MXPA00000001A - Catalytic composition for the upgrading of hydrocarbons having boiling temperatures within the naphtha range - Google Patents

Abstract

The present invention relates to a catalytic composition which comprises an ERS-10 zeolite, a metal of group VIII, a metal of group VI and optionally one or more oxides as carrier. According to a preferred aspect, the catalytic composition also contains a metal of group II B and/or III A. The catalytic system of the present invention can be used in the upgrading of hydrocarbon mixtures having boiling ranges within the range of C4 to 250 DEG C, preferably mixtures of hydrocarbons which boil within the naphtha range, containing impurities of sulfur, i.e. in hydrodesulfuration with the contemporaneous skeleton isomerization of olefins contained in these hydrocarbons, the whole process being carried out in a single step.

Description

CATALYTIC COMPOSITION FOR THE IMPROVEMENT OF HYDROCARBONS WHICH HAVE BOILING TEMPERATURES WITHIN THE INTERVAL OF THE NAFTA SUMMARY The present invention relates to a catalytic composition which comprises a zeolite ERS-10, a metal of group VIII, a metal of group VI and optionally one or more oxides as carriers. According to a preferred aspect, the catalyst composition also contains a metal of group II B and / or III A. The catalyst system of the present invention can be used in the improvement of mixtures of hydrocarbons having boiling ranges within the range of C4 up 250 ° C, preferably mixtures of hydrocarbons that boil within the range of naphtha, which contain sulfur impurities, that is, in hydrodesulfurization with the isomerization of the contemporary main structure of olefins contained in these hydrocarbons, the complete process is carried Finish in one stage. This catalytic system can be used, e? particular, for the improvement of mixtures of hydrocarbons which boil within the range of naphtha deriving from the cracking process, preferably mixtures of hydrocarbons having a boiling point within the range of naphtha which are derived from the catalytic cracking of FCC ( fluid catalytic cracking). The hydrocarbons which boil within the naphtha range that are derived from FCC (ie gasoline cut) are used as a gasoline combination component. For this purpose, it is necessary that they have a high octane number along with a low sulfur content, to adapt to the legal restrictions which are becoming stricter, in order to reduce the emission of pollutants. The sulfur present in gasoline blends in fact comes mainly (> 90%) from the gasoline cut that is derived from FCC. This cut is also rich in olefins which have a high octane number. The hydrogenation processes used for the desulfurization also hydrogenate the olefins present with a consequent considerable reduction of the octane number (RON and MON). Therefore, until now there has been a need to find a catalytic system which decreases the sulfur content in the hydrocarbon mixtures which boil within the range of the naphtha and, at the same time, minimize the loss of octane (RON). and MON) which can be obtained, for example, by the isomerization of the main structure of the olefins present. The use of zeolites with an average dimension as isomerization catalysts and the consequent recovery of octane in the charges that have already been subjected to desulphurisation are known (US 5298150, US 5320742, US 5326462, US 5318690, US 5360532, US 5500108, US 5510016, US 5554274, US 599439). In these known processes, in order to obtain hydrodesulphurisation with a reduced number of octane, it is necessary to operate in two stages, using in the first stage a catalyst suitable for desulfurization, and in the second stage a catalyst to recover the octane number . US Pat. No. 5,378,352 describes a single stage process for desulfurizing hydrocarbon fractions, with boiling points within the range of gasolines, using a catalyst which comprises a group VIII metal, a group VI metal, a zeolite which is selected from ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, MCM-22 and mordenite, and a metal oxide as a ligand, with a temperature of process preferably May at 340 ° C. Some catalytic materials contain metals of groups VI and VIII, a refractory carrier and a zeolite which is selected from ZSM-35, ZSM-5, mordenite and fajasite, and are described in EP 442159, EP 437877, EP 434123 for the isomerization and disproportionate olefins; in US 4343692 for hydrodesceration; in US 4519900 for hydrodesnitrogenation and EP 072220 for a two stage process comprising stripping and hydrodesulfurization, in US 4959140 for a two step hydrocracking process.

We have now surprisingly found a new catalytic system with which it is possible to desulfurize, with high conversion values, mixtures of hydrocarbons that boil within the range of naphtha containing sulfur and olefins and simultaneously obtain the isomerization of the main structure of the olefins present . This new catalyst system is also active at temperatures and pressures that are lower than those preferably used in the known art for desulfurization. The main structure allows hydrocarbons to be obtained which boil within the naphtha range and at the same time have very low losses of RON (research octane number) and MON (motor octane number). The results obtained are not only related to the desulphurization of hydrocarbon cuts that boil within the range of "heavy naphtha" (130-250 ° C), ie cuts low in olefins, but also in feeds of "interval naphtha". "which boils within the range of 35 ° -250 ° C, that is, in the case of cuts rich in olefins. In fact, the catalytic system of the present invention has a high selectivity by desulfurization with respect to hydrogenation, which represents an additional advantage in terms of recovery of octane in the final gasoline. A first objective of the invention therefore relates to a catalytic composition which comprises an ERS-10 zeolite, a group VIII metal, a group VI metal and optionally one or more oxides as a carrier. According to a particular aspect of the present invention, the catalyst composition also comprises a metal of group II B and / or III A. This metal is preferably deposited on the surface of the zeolite. The zeolite ERS-10 is a porous crystalline material described in EP 796821, which has in its calcined and anhydrous form, a composition of oxides corresponding to the following formula: m M2 / n0 x X203 YO, where m is a number between 0.01 and 10, m is H + and / or a cation of an alkaline or alkaline earth metal with a valence n, z is a number between 0 and 0.02, x represents one or more elements that are selected from aluminum , iron, gallium, boron, vanadium, arsenic, antimony, chromium and manganese, and Y represents one or more elements that are selected from silicon, germanium, titanium, zirconium, characterized by the following effect of X-ray diffraction from powders (recorded by means of a vertical geonometer equipped with an electronic pulse counter system using CuKa radiation (1 = 1.54178 A) containing the main reflections in Table A: Table A D (A) I / ID -100 11. 0 ± 0 .1 vs 6 .80 ± 0 .08 w 5. .79 ± 0, .06 w 4 .59 ± 0. .05 m 4 .29 ± 0. .05 vs 3 .96 ± 0. .04 m 3 .69 ± 0. .03 w 3 .41 ± 0. .03 w 3 .33 ± 0. .03 w 3, .26 ± 0. .02 m 3. .07 ± 0, .02 w 2, .68 ± 0, .01 w 2. .57 ± 0, .01 w 2, .51 ± 0, .01 w 2. .38 ± 0. .01 w 2. .31 ± 0. .01 w 2. .28 ± 0. .01 2. .11 ± 0. .01 2. .03 ± 0. .01 w 1. .94 ± 0. .01 w where d indicates the interplanar distance, Y / I0.100 represents the relative intensity calculated by measuring the height of the peaks and which is related in percentage to the height of the most intense peak, the symbol vs indicates a very strong intensity (60-100), s a strong intensity (40-60), m a average intensity and w a weak intensity (0-20). M is preferably selected from sodium, potassium, hydrogen or mixtures thereof. According to a particularly preferred aspect of the present invention, ERS-10 zeolite is in acid form, ie, in the form in which the M cationic sites of the zeolite are predominantly occupied by hydrogen ions. It is specifically preferably that at least 80% of the cationic sites are occupied by hydrogen ions. The ERS-10 zeolite is based on silicon oxide and aluminum oxide, that is, an ERS-10 zeolite in which X is aluminum and Y is silicon, is preferably used. According to one aspect of the present invention, when the catalyst composition comprises zeolite ERS-10 and metals of group VI and VIII, the zeolite is preferably present in an amount ranging from 70 to 90%; When the catalyst composition also comprises one or more oxides as a carrier, the zeolite is preferably present in an amount ranging from 5 to 30% by weight with respect to the total weight of the catalyst.

The catalysts used in the present invention preferably contain cobalt or nickel as the group VIII metal, while the group VI metal is preferably selected from molybdenum or tungsten. According to a particularly preferred aspect, Co and Mo are used. The weight percentage of the group VIII metal preferably ranges from 1 to 10% with respect to the total weight of the catalyst, even more preferably from 2 to 6%; the weight percentage of group VI preferably ranges from 4 to 20% with respect to the total weight of the catalyst, even more preferably from 7 to 13%. The percentages by weight of the metal of group VI and the metal of group VIII refer to the content of metals expressed as metal element of group VI and metal element of group VIII; in the final catalyst the metals of group VI and VIII are in the form of oxides. According to a particularly preferred aspect, the molar ratio between the metal of group VIII and the metal of group VI is less than or equal to 2, preferably less than or equal to 1. The oxide used as carrier is preferably the oxide of a Z element that is selected from silicon, aluminum, titanium, zirconium and mixtures thereof. The carrier of the catalyst composition may consist of one or more oxides and the oxide used preferably is alumina or alumina mixed with an oxide that is selected from silica and zirconia.

When the catalyst contains a Group II B and / or III A metal, such metal is preferably present in an amount ranging from 0.1 to 5% by weight of the total weight of the catalyst, expressed as a metallic element, even more preferably between 0.1 and 3%. Zinc is preferably used. The catalytic compositions of the present invention can be prepared by traditional methods, for example by impregnating the zeolite ERS-10 with a solution containing a salt of a metal of group VI and a salt of a metal of group VIII, drying and calcination. . The impregnation can also be carried out using a solution containing a metal salt of group VI and a solution containing a salt of a metal of group VIII. By means of impregnation of a solution containing a salt of a metal of group II B and / or III A, catalytic compositions can be prepared which contain, in addition to the zeolite, metal of group VI and metal of group VIII, also a metal of group II B and / or III A. When the catalyst contains one or more oxides as carriers, it can be prepared by mixing the zeolite with the oxide, followed by extrusion, calcination, an optional exchange process which reduces the content of the sodium, dried, impregnated with a solution containing a salt of a Group VI metal, dried, calcined and impregnated with a solution of a salt of a Group VIII metal, dried and calcined. According to a particularly preferred aspect of the present invention, the catalytic compositions which contain one or more oxides as a carrier are prepared by means of the sol-gel technique as follows: a) an alcohol dispersion containing a soluble salt is prepared of Group VIII metal, ERS-10 zeolite and one or more organic compounds capable of generating the oxide or support oxides; b) an aqueous solution containing a soluble salt of the group VI metal and, optionally, tetraalkylammonium hydroxide having the formula R4N0H is prepared; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 to 40 ° C; e) the gel is dried; f) the gel is calcined. The catalytic compositions obtained in this way have a high surface area (> 200 m2 / g) and a high pore volume (> 0.5 cm3 / g) with a distribution within the range of mesoporosity. In step a) of this preparation, the metal salt of group VIII is, for example, a nitrate, a hydroxide, an acetate, an oxalate and preferably a nitrate. When a catalytic composition is desired which also contains a metal of group II B and / or III A, a salt of this metal will also be present in the alcohol dispersion. The organic compound capable of generating the support oxide or oxides, by means of subsequent hydrolysis and gelling and calcination, is preferably the corresponding alkoxide or alkoxides, in which the alkoxide substituents have the formula (R'O) -where R 'is an alkyl containing from 2 to 6 carbon atoms. The alkoxide is preferably a Z element which is selected from silicon, aluminum, titanium, zirconium and mixtures thereof, - in particular when Z is aluminum, it is a trialkoxide having the formula (R'0) 3A1, wherein R 'is preferably an isopropyl or a sec-butyl; when Z is silicon, it is a tetraalkoxide having the formula (R'0) 4 Si where R 'is ethyl and, when Z is Zr; is an alkoxide having the formula (R'0) 4Zr wherein R 'is preferably isopropyl. In step b) the soluble salt of the group VI metal can be an acetate, an oxalate or ammonium salts, and preferably is an ammonium salt. The tetraalkylammonium group containing from 2 to 7 carbon atoms. According to a preferred aspect, the solution in step b) also contains formamide (chemical agent for drying control) which favors the stabilization of the porous structure during the drying phase.

The amounts of the reagents are selected in relation to the composition of the final catalyst. In step c) according to the preferred sequence, the solution of step b) is added to the suspension of step a). In step d) the gel obtained is obtained at a temperature ranging from 10 to 40 ° C for a time of 15 to 25 hours. Step e) is carried out at a temperature ranging from 80 to 120 ° C. Step f) is carried out at a temperature ranging from 400 to 600 ° C. According to another aspect of the present invention, the catalytic system containing one or more oxides as a carrier can be prepared as follows: a) an alcohol dispersion containing ERS-10 zeolite and one or more organic compounds capable of generating the oxide or support oxides; b) an aqueous solution containing tetraalkylammonium hydroxide having the formula R4N0H is prepared; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 to 40 ° C; e) the gel is dried; f) the gel is calcined; g) the calcined product is impregnated with a solution containing a group VI metal salt, dried, calcined and impregnated with a solution of a group VIII metal salt, dried and calcined. The amounts of the reagents are selected in relation to the composition of the final catalyst. The reagents used are the same as in the sol-gel synthesis. According to another aspect of the present invention, the catalyst compositions containing the oxide or support oxides can be prepared as follows: a) an alcohol dispersion containing a soluble salt of the group VIII metal and one or more organic compounds is prepared capable of generating the oxide or support oxides; b) an aqueous solution containing a soluble salt of a group VI metal and, optionally, tetraalkylammonium hydroxide having the formula R4N0H is prepared; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature that varies from to 40 ° C; e) the gel is dried; f) the dry product is mechanically mixed with zeolite ERS-10; g) it is calcined.

The reagents used are the same as the sol-gel synthesis. The amounts of the reagents are selected in relation to the composition of the final catalyst. This latter preparation is preferably used for the synthesis of the catalytic composition of the present invention which also contains a group II B and / or III A metal deposited on the surface of the zeolite. In this case, in step f) an ERS-10 zeolite is used, on the surface of which a group II B and / or III A metal has been deposited by impregnation, using the known techniques. The ERS-10 zeolite formed in this way is new and is a particular aspect of the present invention. According to another aspect of the present invention, catalytic compositions containing one or more oxides can be prepared as carrier: a) impregnation of the carrier consisting of one or more oxides, with a salt of a group VI metal and with a salt of a metal of group VIII, b) drying and calcining the material obtained in step a), c) mixing the impregnated oxide obtained in step b) with zeolite ERS-10. The amounts of the reagents are selected in relation to the composition of the final catalyst.

The impregnations of step a) are carried out with any traditional method, the salts of group VI and VIII metals are in aqueous solution. When separate aqueous solutions are used for the group VI metal and for group VIII metal, a drying and calcination step can be inserted between the two impregnations. Prior to step c) the impregnated oxide is milled and sieved into < 0.2 mm and then, in step c) is mixed with the zeolite by physical mixing or dispersion of the particles in an organic solvent of the cyclohexane or cyclohexanol type. The solvent vaporizes and the catalyst particles are dried and calcined. The mixing of step c) can also be carried out by mixing and homogenizing a solid mixture comprising the impregnated oxide (with particle dimensions of <; 2 mm), the zeolite, a ligand and, optionally, combustible organic polymers. The mixture obtained in this way can be mixed with a peptizing acid solution, can be extruded and calcined by any traditional method. Alternatively, the paste can be pelletized, dried and calcined with any traditional method. The catalysts used in the process of the present invention can be used as such or, preferably, extruded according to known techniques, for example using a peptizing agent such as a solution of acetic acid and optionally a ligand of the pseudo-boehmite type, added to the catalyst to form a paste which can be extruded. In particular, when the catalysts are prepared by solid to a gel, the addition of the ligand is not necessary during the extrusion process. The materials of the present invention can be used as catalysts for the improvement of hydrocarbon mixtures which boil within the range of naphtha, and even more genetically within the range C4 and 250 ° C. A further objective of the present invention therefore relates to a hydrodesulfurization process of hydrocarbon mixtures having boiling ranges in the range of C4 to 250 ° C, containing olefins and at least 150 ppm of sulfur, with the isomerization of the contemporary main structure of these olefins which is carried out with hydrogen in the presence of a catalytic composition which comprises an ERS-10 zeolite, a group VIII metal, a group VI metal and optionally one or more oxides as a carrier . According to a particular aspect of the present invention, the catalyst composition also comprises a group II A and / or III A metal deposited preferably on the surface of the zeolite. When a catalytic composition containing the ERS-10 zeolite, a Group VI metal, a Group VIII metal and optionally a Group II B and / or III A metal is used, the process of the present invention is carried out at a temperature that varies from 220 to 360 ° C, preferably between 300 and 350 ° C, at a pressure that varies from 5 to 20 kg / cm2 and to a WHSV that varies from 1 to 10 hours "1. The amount of hydrogen is between 100 and 500 times the amount of hydrocarbons present (Nl / 1) When the catalytic composition also contains one or more oxides as carrier, the hydrodesulfurization process and the contemporary isomerization of the main structure of the olefins present is carried out at a temperature ranging from 220 to 320 ° C, preferably between 250 and 290 ° C, at a pressure ranging from 5 to 20 kg / cm2 and to a WHSV between 1 and 10 hours "1. The amount of hydrogen is between 100 and 500 times the amount of hydrocarbons present (Nl / l). The hydrocarbon mixture which can be desulfurized according to the present invention contains more than 150 ppm sulfur. For example, mixtures of hydrocarbon with a sulfur content of more than 600 ppm, or even higher than 10,000 ppm can be hydrodesulfurized. The hydrocarbon mixtures which are subjected to hydrodesulfurization according to the process of the present invention are mixtures having boiling ranges in the range of C4 to 250 ° C, C4 refers to the boiling temperature of a mixture of hydrocarbons with four carbon atoms. Mixtures of hydrocarbons which boil within the range of the naphtha, ie having boiling ranges in the range of C5 to 220 ° C, are preferably subjected to hydrodesulfurization. The catalysts of the present invention are activated, prior to their use, by sulfurization according to known methods. According to a particular aspect of the present invention, it is possible to carry out the desulphurisation and isomerization processes in a reactor in which the catalytic composition is divided into two beds, the former contains the zeolite ERS-10, which optionally may contain a group II B and / or III A metal, the second contains the remaining catalytic component containing a group VI metal, a group VIII metal and one or more oxides as a carrier. The following examples describe different catalyst preparations of the present invention and improvement tests in both the model charge and full-range naphtha from FCC. An ERS-10 zeolite in acid form, prepared as described in Example 1 of EP 976821, having a molar ratio Si02 / Al203 = 67, is used in all of the examples.

EXAMPLE 1 - Preparation of catalyst A 1,185 g of Co (N03) 2.6H20 (CON) are dissolved in 36.18 g of BuOH at room temperature. 0.74 g of ERS-10 zeolite is added which is suspended in the alcoholic solution, heated at 60 ° C for 10 minutes. To this suspension is added 31.8 g of Al (OC4H9) 3 (aluminum sec-butoxide) which is heated at 80 ° C for 20 minutes to obtain the Al suspension. 1.66 g of (NH4) sMo7024.4H20 are dissolved (heptamolybdate 5 of ammonium, AHM) in 19.41 g of (C3H7) 4NOH (tetrapropylammonium hydroxide, solution at 19.2%) at room temperature, obtaining solution A2 (pH = 10). The solution A2 is slowly poured into the Al suspension, under heating and under stirring, obtaining a gel which is maintained at 80 ° C during 1 hour (pH = 10). This is followed by aging at room temperature for 22 hours, drying in a vacuum oven at 100 ° C for 6 hours, calcination in a muffle with the following temperature program: heating at 200 ° C (5 ° C / min); a pause at 200 ° C for 2 hours; heating to 550 ° C (5 ° C / min); a pause at 550 ° C for 3 hours, spontaneous cooling to room temperature. Table 1 shows the characteristics of the material.

EXAMPLE 2 - Preparation of catalyst B 20 1.33 g of CON are dissolved in 36.19 g of BuOH at room temperature. Add 2.05 of ERS-10 zeolite which is suspended in the alcoholic solution, heated at 60 ° C for 10 minutes. 31.7 g of Al (OC4H9) 3 (aluminum sec-butoxide) are added to this suspension which is heated at 80 ° C for 20 minutes, obtaining a suspension Bl. 1.59 g of AHM (ammonium heptamolybdate) are dissolved in 19.35 g of (C3H7) 4NOH (tetrapropylammonium hydroxide, 19.2% solution) at room temperature, obtaining solution B2 (pH = 10). Solution B2 is poured slowly into suspension Bl, under heating and under stirring, and then the procedure described in example 1 is followed. Table 1 shows the characteristics of the material.

PREPARATION OF CATALYST C 6.5 grams of zeolite ERS-10 is impregnated with an aqueous solution containing 1.07 g of CON and 1.48 g of AHM in 10.35 g of distilled H20 having pH = 5. The impregnated product is allowed to stand in air at room temperature for 23 hours. hours, then dried in an oven at 100 ° C for 6 hours and calcined in a muffle as described in example 1. Table 1 shows the characteristics of the material.

Example 4 - Preparation of catalyst D 0.88 g of CON are dissolved in 33.55 g of BuOH at room temperature. 0.99 g of ERS-10 zeolite, which is suspended in the alcohol solution, is added at 50 ° C for 10 minutes. To this suspension is added 28.07 g of Al (OC4H9) 3 (aluminum sec-butoxide) which is heated at 60 ° C for 20 minutes, obtaining a Dl suspension. 1.29 g of AHM (ammonium heptamolybdate) are dissolved in 8.89 g of H20 at room temperature; then add 1.39 g of HCONH2 (formamide), obtaining the solution of D2 (pH = 5). Solution D2 is poured into suspension Dl and then the procedure described in example 1 is followed. Table 1 shows the characteristics of the material.

Example 5 - Preparation of catalyst E 0.74 g of ERS-10 zeolite is dispersed in 36.18 g of BuOH, heated at 50 ° C for 10 minutes. To this suspension is added 32.25 g of A1 (0C4H9) 3 (aluminum sec-butoxide) which is heated at 60 ° C for 20 minutes, yielding the El suspension. 18.81 g of (C3H7) 4NOH (hydroxyl) are slowly added. tetrapropylammonium, solution at 19.2%, solution E2, pH = 14) to the suspension, under heating and under stirring, obtaining a gel which is maintained at 80 ° C for 1 hour (pH = 13). This is followed by rest at room temperature for 21 hours, drying in a vacuum oven at 100 ° C for 6 hours, calcination as in example 1. An aliquot of the calcined product (7.68 g) is impregnated with a solution containing 1185 g of CON and 1.75 g of AHM in 10.9 ml of H20 (pH 0 5); this is followed by digestion for 22 hours in the air. The impregnated product is dried in an oven at 100 ° C for 6 hours and calcined as described in example 1. Table 1 shows the characteristics of the material obtained.

Example 6 - Preparation of catalyst F One gram of zeolite ERS-10 is impregnated with an aqueous solution containing 0.135 g of Zn (N03) 2.6H20 in 1.59 g of distilled H20 having pH = 6. The impregnated product is allowed to stand in air at room temperature for 16 hours. hours; then it is dried in an oven at 100 ° C for 6 hours and calcined in a muffle as described in example 1. Table 1 shows the characteristics of the material obtained, which contains 3.6% zinc oxide.

Example 7 - Preparation of catalyst G 1,185 of CON are dissolved in 42.5 g of iProH at room temperature. 2.985 g of a 70% solution of Zr (0C3H7) 4 (zirconium isopropoxide) and 31.9 g of Al (OC4C3_4H9) 3 (aluminum sec-butoxide) are added and the mixture is heated at 60 ° C for 20 minutes, obtaining the suspension Gl. 1.66 g of AHM (ammonium heptamolybdate) are dissolved in 18.77 g of (C3H7) 4NOH (tetrapropylammonium hydroxide, 20% solution) at room temperature, obtaining the G2 solution, pH = 11. The G2 solution is slowly poured into the solution. suspension Gl, under heating and under stirring, obtaining a suspension which is maintained at 80 ° C for 1 hour (pH = 10). This is followed by resting at room temperature overnight and drying in a vacuum oven at 100 ° C for 6 hours. 8 g of the catalyst dried in this manner are mechanically mixed in a ball mill with 3.43 g of ERS-10 zeolite and the mixture is then calcined as in example 1. Table 1 shows the characteristics of the material obtained.

Example 8 - Preparation of catalyst H Dissolve 1.18 g of CON in 53,505 BuOH, at room temperature. 1.14 g of Si (0C2Hs) 4 are added (tetraethylorthosilicate) and 29.92 g of Al (OC4H9) 3 (aluminum sec-butoxide) and the mixture is heated at 60 ° C for 20 minutes, obtaining the Hl suspension. 1.76 g of AHM (ammonium heptamolybdate) are dissolved in 18.3 g of (C3H7) 4NOH (tetrapropylammonium hydroxide, 20% solution) at room temperature, obtaining the H2 solution, pH = 10.

The H2 solution is slowly poured into the suspension Hl, under heating and under stirring, obtaining a suspension which is maintained at 80 ° C for 1 hour (pH = 10).

This is followed by rest at room temperature overnight and drying in a vacuum oven at 100 ° C for 6 hours. Mechanically, 8.27 g of the dry product is mechanically mixed with 3.505 of ERS-10 zeolite and the mixture is calcined as in example 1. The characteristics of the material obtained are shown in table 1.

Example 9 - Preparation of catalyst K Dissolve 1.04 g of CON in 47.16 g of BuOH, at room temperature. 1.03 g of Si (OC2H5) 4 (tetraethyl orthosilicate) and 26.53 g of A1 (0C4H9) 3 (aluminum sec-butoxide) are added and the mixture is heated at 60 ° C for 10 minutes, obtaining suspension II. 1.47 g of AHM (ammonium heptamolybdate) are dissolved in 17.56 g of (C3H7) 4N0H (tetrapropylammonium hydroxide, solution at 19.2%), at room temperature, obtaining solution 12, pH = 11. Solution 12 is poured into the suspension II and then the same procedure as in example 1 is followed. Table 1 shows the characteristics of the resulting material, called material I.

A catalytic composition, named K, is prepared by mechanically mixing material I with Zn-containing zeolite ERS-10 prepared as in example 6 (catalyst F). The catalytic composition K contains F in an amount equal to 30% by weight of the total weight of the catalyst.

EXAMPLE 10 - (comparative) Preparation of catalyst L 1.18 g of CON are dissolved in 42.52 g of iPrOH at room temperature. 2.99 g of a 70% solution of Zr (OC3H7) 4 (zirconium isopropoxide) in iPrOH are added and 30 g of Al (0C4C3.4H9) 3 (aluminum sec-butoxide) are added and the mixture is heated to 60 g. ° C for 20 minutes, obtaining the suspension Ll. 1.66 g of AHM (ammonium heptamolybdate) are dissolved in 19.06 g of (C3H7) 4N0H (tetrapropylammonium hydroxide, solution at 19.2%) at room temperature, obtaining the solution L2, pH = 11. The solution L2 is slowly poured into the suspension Ll, and the same procedure as in example 1 is followed. Table 1 shows the characteristics of the material.

Example 11 - (comparative) Preparation of catalyst M 1.18 g of CON are dissolved in 36.17 g of BuOH at room temperature. Suspend under heating (60 ° C for 10 minutes, pH = 7) 0.63 g of ZSM-5 zeolite (PQ, Zi02 / Al203 = 32.3, in acid form), and add 30.11 g of A1 (0C4H9) 3 (sec. - aluminum butoxide); The mixture is heated at 60 ° C for 20 minutes, obtaining the suspension Ml. 1.67 g of AHM (ammonium heptamolybdate) are dissolved in 19.41 g of (C3H7) 4NOH (tetrapropylammonium hydroxide, solution at 19.2%), at room temperature, obtaining the M2 solution, pH = 10. The M2 solution is slowly poured into the Ml suspension, under heating and under agitation, obtaining a gel which is kept under heating (80 ° C for 1 hour, pH = 9). This is followed by rest at room temperature for 22 hours, drying in a vacuum oven at 100 ° C for 6 hours and calcined as in example 1. Table 1 below shows the characteristics of the material obtained.

Table 1 CATALYTIC TESTS ON THE LOAD OF MODEL The catalytic results that are obtained when treating a feed, defined as model load, representative of the composition of a FCC gasoline in terms of fuel content.

S and olefinic cut, are provided in the following. The model charge has the following composition: 30% by weight of 1-pentene; 0.25% by weight of thiophene (1000 ppm of S); the complement up to 100 is n-hexane. The catalysts are activated, all following the same procedure, in a stream of H2S / H2. The catalytic activity is evaluated as follows: conversion of HDS: 100 x (ppm Sentrada - ppm S3alida / ppm Isomerization property ISO: 100 x (i-pentane + l-pentenes) / S Cs HYD hydrogenation property: 100 x (n-pentanosalide / l -pentenoentry) EXAMPLE 12: Catalyst activity of catalyst A 1.5 g of catalyst A are diluted with corundum and loaded into a reactor (30-50 mesh) and activated in the presence of H2S / H2 (10% by volume) up to 400 ° C for 3 hours; the system is then placed under H2 pressure up to 10 bar and the power model is sent, with a H2 / HC ratio equal to 300 Nl / 1. Table 2 shows the operating conditions and the catalytic results.

EXAMPLE 13: Catalyst activity of catalyst B 1.5 of catalyst B is treated as in example 9 when considering the activation procedure and then tested on model loading using the operating conditions described in table 2. Table 2 also indicates the catalytic results.

EXAMPLE 14: Catalyst activity of catalyst D 1.5 of the catalyst D are treated as in example 9. Table 2 shows the operating conditions and the catalytic results.

EXAMPLE 15: Catalyst activity of catalyst E 1.5 of the catalyst E are treated as in example 9. Table 2 shows the operating conditions and the catalytic results.

EXAMPLE 16: Catalyst activity of catalyst G 1.5 of the catalyst G are treated as in example 9. Table 2 shows the operating conditions and the catalytic results.

EXAMPLE 17: Catalyst activity of catalyst H 1.5 of catalyst H are treated as in example 9. Table 2 shows operating conditions and catalytic results.

EXAMPLE 18 - (comparative) Catalytic activity of catalyst I 1.5 g of catalyst I, which does not contain a zeolitic component, is treated as in example 9. Table 2 shows the operating conditions and the catalytic results.

EXAMPLE 19 - (comparative) Catalytic activity of catalyst L 1.5 g of the catalyst L, which does not contain a zeolitic component, is treated as in example 9. Table 2 shows the operating conditions and the catalytic results.

EXAMPLE 20 - (comparative) Catalyst activity of the catalyst M 1.5 g of the catalyst M, containing ZSM-5, is treated as the catalyst component, as in example 9. Table 2 shows the operating conditions and the catalytic results.

Table 2 From the data provided in Table 2, it can be seen that under the same reaction conditions, considered as the result of the combination of the operation variables, the catalysts of the present invention allow desulfurization conversions to be obtained much higher compared to those of a catalytic composition containing a zeolite different from the zeolite ERS-10 (catalyst M). In particular at low temperatures (250-256 ° C), conversion values are obtained which are at least double those obtained with the catalytic composition containing ZSM-5. At these temperatures, with the comparative catalyst M, an isomerization is obtained which is comparable with that obtained with the catalysts of the present invention, while at higher temperatures (280-297 ° C), the isomerization values obtained with the catalysts of the present invention they are much higher than those obtained with the catalyst composition of the prior art which contains ZSM-5 zeolite. The comparative catalysts I and L, which do not contain zeolite, have high conversion values for desulfurization but have a negligible isomerization capacity. Furthermore, under the same reaction conditions, the catalysts of the present invention have a greater selectivity for isomerization of the charge, with respect to the hydrogenation of the olefins, as can be demonstrated by comparing the values indicated in the HYD / ISO column. of Table 2.

EXAMPLE 21: catalytic activity of catalyst C 1.5 g of catalyst C are treated as in example 9, considering the activation procedure and then tested on the model load under the following operating conditions: T = 336 ° C WSHV = 4.8 hours "1 H2 / HC = 300 Nl / 1 The following catalytic results are obtained: HDS (%) 89.4 ISO (%) 61.5 HDS / HYD 8.6 HYD / ISO 0.2 From the above data it can be seen that at high temperatures the catalyst C, in addition to having good desulphurisation capacity, has a very high performance in terms of isomerization capacity and contemporary activity of reduced hydrogenation (HYD / ISO = 0.2), maintaining a strict verification, in the case of the FCC gasoline desulfurization treatment, by decreasing the octane number.

CATALYTIC TESTS IN REAL LOAD Following are some examples of the operation of the catalysts of the present invention evaluated in a full-range FCC gasoline having the composition and characteristics indicated in Table 3 below.

Table 3 where S ppm is the sulfur content and the third to seventh columns indicate the volume percentage of normal paraffins and isoparaffins, naphthenes, normal olefins and isoolefins, cycloolefins, and aromatic substances, respectively. The last column indicates the percentage by volume of the fraction which boils at a temperature higher than 200 ° C.

Example 22 A 1.5 g catalyst C, diluted with corundum, is charged in a reactor (30-50 mesh) and activated in the presence of H2S / H2 (10% by volume) up to 400 ° C for 3 hours; the system is then subjected to pressure of H20 up to 10 bar and the feed consists of full-range FCC gasoline from table 3 which is sent, with a H2 / HC ratio of 300 to 300 Nl / 1. The treatment conditions and the results obtained, expressed as characteristics and composition of the resulting gasoline, are indicated in the following table: EXAMPLE 23 2.2 g of the catalytic composition K, diluted with corundum, are charged to a reactor (30-50 mesh) and activated in the presence of H2S / H2 (10% by volume) up to 300 ° C for 3 hours; the system is then placed under H2 pressure up to 10 bar and a feed consisting of full-range FCC gasoline from table 3 is sent, with a H2 / HC ratio equal to 300 Nl / 1.

The process conditions and the results obtained are shown in the following table: EXAMPLE 24 0.6 g of ERS-10 and 1.4 g of material I are loaded into two separate beds in a reactor (30-50 mesh): ERS-10 zeolite is loaded in the first bed and material I in the second bed. The ERS-10 zeolite forms 30% of the total weight of the catalyst. The activation is carried out as in the previous examples and then the FCC gasoline having the composition indicated in table 3 is sent. The process conditions and the results are specified in the following table: EXAMPLE 25 A 1.65 g of the catalytic composition G, diluted with corundum, is charged to a reactor (30-50 mesh) and activated in the presence of H2S / H2 (10% by volume) up to 400 ° C for 3 hours; the system is then placed under a H2 pressure of up to 10 bar and the feed consisting of full-range FCC gasoline from table 3 is sent, with a H2 / HC ratio = 300 Nl / 1. The process conditions and the results obtained are shown in the following table:

Claims (51)

1. A catalyst composition comprising an ERS-10 zeolite, a group VIII metal, a group VI metal and optionally one or more oxides as a carrier.

2. The catalyst composition as described in claim 1, which contains a metal of group II B and / or III A.

3. The catalyst composition as described in claim 2, wherein the group II B and / or III A metal is deposited on the surface of the zeolite.

4. The catalyst composition as described in claim 2 or 3, wherein the metal is zinc.

5. The catalyst composition as described in claim 1 or 2, wherein the zeolite ERS-10 is in the form in which the cationic sites of the zeolite are occupied predominantly by hydrogen ions.

6. The catalytic composition as described in claim 5, wherein at least 80% of the cationic sites are occupied by hydrogen ions.

7. The catalyst composition as described in claim 1, 2 or 5, wherein the ERS-10 zeolite is based on silicon and aluminum oxides.

8. The catalyst composition as described in claim 1, containing zeolite ERS-10, a metal of group VI and a metal of group VIII, wherein the zeolite is present in an amount ranging from 70 to 90% by weight.

9. The catalyst composition as described in claim 1, which contains zeolites ERS-10, a metal of group VI, a metal of group VII and one or more metal oxides, wherein the zeolite is present in an amount ranging from 5 to 30% by weight with respect to the total weight of the catalyst.

10. The catalyst composition as described in claim 1, wherein the group VIII metal is selected from cobalt and nickel.

11. The catalyst composition as described in claim 1, wherein the group VI metal is selected from molybdenum and tungsten.

12. The catalyst composition as described in claim 10 and 11, wherein the metal of group VI is Mo and the metal of group VIII is Co.

13. The catalyst composition as described in claim 1, wherein the percentage by weight and the metal of group VIII varies from 1 to 10% with respect to the total weight of the catalyst.

14. The catalyst composition as described in claim 13, wherein the weight percentage of the group VIII metal ranges from 2 to 6% with respect to the total weight of the catalyst.

15. The catalyst composition as described in claim 1, wherein the weight percentage of the group VI metal ranges from 4 to 20% with respect to the total weight of the catalyst.

16. The catalyst composition as described in claim 13, wherein the weight percentage of the group VI metal ranges from 7 to 13%.

17. The catalyst composition as described in claim 1, wherein the molar ratio between the metal of group VIII and the metal of group VI is less than or equal to 2.

18. The catalytic composition as described in claim 17, wherein the molar ratio between the metal of group VIII and the metal of group VI is less than or equal to 1.

19. The catalyst composition as described in claim 1, wherein the oxide or oxides used as a carrier are oxides of a Z element selected from silicon, aluminum, titanium, zirconium and mixtures thereof.

20. The catalyst composition as described in claim 19, wherein the oxide is selected from alumina or alumina mixed with an oxide that is selected from silica and zirconia.

21. The catalyst composition as described in claim 2, wherein the group II B and / or III A metal is in an amount ranging from 0.1 to 5% by weight with respect to the total weight of the catalyst.

22. The catalyst composition as described in claim 21, wherein the group II B and / or III A metal is in an amount ranging from 0.1 to 3% by weight with respect to the total weight of the catalyst.

23. A process for the preparation of catalytic compositions as described in claim 1, which contains zeolite ERS-10, a metal of group VI and a metal of group VIII by impregnating the zeolite ERS-10 with a solution containing a salt of the Group VI and one salt of a Group VIII metal, dried and calcined.

24. A process for the preparation of catalytic compositions as described in claim 1, containing zeolite ERS-10, a metal of group VI and a metal of group VIII comprising the impregnation of zeolite ERS-10 with a solution containing a salt of group VI and with a solution of a metal salt of group VIII, drying and calcination.

25. A process for the preparation of catalytic compositions as described in claim 1, which contains zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as carrier, which comprises mixing the zeolite with the oxide , extrusion, calcination, an optional exchange process which reduces the sodium content, drying, impregnation with a solution containing a salt of a group VI metal, drying, calcination, impregnation with a solution of a salt of a metal of the Group VIII, drying and calcination.

26. A process for the preparation of the catalytic compositions as described in claim 1, containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as a carrier, by means of the sun technique -gel, as follows: a) an alcohol dispersion is prepared which contains a soluble salt of the group VIII metal, ERS-10 zeolite and one or more organic compounds capable of generating the oxide or support oxides; b) an aqueous solution containing a soluble salt of the group VI metal and, optionally, tetraalkylammonium hydroxide having the formula R4N0H is prepared; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 to 40 ° C; e) the gel is dried; f) the gel is calcined.

27. A process for the preparation of the catalyst compositions as described in claim 1, which contains zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as a carrier, as follows: a) an alcohol dispersion containing ERS-10 zeolite and one or more organic compounds capable of generating the support oxide or oxides is prepared; b) an aqueous solution containing tetraalkylammonium hydroxide having the formula R4N0H is prepared; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 to 40 ° C; e) the gel is dried, • f) the gel is calcined; g) the calcined product is impregnated with a solution containing a group VI metal salt, dried, calcined and impregnated with a solution of a group VIII metal salt, dried and calcined.

28. A process for the preparation of the catalyst compositions as described in claim 1, containing zeolite ERS-10, a metal of the group

VI, a metal of group VIII and one or more oxides as a carrier, as follows: a) an alcohol dispersion containing a soluble salt of the group VIII metal and one or more organic compounds capable of generating the supporting oxide or oxides is prepared; b) an aqueous solution is prepared which contains a soluble salt of a Group VI metal and, optionally, tetraalkylammonium hydroxide having the formula R4NOH; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 10 to 40 ° C; e) the gel is dried; f) the dry product is mechanically mixed with zeolite ERS-10; g) it is calcined. 29. The process as described in claim 26, 27 or 28, characterized in that the metal salt of group VIII is nitrate.

30. The process as described in claim 26, 27 or 28, characterized in that the source of organic oxide is the corresponding alkoxide in which the alkoxide substituents have the formula (R'O) - wherein R ' is an alkyl containing from 2 to 6 carbon atoms. 5

31. The process as described in claim 30, wherein the alkoxide of a Z-element selected from silicon, aluminum, titanium, zirconium and mixtures thereof is used.

32. The process as described in claim 31, wherein a trialkoxide is used, having the formula (R'0) 3A1, wherein R 'is isopropyl or sec-butyl.

33. The process as described in claim 31, wherein a trialkoxide is used, having the formula (R'0) 4 Si where R 'is ethyl.

34. The process as described in claim 31, wherein a trialkoxide is used, having the formula (R'0) 4 Zr wherein R 'is isopropyl.

35. The process as described in claim 26, 27 or 28, wherein the soluble salt of the group VI metal is an ammonium salt.

36. The process as described in claim 26, 27 or 28, wherein the tetraalkylammonium hydroxide has the formula R 4 NH 0 wherein R is an alkyl group containing from 2 to 7 carbon atoms.

37. A process for the preparation of catalytic compositions, as described in claim 3, comprising: a) preparing an alcohol dispersion containing a soluble salt of the group VIII metal, and one or more organic compounds capable of generating the oxide or support oxides; b) an aqueous solution containing a soluble salt of the group VI metal and, optionally, tetraalkylammonium hydroxide having the formula R4N0H is prepared; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 to 40 ° C; e) the gel is dried; f) mechanical mixing of the dried product with an ERS-10 zeolite on whose surface a metal of group II B and / or III A has been deposited by impregnation; g) calcination.

38. A process for the preparation of catalytic compositions as described in claim 1, containing zeolite ERS-10, a metal of group VI, a metal of group VIII and one or more oxides as a carrier, comprising: a) impregnation of the carrier oxide with a salt of a metal of group VI and with a salt of a metal of group VIII, b) drying and calcining the material obtained in step a), c) mixing the impregnated oxide obtained in step b) with the zeolite ERS-10.

39. The process as described in claim 23 or 24, comprising an impregnation with a solution of a metal salt of group II B and / or III A.

40. A process for the preparation of catalytic compositions as described in claim 2, containing zeolite ERS-10, a metal of group VI, a metal of group VIII, one or more oxides as a carrier and a metal of group II B and / or III A, by means of the sol-gel technique, as follows: a) an alcohol dispersion containing a soluble salt of the metal of group VIII, a salt of a metal of group II B and / or III A, zeolite ERS- is prepared 10 and one or more organic compounds capable of generating the support oxide or oxides; b) an aqueous solution is prepared which contains a soluble salt of the group VI metal and, optionally, tetraalkylammonium hydroxide having the formula R4NOH; c) the alcohol dispersion and the aqueous dispersion are mixed and a gel is obtained; d) the gel is allowed to stand at a temperature ranging from 10 to 40 ° C; e) the gel is dried; f) the gel is calcined.

41. A process for the desulfurization of hydrocarbon mixtures having boiling ranges in the range of C4 to 250 ° C, containing olefins and at least 150 ppm of sulfur, with the contemporary isomerization of the olefin main structure, which it comprises placing the mixtures in contact, in the presence of hydrogen, with a catalytic composition which comprises a zeolite ERS-10, a metal of group VIII, a metal of group VI and optionally one or more oxides as a carrier.

42. The process as described in claim 41, wherein the catalytic composition comprises a metal of group II B and / or III A.

43. The process as described in claim 42, wherein the group II B and / or III A metal is deposited on the surface of the zeolite.

44. The process as described in claim 41 or 42, which is carried out in the presence of a catalyst composition containing an ERS-10 zeolite, a group VI metal, a group VIII metal and optionally a group II B metal. and / or III A, at a temperature ranging from 220 to 360 ° C, at a pressure ranging from 5 to 20 kg / cm2, to a WHSV that varies from 1 to 10 h "1, with an amount of hydrogen that it varies from 100 to 500 times the amount of hydrocarbons present (Nl / 1).

45. The process as described in claim 44, which is carried out at a temperature ranging from 300 to 350 ° C.

46. The process as described in claim 441 or 42, which is carried out in the presence of a catalyst composition containing an ERS-10 zeolite, a group VI metal, a group VIII metal, one or more oxides as carriers and optionally a metal of group II B and / or III A, at a temperature ranging from 220 to 320 ° C, at a pressure ranging from 5 to 20 kg / cm2, to a WHSV that varies from 1 to 10 h "1 , with an amount of hydrogen that varies from 100 to 500 times the amount of hydrocarbons present (Nl / 1).

47. The process as described in claim 46, which is carried out at a temperature ranging from 250 to 290 ° C.

48. The process as described in claim 41, wherein the hydrocarbon mixture which is subjected to desulfurization contains more than 600 ppm sulfur.

49. The process as described in claim 41, which is carried out in a reactor, in which the catalytic composition is divided into two beds, the first contains zeolite ERS-10, which optionally contains a metal of group II B and / or III A, the second contains a metal of group VI, a metal of group VIII and one or more oxides as a carrier.

50. The process as described in claim 41, wherein the hydrocarbon mixtures which are subjected to hydrodesulfurization have boiling ranges in the range of C5 to 220 ° C.

51. An ERS-10 zeolite on whose surface a group II metal and / or a Group III A metal is deposited.