DE1645729A1 - Process for the selective hydrocracking of straight-chain hydrocarbons - Google Patents

Description

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Our No. 13 89O] g 4 572 D

It's like Research and Engineering Company Elizabeth, N.J., V.St.A.

Get lost in the selective Hydrooracken ^ eradkettiger

Hydrocarbons

The invention relates to the removal of straight chain hydrocarbons from petroleum feeds by selective conversion thereof in the presence of hydrogen. In particular, the invention relates to a selective hydrocracking process which is carried out in the presence of a crystalline metalloaluminosilicate containing rare earth elements which has uniform pore openings of less than about 6 i £ - Units s, preferably about 5 $ ■ diameter.

The Kohlenwasserstoffumwaiidlung and remuneration with catalysts of crystalline aluminosilicate zeolites is known ™ The use of these materials for such purposes as Z ₀ B. hydrocracking extended generally to typical petroleum feeds such as gas oils etc. which are usually useful to as gasoline, lower-boiling products are converted. The crystalline zeolites usually used for such purposes have uniform pore openings of about 6 to 15 S and are therefore nonselective, ie largely all molecules of the charge have access to the zeolite pore structure and are converted. For many purposes, selective hydrocracking is all

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certain types of molecules in the charge to a large extent excluded other molecules desired. For example, this can improve the octane number of heavy gasoline fractions that only the straight-chain hydrocarbons (e.g. olefins, Paraffins, etc.), which lead to a low octane rating, selectively hydrocracked, whereupon the hydrocracked products are removed and finally a product with a higher octane number is obtained. The selective hydrocracking of lubricating oil or gas oil fractions straight chain hydrocarbons contained in it is also a valuable one Means for the purpose of lowering the G-point lowering and for removing wax. The use of a non-selective zeolite with large pores (e.g. from 6 to 15 Å) for individual purposes is largely pointless, since the desired molecules of the charge (e.g. aromatics), Have entry into the zeolite pores and together with the straight-chain Hydrocarbons are converted.

Especially in the remuneration of gasoline fractions for highly qualified Motor gasoline for modern automobiles is common - the octane number and the "purity" or the consistency by means of such Methods to improve such as thermal or catalytic reforming. The extent of the octane number improvement through reforming is usually limited by the formation of coke and gas with increasing reaction temperature. Likewise is the octane number improvement olefinic gasolines by other methods are often unsuccessful; for example, catalytic cracking leads to undesirably high gas and coke formation and hydrofining leads to a loss of octane number. Attempts to solve these problems have generally made use of one or several hydrqyer methods, such as hydrocracking, hydroforming, Hydrodealkylation, etc., as these processes are lesser amounts

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Coke and drying gas form and at the same time deliver a product with a better octane number * However, the indiscriminate use of ZeB. Hydrocracking processes are often nonsensical because products are formed that boil below the gasoline range and thus the gasoline yield is reduced. Hydroforming or catalytic heating is _{also not advisable for certain gasoline feeds, Z 0} B ₀ coker fuels, which contain considerable amounts of sulfur, nitrogen and diolefins, because of excessive coke formation and catalyst deactivation that is too rapid. .Catalytic hydroforming with the formation of aromatics to improve the octane number is ineffective with restrictions that have a low content of cyeloparaffins.

In view of these problems, it is understandable that a selective conversion process that is able to Components in the gasoline charging system that have a low octane rating Removing high octane products with minimal conversion is very desirable. The distance of the low octane components would thus be much better the gasoline octane number without any significant shift in the boiling point

lead empire.

For the removal of wax from loads containing waxy, such as Lubricating oils, middle distillates, etc. for the purpose of lowering the crack point and / or cloud point are currently available Methods available including extraction and adsorption processes etc. In the case of adsorption on "molecular sieves" occur certain difficulties in the large-scale removal of

normal paraffins made from branched-chain and cyclic hydrocarbons. For example, it is generally necessary to use a To use two-stage cycle process, in which the normal paraffins are first selectively adsorbed and then in a separate one Stage are desorbed. Such cycle processes are relative because of the frequency with which the sieves have to be desorbed expensive. In addition, the currently available desorption methods only partially effective because the selectivity and ca-

• The capacity decreases rapidly during operation as a result of carbon-containing build-ups on the adsorbent. Frequent regeneration is therefore required.

The inventive method for removing straight-chain Hydrocarbons is characterized by the use of certain Types of crystalline aluminosilicate zeolites that are uniform Pore openings of less than 6, preferably about 5 A-units to have. The type of zeolite used is explained in more detail below. First, let's look at the differences between the method according to the invention and conventional

φ drive can be shown. The process according to the invention differs from conventional adsorption processes in that the molecular sieves are used to carry out a chemical conversion of the normal paraffins on a selective basis, but not a mechanical separation. This selective conversion is carried out in the presence of hydrogen under critical conditions with regard to temperature, pressure, feed rate and hydrogen rate. The present process has numerous advantages over the conventional processes proposed for removing wax from hydrocarbon oils.

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Normal paraffins that would otherwise be adsorbed on the molecular sieves, continuously become lower-boiling, gaseous products converted that do not remain in the zeolite pores »A desorption is therefore not necessary, also the can be lower boiling products such as kerosene, gasoline, butane etc. easily from the normally liquid portions of the dewaxed product stream separated and recovered as valuable by-products. This one The simplified procedure used is significantly more economical than previous procedures.

An extensive literature has recently been published on the use of crystalline zeolites as hydrocarbon conversion catalysts. For example, United States patents 2971903 and 2971904 describe various hydrocarbon conversion processes in which crystalline aluminosilicates with uniform pore openings between about 6 and 15 Å are used. The zeolites used in the present process have a pore size below 6 Å and preferably of about 5 - & $ this pore size has been found to be necessary and critical for successful penetration. proven leadership of the proposed selective hydrocracking. The use of 5 Å zeolites for s-elective, catalytic conversions, such as Z ₀ B. to dehydrations and hydrogenations, and the possibility of selective cracking of membrane paraffins with the aid of 5 S molecular sieves for the purpose of wax removal, etc. is also has already been recognized. These applications are based on the ability of these crystalline zeolites to prevent molecules of a certain size from entering and to exclude others. . ■

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The very essence of the present invention, what makes it differs from known working methods is that certain, unique 5-Ä-aluminosilicates surprisingly as superior catalysts for selective hydroconversion reactions have shown in general and selective hydrocracking reactions in particular »

It has been found that crystalline zeolites of the 5 Å type, in terms of their selectivity for the conversion of straight-chain hydrocarbons in the presence of hydrogen, through incorporation of rare earth metals, preferably by means of base exchange, can throw even more improved. IT was found to be based on this Catalysts formed in this way are more effective than other zeolite catalysts described so far, and that higher as a result of these Effectiveness in the area in question lower operating temperatures can be applied so that excessive conversion of other desired molecular types of the feed stream is avoided »This leads to increased yields of the desired Product at maximum removal of straight-chain hydrocarbons through their selective conversion into lower-boiling, easily removable materials.

The catalysts used according to the invention are explained in detail below. The starting material is a crystalline aluminosilicate with relatively small, uniform pore openings, ie, openings below 6 Å, in particular between 4 and less than 6 R, z, B. Openings of about 5 5. In particular, the zeolites used have uniform pore openings that are able to

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are to allow the undesired normal paraffinic hydrocarbons access, but largely deny entry to the more valuable branched and cyclic hydrocarbons. The preferred crystalline aluminosilicate zeolites according to the present invention include "Zeolite A" and the natural and synthetic form of erionite. According to the US patent, "Zeolite A" has the following molecular formula in dehydrated form: 1.0 ± 0.2 MgO ί Al2O3: 1.85 ± 0.5 SiO ₂

- ** ■■ '■■ - ' ~

where M is a metal, usually sodium, and η is its valence. The zeolite can be made by heating a mixture? from NapO ^ lpCU »SiOp and HpO (which are supplied by suitable materials) to about 100 G for a period of 15 minutes" to 90 hours or longer. Suitable proportions for these components are described in the patents cited. The products have gleichraässige pore openings of about 4 p in the sodium form, you "can then have materials that same massive pore openings of about 5 A, by · replacement of sodium are converted nenaustauschverfahren by various nations through herköiÄöalieher Io" Except ^H zeolite A * other, relatively small-pore zeolites are used "s» B. the naturally occurring mineral erionite, has elliptical pore openings of about 4.7 to 5.2 R in the larger axis'. The synthetic form of erionite is also suitable and can be produced according to known liethodes, as described in US Pat. No. 2,950,952. Synthetic erionite is characterized by pore openings of about 5 S and differs from the naturally occurring form in its potassium content and the lack of other metals. Other natural zeolites with effective pore diameters less than

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6 R, preferably 5 S _1, are also suggested, for example ghabasite, analzite, mordenite, lebrynite ₌ , natrolite, etc. Both the synthetic and the natural forms of 5 a-zeolites can be used, the only restriction being the pore size. However, it must be too small to allow valuable high-octane components, such as aromatics, to enter, so that their hydrocracking is avoided. The zeolites must therefore exhibit this property under the corresponding hydrocracking conditions, since the effective pore diameters often fluctuate with temperature and pressure. According to the present invention, the alkali metal form of the relatively small-pore crystalline zeolite after its synthesis, ie the sodium and / or potassium form, is treated for the purpose of incorporating rare earth metal cations. This is expediently done by base exchange processes which are familiar to the person skilled in the art. In the most preferred embodiment, W is the relatively small pore zeolite initially a Basenaustii ^ Bch with a hydrogen-containing "cation, _a B _{= a} an ammonium ion, by treating with Ejner solution of an ammonium salt, for example the chloride, nitrate, sulfate, etc. _o, or subjected to a mild acid treatment, in the case of an ammonium ion exchange, the subsequent calcination leads to the release of ammonia and the formation of the "hydrogen form" of the zeolite

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- g. _

contained in the zeolite structure to replace; The rare earth metal cations can be exchanged for hydrogen and / -> ammonium cations more easily than for alkali metal cations. The amnionium ion exchange table carried out first is carried out to such an extent that the alkali metal content of the zeolite is reduced to below about 5 (Jew..Yes, preferably below e ^ v / a 4 jev / .f '·, 90 that ot ^ / a 60f- _t preferably about 30> »c-ler more of the alkali metal cations originally contained in the zeolite. :: ■? n replaced by hydrogen-containing cations With cations containing water, the zeolite is brought into contact with a suitable rare earth metal compound, and rare earth metal ions are introduced into the zeolite by exchange for hydrogen-containing and / or residual alkali metal cations. It is therefore preferable to use such compounds in Rare earth metal ions are sufficient as a cation, Al? a supplier for the rare earth metal ions can be

Large number of rare earth metal compounds wer'len ^ To the ⁿ ora \ i "b? .R> in 7erbin: limg ^ci ii belong the rare earth metal chlorides, bromides, iodides, sulfates, thiocyanates, peroxy sulfates, -ac ^ ta-tn, -sim ^ te, -citrate, -fluoride, -ni ^f r? te, -formiaue, -propionfj.fca, --bu t j-rate, -valerate, -laetate, -tartrete ", etc. _o the only Psschränkung hi νιε-loht lent 1er usable, -seltenen earth metallmli _T ', "hest ° hb that pie müsrcn be sufficiently soluble in the liquid medium used to ensure the necessary transfer of reltenen earth metal ions. As examples of r-filte earth metals - the rare earths with Aborazan! S from 57 to 71 including, as well as Seandi \ un and yttrium are mentioned.

BAD 0 0 9 Ö A 4/1 6 8 1

The rare earth metal salts used can be either salts one. ¹ single rare earth element? or of mixtures of rare earth metals ^? In, z, 3, the rare Erdrr.etallckloride eier Dilymchlorid. A * ¹ enerd chi orid solution let a mixture -: ur rare earth chlorides, which essentially consists of The ChIηriden des "Le 'ithE: n £ ·, Oers, Neodyms and Praseodyms besides smaller amounts of. Samarium, Gadolinium and Yttrium consists;, Rare earth chloride solutions are commercially available and contain the chlorides of the rare earth metals in the following composition:, 45 lew.? ' Cerium (as CeC ₉ ), 24 wt. ^ Lenthanfsls La ₅ O ₇ ), 5 wt. ^ Praseodymium (al ρ Pr ₆ O ₁₁ ), 17 wt. ^ S neodymium (as M ₉ C ₁ ), 3 wt. ^ Saqjarium (as Sm ^ O-,),? Ge-w.jS GcdOliriiurr: (as GdpO ~) .tind 0.8 Gev;, ^ other -rare earth oxides. Didymchlcrid, as it is specifically mentioned in the examples, ie-t alsoc A gem "" l ^r iGh av-5 S il 'finex ^ iol lor ^; den, but has a, lower cerium content »IT consists of the following weight sir. close to rare earths, given as oxides: 45-46 $ Lanthanum, 1-2 # cerium, 9-1 C? S praseodymium, 32-22 $ neodymium, 5-6 $ samarium, 3-4 $ gadolinium, 0.4 $ yttrium and 1-2; * other brine earths, of course are also other rare earth mixtures for the preparation of the compositions according to the invention. ~ eei, ^ net, however, lanthanum, neodymium, prseodymium, samarium and gadolinium, as well as mixtures of rare earth cations, which contain a predominant amount of one or more cations of these types. The exchange medium used is usually water, but I also use other solvents, provided that the rare-erimetallic compound dissociates in this solvent to form ions which are used in the base exchange solution; Ionization of the rare earth metal compound varies depending on the

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respective alkali and / or hydrogen content of the zeolite and the conditions under which the treatment is carried out »However the ion exchange process should be carried out so that the alkali metal content of the original zeolite to below about 5, preferably to less than about 4 wt. $, And about 0.3 "to 10.0, preferably about 1.0 to about 7.5 wt incorporated into the zeolite. The rare earth metal cation exchange is preferably buffered under conditions ^ Acidity performed in the pH range of about 3 to 7.0. The temperature, at which the base exchange is carried out, can be done within a wide range and from room temperature up to elevated temperatures below the boiling point of the treatment solution are sufficient. .

In general, an excess f is applied in Easenaustauschlösung and the contact time between the zeolite and the Basensustauschlösung is controlled by the above-mentioned conditions "Instead of the stepwise base-exchange treatment, the anscfrlieosen in a first treatment with hydrogen-containing cations, and a is the Seltenerdkationbehandlung also Bäsenaustauschlosungen can be used which contain both the hydrogen-containing liatmons and the side metal cations, the necessary limits are observed.

Instead of using the water-stiff / rare-metal form *, it * is According to another embodiment of the invention, it is possible to use a To use rare earth metal-containing zeolites that still have a metal cation of group ΙΪ-Β of the Periodic Table of the Elements.

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In certain cases and / or with certain loads, this form of the zeolite may be desirable. For example, if the alkali metal cations have largely been replaced by the hydrogen-containing ions, complete replacement by rare earth ions can be uneconomical. In addition, the incorporation of cations from the HB group often results in a greater selectivity in the conversion of heavy gasoline, probably because of the smaller pore diameter a solution of a Group II-B metal cation occurs * Suitable Group II-B metals include cadmium and zinc, with zinc being preferred. For example, ordered a preferred solution from the aqueous solution of a zinc salt such as zinc chloride, zinc acetate, etc .. In this embodiment, to be so operated largely ₌ ion exchange, that a final Zeölithprodukt is obtained which in its alkali metal content to less than about 5 weight "$, preferably has been reduced below 2.5 wt. $, with the remainder of the cation content of the zeolite consisting of the rare earth and Group II-B metal ions in addition to occasional amounts of hydrogen. The preferred weight ratio of the Group II-B metal to the rare earth metal is in the range from about 0.5: 1 to about 10: 1, preferably from about 1: 1 to about 7: 1. =

In general, the end result should be the various stages of ion exchange in a reduction of the alkali metal content to the Above amount range exist, and the ion exchange is

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preferably carried out in such a way that at least 60 fo, preferably more than 80 fo, of the exchangeable cation content consist of the rare earth and hydrogen-containing and / or group II-B metal cations. In summary, it can be said that the selective hydrocracking of straight-chain hydrocarbons according to the present invention is carried out with a catalyst which consists of a relatively small-pore, crystalline zeolite, which has a base exchange both with hydrogen-containing cations and with side earth metal cations, or with group ΙΪ -Β-metal cations and rare earth metal cations, or with hydrogen-containing cations, rare earth metal cations and group II-B metal cations, or with rare earth metal cations all one _{: has been} subjected »

In a further stage in the production of the zeolite materials used according to the invention, the exchanged zeolite is preferably combined with an active hydrogenation metal component of groups VB, VI-B, VII-B or VIII of the Periodic Table. Examples of such hydrogenation components are the metals cobalt, nickel, platinum, palladium, etc. These metals can be present in the form of the free metal or the oxide or the sulfide or as mixtures of such metals, oxides or sulfides. Metals of the platinum group (doho, metals of the platinum and palladium series) are preferred for the present invention, and palladium in particular o The incorporation of the active metal can be done by any known method, e.g. B _{0 by} ion exchange with subsequent reduction, by impregnation, etc. If Pal-Indium "is used, then the zeolite is preferably with

■ ■: ■■ ■. ■■■■■: ■ ; '.-. ■' ■ -><*** ■

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an ammoniakali see solution of palladium chloric! (Pd (NH-,) λ CIp) brought into contact in sufficient amount to achieve the desired amount of palladium in the end product, and then dried at low temperatures and calcined at a temperature of 425 to 540 C. If the zeolite was previously subjected to an ammonium ion exchange, then the calcination in this stage serves to release ammonia and to form the "hydrogen form" of the zeolite. If a metal from the platinum group is used, a reduction stage is generally preferred, for example by treatment with hydrogen. The amount of active hydrogenation metal component can range from about 0.1 to about 25 weight percent based on the weight of the final product. In the case of use of platinum group metals, e.g. _o B "palladium, the preferred amount is between about 0.1 and 6, for example is between o, 3, and 1.3 wt» $, based on dry zeolite. The presence of an additional hydrogenation factor is preferred, but not always necessary, especially when group II-B metal cations, for example ₃ zinc cations, have been incorporated into the zeolite. In this case the platinum metal 3.11 need not be introduced] to achieve selective hydroconversion, although its presence will contribute somewhat to the overall activity of the catalyst «,

According to a further form of exercise of the present invention ' the activity and effectiveness of the cation-exchanged here described Zeolites are significantly improved in that the zeolites are used for treating normal paraffins before they are used containing hydrocarbon oils with sulfur in

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Be brought into contact. The zeolite is preferably sulphurized in order to increase its paraffin removal ability, either by contact with a sulfur-containing charge or, if the charge is low in sulfur, with hydrogen sulphide or an added sulfur compound which easily increases under the conditions used Hydrogen sulphide can be converted, for example with carbon disulfide, etc. This sulphurisation should be carried out to such an extent that about 0.5 to 15 parts by weight of the zeolite material are incorporated. When the catalyst contains no additional hydrogenation, however, the group II-B-metal, for example zinc _0, then a Sulfaktivierung is usually required.

In order to improve the Gkt number improvement by the process according to the invention, charges of gasoline or heavy gasoline are generally used, which can consist of either low-boiling or high-boiling gasoline. A typical low-boiling Beechi ~ !: has a v.ig Sieber calibration of about 10-177 ⁰ C, preferably from about Tj to 93 ° C, while a SchwertenzinheSchickung a Siedebe-

rich, has from 125 to 288, preferably 149 to 232 ⁰ C. Examples of such gasolines, both low-and high-boiling, are not distilled Benz infractions such as E ^ - to CSS gasolines, serious non-distilled spirits, heavy Kokerbenzin, heavy steam cracked gasoline, heavy catalytic gasoline etc, "*

The charges that are used to remove wax according to the invention Processes suitable may generally refer to hydrocarbon oils ranging between about 150 "-. And

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about 595 ° C and instesondere boil between about 205 and about 345 C »öelen to sqlchen include heavy gasolines, kerosenes (e.g." B, between 150 and 26O ⁰ C boiling point), diesel fuels, jet fuels, heating oils, gas oils, middle distillates, oil bases, etc. _o The process according to the invention is particularly effective in removing wax and similar normal paraffinic constituents from middle distillate and gas oil fractions in order to reduce their pour point, cloud point and tendency to solidify. The preferred middle distillate fractions have a total normal paraffin content in the range from about 5 to 50% by weight, in particular 10 to .30% by weight; and the preferred gas oil fractions have a total normal paraffin content of about 10 to 50, in particular 20 to 30 wt. ^ ₀ According to the invention, the feed is preferably preheated to the contact temperature and then, preferably in the vapor phase or mixed vapor-liquid phase (in the case of a high-boiling gas oil feed) and with a fixed catalyst bed arrangement, brought into contact with the crystalline zeolite material at the same time with a hydrogen-containing gas stream. The feed stream is preferably passed through the bottom of the catalyst bed, and the normal paraffin contained therein are hydrocracked selectively to give products with lower molecular weights. The product stream is withdrawn from the zeolite catalyst contact zone and passed to a vapor-liquid separation zone in which the lower boiling, normally gaseous hydrocarbons are removed and the normally liquid bottoms product recovered, and preferably in bulk tere fractions, gasoline and / or dewaxed fractions with desirable boiling ranges etc. is further broken down.

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.For the implementation of erfindüngsgemässen process operating conditions depend on the particular feedstock and the end products from "For the octane improvement of gasoline feedstocks see typical conditions as follows: a temperature from 205 to 510 ⁰ C, preferably 345 to 455 ° C; a pressure of 14 to 280 atmospheres, preferably 35 to 175 atmospheres; a space velocity of 0.2 to 20, preferably 0.4 to 2 vol / vol. / h, and a hydrogen speed of 17.8 to 178 nr / l, preferably 26.2 to 89 nr / hl feed »For the GasbT and middle distillate feeds (For wax removal purposes) the following typical conditions are used: a temperature of 345 to 480 G, preferably 370 to 455 ° C; a pressure of 7 to 350 atmospheres, preferably 28 to 70 atmospheres; a space velocity of 0.1 to 10, preferably 0.5 to 2 volumes of feed per volume of crystalline zeolite per hour; and the presence of hydrogen, which is preferably simultaneous with the feed at a rate of about. 8.9 to 178 »preferably 17» 8 to 53.3m / hl feed is introduced.

The following examples explain the invention and its implementation.
example 1

This example explains the production of the invention Catalysts., The starting material was a synthetic form of Mineral erionite, which had been synthesized by known processes and had elliptical pore openings of about 5> 2 Å in the longer axis and a silica / alumina molar ratio of about 7 «

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A 500 g sample of the synthetic erionite was mixed with an ammonium chloride solution treated to remove the alkali metal cations (i.e., potassium and Sodium cationan) to be exchanged for ammonium ions «, The ammonium exchange was carried out by suspending the sample in 1000 g of water and 1954 g of a 23% by weight ammonium chloride solution were admitted. The mixture was agitated for four hours, the product recovered by filtration and suspended in 2000 g Water washed with further agitation for an hour. This procedure was repeated three times, making the total number of replacement stages was four.

Following the ammonium ion exchange, part of the Erionite sample is further exchanged with a side earth metal cation solution, which consists of a 3.7% strength by weight aqueous solution of didymium chloride duration. 200 g of the DiCl-, «öHoO salt became 300 g of the Ammonium form of erionite (on a dry basis) given in 1800 g Were suspended in water. The slurry was heated to about 71 ° C heated and kept for 6 hours with stirring at this temperature. The hot slurry was filtered, washed with 7 / water and ash dried overnight at 121 to 177 ° C.

Then 0.5% by weight of palladium was added to the rare earth metals Erionite incorporated by adding 126 g of the oven-dried product (112 g on dry basis) suspended in 200 water and 15 cm Palladium ammonium chloride, which contained 37.5 mg palladium / cm 2, was added with agitation. The agitation was continued for three hours continued at room temperature. The excess liquid

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was decanted and the material dried. The analysis of the catalyst obtained gave the following values: (wt. Fo)

Alkali metal 2.4

Silica 74.0 Clay it, 7 palladium 0.5 Rare earth oxide 3.4

The catalyst was then calcined at a high temperature, gradually heating it to 54O ° C. and maintaining it at this temperature for about three hours. During the oilisation stage, ammonia was released so that hydrogen cations remained at the points on the zeolite structure that were previously occupied by ammonium ions. This catalyst was designated as F.atHly <? Ator "A". For comparison purposes, two other catalysts prepared Catalyst "B" were prepared in an identical manner to the catalyst "A", with the exception that the Se3 tenercirnetnll -Cation exchange level was omitted / left. The An ^? Ily.p? Diec · -? Kai-alj ^r sstcrr resulted in the following values: ('jew.fS)

Alkali metal 2.5

Silica 76.7

Tcnerde. 18, 1

Palladium O ₁ ?

Katal3 ^r sator "C" w "? R, a similar, relatively small pore zeolite catalyst made from Denx natural mineral erionite by Austauec 'with Zinkkntionen v / ar. This catalyst was prepared as follows: a 3 "1c g sample vcn erionite wurSe suspended in 2000 g water Sine lös-ang from 453 g ZInIcCiIlM- ¹ Id in 5 ^ 0 g (from a deposit in Pine Valley, Nevaa?). V / srser 'varde

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Added to room temperature and agitated the mixture for 4 hours. Dn-s product was obtained by filtration and washed by suspending it in 2,000 g of water with stirring for one hour. No ch filtering was this procedure. repeated twice so that the total number of replacement levels was three. The zinc-containing product was dried overnight at 121 to T49 ° C; it weighed 236 g. In order to incorporate palladium into the zinc erionite, the 236 g of product were suspended in 600 g of water, and 50 cm of palladium-ammonium chloride containing 37.5 mg of Pd / cm ^ were added with agitation. Stirring was continued for one hour continued at room temperature. After filtering, washing, drying and calcining the catalyst showed the following analysis: 0.6 G-ev / o ^ palladium, 7.7 Gew.fi zinc, SiO ₂ / Al _P O -, - ratio of 7.3: 1 «The Catalyst ¹¹ C ″ represents an excellent, selective hydrogen cracking catalyst which has been known for a long time.
Example 2 - ".

Catalysts "A ¹ ·," B "and" C "of Example 1 were tested for their effectiveness in the selective hydrocracking of a gasoline charge derived from an Arabian crude oil 0.65, a Sieber calibration of 4-3 to 85 ⁰ C, a Normalp ent is dependent of 17.0 $ and a Normalhexangehalt of 35, ¹ / £. All catalysts were initially by contact with the same feed containing 1.0 wt contained. fo carbon disulfide, sulfaktiviert. Then fresh gasoline feed to the · was passed down through a fixed bed in the form of sulfaktivierten Kügeichen present catalyst, under

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simultaneous supply of hydrogen. The conditions used were: a space velocity of 0.5 "volume charge per volume of catalyst per hour; an initial water toffee speed of about 35 »6 m / hl feed, and a pressure of 35 atmospheres “The catalyst performance was measured by the disappearance of normal paraffins as a result of conversion to C, gases. With The results obtained for the three catalysts are as follows Table summarized:

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¹ j table

Selective Hydro crack en by nraMnchem C ^ -

C, _r - gasoline

0; 5 v / v / h; 35 atm; 35.6 m ³ H ₉ / hl

catalyst

Palladium content, wt. ^ Predominant cation Temperature, C

Product channel

Weight ^

nC

Urnw ^ nii.ung nO,., Conversion ηGV,

0 17.0

35.1

0.5 0.5

Didym / Wnnr.eretoff Wassere! .Off 399 371 .399

7.1.3 5 6.6 0.3 0.5 0.0 0.0 9 a 100 100

43.3

0.9

9? 99

0.5 zinc

427

399

371

61, 5 63.8, 56.7 37, 2 O ₁ 1.9 4.7 13 ,? O, 3 0.1 0.4 .-L ₁ -1 88 39 7? ? P 100 99 37

As can be seen from the table, a catalyst according to the invention, ie the catalyst "/!" in terms of effectiveness and / or selectivity than the comparison catalysts "B." and "2" superior. Di ° understanding 2ate> i can. are upgraded by comparing (1) the conversion of the nC ^ and n-Cg paraffins, (2) formation of C _/ product, and (3) the temperature required for an almost 100 $ conversion, if taken into account these criteria is readily apparent, dans of catalyst "/ -"; d: -m Kataiyrator "? B i is superior because it causes a higher conversion of Normalpnraffinen in gHiiWnm .gleichen temperatures, however, is the catalyst.""" the. Catalyst “? Excessive cracking in the case of catalyst "A" is refluxed to a minimum. Thus at comparable temperatures of 399 and-371 ⁰ C, the amount of C.-product formed approximately equal to the Nermalpsraffingeh lt ^ in the feed in the case of the catalyst "A", while in the case of the catalyst "B", the CL formation in these temperatures is significantly higher, which indicates. that excessive cracking. of other substances than the undesirable normal paraffins took place. The superior effectiveness and selectivity of the catalyst according to the invention is thus proven. Compared to catalyst “C”, catalyst “A” shows a clear superiority at comparable temperatures, as can be seen, for example, from the n-Cc conversion values. In addition, the '' ^ "results obtained at 371 ⁰ C is still better than that with the catalyst" C scored "at 427 ° C results, with the catalyst

from which in turn; _s results in the superiority of the catalyst according to the invention. With the catalysts of the invention, significantly lower temperatures can thus be used, whereby excessive cracking of desired products can be reduced to a minimum, but the conversion of the undesired normal paraffinic constituents in the feed can be kept at a maximum value it should be noted that the catalyst "C" represents a well-known, excellent selective hydrocracking catalyst,
Example 3

The catalysis before "A" of Examples 1 and 2 (palladium / didymium / hydrogen-erionite) was used to treat a Eouisiana / Mississippi-Gasolbe slurry in order to achieve a lowering of the pouring point by selective hydroconversion of the waxy components. The awake gas oil charge vnxrae down through a plague bed 'es catalyst with a raurage ε chwindigke.it of 0.5 Vol./Volv/h , a pressure of 35 ^r -t ^f i and a temperature of 371, respectively. 427 ° G, the yield of boiling product XSO 0 and its pour point and turbidity v.nk ^ were tested. The results obtained are compared below with those of a conventional wax removal process - each of which is a solvent mixture. from methyl ethyl ketone / r-: ethylisobu ~ ylko-- ^i; cn (3; 1-ratio) in an amount _{= of} 3 parts by volume, solution gFm: tt-rZ. ^r "jf 1 part of gas oil application, = In these experiments v -.-. rf'- the Eepohcikixng heated to € 6 C and then long? am ^ b" g§k "ihlt, -Ψ: r? cA ^ v ^ . Increasing amounts of solvent generically added "Vrurden. ? ei -? 0 ° C 'Λ-the wax is filtered and dewaxed _ ^X L gev.-orxc-n = I'ie Zr'je'misse- are summarized in Table 2 ;

^: 0098U / 1681

κ - / ■■ ·

2 Temp., ⁰ C / Vol. Ai 0.860
4.5
4.5 35 C. atü; 35.6 m ³ H ₂ Al 427 with Tabel Selective hydrocracking 34.6 371 0.871
-48.5
-23.5 Wax removal
d.Lösgsmtl. Wax removal from Louisiana / Mississippi gas oil
a palladium rare earth erionite ■ Yield of per feed
duct over 16O ⁰ C
(Wt. $) "'". 100
Analysis of the fraction above 160 ⁰ C: 89 -20 0.5 vol / Density at 15.6 ^° C
Pour point, ⁰ C
Cloud point, ⁰ C 0.869
-6.5
-5.5 80 0.369
- £ 23.5
-17.5 ^

The superiority of the inventive catalyst is manifested in the higher yield, the lower pour point and the lower cloud point in the 427 ° C. test compared to the normal solvent-wax removal process.
Example 4

A catalyst ¹¹ D "was prepared by using a 147 g sample of the oven-dried, didymium-exchanged ammonium ion of Example 1 (13-P - * ^ on a dry basis) which had a Di _o 03-G content of 3.4 Gevv was slurried in 1 liter: hot water and added 46.3 g of ZnSO, .7 H ₀ O. The slurry was heated and stirred for 30 minutes, filtered, washed with water and dried in the oven Material was analyzed and found 2.2 wt.% DipO-> and 13.8 wt. % ZnO, from which it can be seen that some of the rare earths had been replaced by zinc cm ^ of a Pd (NH ^). Clp solution containing 0.615 g of Pd. The slurry was intermittently stirred for 3 hours at room temperature and then oven dried

00 98 44/168 1

- "2fr - ■■■ .-" ■

• 16Λ5729

The catalyst contained 0.5% by weight of Pd. It was then shaped into cylindrical bodies of 5 χ 5, which were ground and sieved to give particles from 0.21 to 1.17 in size.
Example 5

The procedure described in Example 3 for lowering the pouring point of the Luuisiana / Iviississippi gas oil charge was repeated, using the '¥ Xji palladium / zinc / didymium erionite from Example 4. The results obtained are those of the conventional solvent in Table 3 Kit

tel wax removal procedure compared: -

Table 3

Removal of wax from Louisiana-Kississippi-Gascl
Palladium-rare earth-zinc-erionite Temp., ⁰ C / ⁵ ZoI.A; 35 atm; with e iiie'm 3.2 -20 0.5 vol., Yield of product
above 160 ⁰ C
Analysis of the fraction Selective ^ H ..Ai , Ö7C
-43 - 30 Density at 15.6 ^° C.
Pouring point, C
Cloud point, ⁰ C 371 Hydrocracking wax removal.
" d _a Lcsuhgsmtl. 0.569.
-23/5
-Π, 5 feed
1st floor .. "c8
over 160 ^u C: - 427 0.660 o;
4.5 "-9
4.5 -7 , 9. e 565 0
, 5
, 5

The superiority of the catalysts according to the invention in selective hydrocracking is expressed in turn in the higher yields and the lower pouring points in the 427 ^C C experiment compared with aeri. Solvent removal process carried out at -20 ^{0 C.}

009844/1681

Claims (6)

Claims 1. A process for the selective hydrocracking of straight-chain hydrocarbons contained in a hydrocarbon feed, characterized in that the feed is brought into contact under hydrocracking conditions in the presence of hydrogen with a catalyst which consists of a crystalline aluminosilicate zeolite containing rare earth metals, which has uniform pore openings of less than about 6 Å units, preferably about 5 S. units . 2. The method according to claim 1, characterized in that one Catalyst used, which additionally has a metallic hydrogenation component of groups V-B, VI-B, VII-B or VIII of the periodic System of elements contains. 3. The method according to claim 2, characterized in that the, metallic The hydrogenation component is a platinum group metal. 4 * Method according to claim 1 to 3 »characterized in that one a zeolite is used which additionally contains cations of group II-B * i of the periodic table or hydrogen-containing cations or mixtures which contains two cations. 5. The method according to claim 4, characterized in that the cation of Group II-B is zinc cation. 6. The method according to claim 1 to 5, characterized in that one a zeolite used, which is a base exchange with hydrogen shark * term cations has been subjected. 0 0 9 8 U k I \ 6 81 7 «Procedure according to. Claim 1 to 6, characterized. That one a! catalyst used by contact with a sulfur compound has been sulfactivated. ■ 8, method according to claim 1 to 7, characterized in that one as feed gasoline fractions, gas oil fractions or middle-style lat used fractionally. 9 "catalyst for the selective hydrocracking of linear Kohlenwas-'serstoffe, consisting of the combination of a metallic hydrogenation ungskomponente with a rare earth containing crystalline zeolites Aluminosilifcat mitgleiehföriaigen pore openings of from about 4 to less than 6 _v S units. 10 «catalyst according to claim 9», characterized in that the
metallic hydration components from a metal of group ¥ 11
of the periodic table. 13 »Catalyst according to claim 9-10» characterized in that the zeolite additionally cations of group II-B of the periodic system or hydrogen-containing cations © of the semis of the two
contains. Esso Re Beareh and Engineering Company