JPH0631327B2 - Method for simultaneous catalytic hydrocracking and hydrodewaxing of hydrocarbon oil by zeolite beta - Google Patents

Description

The present invention relates to the catalytic hydrocracking and hydrodewaxing of hydrocarbon feedstocks to produce low pour point distillates and reduced viscosity heavy fuel oils.

Catalytic dewaxing of hydrocarbon oils, which lowers the temperature at which separation of waxy hydrocarbons occurs, is a known method. A process of this nature is described in Oil and Gas Journal, Jan. 6, 1975, pages 69-73, and US Pat. Nos. 3,668,113 and 3,894,938 also describe dewaxing and hydrofinishing. ing.

Reissued U.S. Pat. No. 28,398 describes a catalytic dewaxing process using a catalyst comprised of ZSM-5 type zeolite. There may be coexistence of hydrogenation / dehydrogenation components. ZSM-5
Dewaxing process of light oil using type catalyst is disclosed in US Pat. No. 3,956,102.
No. As described in U.S. Pat. No. 4,110,056, a Mordenalto catalyst containing a Group VI or Group VIII metal is used to dewax a waxy crude oil to a low VI (viscosity index) distillate. U.S. Pat.No. 3,755,138
A method is described in which a high-grade wax is removed from a lubricating oil raw material by a mild solvent dewaxing operation, and then catalytically dewaxed to a specific pour point. U.S. Pat. No. 3,923,641 describes a naphtha hydrogenation method using zeolite beta as a catalyst.

Hydrocracking is a well-known process, and various zeolite catalysts have been used as catalysts in the hydrocracking process, but they have one or two properties that match the purpose of using distillate oil. Although effective in obtaining the distillate yields that it had, it had the drawback of not being useful in the production of products with good cold flow properties, especially low pour points and viscosities. The catalyst used for hydrocracking consists of an acidic component and a hydrogenating component, the hydrogenating component being a noble metal such as platinum or palladium or a non-noble metal (base metal) such as nickel, molybdenum, tungsten or combinations of such metals. Will. The acidic cracking component may be zeolite or acidic clay or an amorphous material such as amorphous silica-alumina or in its place. Large pore zeolites such as zeolites X and Y have been conveniently used for this purpose. The reason for this is that the main components of the feedstock (light oil, coker tower bottom oil, atmospheric residual oil, recycled oil, FCC bottom oil) are high molecular weight hydrocarbons, and the internal pore structure of small pore zeolites This is because they cannot enter and therefore are not converted. When a waxy feedstock such as Amal gas oil is hydrocracked by combining a large pore zeolite such as zeolite Y with a hydrogenation component, most of the substances at 343 ° C + (343 ° C or higher) Is decomposed into a substance having a boiling point of 165 ° C. to 343 ° C., and the viscosity of oil decreases. What remains as unconverted 343 ° C. + material consists of the majority of the paraffinic components of the feedstock as aromatics are preferentially converted to paraffins. Accordingly, the unconverted 343 ° C + material will only have a high pour point, so that the final product of the hydrocracking will also have a relatively high pour point of about 10 ° C. Therefore, although the viscosity has decreased, the pour point is still unpleasant. Even when the conditions are adjusted to complete or near complete conversion, high molecular weight hydrocarbons, which are mainly present in the feed as polycyclic aromatics, result in a further reduction of the product viscosity. It will be disassembled. However, the decomposition product powder contains a substantial amount of the straight-chain component (n-paraffins), and even when the straight-chain component itself does not have a sufficiently high molecular weight, it often happens that this is the case. Will make up. Therefore, relative proportions, the final product is more "waxed" than the feedstock.
And will have an unsatisfactory pour point equal to or even higher than the feedstock. Operation at high conversion conditions has the additional disadvantage of increasing hydrogen consumption. The attempt to reduce the molecular weight of these linear paraffinic products only increases the lighter fractions, such as propane, which reduces the desired liquid product yield.

On the other hand, in the dewaxing process, small pore zeolites or shape selective zeolites such as ZSM-5 are used as the acidic component of the catalyst, and the normal and slightly branched paraffins present in the feedstock are It can enter and be transformed into the internal pore structure of the zeolite. Most of the feed-typically about 70% -boiling point above 343 ° C-will remain unconverted. The reason is that bulky aromatic components, especially polycyclic aromatics, cannot enter the zeolite. The paraffinic wax component is subsequently removed and the pour point of the product is reduced, but other components remain, so the final product may have a satisfactory pour point but an unacceptably high viscosity. Would have.

It has now been found that heavy hydrocarbon oils can be hydrocracked, hydrocarbon dewaxed simultaneously to obtain liquid products of satisfactory pour point and viscosity. The desired result is that zeolite as an acidic component that induces a decomposition reaction.
Obtained using a catalyst containing beta. The catalyst preferably also contains a hydrogenation component that accelerates the hydrogenation reaction.
The hydrogenation component may be a noble metal or a non-noble metal and is suitably of the known type, for example nickel, tungsten, cobalt, molybdenum or combinations thereof.

In accordance with the present invention, there has been provided a process for cracking and dewaxing heavy hydrocarbon oils which comprises contacting the oil with a catalyst containing zeolite beta.

In the process of the present invention, a hydrocarbon feedstock is heated with a catalyst under conversion conditions suitable for hydrocracking. During the conversion reaction, aromatics and naphthenes present in the feedstock undergo hydrocracking reactions such as dealkylation, ring opening and decomposition followed by hydrogenation. Long-chain paraffins present in the feedstock are converted with paraffins produced by aromatic hydrogenolysis into products that are less waxy than straight-chain paraffins and undergo simultaneous dewaxing in this process. Will be there. The use of zeolite beta is believed to be unique in that it not only lowers the product viscosity by hydrocracking but also simultaneously lowers the pour point by catalytic hydrodewaxing. .

This process produces heavy feedstocks such as gas oils with boiling points above 343 ° C in the boiling range below 343 ° C, in contrast to prior art processes that use large pore catalysts such as zeolite Y. Can be converted into things. Hydrogen consumption will be low even if the product passes the desired specifications of pour point and viscosity. In contrast to dewaxing processes using shape selective catalysts such as zeolite ZSM-5, the overall conversion reaction, which also involves the decomposition of aromatic components, is acceptable for products in the spilled oil range. Guaranteed low viscosity. Therefore, the present invention allows simultaneous dewaxing and overall conversion reactions to occur. In addition, this method was able to reduce hydrogen consumption compared to other types of methods. It is also possible to carry out partial conversion reactions to further reduce hydrogen consumption while meeting pour point and viscosity requirements. The process also achieves good selectivity for the production of materials in the middle distillate range; reducing the yield of gas and lower boiling product than the middle distillates.

As mentioned above, the process of the present invention is a combination of hydrocracking and dewaxing factors. The catalyst used in the process has an acidic component and a hydrogenation component, the type of which will be known. The acidic component consists of zeolite beta, which is described in U.S. Pat.No. 3,303,069 and U.S. Reissue Patent No. 28,341, which are hereby incorporated by reference for details of this zeolite and its preparation method. deep. Zeolite beta is a crystalline aluminosilicate zeolite with a pore size greater than 5 Angstroms. The composition of the zeolite is described in U.S. Pat. No. 3,303,069 and U.S. Reissue Pat. No. 28,341, and in the synthesized form can be represented by the following formula.

[XNa (1.0 ± 0.1-X) TEA] AlO ₂ · YSiO ₂ · WH ₂ O where X is less than 1, preferably less than 0.7; TEA represents tetraethylammonium ion; Y is greater than 5 W is less than 100, and W is up to about 60 depending on the degree of hydration and coexisting metal ions (the degree of hydration is higher than the initial measurement in which W was up to 4). It has been discovered.) The TEA component is calculated from the analytical value of sodium and the difference from individual cation-pair structural aluminum. In the fully base-exchanged form, beta has the following composition: However, X, Y, and W are the above-mentioned values, and n is the valence of the metal M. From the original sodium form of theolite to the partially ion-exchanged form obtained by ion exchange without calcination, the zeolite beta has the formula: When used as a catalyst, this zeolite is at least partly in the hydrogen form, since it must have an acidic function for the decomposition reaction to be carried out.

It is usually preferred to use the zeolite in a form that provides sufficient acidic function to provide an α (alpha) value of 1 or greater. The α value is a measure of the acidic function of zeolite, and it is described in US Pat. No. 4,016,218 and Journal of the Catalysis Vol. 6, pp. 278-87 (1966) together with the details of its measuring method. The references are cited here for reference. The acidic function (acidity) can be adjusted by base exchange of the zeolite, especially by exchange with alkali metal cations such as sodium, by steaming, or by adjusting the silica to alumina ratio of the zeolite. When synthesized with the alkali metal type,
Zeolite beta can be converted to the hydrogen form by forming an intermediate stage ammonium form as a result of exchange with ammonium ions and calcining the ammonium form to obtain the hydrogen form. In addition to the hydrogen form, other forms of zeolite that have been reduced to less than about 1.5 weight percent of the original alkali metal can also be used. Thus, the initial alkali metal of the zeolite can be replaced by ion exchange with other suitable metal cations, including nickel, copper, zinc, palladium, calcium and rare earths, by way of example.

In addition to having the composition defined above, Zeolite Beta is not limited to U.S. Patent No. 3,308,069 and U.S. Reissue Patent No. 28,
It can also be characterized by the X-ray diffraction data disclosed in No. 341. The following table shows specific d values (unit: angstrom, light source: copper Kα doublet, and Geiger counter spectrometer).

Table 1 Zeolite beta d-value for diffraction 11.40 + 0.2 7.40 + 0.2 6.70 + 0.2 4.25 + 0.1 3.97 + 0.1 3.00 + 0.1 2.20 + 0.1 The preferred type of zeolite beta for use in the process of the present invention is It is a highly siliceous type having a ratio of silica to alumina of 30 or more and 1: 1. 10 as most characterized in claims 3,308,069 and US reissue patent 28,341
It has been found that zeolite betas having a silica to alumina ratio of greater than or equal to 0: 1 can in fact be prepared and that such forms of zeolite provide the best effect in the process. At least 50 to 1 and preferably at least 1
A ratio of 00: 1 or higher, for example 250: 1, 500: 1, can be used.

The ratio of silica to alumina as defined herein is the ratio of structural or network, ie the ratio of SiO ₄ tetrahedra to AlO ₄ tetrahedra which together make up the structure by which the zeolite is composed. It should be noted that the physical and chemical methods used to measure the ratio of silica to alumina may vary. For example, gross chemical analysis incorporates aluminum present in the cation form with acidic sites on the zeolite, thus giving a low silica to alumina ratio. Similarly, when determining the ratio value by thermogravimetric analysis (TGA) of ammonia desorption, if the cation aluminum interferes with the exchange of ammonium ions onto acidic sites, a low ammonia titration value is obtained. right. The discrepancies in these values are particularly tricky when using certain treatments, such as dealumination below, which result in the absence of ionic aluminum in the zeolite structure. Therefore, great care must be taken to ensure that the silica-to-alumina ratio of the reticulate is measured correctly.

The silica to alumina ratio of the zeolite can be determined by the nature of the starting materials used in its preparation and their relative amounts to each other. Therefore, it is possible to change the relative concentration of the silica precursor to the alumina precursor to change the ratio to some extent, but it is recognized that there is a certain limit to the maximum silica to alumina ratio of the resulting zeolite. For zeolite beta this limit is usually around 100
It is 1 (although higher ratio values are obtained), but for ratios above this value other methods are needed to prepare the desired highly siliceous zeolite. One such method is zeolite extraction with an acid, which comprises contacting the zeolite with an acid, preferably a mineral acid such as hydrochloric acid. Dealumination proceeds at ambient temperature (room temperature) or mild heating temperature (100 ° C.) with only a slight reduction in crystallinity, and at a ratio of at least 100: 1 silica to alumina. It is not readily achievable to produce a highly siliceous form of zeolite beta at a ratio of 200, 200 or higher to 1.

Zeolites are in the hydrogen form and are conveniently used for dealumination processes, but other cation forms such as, for example, the Natriu form can also be used. When using these types, sufficient acid should be used to also replace the original cation moieties in the zeolite. The amount of zeolite in the zeolite-acid mixture should generally be 5 to 60% by weight.

The acid may be a mineral acid, which is an inorganic acid or an organic acid. Representative inorganic acids that can be used include hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, peroxodisulphonic acid, dithionic acid, sulfamic acid, peroxomonosulfuric acid, amidodisulphonic acid, nitrosulphonic acid, chlorosulfuric acid, pyrosulfuric acid, and sulfite. There are mineral acids such as nitric acid. Representative organic acids that can be used include formic acid, trichloroacetic acid, and trifluoroacetic acid.

The concentration of acid added should be such that it does not lower the pH of the reaction mixture to undesirably low levels that affect the crystallinity of the treated zeolite. The acidity that a zeolite can withstand will be due, at least in part, to the starting silica to alumina ratio. It has been found that zeolite beta generally tolerates concentrated acids without excessive loss of crystallinity, but as a general indicator acid should be 0.1N to 4.0N, usually 1 to 2N. These values hold regardless of the silica to alumina ratio of the zeolite beta starting material. Stronger acids tend to have a greater effect on the relative degree of aluminum removal than weaker acids.

The dealumination reaction readily proceeds at ambient temperatures, but mild heating temperatures up to 100 ° C can be used. Extraction time will affect the silica-to-alumina ratio of the product, as the diffusion is rate limiting and time dependent.
However, as the silica-to-alumina ratio increases, the resistance of the zeolite to a decrease in crystallinity gradually increases, i.e., the zeolite becomes more stable as aluminum is removed, thus increasing the crystallinity. Higher temperatures and more concentrated acids are available closer to the end of the process than at the beginning without the risk of loss of. After the extraction process, the product is washed free of impurities, preferably with distilled water, until the wash process effluent has a pH in the range of about 5 to 8.

Although the silica to alumina ratio is increasing, the crystalline dealumination product obtained by the process of the present invention has substantially the same crystalline structure as the starting aluminosilicate zeolite. The formula for dealuminated zeolite beta is therefore Where 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 IA, IIA, or IIIA metal or mixtures thereof. The ratio of silica to alumina, Y is generally in the range of 100: 1 to 500: 1, most commonly for example 200
Alternatively, it is within the range of 150: 1 to 300: 1, which is 1: 1 or more. The X-ray diffractogram of the dealuminated zeolite is substantially the same as that of the original zeolite shown in Table 1. If desired, the zeolite can be steamed prior to acid extraction to increase the ratio of silica to alumina ratio and to make the zeolite more stable to acids. Steaming has the effect of facilitating the extraction of zeolite with an acid and suppressing the decrease in crystallinity during the extraction process.

The zeolite beta is preferably the Vth of the periodic table.
For use with hydrogenation components derived from Group A, VIA or VIIIA metals. The preferred non-precious metal is tungsten,
Vanadium, molybdenum, nickel, cobalt, chromium, manganese, etc., and preferred noble metals are platinum,
Palladium, iridium, and rhodium. Combinations of two or more non-precious metals such as cobalt-molybdenum, cobalt-nickel, nickel-tungsten or cobalt-nickel-tungsten are exceptionally effective for many feedstocks. In the preferred combination, the hydrogenation component, expressed as metal, comprises 0.7 to about 7 weight percent nickel and 2.1 to about 21 weight percent tungsten. The hydrogenation component can be exchanged with the zeolite, impregnated into the zeolite or physically mixed with the zeolite. When the metal is impregnated into the zeolite or exchanged with the zeolite, it can be carried out, for example, by treating the zeolite with ions containing platinum metal. Suitable platinum compounds include various compounds including chloroplatinic acid, platinum chloride and platinum ammine complexes. The catalyst can be treated with a conventional presulfiding water treatment, for example by heating in the presence of hydrogen sulfide, for the purpose of converting the morphology of the oxide of the metal, eg CoO or NiO, into the corresponding sulfide.

The metal compound may be one in which the metal is present as the cation of the compound, and the other is present as the anion of the compound. Both types of compounds are available. Cation or, for example, Pt
Compounds in which the metal is present in the form of a cationic complex such as (NH ₃ ) ₄ Cl ₂ are particularly useful, as are anionic complexes such as vanadate and metatangranate ions. Other forms of metal cations are also very useful as they can be ion exchanged or impregnated into the zeolite.

The zeolite must be at least partially dehydrated prior to use. This is accomplished by heating to a temperature of 200 ° C. to 600 ° C. for 1 to 48 hours in air or an inert atmosphere such as nitrogen. Dehydration is possible at lower temperatures using vacuum, but it takes longer to obtain a sufficient amount of dehydration.

It is desirable to include other properties in the catalyst that will withstand the temperatures and other conditions used in the process. Such matrix materials include synthetic and natural materials such as clay, silica, inorganic materials such as metal oxides. The metal oxides can be natural, gel-precipitated or gels containing a mixture of silica and metal oxides. Natural clays that can be composed with zeolites include those of the Montmoriomate and Kaolin families. The clay can be used in the raw material state as it is as it is mined, or it can be used by first calcination, acid treatment or chemical modification. Zeolites are porous matrix materials such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania or silica-alumina-tria,
It can be a ternary porous matrix material and composition such as silica-alumina-zirconia or magnesia, and silica-magnesia-zirconia. The matrix may be in the form of co-gel. The relative ratio of the zeolite component to the inorganic oxide germanix on an anhydrous basis can vary widely and the zeolite content is from 10 to 99 weight percent of the composition, most commonly 20 to 80 weight percent. . Matrices themselves have generally acidic, catalytic properties.

The feedstock of the process of the present invention is a heavy hydrocarbon oil such as light oil, coker tower bottoms, atmospheric bottoms, vacuum distillation bottoms, degassed vacuum bottoms, FCC bottoms, or FCC cycle oils. Is. Synthetic oils from coal, sire and tar sands can also be processed in this way. Oils of this type are typically 343 ° C.
The method is also effective for oils with higher boiling points but lower initial boiling points up to 260 ° C. These heavy oils consist of high molecular weight long chain paraffins and high molecular weight aromatics which are mostly fused ring aromatics. In the process, fused ring aromatics and naphthenes are decomposed by acidic catalysts to paraffinic decomposition products. This paraffinic decomposition product is converted into isoparaffins together with the paraffinic components in the feedstock from the beginning, and some of them are decomposed into low molecular weight substances. The unsaturated side chains of the cracking residue, which were initially polycyclic but converted to monocycles by treatment, become highly preferred end products, monocyclic aromatics with substituents, by catalysis of hydrogenation components. Heavy hydrocarbon feedstock is usually 2
Containing a substantial amount of boiling point above 30 ° C. and usually about 290
It will have an initial boiling point of C, most commonly about 340C. A typical boiling range would be about 340 ° C to 565 ° C or about 340 ° C to 510 ° C, although narrower boiling range oils, of course, may also be processed, for example those of about 340 ° C to 455 ° C. right. Heavy heavy oils such as cycle oils or other non-residual substances are common. Substances with a boiling point of 260 ° C or lower can be treated at the same time, but the conversion of such components will be low. Usually 1 for feedstocks containing light components of this species
The initial boiling point is 50 ° C or higher.

When this method is specifically applied to highly paraffinic feedstocks, the pour point can be greatly improved due to its properties. However, most raw materials contain some polycyclic aromatics.

Although the use of advanced siliceous zeolite catalysts lowers the total pressure required, the process of the present invention is conventionally carried out under conditions similar to those used for hydrocracking. 230 ° C to 5
A process temperature of 00 ° C can be conveniently used, but 425
Temperatures above 425 ° C. are not normally used because temperatures above ° C. render the hydrocracking reaction thermodynamically less favorable. Generally, temperatures of 300 ° C to 425 ° C are employed. The total pressure is in the range of 500 to 20,000 kPa, and high pressures of 7,000 kPa or higher in this range are usually preferred. The process operates in the presence of hydrogen and the hydrogen partial pressure is usually 600 to 6,000.
It will be 0 kPa. The ratio of hydrogen to hydrocarbon feedstock (hydrogen circulation ratio) will typically be from 10 to 3,500 nll ^-1 . The space velocity of the feed will typically be 0.1 to 20 LHSV, preferably 0.1 to 10 LHSV. At low conversion rates, n-paraffins in the feedstock are converted compared to iso-paraffins, but at high conversion rates under high temperature severity conditions, iso-paraffins are converted to iso-paraffins.
Paraffins will also be converted. The product is 150 ℃
Fewer lower boiling fractions, in most cases the product is 1
It will have a boiling point of 50 ° to 340 ° C.

The conversion reaction is carried out by contacting the feed with a stabilized fixed bed, stable fluidized bed or moving bed of catalyst. The simplest form is a trickle-bed operation in which the feed is run through a stationary fixed bed. In such a form, it is desirable to start the reaction at a mild temperature using a new catalyst, and to raise the temperature, needless to say, in order to maintain a certain catalytic activity according to the deterioration of the catalyst. The catalyst can be regenerated at high temperature, for example by contact with hydrogen gas, or the deposit can be incinerated in air or with other oxygen-containing gases. A pretreatment hydrorefining process that removes nitrogen and sulfur and saturates aromatics to naphthenes without substantially changing the boiling range usually improves the practical performance of the catalyst, lower temperatures, higher space velocities. , Allows the use of lower pressures or combinations of these conditions.

The method of the present invention will be specifically illustrated by the following examples. Unless stated otherwise, all percentages and percentages are by weight.

Example 1 This example illustrates a method for preparing the catalyst.

A mixture of zeolite beta (SiO ₂ / Al ₂ O ₃ = 30) with a crystallite size smaller than 0.05 micron and an equal amount of γ-alumina on an anhydrous basis was extruded into 1.5 mm pellets.
The pellets were calcined in nitrogen at 540 ° C., exchanged for magnesium, and then calcined in air.

100 g of air calcined extrudate was impregnated with 13.4 g ammonium metatungstate (72.3% W) in 60 ml water. It was then dried at 115 ° C and calcined at 540 ° C in air. The extrudate was then impregnated with 15.1 g nickel nitrate hexahydrate in 60 ml water. The moist pellets are then dried 54
It was calcined at 0 ° C.

The finished catalyst has a nickel content of about 4% as NiO and W
It had a calculated tungsten content of about 10.0% by weight as O ₃ . Sodium content is 0.5 as sodium oxide
It was less than wt%.

Example 2 This example describes the preparation of advanced siliceous zeolite beta.

A sample of the zeolite Beta in the as-synthesized form having a silica to alumina ratio of 30: 1 was calcined at 500 ° C. for 4 hours in a stream of nitrogen. It was then calcined at the same temperature for 5 hours with air. The calcined zeolite was then refluxed with 2N hydrochloric acid for 1 hour at 95 ° C for the production of dealuminated products. The highly zeolite type of the obtained zeolite beta is 28
It had a silica to alumina ratio of 0 to 1, an α-value of 20. Assuming 100% crystallinity of the starting material,
As a result of comparison therewith, the crystallinity was 80%.

This zeolite was converted to ammonium form by refluxing with 1N ammonium chloride solution at 90 ° C. for 1 hour. Then 1
The mixture was refluxed with N magnesium chloride solution at 90 ° C. for 1 hour. Platinum was introduced into this zeolite by ion exchange with a tetraammine complex at room temperature. The metal-exchanged zeolite was thoroughly washed and oven dried at 350 ° C. for 2 hours by air calcination. The finished catalyst contained 0.6% platinum. This was made into small spheres and crushed to a size of 0.35 to 0.5 mm.

Example 3-5 The catalyst of Example 1 was evaluated by a catalytic conversion reaction of an arabyanlite gas oil (heavy vacuum gas oil HVGO) having a boiling range of 354 ° C to 580 ° C. For comparison, a magnesium-exchanged zeolite Y (SiO ₂ / Al ₂ O ₃ = 5) extruded with an equal amount of γ-alumina and containing 4 wt% nickel and 10 wt% tungsten was also prepared and used. .

The feedstock composition, the conditions used and the results of the product analysis are shown in Table 2.

As is clear from Table 2, at a relatively high conversion rate of about 60%, the beta catalyst has a temperature of 343 ° C + (boiling point of 343 ° C or higher).
Although the pour point of the product was significantly reduced, the same product obtained from zeolite Y was still waxy. Not only that, the beta catalyst converted the high-boiling components of the feedstock to a greater extent. As a result, the end point of 343 ° C. + product of Example 3 was about 55 ° C. lower than that obtained in Example 4.

For comparison with Example 3, rare earth-exchanged ultrastable zeolite Y (SiO ₂ / Al ₂ O ₃ = 75) was used to hydrogenate a similar arabian light heavy vacuum gas oil with a boiling range of 370 ° C to 550 ° C. Disassembled. The zeolite was prepared by steam calcination and acid dealumination treatment of zeolite Y to a ratio of 75: 1 reticulated silica to alumina. It was then exchanged for rare earth and extruded with an equal amount of gamma-alumina to impregnate it to contain 2 wt% nickel and 7 wt% tungsten.

Table 3 shows the feedstock properties, reaction conditions, and product analysis results.
It was shown to.

Front Page Continuation (56) References JP-A-55-131091 (JP, A) JP-A-54-6 (JP, A) JP-B-49-34444 (JP, B1) JP-B-47-32723 (JP , B1) US Pat. No. 3308069 (US, A) US Pat. No. 3923641 (US, A)

Claims (10)

[Claims] 1. A method for decomposing and dewaxing a heavy hydrocarbon oil, which comprises contacting the heavy hydrocarbon oil with a catalyst containing a zeolite beta. 2. A process according to claim 1, characterized in that the oil is contacted in the presence of hydrogen with a catalyst consisting of (i) a zeolite beta as acidic component and (ii) a hydrogenation component. 3. The method of claim 2 wherein said zeolite beta has a silica to alumina ratio of 50: 1 or greater. 4. A process according to claim 2 or 3 in which the hydrogenation component comprises nickel, tungsten, cobalt, molybdenum or a mixture of two or more of these metals. 5. The method of claim 4 wherein the hydrogenation component comprises nickel or tungsten. 6. The method according to claim 2 or 3, wherein the hydrogenation component comprises platinum, palladium, iridium, rhodium, or a mixture of two or more of these metals. 7. The method according to any one of claims 1 to 6, wherein the oil has an initial boiling point of 290 ° C or higher. 8. The method according to claim 7, wherein the oil has an initial boiling point of 340 ° C. or higher. 9. A method according to claim 8 wherein said oil has a boiling point of 340 ° to 565 °. 10. A temperature of 230 ° C. to 500 ° C., a pressure of 500 to 20000 kPa, a space velocity of 0.1 to 20 and 1
The oil according to any one of claims 2 to 9, wherein the oil is contacted with the catalyst in the presence of hydrogen gas under the condition of a hydrogen circulation ratio of 0 to 3500 n.ll ^-1. Method.