DK161461B - PROCEDURE FOR CRACKING AND DEVELOPING CARBON HYDRODES - Google Patents

Description

DK 161461 B

The invention relates to a process for catalytic hydrocracking and hydro-dewaxing of a hydrocarbon-containing starting material for the production of low pour point distillates and heavy fuel oils of reduced viscosity.

Catalytic dewaxing of hydrocarbon oils to reduce the temperature at which separation of waxy hydrocarbons occurs is a known process.

A process of this nature is described in The Oil and 10 Gas Journal dated January 6, 1975, on pages 69 - 73.

U.S.A. U.S. Patent No. 3,668,113 and U.S.A. patent no.

3,894,938 also discloses dewaxing followed by hydrotherapy.

Reissue Patent No. 28,398 discloses a method 15 for catalytic dewaxing with a catalyst comprising a zeolite of type ZSM-5. A hydrogenation / dehydrogenation generation component may be present.

A process for hydro-dewaxing a gas oil with a ZSM-5 catalyst is described in U.S.A. pa tent No. 3 956 102.

A mordenite catalyst containing a Group IV or Group VIII metal is used to degrade a low viscosity index distillate from a waxy crude material, as described in U.S.A. Patent No. 4,110,056.

U.S.A. Patent No. 3 755 138 discloses a process for gentle solvent dewaxing to remove high quality wax from a lubricant starting material which is then catalytically dewaxed to the specified pour point.

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U.S.A. Patent No. 3,923,641 discloses a process for hydrocracking naphthas using zeolite beta as a catalyst.

Hydrocracking is a known process and 5 different zeolite catalysts have been used for hydrocracking processes, but these catalysts usually suffer from the disadvantages of not providing product yields that have good temperature properties in terms of flowability, especially reduced pour point and viscosity. -10 site, although they can effectively provide the scaffold yields, one or more of which are consistent with the distillate's intended use. The catalysts used for hydrocracking include an acidic component and a hydrogenation component. The hydrogenation component may be a noble metal such as platinum or palladium, or a non-precious metal such as nickel, molybdenum or olefin or a combination of these metals. The acidic cracking component may be an amorphous material, such as an acidic clay or amorphous silica alumina, or alternatively a zeolite. Large-pore zeolites, such as zeolites X and Y, have been conventionally used for this purpose because the major components of the starting materials (gas oils, coke oven bottom fractions, reduced crude oils, recycled oils, fluid fractionated catalytic cracking unit) are high molecular weight. hydrocarbons which will not enter it into the internal pore structure of the smaller pores zeolites and therefore will not undergo any conversion. Thus, if 30 waxy starting materials such as Amal gas oil are hydrocracked with a large pore catalyst such as in zeolite Y in combination with a hydrogenation component, the viscosity of the oil will be reduced by cracking most of the 343 ° C + material into materials that boils between 343 ° C and 165 ° C. The remaining 343 ° C + material that has not been converted contains 3

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holds most of the paraffinic components of the starting material because the aromatics are preferably converted to paraffins. The unconverted 343 ° C + material therefore maintains a high pour point, so that the final product will also have a relatively high pour point of approx. 10 ° C. Thus, although the viscosity is reduced, the pour point is still unacceptable. Although the conditions are adjusted to achieve complete or almost complete conversion, the high molecular weight hydrocarbons present in the starting material, principally polycyclic aromatics, will be subjected to cracking, resulting in further reductions in the viscosity of the product. However, the cracking products will include a substantial proportion of straight-chain components (n-paraffins) which, in case they themselves have a sufficiently high molecular weight, which they often will constitute a waxy component of the product. Therefore, the final product may be of a relatively more waxy nature than the starting material, and may consequently have a pouring point which is equally unsatisfactory or even more unsatisfactory. A further disadvantage of working under high conversion conditions is that hydrogen consumption is increased. Attempts to reduce the molecular weight of these straight-chain paraffin products will only serve to produce very light fractions, e.g. propane, thereby reducing the desired liquid yield.

During the dewaxing process, on the other hand, a small pore zeolite or a form-selective zeolite such as ZSM-5 as the acidic component of the catalyst and the normal and slightly branched paraffins present in the starting material will be capable of to enter the internal pore structure of the zeolite so that they will undergo conversion. The majority,

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4: in a typical case, approx. 70% of the starting material, boiling above 343 ° C, will remain unconverted because molecularly volatile aromatic components, especially the polycyclic aromatics, are unable to enter the zeolite. Therefore, the paraffinic wax components will be removed to lower the pour point of the product, but the other components will remain so that the final product will have an unacceptably high viscosity, although pour point 10 may be satisfactory.

It has now been found that the heavy hydrocarbon oils can be simultaneously hydrocracked and hydro-dewaxed for production. of a liquid product with satisfactory heel point and viscosity. This desirable result is achieved using a catalyst containing zeolite beta as an acidic component to induce the cracking reactions. The catalyst preferably comprises a hydrogenation component to induce hydrogenation reactions. The hydrogenation component may be a precious metal or a non-precious metal, and it is preferably of a conventional type, e.g. nickel, tungsten, cobalt, molybdenum or combinations of these metals.

According to the invention, there is provided a method for cracking and dewaxing a heavy hydrocarbon oil, comprising contacting the oil with a catalyst comprising zeolite beta. in

In the process of the invention, the hydrocarbon starting material is heated with the catalyst under conversion conditions suitable for hydrocracking. During the conversion, the aromatics and naphthenes present in the starting material undergo hydrocracking reactions such as dealkylation, ring opening and

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cracking, followed by hydrogenation. In addition, the long-chain paraffins present in the starting material, together with the paraffins produced by the hydro-cracking of the aromatics, are converted into products less waxy than the straight-chain n-paraffins, thereby producing a simultaneous dewaxing -ing. The use of zeolite beta is believed to be unique in this regard, thereby producing not only a reduction of the viscosity of the product 10 by hydrocracking, but also a simultaneous reduction of the pour point by catalytic hydrodevelopment.

The process allows heavy starting materials, such as gas oils boiling above 343 ° C, to be converted into products with distillate ranges corresponding to boiling points below 343 ° C, but contrary to known processes using large pore catalysts such as zeolite Y, hydrogen consumption will be reduced, although the product will meet the desired pour point and viscosity specifications. In contrast to dewaxing processes using form selective catalysts, such as zeolite ZSM-5, there is mainly a conversion involving cracking of aromatic components, which ensures an acceptable low viscosity of the product in that distillate. territory. Thus, the present method is capable of producing a major conversion together with a simultaneous dewaxing. This is also achieved with a reduced hydrogen consumption compared to the other types of processes. It is also possible to work 30 with partial conversion, thus affecting the economy of hydrogen consumption while still meeting the pour point and viscosity requirements. The process also produces improved selectivity for the production of materials in the distillate range; the yield of gas and products boiling under the distillate range is reduced.

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As previously mentioned, the process combines elements of hydrocracking and dewaxing. The catalyst used in the process has an acidic component and a hydrogenation component which may be of the conventional type. The acidic component comprises zeolite beta described in U.S.A. Patent Nos. 3,303,069 and Re 28,341, and reference is made to these patents with respect to the | talks about this zeolite and its manufacture. j i}

Zeolite beta is a crystalline aluminum silica zeolite j 10 with a pore size, where there is more than 5 Angstroms. The composition of the zeolite as described in U.S.A. patent no.

3 303 069 and Re 28 341, in the state in which it has just been synthesized, can be expressed as follows: ji 15 [XNa (1.0i0.1-X) TEA] AlQ2.YSi02.WH20 j where X is below 1, preferably below 0.7; TEA represents tetraethylammonium ions; Y is greater than 5 but less than 100 and W is up to approx. 60 (it has been found that the degree of hydration may be greater than originally determined where W was defined as being up to 4), depending on the degree of hydration of the added cation. The TEA component is calculated by difference based on the analyzed value of sodium and the theoretical! c ratio of cation to structural aluminum which should be equal to 1. j 'In the fully base-exchanged form, the zeolite has the beta composition: in [RM (lifl.lX) H] .. A102.YSi02.WH 2 O where X, Y and W have the values given above and n is the valence of the metal M. ji 30 In the partially base-exchanged form obtained on the basis of 7

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the initial sodium form of the zeolite by ion exchange without calcination, the zeolite beta has the formula: (ΐΐΰ.1-X) TEA] A102.YSi02.WH20 When the zeolite is used in the catalysts, it appears at least partially in hydrogen form to provide the desired acidic functionality for the cracking reactions to take place. It is usually preferred to use the zeolite in a form which has sufficient acidic functionality to give it an alpha value of 1 or greater. The alpha, which is a measure of the acidic functionality of the zeolite, is, along with details of the measurement thereof, described in U.S.A. Patent No. 4,016,218 and in J. Catalysis, Vol. V, pages 278-287 (1966), and reference is made to these publications for such details. The acidic functionality can be controlled by base exchange of the zeolite, especially with alkali metal cations such as sodium, by water vapor treatment or by controlling the silica: alumina ratio in the zeolite.

When zeolite beta is synthesized in the alkali metal form, it can be converted to the hydrogen form by forming the intermediate ammonium form as a result of ammonium ion exchange and calcining the ammonium form to form the hydrogen form. In addition to the hydrogen form, other forms of the zeolite can be used in which the original alkali metal has been reduced to less than ca. 1.5% by weight. Thus, the original alkali metal in the zeolite can be replaced by ion exchange with other suitable metal cations, including e.g. nickel, 30 copper, zinc, palladium, calcium and the rare earth metals.

In addition to zeolite beta exhibiting a composition such as

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in

8 I

i i in the veneer of the foregoing, it may also be characterized j by its x-ray diffraction data given in U.S.A. ] Patent No. 3,308,069 and Re. 28 341. The significant j d values (Angstrom, radiation: K alpha doubled by copper, j 5 Geiger counter spectrometer) are as shown in the following Table 1: TABLE 1! - j d values of reflections in zeolite beta

11.40 +0.2 I

1Q 7.40 + 0.2 I

6.70 + 0.2 I

4.25 + 0.1! in

3.97 ± 0.1 I

3.00 + 0.1 j 15 2.20 + 0.1 i

The preferred forms of zeolite beta for am / end in the process are those having high silica content, with a silica: alumina ratio of at least 30: 1. It has ! in fact, it has been found that zeolite beta can be manufactured with a silica: alumina ratio above the maximum of 100: 1, 20 specified in U.S.A. patents 3,308,069 and

Re. 28 341, and these forms of the zeolite provide the best properties of the process. ' Ratio of at least 50: 1 and preferably at least 100: 1 or even higher, e.g. 250: 1, 500: 1, can be used.

The ratios of silica: alumina referred to herein | are the structural conditions or the gridwork conditions, 'i.e. the ratio of the SiO 2 to A 10 tetrahedra which;

^ ** I

together they form the structure of which the zeolite consists. in

It should be understood that this ratio may differ from the ratio of silica: alumina determined by different

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9 ge physical and chemical methods. Eg. For example, a total chemical analysis may comprise aluminum present in the form of cations associated with the acidic positions of the zeolite to give a low ratio of silica: alumina. Similarly, if the ratio is determined by thermogravimetric analysis (TGA) of ammonia desorption, a low ammonia titration can be obtained if cationic aluminum prevents the exchange of the ammonium ions at the acidic positions. These irregularities are particularly troublesome when using certain treatments, such as the dealuminization method described below which results in the presence of ionic aluminum released from the zeolite structure. Care should therefore be taken to ensure that the silica: alumina ratio in the git crosslink is determined correctly.

The ratio of silica: alumina of the zeolite can be determined by the nature of the starting materials used in its preparation and their amounts relative to one another. Therefore, some variation in the ratio can be obtained by changing the relative concentration of the silica precursor relative to the alumina precursor, but definite limits on the maximum achievable ratio of silica: alumina of the zeolite can be observed. For zeolite 25 beta, this limit is usually approx. 100: 1 (although higher ratios can be obtained), and for ratios above this value, other methods are usually required to prepare the desired high silica zeolite. Such a method involves dealuminization by acid extraction and this method involves contacting the zeolite with an acid, preferably a mineral acid such as hydrochloric acid. The dealuminization process proceeds readily at ambient temperature and slightly elevated temperatures, and occurs with minimal losses of 35 crystallinity to form high content forms 10

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also of silica beta with a silica: alumina ratio of at least 100: 1, thereby obtaining ratios of 200: 1 or even higher easily.

The zeolite is suitably used in the hydrogen form j for the dealuminization process, although other cationic j forms can also be used, e.g. sodium. If j these other forms are used, sufficient | !

acid to enable the original cations S

\ The zeolite can be replaced with protons. The amount of 10 zeolite in the zeolite / acid mixture should generally be between limbs 5 and 60 weight- 0.

The acid may be a mineral acid, ie. an inorganic acid | or an organic acid. Typical inorganic acids which can be used include mineral acids such as hydrochloric, sulfuric, nitric and phosphoric acids, peroxydisulfonic acid, dithionic acid. acid, sulfamic acid, peroxymonosulfuric acid, amidodisulfonic acid, nitrosulfonic acid, chlorosulfuric acid and nitric acid. Representative organic acids which may be used include formic acid, trichloroacetic acid and trifluoroacetic acid.

The concentration of added acid should be such that one does not lower the pH of the reaction mixture to an undesirably low level, which could affect the crystallinity of the zeolite being treated. The acidity that the zeolite can tolerate will depend, at least in part, on the silica: alumina ratio of the starting material. ]

In general, it has been found that zeolite beta can withstand concentrated acid without undue loss of crystallinity, but as a general guideline the acid concentration will be between 0.1 N and 4.0 N, usually J 1 between 1 and 2 N. These values are valid regardless of the silica: alumina ratio of the starting zeolite beta. Stronger acids tend to i

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11 to produce a relatively greater degree of aluminum removal than weaker acids.

The dealuminization reaction proceeds easily at ambient temperature, but slightly elevated temperatures 5 can be used, e.g. up to 100 ° C. The duration of the extraction will affect the silica: alumina ratio of the product because the extraction, which is diffusion controlled, is time dependent. Because the zeolites become progressively more resistant to loss of crystallinity as the silica alumina ratio grows, i.e., to become more stable as the aluminum is removed, higher temperatures and more concentrated acids towards the end of treatment can be used than at the beginning thereof, without the accompanying risk of loss of crystallinity.

After the extraction treatment, the product is washed free of impurities with water, preferably with distilled water, until the outgoing wash water has a pH in the approximate range between 5 and 8.

The crystalline dealuminized products obtained using the method according to the invention have essentially the same crystallographic structure as the starting alumina alloy litholite but with increased silica: alumina ratio.

The formula for the dealuminized zeolite beta will therefore be

[xM (100.1-X) H] A109.YSi0 „.WH90 TT L L L

wherein X is less than 1, preferably less than 0.75, Y is at least 100, preferably at least 150, and W is up to 60. M is a metal, preferably a transition metal or a group ΙΑ, 2A or 3A metal, or a mixture of metal

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12 -lil. The ratio of silica: alumina, Y, will usually be in the range of 100: 1 to 500: 1, especially 150: 1 to 300: 1, e.g. 200: 1 or more. The X-ray diffraction pattern of the dealuminized zeolite will be substantially the same as that of the original zeolite, as shown in Table 1 before.

If desired, the zeolite can be steam treated before acid extraction, thus increasing the silica: aluminum ratio and making the zeolite more stable to the acid. The steam treatment also serves to increase the ease with which the acid is removed and to promote the retention of crystallinity during the extraction procedure. j i]

Zeolite beta is preferably used in combination with a]! hydrogenation component usually derived from! in a metal from the groups UA, VIA or VIIIA in the periodic table. Preferred non-precious metals are such as tungsten, vanadium, molybdenum, nickel, cobalt, chromium and manganese, and the preferred precious metals are platinum, palladium, iridium and rhodium. Combinations of 20 non-precious metals such as cobalt-molybdenum, cobalt-nickel, nickel-tungsten or cobalt-nickel-tungsten are exceptionally useful for many starting materials, and in a preferred combination, the hydrogenation component comprises from 0.7 to 7 wt.% Nickel and 2.1 j! 25 to approx. 21 wt% tungsten, expressed as metal. The hydrogenation component can be ion exchanged on the zeolite, impregnated! are nourished therein or physically mixed therewith. If the j metal is to be impregnated in or ion exchanged on zeo- j

left, this may e.g. is done by treating zeo- I

30 left with a platinum metal-containing ion. Suitable platinum compounds include chloroplatinic acid, platinum chloride and various compounds containing platinum amine complex.

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The catalyst can be treated by conventional presulfidation treatments, e.g. by heating in the presence of hydrogen sulfide, to convert oxide forms of the metal, such as CoO or NiO, into corresponding sulfides.

The metal compounds can be either compounds in which the metal is present in the cation of the compound, or compounds in which it is present in the anion of the compound. Both types of connections can be used. Platinum compounds in which the metal is in the form of a cation or a cationic complex, e.g. Pt (NH 2), are particularly useful, as are anionic complexes, such as vanadate and tungsten fractions. Cationic forms of other metals are also very useful because they can be ion exchanged on the zeolite or impregnated therein.

Prior to use, the zeolite should be dehydrated at least partially. This can be done by heating to a temperature in the range of 200 ° C to 600 ° C in air or in an inert atmosphere, such as nitrogen, for 1 to 48 hours. Dehydration can also be carried out at lower temperatures simply by applying vacuum, but longer time is required to achieve sufficient dehydration.

It may be desirable to incorporate the catalyst into another material resistant to the temperature and other conditions used in the process.

Such matrix materials include synthetic and naturally occurring substances such as inorganic materials, e.g. clay, silica and metal oxides. These latter can be either naturally occurring or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. Naturally occurring clays can be mixed with the zeolite, including such 14

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of the montmorillonite and kaolin families. The clays may be used in the crude state as they initially appear in mining, or may initially be subjected to calcination, acid treatment or chemical modification.

The zeolite can be mixed with a porous matrix material such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and tertiary mixtures such as silica-alumina. thoria, silica-alumina-zirconia, magnesia and silica-magnesia-zirconia. The matrix can be in | form of a cogel. The relative proportions of zeolite component and gel matrix of anhydrous oxide on anhydrous basis j can vary widely, whereby the zeolite content j 15 is between 10 and 99 weight percent of the dry mixture, usually between 25 and 80 weight 50 . The matrix itself j may possess catalytic properties, generally of acid | nature. j \

The starting material for use in the process of the invention comprises a heavy hydrocarbon oil such as gas oil,

bottom fractions from coke oven towers, reduced crude oil, I

in bottom fractions from vacuum towers, decontaminated vacuum residues, bottom fractions from a fluidized catalytic cracking unit, or circulating oils. Oils derived from coal, shale or tar sands can also be treated in this way. Oils of this kind usually boil above 343 ° C, although the process is also applicable to oils having initial boiling points as low as 260 ° C.

These heavy oils include high molecular weight, long chain paraffins and high molecular weight aromatics with a high proportion of fused ring aromatics. During the treatment, the fused ring aromatics and the naphthenes are cracked by the acidic catalyst and the paraffinic cracking products undergo together with paraffinic 15

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components of the initial starting material conversion to iso-paraffins with a certain amount of cracking to lower molecular weight materials. Hydrogenation of unsaturated side chains on the monocyclic cracking residues of the original polycyclic compounds is catalyzed by the hydrogenation component to form substituted monocyclic aromatics which are highly desirable end products. The heavy hydrocarbon oil starting material will normally contain a substantial amount of boiling above 230 ° C and will normally have an initial boiling point of approx. 290 ° C, especially approx. 340 ° C. Typical cooking intervals will be approx. 340 ° C to 565 ° C or approx. -340 ° C to 510 ° C, but oils with a narrower boiling range can of course be treated, e.g. such with a boiling interval of approx. 340 ° C to 455 ° C. Heavy gas oils are often of this nature, as are circulating oils and other non-residual materials. It is possible to co-treat materials boiling below 260 ° C, but the conversion rate will be lower for such components. Starting materials containing lighter fractions of this kind will usually have an initial boiling point above 150 ° C.

The process according to the invention has particular utility in connection with highly paraffinic starting materials, because with the starting materials of this kind the greatest improvement of the pour point can be achieved. However, most starting materials will contain a certain amount of polycyclic aromatics.

The process is carried out under conditions similar to those used for conventional hydrocracking, although the use of the highly silicon-containing zeolite catalysts enables the overall pressure requirements to be reduced. One can expediently

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16 in using process temperatures between 230 ° C and 500 ° C, although temperatures above 425 ° C will not normally be used because the thermodynamic conditions of the hydrocracking reactions become unfavorable at temperatures 5 above this point. Generally, temperatures of 300 ° C to 425 ° C will be used. The total pressure is usually in the range between 500 and 20,000 kPa, and the higher pressures within this range are usually preferred over 7000 kPa. The process is carried out in the presence of hydrogen, and the partial hydrogen pressure will normally be between 600 and 6000 kPA. The ratio of hydrogen to the starting hydrocarbon (hydrogen circulation ratio) will normally be between 10 and 3500 n.1.1. Space speed! 15 of the starting material will normally be between 0.1 and 20 LHSV, preferably between 1.0 and 10 LHSV. At low j conversions, the n-paraffins in the starting material are preferably converted to iso-paraffin veneer, but at higher conversions under more extreme conditions, the iso-paraffins will also be converted. The product contains small amounts of fractions boiling below 150 ° C and in most cases the product will have a boiling range between 150 ° C and 340 ° C.

The conversion can be accomplished by bringing the output! The material in contact with a fixed stationary mass;

of catalyst, a fixed fluidized mass, or I

a mass of transport. A simple configuration is a screen mass operation in which the feed material is let through a stationary, fixed mass. With such a configuration, it is desirable to initiate the reaction with fresh catalyst at a moderate temperature. course, which naturally increases as the catalyst ages, to maintain catalytic activity. The catalyst can e.g. regenerated by contact at elevated temperature with hydrogen gas or by burning i

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17 air or other oxygen-containing gas.

A preliminary hydrotreating step to remove nitrogen and sulfur and to saturate aromatics to naphthanes without significant conversion of the boiling interval 5 will usually improve the catalyst properties and allow the use of lower temperatures, higher room rates, lower pressures or combinations of these conditions.

The process of the invention is illustrated by the following 10 examples. All parts and parts of these examples are by weight unless otherwise specified.

EXAMPLE 1

This example illustrates the preparation of a catalyst.

A mixture of zeolite beta (SiO 2 O = 30) with a crystalline size below 0.05 µ, u and an equal anhydrous gamma alumina was extruded to form 1.5 mm tablets. The tablets were calcined at 540 ° C in nitrogen, the magnesium ion exchanged and then calcined in air.

100 g of the air-calcined extrudate was impregnated with 13.4 g of ammonium tungsten (72.3¾ W) in 60 ml of water, followed by drying at 115 ° C and calcination in air at 540 ° C. The extrudate was then impregnated with 15.1 25 g of nickel nitrate hexahydrate in 60 ml of water and the wet tablets were dried and calcined at 540 ° 0Γ

The final catalyst had a nickel content of approx. 4 by weight as NiO and a calculated tungsten content of approx. 10.0 by weight as W0 ^. The sodium content was below

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18.

0.5% by weight as sodium oxide.

EXAMPLE 2

This example describes the preparation of high silica zeolite beta.

A sample of zeolite beta in the form in which it exists just after the synthesis and with a silica alumina ratio of 30: 1 was calcined in flowing nitrogen at 500 ° C for 4 hours, followed by air at the same temperature for 5 hours. hours. The calcined zeolite was then boiled un-.

Reflux with 2N hydrochloric acid at 95 ° C for 1 hour to |

preparation of a dealuminized form of zeolite beta J

with a high content of silica and with a ratio of silica: i in alumina of 280: 1, an alpha value of 20 and a crystallinity of 80% compared to the original one which! 15 is taken to be 100% crystalline. j

The zeolite was ion exchanged to the ammonium form with 1N ammonium chloride solution at 90 ° C reflux for 1 hour followed by ion exchange with 1N magnesium chloride solution at 90 ° C reflux for 1 hour. Platinum 20 was introduced into the zeolite by ion exchange of tetraamine-; complex at room temperature. The metal-exchanged zeolite was thoroughly washed and oven-dried by air calcination-at 350 ° C for 2 hours. The finished catalyst contained 0.6% platinum and tableted, crushed and graded to 0.35 to 0.5 mm. | in Examples 3-5,

The catalyst from Example 1 was evaluated for the catalyst; conversion of an Arabic light gas oil (HUGO), with a boiling range between 354 and 580 ° C. For comparison, a magnesium ion form was also prepared.

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19 exchanged catalyst of zeolite Y (SiC₂ / A₂O₂ = 5) by extrusion with an equal amount of gamma-alumina and impregnated to a content of 4% by weight nickel and 10% by weight u / rem ain.

5 The composition of the starting material, the conditions used and the product analysis are given in the following Table 2.

TABLE 2

Hydrocracking / dewaxing 10

Ex. No. of material 3 4

Catalyst - Mg beta MgY

conditions;

Temp. QC - 423 414 15 Pressure, kPa - 70dtj 7000 LHSl /, hr "1 - 0.54 0.54 H2, n.1.1. ~ 1 - 1674 1318 H2 consumption, n.1.1 1 - 125 193 343 ° C + conversion, 20% by weight - 62.2 56.6

Features: Dry gas + - 3.5 4.1 C ,. - 165 ° C naptha, wt% - 16.6 24.7 165 ° C - 343 ° C distillate, 25 wt% - 40.6 26.3 343 ° C + wt% 100 37.8 44.0 343 ° C + pour point, ° C 40 -1 35 343 ° C + 95% 552 468 528 actual boiling point, ° C 1 ° C + properties; Density, ° API 22.0

Hydrogen,% by weight 12.07 12.7 13.7

Sulfur 2.45 0.04 0.03

Nitrogen 600 80 18

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20 µ TABLE 2 (continued) Pour point, ° C 40 -1 35

Paraffins, vol — S 24.0 31 40

Naphthenes, vol-K 25.3 28 35 5 Aromatics, νο1-? ,7 50.7 41 25

As shown in Table 2 above, the beta catalyst significantly lowered the pour point of the 343 ° C + product at a relatively high conversion of approx. 6Q? I, while the products obtained with zeolite 10 Y catalysts remained waxy. In addition, the beta catalyst converted significantly more of the high-boiling components of the batch, resulting

at a boiling point of the final product of approx. 60 ° C

lower than achieved with the catalyst in Example 4. Hydrogen consumption was also significantly lower, whether calculated on an absolute basis or in relation to the conversion.

For comparison with Example 3, a similar Arab light HVG0 with a boiling range between 370 ° C and 550 ° C over a rare earth metal ion exchange ultrafast zeolite Y (5102: 41 ^ 0 ^ = 75) was hydrocracked. . The zeolite is prepared by water vapor calcination and acid denumination of zeolite Y to a lattice-to-SiO ^^ O ratio of 75: 1, followed by | 25 ion exchange with rare earth metals, extrusion with an equal amount of gamma alumina, and impregnation to a content of 2 wt% nickel and 7 wt% tungsten.

The composition of the starting materials, the conditions used and the product analysis are given in Table 3 below.

in

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21 TABLE 3

Hydrocracking over REY catalyst

Ex. no. material 5 5 Conditions;

Temp. , ° C - 416

Pressure, kPa - 7000 L H S V, hr-1 - 0.67 H2, n.1.1.'1 - 1338 10 Η2 consumption, n.1.1

Properties; Dry gas + - 3.6 - 165 ° C naphtha, wt% - 14.2 165 ° C - 343 ° C distillate, wt% - 41.4 343 ° C + wt% 100 39.6 343 ° C + pour point, ° C 43 32 343 ° C + 95% TBP, ° C 540 504 20 343 ° C + properties;

Density, API 21.7

Hydrogen, wt% 12.17 13.26

Sulfur 2.41 0.01

Nitrogen 555 33 25 Pour point, ° C 43 32

yields;

Paraffins, νο1-? Ό 19 41

Naphthenes, vol% 27 26

Aromatics, vol% 54 33

Claims (10)

A method of cracking and dewaxing a heavy hydrocarbon oil, characterized by contacting the oil with a catalyst comprising zeolite beta. Process according to claim 1, characterized in that the oil is contacted in the presence of hydrogen with a catalyst comprising (i) zeolite beta as an acidic component and (ii) a hydrogenation component. Process according to claim 2, characterized in that zeolite beta has a silica: alumina ratio of over 50: 1. IN 4. A process according to claim 2 or 3, characterized in that the hydrogenation component comprises 15 nickel, tungsten, cobalt, molybdenum or a mixture of two or more of these metals. Process according to claim 4, characterized in that the hydrogenation component comprises nickel and tungsten. 6. A process according to claim 2 or 3, characterized in that the hydrogenation component comprises platinum, palladium, iridium, rhodium or a combination of any two or more of these metals. Process according to claims 1-6, characterized in that the oil has an initial boiling point above 290 ° C. DK 161461 B Process according to claim 7, characterized in that the oil has an initial boiling point above 340 ° C. Process according to claim 8, characterized in that the oil has a boiling point between 340 and 565 ° C. Process according to claims 2-9, characterized in that the oil is contacted with the catalyst in the presence of hydrogen gas at a temperature of 230 ° C to 500 ° C, a pressure of 500 to 20,000 kPa, a room velocity of 0 , 1 to 20, and a hydrogen circulation rate of 10 to 3500 n.1.1 ^.