)

2.70

14.85

5.06

12.51 2.97 9.69

14.61 7.86

48.11

33.2

amorphous

(1500) (552)

1.0 (7500)

46.8 (826)

0.80

1.75

1.31

4.74

o, 56

8.35

41.68

33.04

20.10

88.9

From Table IV it can be seen that the amorphous supported catalyst had significantly better selectivity for cracking the heavy resistant compounds of a hydrocarbon mixture into products in the
Gasoline boiling range compared to the catalyst
with zeolite carrier.

009820/1476

Example 4-

This example demonstrates the improved selectivity of a hydrocracking process to produce gasoline Use of a catalyst system which has a zeolite catalyst in a first hydrocracking stage and an amorphous Comprising catalyst in a second hydrocracking stage, as opposed to using only a zeolite catalyst. The zeolite catalyst used in the first

^ Hydrocracking stage of the two-stage system and in the system was used with only the zeolite catalyst, it was the zeolite catalyst described in Example 1. The zeolite catalyst was in operation for 78.1 days without regeneration, but with 2% by volume of the recycle stream during this time were deducted. In the case of the catalyst with amorphous support used in the second hydrocracking stage it was fresh nickel sulfide on silicon dioxide-aluminum oxide.

^ The petroleum hydrocarbon feeds used

genes are described in Table VI.

009820/1426

WkSIl 3 - 4-7 -

table ¥ 1

203 A. B. specific weight 251 0.898 0.903 Density ° £ FI 269 26.2 25 "1 , Q,
ÄTii.li.TiTißhl (J?) 291 144 ^ 2 149.8 Sulfur oil, parts-per-million 310 180 *
310 Nitrogen, parts-oe-million. 330 10 30th Hydrogen, wt * -% 346 11 "98 11-, 68 Distillation (10 mm) 359 Beginning of boiling, ⁰ G ( ⁰ S ¹ ) 374 (398) 192 (378) 5 ° i ° 389 (484) 247 (477) 10 % 416 (517) -263 (505) 20% 440 (555) 283 (540) 30 ^: / o (590) 304 (579) 40 / O (626) 322 (612) 50% (655) 341 (646) 60 % (678) 356 (673) 70 # (705) 370 (698) 80 70 (733) 384 (723) 90% (781) 405 (761) End point, (825) 420 (788) Recovery, % 95 95

In the single-stage hydrocracking with zeolite catalyst, the feed was hydrocracked and then subjected to fractional distillation to recover (380 ⁰ P) boiling products below about 193 ° C. The fraction boiling above about 193 ° G (38O ° 3?) Was returned to the hydrocracker and cracked "until it was used up.

0098.20 / 1476

BATH C

IB45773

In the two stage zeolite catalyst and amorphous catalyst operation, the first stage feed was hydrocracked with the zeolite catalyst. The effluent from the first step was subjected to flash evaporation, wherein ammonia and hydrogen sulfide from the effluent and below about 193 ° C (380 ⁰ F) boiling Konlenwasserstoffprodukte were removed as separate streams. The remaining, greater than about 193 ° C (380 ⁰ F) boiling hydrocracked effluent was then the second stage with amorphous catalyst fed and hydrocracked therein. The effluent of the second stage was fractionally distilled for the recovery of below about 193 ° C (38O ⁰ F) boiling products. The remaining effluent, boiling above about 193 ° C (380 ° F), was returned to the second stage hydrocracking inlet and cracked to use.

The operating conditions and the products obtained are for both catalyst systems in the table VII indicated.

009820 / U76

Table VII A. A. Two 3-step Zeolite amorphous I. —A 86.3 89.8 B. B. -F = -
vD cn Feedstock One stage, zeolite 106.5 109.1 I. JN Operating time, Ta ^ e A. 114 114 cn Operating conditions 83.2 (1625) (1625) 114 114 --J Total pressure, kg / cm 353 356 (1625) (1625) "^ (psi) 114 (668) (672) 359 363 CO Temperature, G (1625) 0.6-0.4 0.6-0.4 (678) (685) VII ( ⁰ F) 352 1335 1335 0.6-0.4 0.6-0.4 - LHSV, V / h / V (666) (7500) (7500) 1335 1335 3 / * 5
^ -Circulation, stm7r 0.6-0.4 97.7 97.3 (7500) (7500) (SOF / B) 1335 329 333 97.3 100.0 Conversion, vol% (7500) (1850) (1870) - 329 ^ -Consumption, tax number / no 97.4 - (1850) (SGF / B) 356 0.02 0.02 Product distribution (2000) 0.34 0.39 0.52 0.61 0.,% by weight 3.34 3.81 0.52 0.61 Cl, wt .- # 0.02 13.1 13.8 2.98 2.97 C $, wt% 0.0 6.7 7.2 12.3 5.7 ic £,% by volume 3.72 14.4 15.3 5.7 12.2 nCTT, vol.% 1 ^, 5 1.8 2.0 13.7 12.2 OK ^, vol.% 8.7 12.7 17.9 1.0 1.2 nCc, vol.% 16.0 73.6
2.3 65.7
2.7 13 5 14.9 52 ^ 8200 (125-180 ° F),% by volume 2.0 76.2
2.7 78.9 82-193 ° C (180-380 ° F), VoI %
+193 ⁶ O (38O ⁰ F), Vol .- # 10.9 Continuation, table 70.3
2.6

Table 711 Port setting

One stage, zeolite Two stages, zeolite-amorphous

Selectivities

G ₄ -193 ° C. (38O ⁰ P) . _t O ₅ -I93 ° 0 (38O ⁰ P) O
O 52-193 ° C. (125-380 ⁰ P) CP
OD 82-193 ° 0 ti80-380 ° P) to O

125.4-101.6

83.1
72.1

125.1 103.8

88.3 75.3

125.2

103.6

85.6

67.5

125.7

107.2

92.1

78.3

123.5

107.2

93.8

78.9

■ »J CO

16A5773

From Table VII it can be seen that the two-stage process according to the invention with zeolite catalyst and ajQorplieni catalyst showed a superior selectivity towards the formation of products in the gasoline boiling range than the one-stage process implementation with zeolite catalyst even after a longer period of operation. Further, the specif ifeohe weight of Eückführstroms in the two-stage Yerfahrensspeise at 0.843 (36.5 API) was approximately constant, as is apparent from curve 1 of Figure 2, compared to a specific gravity of 0.903 (25 »1 ⁰ API) of supplied pretreated charge.

009820/1478

Claims (8)

* U Tejrfaiüreii for the selective production of hydrocarbons. in the gasoline boiling range through hydrocracking, characterized in that one is a heavy petroleum hydrocarbon charges that are less than about 500 parts-per-container contains organic nitrogen, under hydrocracking conditions with an amorphous hydrocracking catalyst Support and a hydrocracking catalyst with zeolite support in a sequence of catalyst beds in which the catalyst with amorphous support arranged separately from the catalyst with zeolite support sjLt, brings into contact, thereby a Amorphous carrier catalyst which contains a hydrogenation component and has a Cat A activity index greater than about 20, and a zeolite-supported catalyst having pore opening sizes between about 6 and about 15 angstrom units and a hydrogenation component and containing less than about 5 weight percent sodium oxide is used, normally one liquid outflow from the last catalyst bed wins, from this liquid outflow a fraction in the gasoline boiling range separates, the portion of the liquid effluent that boils above the gasoline boiling range, to the touch with the amorphous supported hydrocracking catalyst, and the conversion to below about 204- ° C (4-00 ° F) keeps the boiling products at such a level that the hydrocarbon fresh feed and the recycle fraction 009820/1476 essentially completely converted to products boiling below about 204 ⁰ G (40O ^{0 P).} 2. The method according to claim 1, characterized in that that the heavy petroleum hydrocarbon feed in contact with the catalyst with zeolite support under hydrocracking conditions in a first hydrocracking zone brings, withdraws a normally liquid effluent from the first hydrocracking zone, this normally liquid Outflow to obtain a fraction in the gasoline boiling area separates that part of the liquid outflow that is above of the gasoline boiling section, in a second hydrocracking zone with the amorphous hydrocracking catalyst Bringing carrier into contact, withdrawing a normally liquid effluent from the second hydrocracking zone, the effluent separates from the second hydrocracking zone to obtain a fraction in the gasoline boiling range and the above The remainder of the liquid effluent from the second hydrocracking zone for contact with the gasoline boiling range catalyst located in the second hydrocracking zone with an amorphous carrier. 3. The method according to claim 2, characterized in that that one separates the normally liquid effluent from both hydrocracking zones in a common separation zone. 4. The method according to claim 2 or 3, characterized in that the conversion to below 204 ⁰ O (400 ⁰ F) boiling products in ^ eder of the hydrocracking stages 00982Ö / U76 between about 50 and about 70 ToI .-%, based on the Fresh feed to the corresponding hydrocracking stages holds. 5. The method according to claim 2, characterized in that that the first stage hydrocracking zone is a hydrocarbon feed containing less than about 30 parts-per-million organic nitrogen. 6. The method according to claim 1, characterized in that feed a heavy Erdolkohlenwasserstoff, less than about 100 parts-per-million contains organic nitrogen, brings under hydrocracking conditions in a first hydrocracking zone with a hydrocracking catalyst containing amorphous carrier in contact, a normally liquid Withdrawing effluent from the first stage hydrocracking zone, separating this normally liquid effluent to obtain a fraction in the gasoline boiling range, the part of the liquid effluent boiling above the gasoline boiling range in a second hydrocracking zone with the catalyst with zeolite support, the normally liquid effluent the second stage hydrocracking zone to obtain a fraction in the gasoline boiling range and the liquid effluent from the second stage hydrocracking zone boiling above the gasoline boiling range for contact with the catalyst with amorphous carrier in the first hydrocracking zone z leads back, 7. The method according to claim 6, characterized in that the conversion to below 204 ⁰ C (400 ⁰ S ¹ ) sie- 009820 / U7S 1845: 773 äenäen Products »In ,, each of Hydrokraßkstufen: between about 50 -and about 70 ToIj ₁ - ^ ₁ relative to the Irisehbesehikkung to the corresponding i ^ _r fdrokraefcstttfea hältv 8. Verfahre®, nachAnspruchG oder.7 * characterized in that the HydrokraekzQne first stage e a Hydrocarbon feed charged less than. approximately Contains 10 filings-per-million organic nitrogen 9- method according to claim 1, characterized in that one. a heavy petroleum hydrocarbon feed containing less than about 100 parts-ge-million organic nitrogen, reacting on the amorphous and zeolite supported catalysts without separation of liquid effluent between catalyst beds, converting the feed to below about 204- ° C (400 ⁰ F) boiling products on the catalyst with amorphous support and on the catalyst with zeolite support each below about 40% by volume and the conversion of the feed with the total amount of catalyst between about 40 and 80% by volume, one Separating fraction in the gasoline boiling range from the liquid effluent and returning that portion of the liquid effluent boiling above the gasoline boiling range to contact with the amorphous carrier hydrocracking catalyst. 10 «The method according to claim 9», characterized in that the total conversion to below 204 ⁰ C 009820 / U76 F) boiling products ... between-.about 50 and about Holds 70 yol%. 1Ί. Method according to one of Claims 1 to 10, characterized in that the catalyst used is a zeolite carrier a rare earth exchanged zeolite or T containing Hickel tungsten sulfide or platinum, used· 009820 / U76 Blank page