Multimetallic reforming catalyst and catalytic reforming process

Abstract

Naphtha reforming catalysts are described. The catalyst includes a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising AI2O3, and / or 0.01 to 3 wt% of a first metal of Group 2 or Group 15 of the Periodic Table, or a combination thereof. It also includes 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; 0.01 to 2 wt% of at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; 0.03 to 1.0 wt% S; and 0.5 to 2 wt% of a halogen. The catalyst has an average bulk density in a range of 0.25 - 1.50 g / cc and a surface area in a range of 50-300 m2 / g. Catalytic reforming processes are also described.

Description

MULTIMETALLIC REFORMING CATALYST AND CATALYTIC REFORMING PROCESS RELATED APPLICATIONS

[0001] This application claims priority to Indian Provisional Patent Application No.202411049720 filed on June 28, 2024, the entirety of which is incorporated herein by reference. BACKGROUND

[0002] Catalytic reforming is a well-established hydrocarbon conversion process employed in the petroleum refining industry for improving the octane quality of hydrocarbon feedstocks. The primary products of reforming are a motor gasoline blending component or aromatics for petrochemicals. Reforming may be defined as the total effect produced by dehydrogenation of cyclohexanes and dehydroisomerization of alkylcyclopentanes to yield aromatics, dehydrogenation of paraffins to yield olefins, dehydrocyclization of paraffins and olefins to yield aromatics, isomerization of n- paraffins, isomerization of alkylcycloparaffins to yield cyclohexanes, isomerization of substituted aromatics, and hydrocracking of paraffins. A reforming feedstock can be a hydrocracker, straight run, FCC, or coker naphtha, and it can contain many other components such as a condensate or thermal cracked naphtha.

[0003] With catalytic reforming, the most important factor in improving the octane of naphtha is aromatics formation. However, aromatic formation is also the most important contributor to naphtha volume loss. In addition, the aromatics content of gasoline is controlled by environmental regulations, such as the EURO V specification, which can be particularly difficult to meet. In addition, it is difficult to increase C5+ yield without reducing the activity of the catalyst.

[0004] Therefore, there is a need to develop reforming catalysts with improved performance.DESCRIPTION

[0005] A catalyst must have the capability to perform its functions initially and for prolonged periods of time. This is typically measured by activity, selectivity, and stability. Activity is a measure of the catalyst's ability to convert hydrocarbon reactants into products at specified conditions. Selectivity refers to the amount of desired product or products obtained relative to the amount of reactants charged or converted. Stability refers to the rate of change with time of the activity and selectivity parameters; the smaller the rate of change, the more stable the catalyst. In a reforming process, for example, activity commonly refers to the amount of conversion that takes place for a given charge stock at a specified severity level and is typically measured by octane number of the C5+ product stream. Selectivity usually refers to the amount of C5+ yield and other valuable products, relative to the amount of the charge, that is obtained at the particular activity or severity level. Stability is typically equated to the rate of change of activity with time, as measured by octane number of C5+ product, and of selectivity as measured by C5+ yield. The last statement is not strictly correct because generally a continuous reforming process is run to produce a constant octane C5+ product with the severity level being adjusted continuously to attain this result. Furthermore, the severity level for this process is usually varied by adjusting the conversion temperature in the reaction zone so that the rate of change of activity finds response in the rate of change of conversion temperatures, and changes in this last parameter are customarily taken as indicative of activity stability.

[0006] The principal cause of observed deactivation or instability of a dual- function catalyst when it is used in a hydrocarbon conversion reaction is associated with the fact that coke forms on the surface of the catalyst during the course of the reaction. Accordingly, there is a need to develop more active and / or selective catalytic composites that are not as sensitive to the presence of coke and / or have the capability to suppress the rate of the formation of coke on the catalyst. Viewed in terms of performance parameters, the catalyst should have superior activity, selectivity, and stability characteristics. For a reforming process, the problem is typically expressed in terms of shifting and stabilizing the C5+ yield-octane relationship at the lowest possibleseverity level, with the C5+ yield being representative of selectivity and octane being proportional to activity.

[0007] Multimetallic acidic reforming catalysts have been developed with excellent stability, regenerability, and which have a 1 wt% improvement in C5+ yield without activity loss in the start of run (SOR) phase at 98 RON.

[0008] The catalyst comprises a combination of a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al2O3, and a first metal of Groups 2 or 15, or a combination thereof; catalytically effective amounts of platinum and rhenium; at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table or combinations thereof; sulfur; and a halogen component.

[0009] The catalyst can be utilized to substantially improve the performance of a reforming process which operates on a low-octane gasoline fraction to produce a high- octane reformate.

[0010] One aspect of the invention is a catalyst. In one embodiment, the catalyst comprises a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising gamma Al2O3, and 0.01 to 3 wt% of a first metal of Group 2 or Group 15 of the Periodic Table, or a combination thereof. The Group 2 and / or 15 metals are incorporated into the framework of the support.

[0011] The catalyst also includes 0.05 to 5 wt%, or 0.1 to 1.0 wt% Pt and 0.05 to 5 wt%, or 0.1 to 1.0 wt% Re; 0.01 to 2 wt% of at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; 0.03 to 1.0 wt% S; and 0.5 to 2 wt% of a halogen. The catalyst has an average bulk density in a range of 0.25 – 1.50 g / cc, or 0.25-1.30 g / cc, or 0.25-1.25 g / cc, or 0.25-1.20 g / cc, or 0.25-1.10 g / cc, or 0.25-0.90 g / cc, or 0.25-0.80 g / cc, or 0.30 – 1.50 g / cc, or 0.30-1.30 g / cc, or 0.30-1.25 g / cc, or 0.30-1.20 g / cc, or 0.30-1.10 g / cc, or 0.30-0.90 g / cc, or 0.30-0.80 g / cc, or 0.40 – 1.50 g / cc, or 0.40-1.30 g / cc, or 0.40-1.25 g / cc, or 0.40-1.20 g / cc, or 0.40-1.10 g / cc, or 0.40-0.90 g / cc, or 0.40-0.80 g / cc.

[0012] The surface area is in the range of 50-300 m2 / g (BET), or 50-290 m2 / g, or 50-280 m2 / g, or 50-270 m2 / g, or 50-260 m2 / g, or 50-250 m2 / g, or 75-300 m2 / g, or 75- 290 m2 / g, or 75-280 m2 / g, or 75-270 m2 / g, or 75-260 m2 / g, or 75-250 m2 / g, or 100-300m2 / g, or 100-290 m2 / g, or 100-280 m2 / g, or 100-270 m2 / g, or 100-260 m2 / g, or 100-250 m2 / g, 125-300 m2 / g, or 125-290 m2 / g, or 125-280 m2 / g, or 125-270 m2 / g, or 125-260 m2 / g, or 125-250 m2 / g, or 150-300 m2 / g, or 150-290 m2 / g, or 150-280 m2 / g, or 150-270 m2 / g, or 150-260 m2 / g, or 150-250 m2 / g, or 180-300 m2 / g (BET), or 180-290 m2 / g, or 180-280 m2 / g, or 180-270 m2 / g, or 180-260 m2 / g, or 180-250 m2 / g,.

[0013] Any Group 2 or Group 15 metal can be included as the first metal in the support to improve yield and / or selectivity. Suitable Group 2 and Group 15 metals include, but are not limited to, Mg and / or P. The Group 2 and Group 15 metals are present in amounts in the range of 0.01 to 3 wt%, or 0.01 to 2 wt%, or 0.01 to 1 wt%, or 0.05 to 3 wt%, or 0.05 to 2 wt%, or 0.05 to 1 wt%.

[0014] The catalyst includes Pt and Re in the range of 0.05 to 5 wt%, or 0.1 to 1.0 wt% each.

[0015] The rhenium component may be incorporated into the catalytic composite in any suitable manner known to those skilled in the catalyst formulation art which results in a relatively uniform distribution of rhenium in the carrier material such as by coprecipitation, ion-exchange, or impregnation. In addition, it may be added at any stage of the preparation of the composite, either during preparation of the carrier material or thereafter, and the precise method of incorporation used is not deemed to be critical. However, best results are obtained when the rhenium component is relatively uniformly distributed throughout the carrier material in a relatively small particle size, and the preferred procedures are the ones known to result in a composite having this relatively uniform distribution. One acceptable procedure for incorporating this component into the composite involves co-gelling or co-precipitating the rhenium component during the preparation of the preferred carrier material, alumina. This procedure usually comprehends the addition of a soluble, decomposable compound of rhenium such as perrhenic acid or a salt thereof to the alumina hydrosol before it is gelled. The resulting mixture is then finished by conventional gelling, aging, drying, and calcination steps as explained hereinbefore. A preferred way of incorporating this component is an impregnation step wherein the porous carrier material is impregnated with a suitable rhenium-containing solution either before, during, or after the carrier material is calcined. Preferred impregnation solutions are aqueous solutions of watersoluble, decomposable rhenium compounds such as ammonium perrhenate, sodium perrhenate, potassium perrhenate, potassium rhenium oxychloride (K2ReOCl5), potassium hexachlororhenate (IV), rhenium chloride, rhenium heptoxide, and the like compounds. Best results are ordinarily obtained when the impregnation solution is an aqueous solution of perrhenic acid. This component can be added to the carrier material either prior to, simultaneously with, or after the other metallic components are combined therewith. Best results are usually achieved when this component is added simultaneously with the other metallic components. In fact, excellent results are obtained with a one step impregnation procedure using an acidic aqueous solution containing chloroplatinic acid, perrhenic acid, cobaltous chloride, and hydrochloric acid.

[0016] Platinum should exist in the elemental metallic state. It may be incorporated in the catalytic composite in any suitable manner known to result in a relatively uniform distribution of this component in the carrier material such as coprecipitation or cogellation, ion exchange or impregnation. The preferred method of preparing the catalyst involves the utilization of a soluble, decomposable compound of platinum group metal to impregnate the carrier material in a relatively uniform manner. For example, this component may be added to the support by commingling the latter with an aqueous solution of chloroplatinic or chloroiridic or chloropalladic acid. Other water-soluble compounds or complexes of platinum group metals may be employed in impregnation solutions and include ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, platinum tetrachloride hydrate, platinum dichlorocarbonyl dichloride, dinitrodiaminoplatinum, sodium tetranitroplatinate (II), palladium chloride, palladium nitrate, palladium sulfate, diamminepalladium (II) hydroxide, tetramminepalladium (II) chloride, hexamminerhodium chloride, rhodium carbonylchloride, rhodium trichloride hydrate, rhodium nitrate, sodium hexachlororhodate (III), sodium hexanitrorhodate (III), iridium tribromide, iridium dichloride, iridium tetrachloride, sodium hexanitroiridate (III), potassium chloroiridate, potassium rhodium oxalate, etc. The utilization of a platinum, iridium, rhodium, or palladium chloride compound, such as chloroplatinic, chloroiridic, or chloropalladic acid or rhodium trichloride hydrate, is preferred since it facilitates the incorporation ofboth the platinum group components and at least a minor quantity of the halogen component in a single step. Hydrogen chloride or the like acid is also generally added to the impregnation solution in order to further facilitate the incorporation of the halogen component and the uniform distribution of the metallic components throughout the carrier material. In addition, it is generally preferred to impregnate the carrier material after it has been calcined to minimize the risk of washing away the valuable platinum or palladium compounds; however, in some cases it may be advantageous to impregnate the carrier material when it is in a gelled state.

[0017] Any metals of Groups 1, 2, 3, 9, or 15, or combinations thereof are included as an additional metal in the catalyst. Suitable additional metals include, but are not limited to, Na, K, Mg, Ca, Ba, Bi, Y, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Sn, Sb, La, Hf, W, Ir, Au, Pb, Ce, or combinations thereof. This additional metal is present in the range of 0.01 to 2 wt%, or 0.01 to 1 wt%, or 0.05 to 2 wt%, or 0.05 to 1 wt%, or 0.1 to 2 wt%, or 0.1 to 1%. The additional metal improves the activity of the catalyst and reduces coke formation.

[0018] This additional metal may be incorporated into the catalyst in any suitable manner known to those skilled in the catalyst formulation art to result in a relatively uniform distribution in the carrier material such as coprecipitation, cogellation, ion exchange, impregnation, etc.

[0019] The catalyst includes 0.03 to 1.0 wt% S, or 0.05 to 0.8 wt% S. The sulfur helps to maintain the initial activity of the catalyst, and thus, the C5+ yield. It can be added using any suitable process, such as cold sulfiding at room temperature or hot sulfiding. Any suitable sulfur compound can be used, including, but not limited to, H2S.

[0020] The catalyst also includes 0.05 to 2.0 wt% of a halogen, or 0.05-1.90, or 0.05-1.80, or 0.05-1.70, or 0.05-1.60, 0.10 to 2.0, or 0.10-1.90, or 0.10-1.80, or 0.10- 1.70, or 0.10-1.60,.or 0.50 to 2.0, or 0.50-1.90, or 0.50-1.80, or 0.50-1.70, or 0.50-1.60, or 0.90 to 2.0 wt% S, or 0.9-1.90, or 0.90-1.80, or 0.9-1.70, or 0.9-1.60. Any suitable halogen can be used, including, but not limited to, Fl, Cl, Br, and I, or combinations thereof. The halogen may be present in the form of the halide (e.g., as the chloride). The halogen may be added in any suitable manner, either during preparation of the support or before or after the addition of the other components. For example, thehalogen may be added, at any stage of the preparation of the carrier material or to the calcined carrier material, as an aqueous solution of a suitable, decomposable halogen- containing compound such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, ammonium chloride, etc. The halogen component or a portion thereof, may be added during the impregnation with the platinum, the rhenium; or the additional metal, for example, through the utilization of a mixture of chloroplatinic acid and hydrogen chloride. The specified level of halogen can be achieved or maintained during use by continuously or periodically adding a decomposable halogen-containing compound such as organic chloride (e.g. ethylene dichloride, carbon tetrachloride, t-butyl chloride) to the reaction zone.

[0021] The final catalyst generally will be dried at a temperature of about 93°C to about 315°C (about 200° to about 600° F) for a period of at least about 2 to about 24 hours or more, and calcined or oxidized at a temperature of about 371°C to about 593°C (about 700° to about 1100° F) in an air or oxygen atmosphere for a period of about 0.5 to about 10 hours in order to convert substantially all of the metallic components to the corresponding reducible oxide form.

[0022] The catalyst can have any suitable shape, including, but not limited to, spherical, cylindrical, trilobe, and quadra-lobe.

[0023] Another aspect of the invention comprises a catalytic reforming process. In one embodiment, the catalytic reforming process comprises contacting a feed stream comprising naphtha with a reforming catalyst in a catalytic reforming zone comprising a catalytic reforming reactor under catalytic reforming conditions to obtain a product stream. The reforming catalyst is described above. The contacting may be accomplished by using the catalyst in any suitable reactor system, such as in a fixed bed system, a moving bed system, a fluidized bed system, or a batch type operation. In a reforming process, the reforming zone will typically comprise a catalytic reforming zone containing one or more fixed beds or dense-phase moving beds of the catalyst. In a multiple bed system, the present catalyst may be used in all or less than all of the beds, with conventional catalysts being used in the remainder of the beds. This reforming zone may be one or more separate reactors with suitable heating means between the reactors. The reactants may be contacted with the catalyst bed in either upward,downward, or radial flow fashion. In addition, the reactants may be in the liquid phase, a mixed liquid-vapor phase, or a vapor phase when they contact the catalyst, with best results obtained in the vapor phase.

[0024] The hydrocarbon feed stream comprises hydrocarbon fractions containing naphthenes and paraffins that boil within the gasoline range. The preferred charge stocks are those consisting essentially of naphthenes and paraffins, although in some cases aromatics and / or olefins may also be present. This preferred class includes straight run gasolines, natural gasolines, synthetic gasolines, partially reformed gasolines, and the like. On the other hand, it is frequently advantageous to charge thermally or catalytically cracked gasolines or higher boiling fractions thereof. Mixtures of straight run and cracked gasolines can also be used to advantage. The gasoline charge stock may be a full boiling gasoline having an initial boiling point of from about 10°C to about 120°C (about 50°F to about 248° F) and an end boiling point within the range of from about 120°C to about 220°C (about 248°F to about 428° F), or may be a selected fraction thereof which generally will be a higher boiling fraction commonly referred to as a heavy naphtha (C7 and above), for example, a naphtha boiling in the range of about 90°C to about 220°C (194°F to about 428°F). In some cases, it is also advantageous to charge pure hydrocarbons or mixtures of hydrocarbons that have been extracted from hydrocarbon distillates, for example, straight-chain paraffins, which are to be converted to aromatics. It is preferred that these charge stocks be treated by conventional catalytic pretreatment methods such as hydrorefining, hydrotreating, hydrodesulfurization, etc., to remove substantially all sulfurous, nitrogenous, and water-yielding contaminants therefrom and to saturate any olefins that may be contained therein.

[0025] In some embodiments, the feed stream comprises a hydrotreated feed stream comprising hydrocarbons boiling in the gasoline range and having less than or equal to 1.0 ppmw S, or less than or equal to 0.5 ppmw S, or less than or equal to 0.3 ppmw S. EXAMPLES Example 1

[0026] A reference naphtha reforming catalyst, specifically for a fixed-bed semi- regenerative process was prepared. The catalyst support (γ-Al2O3,cylindrical extrudates) was wet-impregnated with Pt & Re solutions and dried at 100 °C for 12 hrs. The dried catalyst was then pre-treated, followed by oxychlorination at 510 °C andreduction with 15 % H2 / N2 at 565 °C. The reduced catalyst was sulfided at ambientconditions. The composition of the sulfided reference catalyst (Catalyst A) was 0.25 wt. % Pt, 0.40 wt.% Re, 1.15 wt.% Cl and 0.06 wt.% S. Example 2

[0027] A catalyst support was prepared by incorporating Mg in the support (i.e., in γ-Al2O3framework itself). On the Mg modified γ-Al2O3(cylindrical extrudates) Pt, Re and Co were simultaneously added using a conventional wet-impregnation route followed by a drying step. The multimetallic catalyst (Catalyst B) was pre-treated and sulfided as done in Example 1. The catalyst B composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.2 wt.% Mg, 1.25 wt.% Cl, and 0.18 wt. % S. Example 3

[0028] The multimetallic catalyst was similar to the catalyst in Example 2 except the catalyst extrudate was of trilobe shape. The catalyst (Catalyst C) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.2 wt.% Mg, 1.25 wt.% Cl, and 0.18 wt. % S. Example 4

[0029] The multimetallic catalyst was similar to the catalyst in Example 2 except the magnesium content was decreased to zero. The catalyst (Catalyst D) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 % Co, 1.25 wt.% Cl and 0.18 wt. % S. Example 5

[0030] The multimetallic catalyst was similar to the catalyst in Example 2 except the magnesium content was increased in the support. The catalyst (Catalyst E)composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.4 wt.% Mg, 1.25 wt.% Cl, and 0.18 wt. % wt.% S. Example 6

[0031] The multimetallic catalyst was similar to the catalyst in Example 4 except the cobalt content was increased. The catalyst (Catalyst F) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 1 wt. % Co, 1.25 wt.% Cl, and 0.18 wt. % S. Example 7

[0032] The multimetallic catalyst was prepared by co-impregnation of Pt, Re, Co, and P over γ-Al2O3cylindrical extrudates. The pre-treatment (oxychlorination / reduction) and sulfiding conditions were the same as in Example 1. The catalyst (Catalyst G) composition was 0.25 wt. % Pt, 0.40 wt.% Re, 0.5 wt. % Co, 0.6 wt.% P, 1.25 wt.% Cl, and 0.18 wt. % S. Example 8 (Catalyst Performance)

[0033] Reference Catalyst A and the multimetallic catalysts B, C, D, E, and F were tested for the fixed bed naphtha reforming process. A naphtha feed having N+2A (naphthenes + aromatics) of around 55, IBP = 35oC and FBP = 162oC, was used for the catalytic reforming testing. The total catalyst volume was fixed to 60 cc divided into three beds (15cc / 15cc / 30cc) over the reactor, which was enclosed in a furnace. The pilot plant testing conditions were as follows; H2:HC = 5, Pressure = 200 psig, and LHSV = 2.5 hr-1. The catalyst comparison was made based on C5+ yield (wt.%) and furnace Temperature required to reach a fixed RONC of 98 (oC). Major pilot plant outcomes have been demonstrated in Table 1. The performance of the multimetallic catalysts was evaluated by comparison with the reference Catalyst A. The C5+ yield at 98 RONC obtained with Catalyst B was 0.8 wt.% higher with an activity loss of 1.8oC compared to the reference Catalyst A. Catalyst C resulted in 1 wt.% C5+ yield gain and an activity benefit of 0.4oC. Catalyst D showed 0.5 wt. % C5+ yield benefit in comparison with reference Catalyst A with an activity benefit of 2oC. With Catalyst E, 1.4 wt.% higherC5+ yield was observed at 98 GC RON as compared to reference Catalyst A, but it showed a significant activity loss of 5oC. Catalyst F showed 0.4 wt. % C5+ yield benefit with 2.7oC better activity as compared to reference Catalyst A. Catalyst G had 1 wt.% higher C5+ yield with activity loss of 0.4oC compared to reference Catalyst A. Among all multimetallic catalysts, Catalyst C performed better in terms of C5+ yield benefit while maintaining overall activity. In addition, during the stability testing, the amount of coke observed was approximately 35 % lower in the case of Catalyst C as compared to reference Catalyst A.Table 1SPECIFIC EMBODIMENTS

[0034] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.

[0035] A first embodiment of the invention is a catalyst comprising (a) a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al2O3, and optionally 0.01 to 3 wt% of a first metal from Groups 2 or 15 of the Periodic Table, or a combination thereof; (b) 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; (c) 0.01 to 2 wt% of at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; (d) 0.03 to 1.0 wt% S; and (e) 0.5 to 2 wt% of a halogen; wherein the catalyst has an average bulk density in a range of 0.25 – 1.50 g / cc and a surface area in a range of 50-300 m2 / g. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises Mg. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises Mg present in an amount in a range of 0.05% to 1% wt%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through thefirst embodiment in this paragraph where the first metal comprises P. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the first metal comprises P present in an amount in a range of 0.05 to 1 wt%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the at least one additional metal comprises Co. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the halogen comprises Cl. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises (a) the support comprising the solid solution or the homogenous mixture of atoms in solid state having the single crystal structure, comprising gamma Al2O3, and 0.05 to 3 wt% Mg or P or the combination thereof; (b) 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re; (c) 0.01 to 2 wt% Co; (d) 0.03 to 1.0 wt% S; and (e) 0.5%-2 wt% Cl. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph where the catalyst comprises 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the catalyst comprises 0.05 to 0.8 wt% S. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the Al2O3comprises gamma Al2O3.

[0036] A second embodiment of the invention is a catalytic reforming process comprising contacting a feed stream comprising hydrocarbons boiling in the gasoline range with a reforming catalyst in a catalytic reforming zone comprising a catalytic reforming reactor under catalytic reforming conditions to obtain a product stream; wherein the reforming catalyst comprises (a) a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al2O3, and optionally 0.01 to 3 wt% of a first metal from Groups 2 or 15 of the Periodic Table, or a combination thereof; (b) 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; (c) 0.01 to 2 wt% of at least one additional metal of Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; (d) 0.03 to 1.0 wt% S; and (e) 0.5 to 2 wt% ofa halogen; wherein the catalyst has an average bulk density in a range of 0.25 – 1.50 g / cc and a surface area in a range of 50-300 m2 / g. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the first metal comprises Mg present in an amount in a range of 0.05% to 1% wt%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the first metal comprises P present in an amount in a range of 0.05 to 1 wt%. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the at least one additional metal comprises Co. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the halogen comprises Cl. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the reforming catalyst comprises (a) the support comprising the solid solution or the homogenous mixture of atoms in solid state having the single crystal structure, comprising gamma Al2O3, and 0.05 to 3 wt% Mg or P or the combination thereof; (b) 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re; (c) 0.01 to 2 wt% Co; (d) 0.03 to 1.0 wt% S; and (e) 0.5%-2 wt% Cl. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph where the catalyst comprises 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the Al2O3comprises gamma Al2O3. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the Al2O3comprises gamma Al2O3. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the feed stream comprises a hydrotreated feed stream having less than or equal to 1.0 ppmw S.

[0037] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departingfrom the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0038] In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.

Claims

What is claimed is:

1. A catalyst comprising: (a) a support comprising a solid solution or a homogenous mixture of atoms insolid state having a single crystal structure comprising Al2O3, and optionally 0.01 to 3wt% of a first metal from Groups 2 or 15 of the Periodic Table, or a combination thereof; (b) 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; (c) 0.01 to 2 wt% of at least one additional metal from Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; (d) 0.03 to 1.0 wt% S; and (e) 0.5 to 2 wt% of a halogen; wherein the catalyst has an average bulk density in a range of 0.25 – 1.50 g / cc and a surface area in a range of 50-300 m2 / g.

2. The catalyst of claim 1 where the first metal comprises Mg present in an amount in a range of 0.05% to 1% wt%.

3. The catalyst of claim 1 where the first metal comprises P present in an amount in a range of 0.05 to 1 wt%.

4. The catalyst of claim 1 where the at least one of the additional metal comprises Co.

5. The catalyst of claim 1 where the halogen comprises Cl.

6. The catalyst of claim 1 wherein the catalyst comprises: (a) the support comprising the solid solution or the homogenous mixture of atoms in solid state having the single crystal structure, comprising gamma Al2O3, and 0.05 to 3 wt% Mg or P or the combination thereof; (b) 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re;(c) 0.01 to 2 wt% Co; (d) 0.03 to 1.0 wt% S; and (e) 0.5%-2 wt% Cl.

7. The catalyst of claim 1 where the catalyst comprises 0.1% to 1.0 wt% Pt and 0.1 to 1.0 wt% Re.

8. The catalyst of claim 1 wherein the catalyst comprises 0.05 to 0.8 wt% S.

9. The catalyst of claim 1 wherein the Al2O3comprises gamma Al2O3.

10. A catalytic reforming process comprising: contacting a feed stream comprising hydrocarbons boiling in the gasoline range with a reforming catalyst in a catalytic reforming zone comprising a catalytic reforming reactor under catalytic reforming conditions to obtain a product stream; wherein the reforming catalyst comprises: (a) a support comprising a solid solution or a homogenous mixture of atoms in solid state having a single crystal structure comprising Al2O3, and optionally 0.01 to 3 wt% of a first metal from Groups 2 or 15 of the Periodic Table, or a combination thereof; (b) 0.05 to 5.0 wt% Pt and 0.05 to 5.0 wt% Re; (c) 0.01 to 2 wt% of at least one additional metal of Groups 1, 2, 3, 9, or 15 of the Periodic Table, or combinations thereof; (d) 0.03 to 1.0 wt% S; and (e) 0.5 to 2 wt% of a halogen; wherein the catalyst has an average bulk density in a range of 0.25 – 1.50 g / cc and a surface area in a range of 50-300 m2 / g.

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