JPS59156437A - Metal catalyst having shape selectivity and catalytic reation using same - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel shape-selective metal catalyst, a method for preparing the catalyst, and a wide variety of catalytic processes using the same.
Shape-selective catalytic action using molecular sieves was developed by P.B.Wine, B.V., and Rieu Frillette (P.).

13, Weisz and V, J-Frillette
) by the Journal of Physical Gummistry (
It was first specified in J. Phys. Chem, Vol. 64, p. 302 (1960).

Since then, the properties of various zeolites as shape-selective catalysts have been extensively elucidated. For example, F. Y. Chin and W. E. Gautsud (1” J-Y,
Chen and.

W, E+Garwood) is the Journal of Catalysis.
) Volume 52, pages 458-458 (1978), “Catalytic Properties of a Novel Shape-Selective Zeolite, ZSM-5”
s of ZSM-6, a New 5hape 5l
The shape selectivity of ZSA(-5) in e-active Zeolites has been fully described.On the other hand, only little attention has been paid to the use of zeolites as shape selective supports for catalytic function.

P.B. Wine, V.L.F., R.W. Martman and F.B.Mower (P, B, WeiszxV, J, Fr1lette+R
, W, Maatmnnαnd F, B, Mo?
I)eγ) is published in the Journal of Catalysis (Jow
nal of Catalysis) Volume 1 807-8
“Catalytic action of crystalline alkinosilicates” on page 12
0Molecular shape (selectivity) reaction (Catalysis by
Crystalline Aluminosilica
te8 H-Aiolecwlar-8hape Re
A shape-selective olefin hydrogenation catalyst consisting of platinum incorporated in zeolite A (hereinafter referred to as "incorporated") was described in "A-ctions". U.S. Pat. No. 8,140°822 to Wine discloses a hydrogenation process using platinum-containing zeolites; U.S. Pat. A method for preparing zeolite catalysts containing platinum or palladium is described.
e) US Pat. No. 8,575,045 discloses the use of platinum on zeolite A for selective hydrogenation.

A catalyst and process for the selective hydrogenation of ethylene in the presence of propylene using a combination of zeolites and hydrogenating metals is disclosed in US Pat. No. 8,496,246. Chemical Engineering Progress Symbodicum (Chem, Eng, Prog,
Kinetics and Catalysis J (Sl/m7)-) No. 73, Volume 63
ysis) 1967, page 86, “Molecular Engineering of Shape-Selective Catalysts”
gineering ofShape-8electi
Nis-Wai-Ching and P-B Wine described hydrogenation by platinum catalysts using phosphine-poisoned (platinum (ion) exchanged sodium mordenite type) zeolite.

The culmination of outstanding technologies related to zeolite-supported metal catalysts and shape-selective catalysis was developed by G.N. Lab (, 7,
A.

Rabo) American Chemical Society Monograph CAC3Mon
og-rah) No. 171 1 Zeolite Chemistry and Catalysis (Ze omite Chemistry and C
K. M. Minachev and Y. I. Isakov (K.

M, Minache? 7and Y, I, l5a
Chapter 10 “Catalytic Pro-perties of Metal-Containing Zeolites” by
of Metal-Ovntaining Zeoli
tes)” and Nis M Sicily (S, M, Cs
1csery) fChapter 12 1 Shape selective catalysis (Shape-Sel g ctiveCat
lysis)'' is particularly important.

This 1 is characterized in that the molar ratio of silica to alumina is 12 or more and the constraint coefficient (C, 1,) as defined later is in the range of approximately 1 to 12, such as ZSM-5. A shape-selective metal catalyst prepared to incorporate the functions of a zeolite metal has never before been prepared.

In accordance with the present invention, a novel shape-selective metal catalyst and method for preparing the same have now been provided. The use of a specific type of zeolite and a novel reduction method, which provides metal catalyst components such as platinum, palladium, nickel, etc., provides shape selectivity. All characteristics are that the molar ratio (hereinafter abbreviated as "silica/alumina molar ratio") is 12 or more and the constraint coefficient is approximately in the range of 1 to 12.

The preparation of novel shape-selective metal catalysts is based on specific types of zeolites (C1I--112: SiO2/Al120) as described above.
s 12 or higher) and then heat the zeolite-supported metal at a high temperature (100°C to 500°C).
) is achieved by reduction with or without hydrogen in the presence of one or more unsaturated hydrocarbons. It will be appreciated that activation of a metal catalyst requires reduction of the catalyst.

The prior art taught such reductions as using hydrogen only in a hydrogen atmosphere or followed by oxygen. Reduction with hydrogen alone without the addition of unsaturated hydrocarbons such as olefins will yield a catalyst with activity but no shape selectivity. Preferred metal catalyst components that can be used in the present invention are selected from Group I metals of the Periodic Table, including platinum, palladium and nickel;
Special platinum is preferred. The shape-selective metal-containing catalyst prepared according to the present invention has a selectivity of 2 for the selective hydrogenation of hexene-1 to 4,4-dimethylhexene-1.
．． It has a value between 0 and υdog.

The present invention relates to a conversion process in which a feedstock consisting of an organic compound is contacted with the novel shape-selective catalyst described above under reaction conditions. Organic compounds in such raw materials include alkenes, dienes, polyenes, alkynes, cyclenes, aromatic hydrocarbon compounds, alkyl aromatic hydrocarbon compounds, and paraffins.

The crystalline zeolites used in certain embodiments of the present invention are members of a specific class of zeolite materials that exhibit unique properties.

Such zeolites have a low alumina content, i.e. a high silica/alumina molar ratio, but even when the silica/alumina molar ratio exceeds 30, they are very sensitive to many reactions, such as decomposition reactions. The catalytic activity generally depends on the aluminum atoms in the framework and/or the cations associated with aluminum and nium, so the high activity of the catalyst is significant.

For example, other zeolites of type X and A are treated with steam at high temperatures, which causes irreversible collapse of the framework (despite these zeolites retaining their crystallinity for long periods of time). ζWhen coke is formed, it can be removed by calcination at a higher temperature than normal reaction conditions in order to maintain its activity. Therefore, long-term continuous operation can be carried out between regenerations by combustion of oxygen-containing gases such as air (difficult carbonaceous deposits).

An important feature of the crystal structure of this particular type of zeolite is the effective pore size intermediate between the small pore ring (Linde) A and the large pore ring (Lind, e) X, i.e. The pore window (p
The reason is that the free space ζ in the crystal has an entrance/exit with selective constraints. These rings are formed from regular memorials of tetrahedra that form the cationic framework of the crystalline zeolite, and the centers of the tetrahedra (which may be silicon (or azbenium, or other elements) It should be understood that the atom and the oxygen atom themselves are bonded.

It should be understood that the term "zeolite" in the present invention should not be limited to those containing both silicon and aluminum entirely.

For the purposes of the present invention, the term "zeolite"
it, e)' means porotect silicate fACporo
tectosilicates), ie, porous crystalline silicates containing silicon and oxygen atoms as major components.

Other components will be present in amounts as low as t1, usually less than 14%, and preferably less than 4%. Such minor components include aluminum, gallium, iron, boron, and similar elements thereof, but aluminum is preferred and aluminum will be used as a representative in this specification for the purpose of explanation. Minor components can be present alone or in combination.

The silica/alumina molar ratio mentioned above can be determined by known analytical methods. The higher the value of this ratio, the more densely possible the formation of strong cationic frameworks of zeolite crystals and the presence of other cations in the binder or in the cationic channels. It shows the ratio that excludes aluminum present in the form. Zeolites with a silica/alumina molar ratio of 12 or more are used, although in some cases it may be advantageous to use zeolites with a higher silica/alumina molar ratio. Zeolites useful in the present invention therefore have silica/alumina molar ratios of 70 or higher, or 300 or higher, or even 500 or higher.

Furthermore, the zeolite ζ moss characterized in this paper contains virtually no alumina, and therefore the silica/alumina molar ratio can reach infinity, and in some cases (amber zeolites are useful). have been discovered and even preferred. Some "high silica" zeolites are also included in this invention. After activation, this particular type of zeolite has a higher resistance to water than It acquires a large intracrystalline sorption capacity for n-hexane, that is, exhibits "hydrophobicity."

The particular type of zeolite used in this invention has an effective pore size such that it is free to sorb n-hexane. Furthermore, its structure restricts the entry of larger molecules.
Must see. In some cases, it is possible to determine the presence or absence of an entrance with constraint conditions from the crystal structure of the core. For example, when the pore windows in the crystal are composed only of 8-membered rings of silicon and aluminum atoms, the entry of molecules with a cross-sectional area larger than n-hexane is excluded, and this type of zeolite is suitable for our needs. It is not intended to be. A 10-member ring pore window is preferred, but even such a zeolite becomes useless if the ring shrinks too much or the pores become blocked.

Theoretically, a 12-membered ring should not provide an effective constraint that would provide effective reaction properties as referred to in the present invention, but T
MA offretite shrunken 12
The membered ring structure indicates that there is an entrance with certain constraint conditions. 12 others that can be used in the present invention for other reasons
Member ring structures may also exist. Therefore, the effectiveness of a particular zeolite should not be judged solely from theoretical structural considerations.

In order to judge whether or not a certain zeolite has an entrance that has the necessary constraint conditions for molecules with a larger cross-sectional area than n-paraffins, it is possible to determine whether or not a zeolite has an entrance that has the necessary constraint conditions for molecules with a larger cross-sectional area than n-paraffins. (By passing an equal N mixture of n-hexane and 8-methylpentane to
It is easy to measure zeolite dex). Zeolite samples, whether tablets or extruded products, are crushed to a particle size similar to coarse sand and filled into a glass tube.
The zeolite is treated at 100°C (1005?) by passing air through it. The zeolite was then flushed with helium and the temperature was increased to 290°C (55°C) such that the overall reaction rate was between 10% and 60%.
Adjust between 55″F) and 510°C (s50″F).

The hydrocarbon mixture was prepared at a liquid hourly space velocity of 1 (i.e., 9 volumes of zeolite per hour to the same volume of liquid hydrocarbons) such that the molar ratio of helium to (total) hydrocarbons was 4:1 (
Dilute with helium and pass over zeolite. Normal operation 2
After 0 minutes, a sample of the reaction mixture is taken and analyzed, most conveniently by gas chromatography, to determine the proportion of unreacted residue of each hydrocarbon.

The above experimental method is suitable for most zeolites.
A given overall reaction rate of 60% to 60% can be obtained by anyone and represents the preferred conditions, but for very low activity samples such as zeolites with exceptionally high silica/alumina molar ratios. In rare cases, it may be necessary to use even more severe reaction conditions. 540°C (10%) to obtain a minimum overall reaction rate of 10%.
Conditions may be adopted in which the temperature is raised by 1 to 05F) and the liquid hourly space velocity CLESV) is 0.1 or less.

There are even cases where the activity is so low (ie, when the silica/alumina molar ratio approaches infinity) that the restraint factor cannot be satisfactorily measured for total heat. In this case, the exact same structure (
In other words, the constraint coefficient of a substance that has the same crystal structure determined by an X-ray diffraction image, etc., but whose constraint coefficient can be measured (that is, a type containing anopena) is defined as the constraint coefficient of the substance.

The constraint coefficient is calculated by the following formula.

The constraint coefficient indicates the ratio of decomposition reaction rate constants for these two types of hydrocarbons. Zeolites suitable for the present invention are those having a constraint coefficient in the range of 1 to 12.

Typical material restraint coefficient ((:’, 1.) C, I.

ZSM-40,5 ZSM-58-8 -8ZS 1 i 8・
7ZSA(-12,2 ZSM-289,I ZSM-854,5 ZSM-882 Beta 1
．． 5REY0.4 Erionite 88
The above-mentioned constraint factors are important and even critical definitions for the zeolites used in the present invention.

The nature of this parameter itself and the iterative method used to determine it allows that a given zeolite may be tested under slightly different reaction conditions and therefore exhibit a different constraint factor than conventional ones. are doing. It appears that the constraint coefficient varies slightly depending on the severity of the operation (reaction rate) and the presence or absence of a binder. Similarly, other factors such as the size of the zeolite crystals, the presence of trapped impurities, etc. Therefore, it should be understood that it is possible to select test conditions to set the constraint coefficient of a particular zeolite at two or more within the range of approximately 1 to 12. Dew.

Such zeolites are shown to have a constrained entry as defined herein and are assumed to have a constraint factor approximately in the range of 1 to 12.

has one constraint coefficient within the range of 1 to 12, and therefore falls within the range of new types of high silica zeolites.
When the zeolites that can be used are tested under two or more conditions within the above specified temperature and reaction rate ranges,
In addition to one or more values within the range of 2, V < O, 9, which is slightly less than 1, or 14 or 1, which is υ thicker than 12.
If you give a constraint coefficient value such as 5, you can expect it to bow. Therefore, the constraint factor values used herein are inclusive rather than exclusive.

What this means is that a crystalline zeolite that is found to have a single constraint coefficient within the range of approximately 1 to 12 under a set of reaction conditions within the range of test conditions thus defined is Approximately 1 to 12 under other conditions
Regardless of whether a value of the constraint coefficient is given outside the range of
5, ZSM-11, ZSM-5/ZSM-11 intermediate product, ZSM-12, ZSM-28, ZSM-88, ZS
M-48, Zeolite Beta and similar materials.

ZSM-5 is described in great detail in U.S. Patent No. 8,702,886 and U.S. Reissue Patent No. 29,949;
The description also includes an X-ray diffraction diagram of the disclosed ZSM-5.

ZSM-11 is described in US Pat. No. 8,709,979, which also includes a characteristic X-ray diffraction pattern for ZSM-11. ZSM-5/ZSM-11 intermediate products are described in US Pat. No. 4,229,424. ZSM-12 is covered by U.S. Patent No. 8,832,449.
The description also includes the characteristic X-scarlet diffraction pattern of the ZSM-12. ZSM-28 is IJ
U.S. Pat. No. 4,076,842 with specification 8 depicting the X-ray diffraction diagram of the zeolite shown in FIG. ZSM-85 was published in U.S. Patent No. 4 covering its X-ray diffraction pattern.
．． This is described in No. 016,245. ZSlvf-
88 is U.S. Patent No. 4 covering the X-ray diffraction diagram of ZSM-88.
．． No. 046,859. The X-ray diffraction diagram of ZSM-48 was published on January 2, 1982.
No. 8'48,181, filed under No. 7El.

- Identification of a class of zeolites with significant characteristics by citing the aforementioned patent which contemplates an identification method for determining the crystalline zeolites disclosed therein on the basis of their respective X-ray diffractograms. It should be understood that this is an example of the type of description. As discussed above, in the present invention, silica/
It is contemplated that catalysts with substantially infinite alumina molar ratios will be used. Therefore, the citation of related patents is not intended to limit the description of the crystalline zeolites disclosed herein to those having the particular silica/alumina molar ratios discussed in those patents.

It has now been discovered that zeolites exist which are substantially free of alumina and yet have the same crystal structure as disclosed in the above-mentioned patents and are useful in the present invention and are preferred for the intended use. It was done. It is the crystal structure that is identified by an X-ray diffraction fingerprint, and the fingerprint identifies a particular crystalline zeolite material.

The specific zeolites detailed above are unsuitable for the purposes of the present invention if they have only been prepared in the presence of organic cations.

This is probably because more free space within the crystal is occupied by organic cations ζ from the produced solution. 540℃ in inert atmosphere
(1005°F) for 1 hour. If necessary, the zeolite Q can then be ion-exchanged with suitable compounds, such as salts, in order to obtain the required cationic form, such as sodium, hydrogen, ammonium, etc.

The presence of organic cations in the preparation solution is not absolutely necessary for the formation of this type of zeolite, however, for certain types of zeolite formation the presence of these cations is preferred. It is supposed to be.

Naturally occurring zeolites can also sometimes be converted to zeolite structures of the type identified herein by various activation methods and treatment methods, either alone or in combination, of base exchange, steaming, alumina extraction, and calcination. It is. Natural minerals that can be processed include ferri
erite), brewsterite (brewste)
rite), stibitite.

Included are dachiardite, episti-lbite, heulandite, and crifLoptilolite.

Preferred crystalline zeolites for use in the present invention include ZSM-5, ZSM-11, ZSM-12, ZSM-
23, ZSM-85, ZSM-88 and Zeolite Beta, with ZSM-5, ZSM'-11 and Zeolite Bake being particularly preferred.

The crystalline zeolites of the present invention generally have a minimum crystal size of about 0.01 micron, but preferably:
Zeolites with crystalline sizes greater than about 0.1 micron are used.

In a preferred embodiment of the invention, the zeolites have a dry hydrogen form crystal framework density of about 1.6.
t/cm'' or more.It was discovered that zeolites that satisfy all three of the criteria discussed above are most desirable for several reasons. Preferred zeolites particularly useful in the invention have a constraint coefficient as defined above of from about 1 to about 12.
So, the silica/alumina molar ratio is about 12 or more and the crystal density under dry conditions is about 1.6? /cm" or more. The degree of precipitation under drying conditions of known structures can be found, for example, in W.M. Meyer (W, M.

Zeoli Meier's paper ``Zeolitic structure''
As shown on page 19 of 'Te Strw-Cture)', it is determined from the number of silicon+aluminum atoms around 10 million angstroms. This paper is 19
In 1968, the Chemical Industry Association of London (th
e 5ociety of Chemical In-
``Proceedixgs of the Conference on Molecular Thieves'' published by
erefLce onMol-ecular S'1
eves)-[London, 1967].

If the crystal structure is unknown, the crystal framework density can be determined using the classical pycnometer method. For example, crystals ζ can be determined by submerging the hydrogen form of a dried zeolite in an unsorbed organic solvent. Alternatively, the crystal density can be determined by mercury porosimetry, since mercury fills the interstices between the crystals but does not invade the free space within the crystals.

The framework density of crystal cations is approximately 1.6t/α
With values as high as 3, this particular class of zeolites can have exceptional sustained activity and stability. This high density is necessarily accompanied by a relatively small amount of free space within the crystal, and the lack of free space is expected to result in a more stable structure. However, This free space is important from the standpoint of catalytic activity.

The crystal framework densities of typical zeolites, including some not included within the scope of this invention, are as follows:

F'errierite 0.2
8CG/(jlL 1.76P/m-E/l/Morderbite, 28 1.7
ZSM-5, 11,291,79 ZSM-12-1,8 ZSM-28-2,0 Dachiardite, 8
2 1.72L
, 82 1.61 Kurinobutchi 0 feet (C1in
optilolite), 84 1.710-
Lavntyntite, 84
L77ZSM-4 (Omega-)
, 88 1.65 Heulat
wlite) -89L69P'
, 41 L57 Offretite, 40 1.
55 Levy Knight (Levy7 Lite),
40 1.54 llionite
), 85 1.51 gmelinite (Gq
nelinite), 44 1.46 Chabazite, 47
1.45A, 5 L8 Y, 48 1
．． 27 When synthesized to the alkali metal type, the zeolite can be conveniently converted to the hydrogen type.As a result of ammonium ion exchange, an intermediate ammonium type is formed, and the hydrogen type is formed from the calcination of the ammonium type. get. Other than that, the initial alkali metal weight Nk contained in the synthesized zeolite has been reduced by about 50% or less, and the total alkali metal content is usually less than 0.5wt%. When this happens, it is possible to use other types of zeolites for conversion to the hydrogen form.

Therefore, the alkali metals in the original zeolite were selected from Group 1 of the Periodic Table to VUX (e.g. nickel, copper, zinc,
Substitution is possible by ion exchange with cations of other metals, including palladium, calcium, or rare earth metals.

Incorporation of metal catalyst components into the particular type of zeolite of the present invention can be carried out by any suitable method, such as ion exchange. If this ion exchange proves difficult, it may be preferable to form a complex of the metal before attempting the exchange. A particularly preferred method of ion-exchanging platinum or palladium metals with the zeolites of the present invention is to use ammine complexes of these metals.

Such complexes can be formed by initially dissolving the metal in an acid, such as aqua regia, and then adding an amine such as ammonium hydroxide, i.e. ammonia solution, until the solution becomes completely basic. As a second option, it is also possible to contact a salt of the metal, such as palladium chloride, with an amine solution, i.e. an ammonia solution, with a reed that becomes basic.The weight of the metal catalyst component relative to the zeolite There is no particular critical value for the ratio, but it is around 0.
．． Desirably, weight percentages range from 0.01% to about 10%, and preferably from 0.2% to about 5%.

Alternatively, it is possible to incorporate the metal catalyst component into the zeolite by impregnating the zeolite with a solution of the metal or metal compound or complex and then stripping the used solvent. sorption of compounds or complexes onto zeolites (this is also achievable).Thus, substances such as nickel carbonyl or rhodium carbonyl chloride can be sorbed onto zeolite structures from solution or from the gas phase. .

When the metal-supported zeolite catalyst has been prepared, the catalyst is heated between about 100°C (210”F) and about 500°C (980?)
and preferably from about 150°C (below 300°C) to about 4°C
The unsaturated hydrocarbon compounds are activated by reduction at temperatures between 5-0°C (840"F). Throughout the reduction process, the unsaturated hydrocarbons remain between about 1% and 100% and preferably 1%. A constant concentration of between about 10% and 50% must be maintained.Once the reduction is complete, the presence of unsaturated hydrocarbons is no longer necessary.The reduction is carried out in a hydrogen atmosphere. It is preferred to carry out this process, but it is also possible to carry out the loading without the presence of hydrogen, for example with olefin alone or with olefin and an inert gas (eg nitrogen).

In a preferred embodiment of the present invention, prior to the aforementioned reduction, an extremely stable catalyst can be obtained by inverting the bulky ions of the catalyst. Here, we will mention cesium and potassium.

The catalyst prepared according to the method of the present invention contains platinum,
Any process or combination process in which palladium, nickel, alone or in combination with others, is used as a metal catalyst component (e.g. hydrogenation, dehydrogenation, cyclodehydrogenation, isomerization) Examples include reactions such as decomposition, dewaxing, (catalytic) modification, alkyl aromatic conversion reaction, and oxidation.

It should be noted that a particular advantage of the novel catalyst prepared by the method of the present invention is its ability to act as a shape-selective catalyst in certain reactions. For example, the use of platinum or palladium types of the present invention (thereby will hydrogenate linear olefins more selectively than branched olefins). It shows excellent stability even in the presence of catalyst poisons such as sulfur and phosphorus (see Table 3).

Enjoy the new method of this invention! Another feature of the prepared catalyst is that it is hardly affected by coking. The catalyst obtained in the present invention can also be used in reactions using metal catalysts in which shape selectivity is not essentially essential, such as oxidation, reforming, synthesis gas conversion, hydroformylation, trimerization, alcohol conversion, etc.

The catalytic reaction conditions for hydrogenation of raw materials such as alkenes, dienes, polyenes, alkynes, cyclones, aromatics, oxygenated compounds, etc. are approximately -20°C (-4'F).
and about 540°C (t005'F), preferably about 25
℃ (777) and 310℃ (590”F) (1), 7)
Warm I, about 100/1Pa (Opsiy) and about 7800k
Pα (1000 psig) and preferably about 100
kPa (Opsi(1) and 1480kPa(200ps
iy) pressure between approximately 0.1 and 20 tl-f! The hydrogen/feedstock molar ratio is in the range of about 4 to 12 and about 0.1 to 100, preferably about 0.5 to 41) LIiSV.

Dehydrogenation reaction conditions, such as the conversion of paraffins to the corresponding olefins or the conversion of ethylbenzene to styrene with the addition of steam or an inert gas such as nitrogen, range from about 200°C (892”F) to 1000°C. (
1832T) Preferably a temperature of 850°C (662″F) to 600°C (1112°F); approximately i o kPa (
1,5 psig) to 10,000 kPa (1470
psig) preferably about 10 kPa (1,5 psir
t) to 100 kPa (14,7 psig) and a LHSV of about 0.1 to 100, preferably about 0.5 to 4.

The dehydrocyclization conditions for paraffins to aromatics (e.g. octane to ethylbenzene or xylene) are approximately 2
00°C (8927) to 1000°C (1882?), preferably about 350°C (662'F) to 600°C (111
2"F) temperature; about 10 kPa (1.5 psig) to 10.00-OkPa (1470 psig), preferably about 10 kPa (1-5 psig) to 100 kPa (1470 psig);
Feed partial pressure of Pa (14-7 psig) and LHSV of about 0.1 to 100, preferably about 0.5 to 4.

Isomerization with or without hydrogen, e.g., isomerization of n-paraffins, is performed at approximately 100°C (212″F) and 500°C (
preferably between about 150°C (800°C)
F) and 290°C (550'F), approximately 0.0
A good 1 stroke between 1 and 50 is about LH between 0.25 and 5.
'SV and a hydrogen/hydrocarbon molar ratio of 0 to 5:1. The decomposition catalytic reaction conditions, with or without hydrogen, are approximately 200°C (400″F) and approximately 5'00°C.
(932″F), approximately 170 kPa (10
psig) and about 17,600 kPa, about 0
hydrogen/feedstock molar ratios of from about 80 to about 80 and LHSV from about 0.1 to about 10.

The shape-selective catalyst of the present invention is also effective in dewaxing operations,
It can also be used as a reforming catalyst or as part of a reforming catalyst. Dewaxing and reforming are carried out at approximately 250°C (482?) to 600°C in the presence or absence of hydrogen.
(1112″F) Approximately 400°C (782″F)
Temperatures between 500°C and 932°F; approximately 10 kPa (
1,5 psig) to 10,000 JcPaC147
0 psig) pressure and about (101 to about 100 psig)
The reaction can be carried out under reaction conditions ranging from about 0.1 to about 10 LHSV.

Catalytic transformation reaction conditions for the conversion of mualkyl aromatics, including dealkylation or hydroisomerization, particularly the isomerization of xylene and the hydroisomerization of hethylbenzene to xylene, are as follows:
Approximately 260°C (500″F) and approximately 600°C (1112″F)
) preferably between about 320°C (below 600°C) and 500°C
(below 932), approximately 240 kPa (20p
sig) and about 7000 kPa (1000 psig), preferably about 2751 cPa (25 psig) and about 2
860 k, Pα (400 psig), hydrogen/feed molar ratio preferably between about 1 and 20, preferably between about 2 and about 8, preferably between about 1 and 50. Conditions of LHSV between about 5 and 15 (this applies).

The metal-containing catalyst of the present invention can also be effectively used as an oxidation or combustion catalyst under oxidation reaction conditions. Therefore, the novel catalyst of the present invention can be used for oxidation or combustion of paraffins, olefins, and alkyl aromatics in which shape selectivity is not essential, and for oxidation reactions in processes in which CO and H2 are reacted (methanol, Fischer-Trobutsch process, etc.). is available. This catalyst can also be used in shape-selective catalytic oxidation reactions such as the selective oxidation of p-xylene in the coexistence of 0-xylene.

The metal-containing catalyst produced according to the method of the present invention is a novel catalyst composite. The catalysts of the present invention differ from prior art catalysts in that they are shape selective. A new theory that will be developed from now on (I do not intend to connect this to anything), but the shape selectivity of the catalyst of the present invention is due to the fact that the functional part of the metal (rather than having a positive valence) has a zero valence. It is believed that this is due to the fact that the functional part of the metal is located on the ``inside'' (as opposed to ``outside'') of the zeolite, with valence.In the case of the Pt-ZSM-5 complex, In the prior art, pt0' instead of Pt0 entered the zeolite through ion exchange.However, upon reduction, Pt0' entered the zeolite.
t2 migrates to the surface and becomes Pt0. Therefore, in the prior art, putting pt+2 into the zeolite results in Pt0f on the surface of the zeolite, but not on the inside, ie in the interstices of the zeolite.

The shape-selective metal catalysts of the present invention are linear olefins, e.g. dimethyl branched olefins of hexene-1, e.g.
-Simethylhexene-I is characterized by a selectivity of more than 2.0 for selective hydrogenation. Such selectivity can be determined in standard competitive olefin hydrogenation tests. In such tests, a fixed bed glass reaction with about 5 m9 to 80 m9, for example 15 m2, of catalyst was treated with ammonia for acid suppression.

A 1:1 molar mixture of linear and branched olefins and hydrogen are passed in downward flow through the tube ζ. Using a 5-fold excess of hydrogen over the olefin, the temperature is between about 200°C (392'F) and 480°C (800°C).
The hydrogenation is carried out at a WESV of about 5 to 100 degrees, for example 25, at a temperature of about 575 degrees Fahrenheit (95'F), for example about 800 degrees Celsius (575 degrees Fahrenheit). The hydrogenation rate of both olefins is 1lIII, respectively.
The total selectivity is calculated according to the following formula based on the percentage of each olefin remaining unreacted as a hydrogenation reaction product.

As mentioned above, shape-selective characteristics are imparted by reducing the metal-containing zeolite to the metal-functionalized catalyst of the present invention in the presence of one or more unsaturated compounds. The shape selectivity of such catalytic metals can also be further improved by adding some additional processing operations to the zeolite.

Selectivity is also increased by increasing the temperature at which shape-selective conversion reactions, such as hydrogenation, are carried out. )! JJilJ
Selectively poisoning the catalyst with a "bulky" catalyst such as rufosphine also increases the shape selectivity of the catalyst of the present invention.

Such bulky catalyst poisons deactivate the metal catalyst components outside the catalyst complex much more severely than they poison all the metal functions in the interstices of the complex.

The following examples are intended to illustrate specific embodiments of the present invention, and are not intended to limit the numerical values thereof.

EXAMPLE This example uses NH4-Z with a crystal size of about 1 to 2 microns.
The method for preparing SM-5 zeolite is specifically shown.

16 parts water and 27.7 parts sodium silicate (SiOt
28.7 wt%, Ha208-9 wt%, H2O6
2.4 wt%), then 0.08 part Dakdad (
A sodium silicate solution was prepared by adding Daxad) 27 (product of W. R. Brace Chem. CW, R., Grace'Chetn, ). The solution was cooled to about 15°C.

1 part aluminum sulfate A (jL620317.2 w
t%] to 104 parts of water, followed by the addition of 2.4 parts of sulfuric acid (98 wt% H2SO,) and 1.2 parts of NaCIJ to prepare an acid solution.

Both solutions were mixed in a stirred vessel while adding 3.9 parts of NaCl.

The molar ratio of the resulting gel expressed in the form of oxide was as follows.

5iOz/1UbOs=78-4 N (L20/Al2O5=49.9 1.9 parts) +7-1.6 to n,-propylamine
An organic bath solution prepared by adding 1 part n-propyl bromide and 3.1 parts methyl ethyl ketone was added to the gel.

The mixture was heated at 65-7-0°C (65-7-0°C) for 29 hours with vigorous stirring.
150-160 below).

The slurry of zeolite product is mixed with 4-5 times of water and o, o (12 times of flocculant) of slurry.
& Haas Prima Flock C-7 (llohm
&Haa's Pr1-αfloc C-7)). After standing still, the supernatant liquid was drained. 90.0000 yen per water and slurry for the solid matter left still as in the previous step.
5 parts of flocculant was added to reslurry to the original volume.

After electrostatics, the aqueous phase was decanted. This operation of reslurrying, standing still, and decantation was repeated until the decanted supernatant liquid ζ C11- disappeared.

The water-washed zeolite was then filtered and dried. It was identified as ZSA(-5) with a silica/anobenamolar ratio of about 70 and a constraint factor of about 8.3. The ammonium form of this zeolite was obtained by calcination and NH,NO8O8 exchange point.

Example 2 A P,t-ZSAi-5 catalyst sample was prepared by the following exchange reaction. NIf+Z prepared according to Example 1
8M5 (0 NH4; It 54rneqAi/
? (containing zeolite) was replaced with CsC1. As a result of the analysis of the obtained Cs-ZSM-5, it was found that there was a slight (
It was found that 0.018 meqN/g remained, so 1.
25 f Pt' (IJHs)4C112・H2
The mixture was mixed with a bath solution in which O was dissolved and stirred at room temperature for 4 hours.

Exhaust gas titration of thermal nitrogen analysis of the resulting material in a hydrogen stream showed an abundance of 0.618 meqNlg.

This indicates that 88% was exchanged with Pt(87H3)t2 ions.

Example a One part of the catalyst material from Example 2 was added to two equal weights of C5CA.
Back conversion was performed with a solution of 0 d in water. The result of analyzing all the obtained substances was 0.216 meqN/result, and the platinum content of the catalyst obtained by smelting was % from the initial amount.
(This decreased C5-P, t-ZSM-5. The percentage of platinum in the catalyst was 1.0 wt%.

In order to carry out the handwritten hydrogenation reaction (C s -P, t prepared in Example 3 using a downward countercurrent fixed bed glass reaction tube)
'-Z SM-5 catalyst was used. The reaction tube was a 12-foot n-octane Durapak tube.
) is coupled with an online gas chromatograph having a columnar C). In order to suppress the decomposition reaction to be measured, mathematical ammonia gas is injected prior to actual sample collection.

The catalyst was used in amounts ranging from about 5 to 2 somts dispersed in two Vllcor glasses. Prior to use, the catalyst in the reaction tube is heated to about 300° C. (570” F.) and 40° C. in the presence or absence of added olefins.
The olefin was reduced in a stream of hydrogen at a temperature between 80°C (895"F). The olefin was injected into the reaction tube by a syringe pump and diluted with hydrogen. Hydrogen flow rate 14 CQ/min and liquid feedstock (olefin) flow rate 1.0ci/Ar,
It was shown that there was a five-fold excess of hydrogen over the olefin.

After the reduction, equimolar solutions of the two olefins were introduced into the reaction tube ζ. Examples 4-7 demonstrate the effect of catalyst pretreatment on hydrogenation selectivity, and the results are shown in Table 1.

In Example 4, the catalyst was pretreated with hydrogen alone for 1 hour at 300°C (570″F). The resulting catalyst had only 29% hydrogenation of the linear olefin (hexene-1) and The hydrogenation rate of branched olefin (4,4-dimethylhexene-1) was 39% and was not selective.The catalyst of Example 5 was heated with hydrogen and olefin at 275°C (525?) I for 1 hour. This catalyst showed extremely good shape selectivity, with a hydrogenation rate of 90% for linear olefins and less than 1% for branched olefins.

In Example 6, the catalyst is olefin alone and 30% without hydrogen.
The resulting catalyst exhibited some shape selectivity, however, the hydrogen-olefin binary pretreatment of Example 5 In Example 7, the catalyst of Example 6 was further treated with hydrogen and olefin at 400°C (below 750°C) for 17 hours. It was shown that a catalyst with extremely good shape selectivity was produced.

That is, the hydrogenation rate of the branched olefin was 1.3% (in contrast, the hydrogenation rate of the straight chain olefin was 100%).

Table 1 Hydrogenation selectivity of pretreatment (4 Hz alone 275 2
5800℃+147 51i2+Olefin 275 706
Olefin alone 254 12300
℃,'Lhr 800 12 more 40
Olefin + 254 12 at 0℃ 7
Effect on B217hr 90% 1%> 57% 19% 95% 20% 100% 1.8% Example 8-14 Example 8-14 shows that when reverse exchange is performed using cesium ions, the improved catalyst is clearly shows what has been obtained.

In Examples 8 to 10, Pt-ZSM prepared in Example 2
-5 was used as a catalyst. In Examples 11 to 14, Example 3 (C s -P, t'-Z
SM-5 was used as a catalyst.

In Examples 8 to 14, hydrogenation reactions were carried out using the same apparatus and experimental method as in Examples 4-5. These results are shown in Table 2.

Table 2 shows that the cesium-containing catalyst was more stable than the cesium-free catalyst.

Examples 15-16 The effect of temperature on a non-selective catalyst and a shape-selective catalyst representative of the present invention was illustrated in Examples 15 and 1.6. Both the non-selective catalyst used in Example 15 and the shape-selective catalyst used in Example 16 were prepared in a manner similar to Example 8c.

The non-selective catalyst is hydrogen alone, the shape-selective catalyst is hydrogen in the presence of added olefin, 8001::(570'F)
? At this point, pretreatment was performed. In Examples 15 and 16, the hydrogenation reaction was carried out using the same equipment and same method as in Examples 4 and 5.

As shown in Table 3, the non-selective catalyst of Example 15 showed that the reaction rate of linear olefin (hexene) decreased at high temperatures. In contrast, the activity and selectivity of the shape-selective catalyst of Example 16 is similar to that of the linear olefin (hexene).
The reaction rate increased with increasing temperature, as shown by the increase.

Table 3 Effect of temperature on reaction rate Hydrogenation rate (%
) Pt ZSM-5 25089,547,9 27529,988,9 16, shape selectivity 200 11.4 0.
2Pt ZSM-5 25082,70,8 2759 (LOO, 2 Using a catalyst prepared according to the same method as in Examples 2 and 3 but with a resulting platinum content of 0.6 wt%,
Experiments were attempted on different olefin mixtures using the same experimental method of hydrogenation reaction employed in Examples 4-7.

The catalyst was pretreated in the presence of this olefin mixture and hydrogen at 400°C (750'F). As a result of this example, selective conversion values of pentene-1 (97% hydrogenated) over 4,4-dimethylpentene-1 (1,7% hydrogenated) were determined.

Examples 18-19 illustrate the hydrogenation of styrenes.

In Example 18, Engelhard
A 0.5% platinum-alumina catalyst was obtained from Co., Ltd. and used. This catalyst had almost equal hydrogenation rates for styrene and 2-methylstyrene and did not exhibit shape selectivity. In Example 19, the same ! as used in Example 17 was used. All J'5i medium was used. The pretreatments applied to both catalysts in Examples 18 and 19 were identical. 40 with olein and hydrogen
The pretreatment was carried out by heating to 0°C (750°C).As shown in Table 4, the results of Example 19 showed that this catalyst hydrogenated only 1.8% of the non-linear 2-methylstyrene. In contrast, linear styrene was hydrogenated by 50%.

Table 4 Hydrogenation rate of styrenes (%) Pt, 20s & 400℃ZSM-5H 2400℃ This example describes the preparation method of ZSM-5 zeolite with a crystal size of approximately 0.02 to 0.05 microns. shows.

1.6 parts n-propyl bromide, 1.9 parts t)-n-propylamine, 8.1 parts methyl ethyl ketone and 10
- An organic salt bath solution was prepared by mixing 4 parts of water. Add this mixture to approx.

The reaction was carried out for about 14 hours at 212'°C (212'F). The aqueous phase of the reacted mixture was designated as Bath Solution A.

16 parts of water and 27.7 parts of sodium silicate (Sz Q
228. '1wt%, Na2O8, 9wt%, B20
62.4 wt%) and then 0.08 part of Dacdad 27 was added to prepare a sodium silicate solution. The solution was cooled to about 15°C.

1 part aluminum sulfate ΩatOs 17.2 wt%
)y, 1'er, 4 parts of water was added, then 2.4
An acid solution was prepared by adding 1 part NaClj and 2.9 parts of Solution A. These baths were mixed in a stirred vessel while adding 3.9 parts of NaCl1. The molar ratio of the gel in the form of oxide was as follows.

SiO2/A1203 = 78.4 Nα20/A120s = 49.9 The gel was stirred for 4 hours at ambient temperature and then 95-110
The temperature was heated to 200-280'F and continued to stir vigorously for 40 hours. When approximately 65% of the gel had crystallized, the temperature was increased to 150-160'C (300-320'F) to stop crystallization. It was kept at that temperature until photon.

The zeolite slurry product was diluted with 4-5 times the total slurry of water and 0.0002 times the slurry of flocculant (Primafloc C-7). After standing still, the supernatant liquid was poured off.

The solid matter left still was reslurried to its original volume by adding water and 0.00005 parts of flocculant per slurry as in the previous step. After standing still, the entire aqueous phase was decanted.

This operation of reslurrying, standing, and decantation was repeated until the sodium content of the zeolite became lower than 1.0 wt%.

The zeolite was washed with water, then filtered and dried. It was identified as ZSAI-5 having a silica/alumina molar ratio of about 70 and a constraint coefficient of about 8.3.

Dry zeolite product kN2 stream for 3 hours at 540
Calcined at 'C (1005°F), INNHdJOsNH
Ion exchange was performed twice with 4 parts of NOx solution to 5 parts of NH4NOx solution for 1 hour at ambient temperature. and dried at about 120°C (250″F).

The catalysts of Examples 21-24 were prepared using the zeolite prepared in accordance with Example 9 (using the zeolite thus prepared, the platinum content L6 wt % ly').
It was prepared using the general method of Examples 2 and 3 so as to reach the small crystal size of s-Pt-ZSM-5. Pretreatment of the catalyst and hydrogenation reaction were carried out according to the general experimental procedure shown in Examples 4-7. The results of Examples 21-24 are shown in Table 5I.

By pre-treating this catalyst in the presence of olefin and hydrogen, a shape-selective hydrogenation catalyst was obtained (as shown in Figure 51).
Additional heat treatment at 840"F (840"F) further improved the selectivity. This result shows that even in the case of small crystals of ZSM-5, platinum, once formed inside the zeolide, rapidly This shows that 2-methylstyrene does not migrate to the surface.In the race reaction experiment, 2-methylstyrene
Although only a small percentage of the reaction occurred, the styrene was completely hydrogenated. Examples 28-24 demonstrate the resistance of the shape distance catalyst of the present invention to poisoning by phosphorus compounds such as phosphine compounds.

Table 5 Small crystal size Cs -Pt -ZSE-521 Olefin + H285008 up to 450°C 22, further 450°C in H2 85
00 16 hours at 20 23 50 ~ Tree p - 850° 20 Tolylphosphine 350° Addition of 8 24 5Qiip Phosphine 350°
Selective hydrogenation by second addition of 8 97% 18% 99% 9% 64% 0.5% Table 6 25 Hexene-1 + H2 89% 18%
Up to 450℃26 Further in H2 alone 86% 47%
400℃, 17hr 27 Further in H2 alone 53% Trace 450
℃r2hr 28 Hexene 134% 25%35
Example 29-84 is a shape-selective Pt-ZS catalyst similar to that of Example 1 but with a significantly higher silica/alumina ratio.
A shape-selective reaction using M-5 catalyst as a catalyst is shown.

Approximately 70000) With SiOt/AezOs k and -1)
A catalyst complex was prepared for the reduction of a ZSM-5 catalyst containing about 0.54% total platinum.
The reaction was carried out in a stream of nitrogen and hexene-1 while increasing the temperature to 50°C at a rate of 2°C/n.

Passing fn-dodecane in hydrogen over the catalyst of Example 29 at 400 DEG C. and 0.4 WIISV gave the following reaction product mixture containing gold at a conversion rate of 50%.

(1) n-undecane and n- along with methane and ethane
Louver fins such as decane...all products exhibit characteristics of metal-conducting decomposition. (2) It is believed that one of the major components is cycloparaffin, n-heptyl cyclopenkune. (3) 2-methyl and 3
- some skeletal isomers of dodecane, mainly methyl undecane, and (4) aromatics, which are exclusively n-hexylbenzene.

In the reaction of n-nonane under similar conditions, mainly 1SO
-/nanfe, TL-octane, n-butylcyclopentane, n-propylbenzene, indane, and several C
8 and C0 aromatics were produced.

Replacing hydrogen with nitrogen increased dehydrocyclization and decreased hydrogenolysis. Furthermore, hydrogen was obtained as the main product.

Therefore, the following conversion reaction was carried out at 465° C. using n-octane as a raw material.

In hydrogen 42 2.6 9.6
7.2 in nitrogen 80 1.6 86.6
19.5 tatami The linear paraffin n
-hexadecane and 2,6,10,14-tetramethylpene, it was observed that only 8% of the branched paraffins reacted.

An equimolar mixture of 1,2-dimethylcyclohexane and 1,4-dimethylcyclohexane (isomer mixture) was passed over the catalyst of Example 29 in hydrogen at 400°C. The exhaust contained only 12.5% 0-xylene, but 29.7% p-xylene, fully reflecting the 3x selectivity factor for the para isomer.

When the reaction of Example 32 (20 m9 of tri)-p-1-lylphosphine was added, the xylene concentration in the exhaust gas was p-
Xylene decreased to 9.8% and O-xylene decreased to 0.7%. This corresponds to a value of selectivity factor 15. Saraζkotree n -1! Addition of rufosphin did not change the reaction rate or selectivity. 400 to 65 of Arabian Light distillate consisting primarily of C12'-C18 hydrocarbons for the purpose of illustrating shape selective dewaxing and reforming.
Example 2 at U'F fraction total 465 °C and WHsVo, 4
9 catalyst. Analysis of the product showed a decrease in exclusively n-paraffins and an increase in aromatic content. The pour point of the product dropped from the feedstock's pour point of -20°C to -42°C.

Continued from page 1

Claims (1)

Claims: A metal catalyst component is incorporated into a zeolite having a silica/alumina molar ratio of 1, 12 or more and a restraint coefficient within the range of approximately 1 to 12, and then at a temperature ζ in the range of 100°C to 500°C. A method for preparing a shape-selective metal catalyst comprising reducing the metal component in the presence of one or more unsaturated hydrocarbon compounds. 2. The method according to claim 1, wherein the reduction step is carried out in the presence of hydrogen. The method according to claim 1, wherein the reduction step is carried out in the presence of nitrogen. Tun Zeolite is ZSM-5, ZSM-11, ZSM-
12, ZSM-28, ZSM-85, ZSM-88, or zeolite beta. & Claim 4, wherein the zeolite is either ZSM-5, ZSM-11 or zeolite beta.
The method described in section. G. The method according to claim 1 or 4, wherein the metal catalyst component is one or more metals of Group M of the Periodic Table. 7. The method according to claim 6, wherein the metal catalyst component is one or more of platinum, palladium, or nickel. & The method according to claim 7, wherein the metal catalyst component is platinum. a. The method according to claim 1.4.6.7 or 8, wherein the unsaturated hydrocarbon compound is an olefin. ζ of any one of claims 1 to 9, wherein the 1α reduction step is carried out at a temperature in the range of 150°C to 450°C.
The method described here. The weight ratio of IL metal catalyst component to zeolite is 0.0
Claims 1 to 10 between 1% and 10%
The method described in any of the paragraphs. 1a) The gold metal catalyst is ion-exchanged into zeolite)
A method according to any one of claims 1 to 12, which includes this. 19. The method according to claim 1, wherein ion exchange is performed using an ammine complex of 14 metal catalyst components. 15. During the reduction process, 1% of unsaturated hydrocarbon compounds
15. A method according to any of claims 1 to 14, wherein the concentration is maintained in the range of 100%. 16. The method of claim 15, wherein the concentration of the 1G unsaturated hydrocarbon compound is within the range of 10% and 50%. (7) Claims 1 to 16 further include a step of converting cations back into the zeolite prior to the reduction step.
The method described in any of the paragraphs. 18. The method according to claim 17, wherein the cation exchanged with 1 and back is cesium. 19. Claim 1 further comprising the step of further improving the selectivity of the catalyst by treatment with a bulky catalyst poison.
The method described in any one of Items 1 to 18. 20. The method of claim 19, wherein the 2α bulky catalyst poison is tri-n-tolylphosphine. 2. A shape-selective metal catalyst prepared by the method ζ according to any one of claims 1 to 20. consisting of a bimetallic catalyst component and a zeolite having a silica/alumina molar ratio of 12 or more and a constraint coefficient in the range of 1 to 12, and selectivity for the selective hydrogenation of hexene-1 to 4,4 dimethylhexene-1. 1. A shape-selective metal catalyst characterized in that the shape-selective metal catalyst is smaller than 2.0. 23. The catalyst of claim 21 or 22, wherein the muzeolite has a crystalline size of about 0.1 micron or more. % zeolite has a silica/alumina molar ratio of 800:1 or more (,
Catalyst described here. Claim 22 The fishing metal catalyst component is platinum, radium (1 is one or more of nickel)
Catalysts listed in Section E. A method for shape-selective catalytic transformation of an organic compound-containing raw material, the method comprising contacting the raw organic compound-containing raw material with the shape-selective metal catalyst according to any one of claims 1 to 25 under reaction conditions. 2'2 The organic compounds in the raw materials are alkenes, dienes,
polyenes, alkynes, cyclenes, aromatic hydrocarbon compounds, alkyl aromatic hydrocarbon compounds or)
(The method according to claim 26, wherein the rough alkyl aromatic hydrocarbon compound is xylenes, ethylbenzene, or a mixture thereof; 28. The method according to claim 27, wherein the paraffins are normal paraffins. 2a The raw material consists of an alkyl aromatic hydrocarbon compound, and the reaction conditions are a reaction temperature of 260 ° C. to 600 ° C., 240 ° C.
reaction pressure of kPa to 70001 cPa and 1 to 2
29. The method of claim 28, wherein the hydrogen/raw material alkyl aromatic hydrocarbon molar ratio is within the range of o. 3α The method according to claim 29, wherein the alkyl aromatic hydrocarbon is xylenes and the shape-selective catalytic conversion reaction is an isomerization reaction. 30. The method of claim 29, wherein the alkyl aromatic hydrocarbon is ethylbenzene and the shape-selective catalytic conversion reaction is a reaction to obtain a product consisting of xylenes. ! Under reaction conditions within the range of a reaction temperature of 250°C to 600°C and a reaction pressure of 10 kPa to 10.000 kPa, the shape-selectable, flexible metal catalyst and raw materials according to any one of claims 21 to 25 are processed. 1. A method for carrying out shape-selective catalytic transformation of a wax-containing raw material, the method comprising bringing the wax-containing raw material into contact with (oil). 8a - under reaction conditions ranging from a reaction temperature of 20°C to 540°C, a reaction pressure of 100kPa to '7800kPa and a hydrogen/raw material unsaturated hydrocarbon molar ratio of 0.1 to 20, claims 21 to 21. A method for carrying out shape-selective catalytic transformation of a raw material containing unsaturated hydrocarbon compounds, the method comprising bringing the shape-selective metal catalyst according to any one of Item 25 into contact with the raw material. 89. The method according to claim 88, wherein the unsaturated hydrocarbon compounds are one or more of alkenes, dienes, polyenes, alkynes, cyclenes, or aromatic hydrocarbon compounds.