CZ160897A3 - Isomerization process of a hydrocarbon raw material - Google Patents

Abstract

Process for isomerisation of a hydrocarbonaceous feedstock substantially boiling in the gasoline range which feedstock comprises linear paraffins having at least five carbon atoms wherein the feedstock is contacted in the presence of hydrogen at elevated temperature and pressure with a catalyst comprising in combination platinum (Pt) and palladium (Pd) each in metallic form supported on an acidic amorphous alumina or molecular sieve, and isomerised hydrocarbons preprared by the process.

Description

Technical field:

The present invention relates to a process for improving the quality of hydrocarbon feedstocks, in particular by isomerizing a feedstock substantially boiling in the gasoline range, wherein the feedstock comprises linear paraffinic hydrocarbons having at least five carbon atoms.

Barefoot _____ state of the artj

An increased demand for oil refineries is the production of gasoline that meets environmental requirements and has high octane numbers. The requirement to reduce the content of aromatics, especially benzene and olefins, in order to reduce the vapor pressure of gasoline and to circumvent additives containing lead, has made it necessary to identify and manufacture alternative high octane gasoline components. These components, for example branched paraffins in the gasoline range, are not typically available from the main refining processes, and must be obtained by improving the quality of the refinery fractions and adding them to the gasoline wells. It is an object of the present invention to provide a process for the manufacture of such branched paraffins.

Methods for isomerizing linear C4-C10 paraffinic feedstocks by contacting with some or amorphous catalysts in the presence of zeolite hydrogen are known. Bifunctional catalysts containing some hydrogenating-dehydrogenating metals deposited on zeolite or amorphous metal oxide, such as commonly available platinum supported on mordenite (MOR) and platinum supported on both chlorine and imported alumina, have been found to provide both good selectivity of reaction and

Improvement in catalyst performance and catalyst lifetime obtained by the presence of a hydrogenating-dehydrogenating metal.

European Patent No. 0 398 416 describes a similar process comprising contacting a similar feedstock with a catalyst comprising zeolite beta (BEA) and a hydrogenating-dehydrogenating metal, or the BEA treated with a pH solution is calcined, the metal preferably being selected from Group VIII periodic table of elements.

its compound, at least 9 and thereafter

These processes yield interesting yields of the desired product, notable in improving the quality of the Cs-C 6 paraffinic feedstocks, with some yield loss resulting from hydrogenolysis and cracking. Because these processes are sensitive to catalyst deactivation as a result of poisoning by sulfur contamination in the feedstock, it is common practice to treat the feedstock with a pretreatment to remove or convert the sulfur, for example by adsorption or hydrotreating, before carrying out the quality enhancing reaction.

Surprisingly, it has now been found that still further improvement in product yield and selectivity can be achieved by a process using a catalyst that contains a specific bi-metal hydrogenation-dehydrogenation function. In addition, it has been found that these catalysts reduce the efficiency of hydrogenolysis and increase sulfur tolerance, thereby reducing the need for pretreatment of the feedstock.

The principle of the invention ^:

Accordingly, the present invention relates to a process for isomerizing a hydrocarbonaceous feedstock substantially boiling in the gasoline range, wherein the feedstock comprises linear paraffins having at least five carbon atoms when the feedstock is in contact with

the presence of hydrogen at elevated temperature and pressure, with a catalyst comprising a combination of platinum and palladium, each in the form of a metal, supported on an acidic amorphous alumina or molecular sieve.

Said reference to the metal form 'is to the zero valence state of substantially both platinum (Pt) and palladium (Pd) present on the catalyst. It is contemplated that the catalyst may be used without prior reduction of the metal components to the metal state, wherein the reduction is achieved in situ under conventional conditions including the presence of hydrogen.

A further reference to the "metal mold" is here to the mold that is effective during contacting.

Reference herein to molecular sieves' means both zeolite and non-zeolite types, for example, molecular sieves containing silicoaluminates or others. Preferred molecular sieves are 10 ring and 12 ring types, i.e. containing 10 or 12 ring members of oxygen atoms.

can be used for paraffin-containing enhancement with the process of the present invention by isomerization with a different number of carbons, in one step. It is

A particular advantage is that the invention is a raw material having, for example, a carbon number of 5 to 8, a particular advantage, since the conversion of the Cy + component of the hydrocarbon feedstock involves the problem of cleavage to undesirable products. The solution to this problem by carrying out a process with a reduced acidity catalyst is not interesting, since it obviously leads to a reduction in conversion and the need to increase the recycling of unreacted feedstock. The remaining options to solve this problem include operating in two stages using, in each stage, a catalyst selective for the conversion of each component. However, it has now been found that the process of the invention allows the isomerization of normal paraffins to multi-branched paraffins to be isomerized. With significant yields in a single stage.

Alternatively, the process of the invention allows a lower total metal dosage than with conventional processes, without limiting yield and loss of activity. Of course, these benefits will contribute to the economy of the routine. It was found that the effect of Pt and Pd in combination on the selectivity of the catalyst was higher than the sum of the effects of both components individually. That is, a synergy of selectivity occurs in the bimetallic catalyst process.

Preferably, Pt and Pd are uniformly dispersed throughout the catalyst, thereby increasing their mutual effect. Without being limited by the following theory, it is believed that the presence of one or both metals affects the other metal, particularly the presence of Pd seems to have a positive effect on the dispersion or the Pt state, since the metals are better transferred to or maintained in the metal form. Preferably, in fixed bed processes or other processes, Pt and Pd are both present at the same site of the catalyst, more preferably at the same catalyst particle, most preferably at the same portion of the amorphous aluminum or molecular sieve.

The catalyst useful in the present invention may contain a binder material containing one or more refractory oxides in addition to the amorphous alumina or molecular sieve (herein and further active catalyst structure).

The Pt and Pd metals may be on the active catalyst structure or may be on a separate support (i.e., a binder) containing, for example, one or more refractory oxides, for example alumina. Preferably Pt and Pd are present on the active catalyst structure.

Preferably, Pt and Pd are applied to the active catalyst structure by methods known in the art, for example

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99 ·· ···· by (competitive) ion exchange, impregnating (competing) pore volume (seed moisture), controlled precipitation, co-grinding in a suitable metal component precursor mixer to the active catalyst structure and / or binder. Preferably, the metals are deposited on the active catalyst structure by impregnating with the germ moisture of an aqueous solution of the tetramine dichloride salt, or by competing ion exchange in the presence of ammonium or competing ont.

A further advantage is that the process of the invention is substantially independent of the way in which they deposit metals on the catalyst. This is in contrast to processes using catalysts containing only Pt or only Pd, and the performance of the process may be affected by the method of depositing the metal on the active catalyst structure.

In particular, known processes using catalysts prepared by competitive ion exchange only Pt or only Pd exhibit a stable, high-performance operation over a typical temperature range, which is believed to result from improved metal dispersion and reduced excess acidity, and reduced hydrogenolysis activity relative to the platinum component. .

It is found that the present process advantageously improves catalyst performance, which seems to overcome any improvement available by the catalyst synthesis method. Without being limited by the following theory, it is believed that the catalysts used in the process of the present invention are characterized by improved metal dispersion and reduction to metal state, as compared to known monometallic catalysts.

Preferably, the metals are introduced simultaneously. Preferably, the metals are distributed in the active catalyst structure. Preferably, the distribution is controlled by controlling the composition of the solution during ·· ····

999 99 • · • ··· by, for example, controlling the pH of the solution and the content of competitive anions and cations. Preferably, the metals are converted to the metal form by reduction procedures known in the art. Preferably, the catalyst comprises from 0.01 to 5% by weight of Pt and Pd in combination, based on the total weight of the active structure of the catalyst, preferably from 0.1 to 3% by weight of combined Pt and Pd, based on the total weight of the active structure of the catalyst. Preferably, Pt and Pd are present in an Pt / (Pt + Pd) atomic ratio between 0.0 and 1.0, more preferably substantially 0.1 to 0.8, even more preferably substantially 0.1 to 0.5.

Amorphous alumina catalysts that can be used in the process of the present invention include those known in the art. Preferred amorphous alumina catalysts are characterized by a small size by reducing the surface, preferably on an area ^of 100-500 m / g. Even more preferably, the amorphous alumina catalysts contain eta aluminum or gamma alumina, 320-430 m ² / g, respectively. 170-220 m ² / g.

The amorphous alumina may contain an additional acidic component. Preferably, the amorphous alumina catalysts contain a chloride component, thereby increasing acidity. Preferably, the amorphous alumina catalysts are chlorinated by known procedures including sublimation of AlCl 3 and reaction with COCl 2, CCl 4, etc. Preferably, the acid components are present in an amount suitable to achieve the desired acidity. In particular, eta alumina may contain chlorine in an amount of 5-15%, gamma alumina in an amount of 3-8%.

Molecular sieves that can be used in the present invention include any zeolitic or non-zeolite molecular sieves capable of selectively converting feedstock molecules within the above defined range. Typically, these molecular sieves are, but are not limited to, those commonly known as the mid-pore type of natural or synthetic molecular sieves. Preferred zeolites are 1 Circular or

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The 12-ring type, i.e. containing 10 to 12 ring members of the oxygen atoms, and preferably are the twelve ring type, including but not limited to MCM-22 and AEL, AFI, AFR, AFS, AFY, ATO, ATS, BEA, BOG, BPH, CAV, EHT, FAU, GME, LTL, MAZ, MEI, MOR, MTW, and OFF as described in Zeoli of those Vol. 12 No. 5 (1992), with the exception of MCM-22, which is described in U.S. Patent 4,954,355. Most preferred are AEL, BEA, FAU, MOR,

MTW, and OFF.

Non-zeolite molecular sieves listed as non-limiting Examples, in particular AEL, AFI, AFR, AFS, AFY, ATD and ATS, which include a metal component, preferably include a Group VIII metal component, preferably selected from magnesium, manganese, cobalt and zinc, more preferably cobalt.

Molecular sieves of the zeolite and non-zeolite type may be selected or modified to obtain the required level of acidity. The salts can be conveniently modified or synthesized by a process to achieve a ratio of SiO 2 to Al 2 O 3 to determine acidity. Suitable proportions of S1O2 and Al2O3 depend on the individual salts used. Typically, an MOR type zeolite in a SiO2 ^: Al2O3 ratio of from 10:60, preferably 15 to 30, for example about 20, is used, for example. The zeolite may be further modified to optimize selectivity, e.g. wherein the modification or treatment is well known and includes an acid or base treatment or modification.

Suitably the process is carried out at 50 to 400 ° C, a pressure up to 5 χ 10 ⁶ Pa (50 bar) and a space velocity from 0.5 to 10 kg / kg.h. and a molar ratio of hydrogen to feedstock of up to 10.0.

If an amorphous alumina catalyst is used, the process is preferably carried out at a temperature of from 50 to 250 ° C, preferably from 100 to 150 ° C, with a total pressure of from 1 to 150 ° C. , 5 χ 10 ⁶ to 4 χ 10 ⁶ Pa (15 to 40 bar), preferably 3 χ 10 ⁶ Pa (30 bar), space velocity 0.3 to 10 kg / kg.h, preferably 0.5 to 5 kg / kg.h, and mole ratio of hydrogen to feedstock is up to 10.0, preferably from 0.01 to 3.0.

If a zeolite molecular sieve catalyst is used, the process is preferably carried out at a temperature of from 150 to 350 ° C, preferably from 180 to 280 ° C, with a total pressure of 1.5 χ 10 ⁶ to 3.5 x 10 ^fe (15 to 35 ° C). bar), for example about 2.5 χ 10 ⁶ Pa (25 bar), space velocity of 0.5 to 5 kg / kg.h molar ratio of hydrogen to feedstock to 5.0, preferably from 0.5 to 4, the 0th

If a non-zeolite molecular sieve catalyst is used, the process is preferably carried out at a temperature of from 250 to 450 ° C, preferably from 275 to 400 ° C, a total pressure of up to 1 χ 10 ⁷ (100 bar), preferably from 1 χ 10 ⁶ to 5 x 10 ^e Pa (10 to 50 bar), a space velocity of 0.5 to 10 kg / kg.h, preferably from 1.0 to 5.0 kg / kg.h, and a molar ratio of hydrogen to feedstock to 5.0, preferably from 1.0 to 3.0.

A hydrocarbonaceous feedstock substantially boiling in the gasoline range may advantageously be obtained by fractionating any hydrocarbonaceous feedstock containing paraffinic gasoline.

Preferably, the feedstock substantially boiling in the gasoline range is obtained by subjecting the primary hydrocarbon oil to fractionation, preferably atmospheric distillation. Other preferred hydrocarbon feedstocks substantially boiling in the gasoline range include product fractions obtained from cracking processes, such as catalytic cracking, thermal cracking, delayed coking, mild thermal cracking to reduce viscosity, and thermic cracking.

Hydrocarbon feedstocks containing unacceptable levels of sulfur and nitrogen may be subjected to a hydrogenation treatment prior to treatment with the process of the present invention, thereby obtaining particularly good results. Preferably, the hydrocarbon feedstock boiling in the gasoline range has a low sulfur content, preferably less than 10 ppm by weight. raw materials.

The hydrocarbon feedstock may consist entirely of a fraction boiling in the gasoline range, that is, in the range of C4-220 ° C. While the fraction boiling entirely in the gasoline range is included in the hydrocarbon feedstock, it may be advantageous to use it as

hydrocarbon feedstock her fraction with point boiling into Mp 180 ° C. Optionally it can be hydrocarbon s urov i on mixture of hay with the reformed faction. Preferably hydrocarbon raw to i basically boiling in range

The gasoline may essentially comprise linear paraffins having at least five carbon atoms, i.e. the feedstock may consist essentially of one or more different types of linear paraffins having at least five carbon atoms.

Preferably, the hydrocarbon feedstock boiling in the gasoline range comprises substantially linear paraffins of five to ten carbon atoms. More preferably, the hydrocarbon feedstock comprises substantially linear paraffins of five to seven carbon atoms. Preferably, the hydrocarbon feedstock comprises substantially n-hexane and / or n-heptane.

A further advantage of the process of the present invention is characterized by an increase in the conversion efficiency of the sulfur contaminated raw materials based on the observed increased overall activity. Furthermore, the process appears to be characterized by an increased mass memory on the effect of poisoning by the sulfur contamination present in the raw material to be converted. A particular advantage is to process the refinery feedstock without the need for pre-treatment of the feedstock or with the possibility of reducing the need for feedstock pretreatment.

• ·

In a further embodiment, the present invention further relates to a process for isomerizing a hydrocarbonaceous feed substantially boiling in the gasoline range wherein the feedstock comprises linear paraffins of at least five carbon atoms and a sulfur content of greater than or equal to 10 ppm contacting the feedstock in the presence of hydrogen. at elevated temperature and pressure, with a catalyst comprising a combination of Pt and Pd, each in a metal form, supported on an acid amorphous aumina or molecular sieve.

Suitably, the process comprises isomerizing a feedstock as defined above with a sulfur content in the range of 10 to 100 ppm, preferably 10 to 50 ppm, even more preferably 10 to 30 ppm, for example about 20 ppm. Processing with a higher sulfur content in the feedstock is slightly more difficult, for example at temperatures slightly higher than required for the conversion of low-sulfur feedstocks.

The unconverted linear paraffins are suitably separated from the branched paraffins downstream of the reaction zone in which the isomerization takes place and recycled to the reaction zone. The separation is preferably carried out by means of a molecular sieve or by distillation.

The process is preferably initiated by introducing the catalyst into the reaction vessel and heating the bed while activating the catalyst by contacting the flowing oxygen at an elevated temperature and subsequently the flowing hydrogen at an elevated temperature. The feedstock to be isomerized is preferably preheated to an elevated temperature that is lower than or equal to the operating temperature, and is introduced at the desired rate along with hydrogen at the desired molar ratio.

The reaction is preferably terminated by partial or complete deactivation of the catalyst, and catalyst regeneration is performed. Regeneration can be carried out after the feedstock is terminated, by introducing a suitable regeneration medium or by raising the temperature of the catalyst to a higher temperature to burn off the inactivating hydrocarbon deposits. Suitably, the reactive or adsorption fluids known, for example, include combustion gas such as dilute air or oxygen / nitrogen mixtures.

prior art regeneration media,

The process can be carried out in any suitable reactor, and is preferably carried out on a fixed bed, slurry or fluidized bed reactor, batch, semi-continuous or continuous. Multiple reactors in series or in parallel can be used. The catalyst regeneration may be carried out in one or more reactors simultaneously with the process in one or more of the remaining reactors.

A further object of the present invention relates to isomerized paraffinic hydrocarbons prepared as described above.

The invention will now be illustrated in a non-limiting manner by the following examples.

Exemplary embodiments;

Example 1 - Preparation of bifunctional bi metal catalyst A

Samples of BEA zeolite having an atomic ratio Si to Al of 12.5, a surface area of 750 m ³ / g and a crystal size of 0.1 to 0.7 microns are converted to ammonium form by contacting the sample with an aqueous solution of ammonium chloride at pH 8 (Pt) palladium (Pd) is then added to the required amounts by contacting with a Pt / Pd competitive ionic solution.

This also applies to sample samples by tetramine dichloride procedures known to be exchanged in the presence of ammonium as a competitive ion. The samples thus obtained are activated in situ by calcination in flowing oxygen (15 mol / kg.s) at 400 ° C, followed by reduction in flowing hydrogen (15 mol / kg.s) at

400 ° C. Catalyst A having Pt and Pd is thus obtained.

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999 99 99 9 present in independently variable amounts, expressed as a Pt / (Pt + Pd) ratio of between 0.0 and 1.0. The total metal dosage (Pt + Pd) is 0.5% by weight, 1.0% by weight. and 1.5 wt.%, based on the weight of the active catalyst structure in the various samples.

Example 2 (Comparative) - Preparation of bi-functional monometallic catalysts B and C

Catalysts B and C were prepared as in Example 1 except that only one of the platinum and palladium metals was introduced in each sample of the ammonium form of the BEA zeolite. Catalyst B is obtained only with Pt present in different amounts corresponding to the input of all metals from Catalyst A, and Catalyst C is obtained only with Pd present in different amounts corresponding to the total metal content supported by Catalyst A, expressed as Pt / (Pt + Pd) , 0 and respectively. 0.0.

Example 3 - Isomerization of n-heptane feed

The heptane conversion is performed in a fully automated continuous flow tubular microreactor. Samples of catalyst A, B, C or mixtures B and C prepared in Example 1 or 2 above were activated in situ in the reactor described above. The heptane vapor saturated hydrogen stream is then generated using a thermostatic saturator. The purity of heptane is at least 99%, with 1% or less of impurities mainly composed of heptane isomers. The reaction product is analyzed on-line by gas chromatography. The conversion was maintained at 82.5% by adjusting the spatial velocity. The conversion was carried out at 220 ° C, a molar ratio of hydrogen to heptane of 60 and a total pressure of 3 bar. The product obtained contains a mixture of cleaved hydrocarbons having less than 7 carbon atoms and isomerized hydrocarbons having 7 carbon atoms.

The results are shown in Tables 1 to 3 below.

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TABLE 1

Isomer yield (%) as a function of Pt / (Pt + Pd) ratio for heptane isomerization with catalysts A, B, C, B and C

and and YIELD ISOMERS (%) j ____________ i CATALYST and j (Pt + Pd) = and and (Pt + Pd) = and and and (Pt + Pd) = 1 AND, B, C, B + C i 0,5% wt. and 1.0 wt. and 1.5 wt. j Pt / (Pt + Pd) and and and and and and and and C 0.00 73, 0 and and and AND 0, 23 and 75, 0 (72.1) and and AND and j and AND 0.50 and 74, 6 (71.0) and and Ά and j 1 AND 0, 69 and i 73, 3 (3, 3) and and 1 AND and j 1 1 (B) 1.00 1 i 69, 1 1 and 1 and and and C 0, 00 and and and and 73, 4 and and 1 1 AND 0.35 and and and and 74.8 (70.5) ~ A and AND AND 0.85 and and and and 71.7 (69.3) AND and (B) 1.00 and and and and 65, 0 AND" and C 0,00 + and i <60, 0 and and and and and and (B) 1.00 and and and and AND 0, 33 ί and and 1 1 J Ά and ....... 1 .....- and 74, 0 |

In the table, the values in brackets correspond to the calculated values expected with a bimetallic catalyst having <4 fy • power equal to the additional power of each metal component, this value is calculated as a simple additional function.

The table shows that the isomer yields with catalyst A containing Pt and Pd in combination exceeded the calculated sum of the isomer yields of catalysts B and C, and significantly exceeded the measured sum of the isomer yield (physical mixture of catalysts B + C). This appears to be reproducible for various completely metallic deposits, with catalysts having a Pt / (Pt + Pd) of from 0.1 to 0.5 being preferred.

TABLE 2

Yield of single-branched and multi-branched isomers (%) as a function of the Pt / (Pt + Pd) ratio for the isomerization of heptane with catalysts A, B and C.

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i SINGLE (%) CATALYST Pt (Pt + Pd) = (Pt + Pd) = and and (Pt + Pd) = j A, B, C, i 0,5? wt. 1.0% wt. and 1.5 wt. j Pt / (Pt + Pd) and 1 (C) 0, 00 í 51.5 and and (A) 0, 23 j 51.6 (51.0) and and (AND) 0.50 53.6 (4, 4) « and and (A) 0, 69 i 52, 7 (50.0) ~ T ~ and (B) 1.00 1 49,3 and -F- AND and 1 j (C) 0, 00 and 51.2 1 and (A) 0, 35 and and 50, 9 (50.3) and and and (A) 0, 85 and and 49, 8 (1, 1) and and (B) 1.00 and and 1 46, 4 and and (A) 0.33 Ť ~~~ and and and “Τ- ι 52, 4

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VICEVETVENE (%)

CATALYZER A, B, C,

Pt / (Pt + Pd) =

0.5 wt.%, (Pt + Pd) = 1.0 wt.

(Pt + Pd) = 1.5 wt.

(C) 0.00 ,6 21.6 and and and (A) 0, 23 and , 23, 4 (21.2) and and and -1 and (A) 0, 50 and 1 21,0 AND (20.7) and and ( "AND and « 1 and and (A) 0, 69 1 i 20, 6 (20.4) 1 and 1 and AND 1 1 (B) 1.00 and i 19,8 and and 1 and t and and 1 (C) 0, 00 and and 1 and and 22, 2 1 and and and (A) 0, 35 1 and AND and 23, 9 (22.1) -and and 1 1 1 (A) 0, 85 and and and and 21.9 (21.9) AND and 1 1 (B) 1.00 and and and 1 18.6 and and and and t (A) 0, 33 and and and and and and 21.6 AND -and

In the table, the values in brackets correspond to the calculated values that were expected with a bimetallic catalyst having a performance equal to that of the individual metal components. This value is calculated as a simple additional function.

It can be seen from the table that the yields of mono- and poly-branched

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In the process using catalysts B and C, the isomers obtained with catalyst A exceeded the sum of the yields of the single-branched isomer and the sum of the yields of the branched isomers.

However, with catalysts A, where Pt / (Pt + Pd) is 0.1 to 0.5, an increase in the yield of an isomer containing predominantly multi-branched isomers is obtained in a single step according to the process of the invention.

TABLE 3

Analysis of product yield from Example 3

A detailed overview of the total product is given in the following table, for the process using Catalyst A, Pt / (Pt + Pd) = 0.23, the Pt + Pd = 0.5 wt%, and for the process using Catalyst C Pd = 0.5% %, and using catalyst B, Pt = 0.5 wt.

Product Determine the octane number

Yield (% mol)

Product

Yield (% mol)

RON AND C (B) AND C (B) n Cy 0 17, 5 17, 5 17, 5 Whose 0, 0 0 0, 3 2-MORE> 42.4 24, 8 25, 1 24, 0 C _Z 0.0 0 0, 4 3-MeC & 52, 0 25, 1 24, 6 23.6 c ₃ 3, 7 4, 6 5.8 3-EtCs 65.0 1.7 1, p 1.7 nC ₄ 0, 0 0, 1 1.4 2,2-diMeCs 92, 8 6, 7 6, 1 5, 3 iC ₄ 3.8 4, 8 4, 5 2,4-diMeCs 83, 1 5, 8 6, 0 5, 7 Cs 0, 0 0 0, 4 3,3-diMeCs 3, 0 2, 5 2, 0 c ₆ 0, 0 0 0, 5 2,3-diMeCs 91.1 7, 7 6, 6 6, 6 2,2,3-tri-eC ₄ > 100 0, 3 0, 4 0, 3

From the above table it is clear that improved product quality is obtained by the process of the present invention substantially free of 99

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Determination of the octane number is obtained from the Automotive Fueks Handbook by K.Owen, T.Coley, SAE International 1990 p 564 (ISBN 1 - 56091 - 064-x). For other catalysts A, with a total metal loading of up to 1.5% by weight, the product quality was almost identical. In contrast, product yields obtained with catalysts B and C show a substantial amount of the cleaved C3 and C4 product and less interesting yields of high octane number components.

raw material, with attractive multi-branched ingredients.

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Claims (13)

PATENTOVÉ Claims A process for isomerizing a hydrocarbon feedstock substantially boiling in the gasoline range, wherein the feedstock comprises linear hydrocarbons having at least five carbon atoms, wherein the feedstock is contacted, in the presence of hydrogen at elevated temperature and flak, with a catalyst containing platinum Pt in combination palladium Pd, each in the form of a metal deposited on an acidic amorphous aluminum or molecular sieve, wherein Pt and Pd are present at an atomic ratio Pf / (Pt + Pd) of greater than 0.0 to 0.8, provided that if: is an acidic molecular sieve of mordenites, Pt and Pd are present in the atomic ratio Pt / (Pt + Pd) between 0.0 and 0.35. Method according to claim 1, characterized in that Pt and Pd are both present at the same site, more preferably on the same catalyst particle, most preferably on the same particle of amorphous alumina or molecular sieve. Process according to claim 1 or 2, characterized in that the catalyst contains from 0.01 to 5% by weight of Pt and Pd in combination with respect to the total weight of the active structure of the catalyst, preferably from 0.1 to 3% by weight. The method according to any one of claims 1 to 3, characterized in that Pt and Pd are present in a Pt / (Pt + Pd) atomic ratio of substantially 0.1 to 0.8, preferably substantially 0.1 to 0, 5, with the proviso that if an acidic molecular sieve is used, it is not a mordenite. Method according to one of Claims 1 to 3, characterized in that the acidic molecular sieve 9 is 999 mordenite and where Pt and Pd are present in the atomic ratio Pt / (Pt + Pd) 0, 1 to 0, 33. Method according to one of claims 1 to 4, characterized in that the a1 umins comprise a moderation of a surface area of 100 to 500 m ³ / kg. in that the catalyst is amorphous to a small surface area, preferably The process according to any one of the claims, characterized in that it comprises an additional acidic component. and that amorphous alumina Method according to any one of claims 1 to 12, characterized in that it is of the twelve circular type, for example MCM-22 and AEL, AFI, BOG, BPH, CAV, FHT, FAU, GME, LTL, MAZ, MEI defined previously. by an acidic molecular sieve defined previously, including AFR, AFS, AFY, ATO, ATS, BEA, MOR, MTW and OFF of claims 1 to 8 by carrying out pressures up to 5 κ 10 ⁶ Pci (50 bar), up to 10 kg / kg.ha mole ratio The process according to any one of the preceding claims, characterized in that at a temperature of 50 to 400 ° C a space velocity of 0.5 hydrogen to a feedstock of up to 10.0. 10. A process according to any one of the preceding claims, wherein the hydrocarbon oil fractionation by distillation is obtained. paraffinic, preferably from claims 1 to 9, characterized in that the feedstock of the hydrocarbonaceous feedstock is subjected to a primary most preferably atmospheric The method according to any one of claims 1 to 10, characterized in that it comprises essentially ten linear carbon atoms. wherein the starting hydrocarbons, which are crude to five to five The method of any one of the above feedstocks is more than 10 ppm or from 10 to 100 ppm, more preferably 10 30 ppm, for example about 20 claims 1 to 11, wherein the sulfur content in the same, preferably is up to 50 ppm, most preferably ppm. input range is 10 to The process of branching according to claim 1, wherein the unconverted hydrocarbon after 12 are characterized by linear hydrocarbons in the reaction zone stream separating from which isomerization proceeds and recycled to the reaction zone.