FR2735395A1 - New catalytic compsns. contg. a dopant metal, a halogen, a noble metal, and a promoter - Google Patents

Abstract

A catalyst system comprises a matrix consisting of a mixt. of epsilon and psi transition aluminas; a dopant metal chosen from Ti, Zr, Hf, Co, Ni, Zn, a lanthanide, and alkali/alkaline earth metals; a noble metal from the Pt family, and a promoter selected from Sn, Ge, In, Ga, Tl, Sb, Pb, Re, Mn, Cr, Mo, and W. Also claimed is the method of prepn. and post-treatment of the catalyst.

Description

CATALYSTS USED IN THE REACTIONS OF
TRANSFORMATION OF IST HYDROCARBONS CONTAINING ALKALI OR ALKALINE EARTH METALS
DESCRIPTION
The present invention relates to a catalyst which comprises a matrix consisting of transition alumina # or transition alumina y, or a mixture of these two aluminas, at least one doping metal selected from the group consisting of alkali metals and alkaline earth, at least one halogen, at least one noble metal and at least one promoter metal. The invention also relates to a support formed of the matrix of alumina or alumina and at least one doping metal.

 The invention also relates to the process for preparing this catalyst. This catalyst can in particular be used for the conversion of hydrocarbons. This process can be used in particular in catalytic reforming processes.

 Catalytic reforming is a process for improving the octane number of petroleum fractions and in particular heavy distillation gasoline by converting n-paraffins and nsaphthenes into aromatic hydrocarbons.

 The catalytic reforming operation therefore consists of converting C7-C1Q n-paraffins into aromatics and light paraffins from a pert, and C7-C10 naphthenes to aromatics and light paraffins. These reactions are illustrated in particular by the conversion by dehydrogenation of the cyclohexanes and the dehydroisomerisation of the alkylcyclopentanes to give aromatics, the methylcyclohexane giving, for example, toluene, as well as by the cyclization conversion of the n-paraffins to aromatics, the n-heptane giving by example of toluene.

 During catalytic reforming also occurs cracking reactions of n-paraffins heavy light paraffins leading in particular to C1-C4 products mainly propane, isobutane: these reactions are detrimental to the reformate yield.

 Finally, there is also the formation of coke by condensation of aromatic rings forming a solid product, rich in carbon which is deposited on the catalyst.

 These reforming catalysts are extremely sensitive, in addition to coke, to various poisons capable of degrading their activity: in particular sulfur, nitrogen, metals and water.

 Coke, by settling on the catalyst surface, causes a loss of activity over time which leads to higher operating temperatures, lower reformate yield, and higher gas yield.

 Therefore, and with regard to the regeneration of the catalyst, the catalytic reforming process can be carried out in two different ways: semi-regeneratively or cyclically and continuously. In the first case, the process is carried out in a fixed bed, in the second in a moving bed.

 In the semi-regenerative process, to compensate for the loss of catalyst activity, the temperature is gradually increased and the plant is stopped to proceed with the regeneration of the catalyst by removing the coke. In cyclic reforming which is actually a variant of the semi-regenerative process, the plant has several reactors in series and each is taken out of service in turn, the coke deposits are removed from the catalyst shut off and the catalyst is regenerated while the other reactors remain in operation.

 In continuous reforming, the reactors used are moving-bed reactors operating at low pressure (less than 15 bar), which makes it possible to significantly improve reformate and hydrogen yields by favoring aromatization reactions. to the detriment of that of cracking, against the formation of coke is strongly accelerated. The catalyst passes through the reactors and then a regenerator section.

 Due to the chemical reactions involved in the reforming processes, it is necessary to use a bifunctional catalyst which combines two types of activity: namely the hydrogenating-dehydrogenating activity of a metal, in particular of a noble metal. such as platinum, optionally combined with other metals such as rhenium or tin, so-called promoter metals, this metal being deposited on the surface of a porous matrix. This alumina matrix contains a halogen, preferably a chloride which provides the acid function necessary for isomerizations, cyclizations and cracking reactions.

 The matrices generally used are chosen from the refractory oxides of metals of groups II, II and IV of the periodic table of elements. Most often aluminum oxide of general formula Al 2 O 3, nH 2 O is used. Its specific surface is between 150 and 400 m2 / g. This oxide, in which n is between 0 and 0.6, is conventionally obtained by controlled dehydration of hydroxides in which 1 <n <3. These amorphous hydroxides are themselves prepared by precipitation in aqueous medium of aluminum salts by The precipitation and ripening conditions determine several forms of hydroxides, the most common of which are boehmite (n = 1), gibbsite and bayerite (n = 3). Depending on the hydrothermal treatment conditions, these hydroxides give several transition oxides or aluminas. There are thus the forms p, y, X, 0, 6, K, and a which are essentially differentiated by the organization of their crystalline structure. During heat treatments, these different forms are susceptible to change between them, according to a complex parentage that depends on the operating conditions of the treatment. Form a, which has a surface area and almost zero acidity, is the most stable at high temperature. For the catalysts, particularly for reforming catalysts, the transitional alumina of the R-form is most often employed because of the compromise it has between its properties of acidity and thermal stability.

 As indicated above, the hydrogenation-dehydrogenation function is preferably provided by a noble metal of Group VIII of the Periodic Table.

 Much work has particularly focused on the dehydrogenating function of these catalysts and more specifically on the nature and mode of introduction of the promoter metal added to platinum. This second metal has the main effect of promoting the dehydrogenating activity of platinum. In some cases, this second metal or promoter also has the effect of limiting the dispersion loss of the platinum atoms on the surface of the support. This loss of dispersion is partly responsible for the deactivation of the catalyst.

 Among all the promoter metals studied, two metals have a predominant role: rhenium and tin. Indeed, these two metals are likely to provide the best platinum promotion effects.

 Thus, the use of rhenium has made it possible, in particular, to increase the stability of the catalyst with respect to its deactivation by coke deposition. This type of catalyst is used most often in fixed bed units. And thanks to this gain in stability, the duration of the reaction cycles included between two regenerations could be increased.

Tin, meanwhile, has improved the performance of these catalysts when used at low pressure. This improvement, combined with their lower cracking activity, made it possible to obtain improved reformate yields, especially in continuous regeneration processes operating at low operating pressure. Catalysts of this type which may contain rhenium, tin or lead have in particular been described in US-A-3,700,588 and
US-A-3,415,737
The catalyst must have a maximum level of activity for the hydrocarbon conversion, but in addition it must activate this transformation with the greatest possible selectivity. In particular, hydrocarbon losses in the form of light products containing from 1 to 4 carbon atoms should be limited. The acid function is necessary for aromatics-producing and octane-improving reactions. Unfortunately, this function is also responsible for cracking reactions that lead to the formation of light products. Therefore, it is clear that the optimization of the quality of this acid function is important to gain further selectivity without, however, reducing the activity of the catalyst.

 The catalysts must also be made more stable, i.e., resistant to coke poisoning.

 On the other hand, it has been seen that the catalysts are used either in fixed bed processes or in moving bed processes. In the latter, the catalysts undergo a large number of regenerations.

These treatments which consist, among other things, in burning the coke deposited on the catalyst, take place at high temperature and in the presence of water vapor.

Unfortunately, these conditions are favorable for the degradation of the catalyst. It is therefore important to seek to increase the resistance of the catalysts under these conditions.

 In addition, these catalysts are in the form of extrudates or beads of sufficient size to leave a relatively easy passage to the reactants and gaseous products. The wear of these catalysts, particularly by friction in the moving bed units, causes the formation of dust and finer grains. These finer grains disturb the gas flow and force to increase the input pressure reagents, or in some cases to stop the operation of the unit. In addition, in mobile bed units, this progressive wear has the effect of disrupting the circulation of the catalyst and requiring the frequent addition of new catalyst.

 A catalyst such as a reforming catalyst must therefore meet a large number of requirements, some of which may appear to be contradictory. This catalyst must first of all have the greatest possible activity making it possible to obtain high yields, but this activity must be combined with the greatest selectivity possible, that is to say that the cracking reactions leading to products containing 1 to 4 carbon atoms should be limited.

 On the other hand, the catalyst must have a high stability vis-à-vis its deactivation by coke deposition; the catalyst must also have excellent resistance to degradation when it has to undergo the extreme conditions prevailing in the repeated regeneration operations that it must undergo.

 In the case of the continuous reforming process employing moving-bed reactors and as mentioned above, the catalysts are also subjected to intense and progressive wear by friction which leads to a significant decrease in their specific surface area and the formation of "fines" detrimental to the operation of the installation. Catalysts currently available, if they can meet one or more of these conditions, do not meet all the requirements mentioned above.

 The object of the invention is therefore to provide a catalyst which has all the properties listed in the foregoing. Another object of the present invention is to provide a process for preparing this catalyst using starting materials commonly used in this field of the art, simple steps that can be easily developed on an industrial scale.

These and other objects are achieved according to the present invention by a catalyst comprising
a matrix consisting of 0 to 100% by weight of transition alumina, the complement at 100% by weight of the matrix being X transition alumina, and
at least one doping metal selected from the group consisting of alkali and alkaline earth metals,
at least one halogen chosen from the group formed by fluorine, chlorine, bromine and iodine,
at least one noble metal of the platinum family,
and at least one promoter metal chosen from the group formed by tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten.

 It is known that in the field of catalysts and in particular in the field of reforming catalysts, form transition alumina is most often used (see above). According to the invention, the catalyst matrix may also surprisingly be constituted by transition alumina n or a mixture of n-alumina and alumina.

 According to the invention, when using a mixture of transition alumina and transition alumina, it may comprise up to 99% or rather up to 84% by weight of alumina. Preferably, this mixture comprises from 3 to 70% by weight, and more preferably from 5 to 50% by weight of transition alumina, the complement to 100% by weight of the mixture being transition alumina y.

 The transition alumina n is obtained by calcining bayerite in dry air, at atmospheric pressure, between 250 and 5000C and preferably between 300 and 4500C. The specific surface area which depends on the final calcination temperature is between 300 and 500 m 2 / g. Alumina comes from boehmite by calcination under air at a temperature between 450 and 6000C. The specific surface area of the alumina obtained there is between 100 and 300 m 2 / g.

 The structures of these transition aluminas are close but differentiable by the X-ray diffraction technique. These crystalline structures are organized according to a cubic lattice of spinel type. The crystalline parameter of the form n is a = 7.90A and c = 7.79A.

 The catalyst thus prepared surprisingly meets all the requirements set out above for a catalyst. The presence on the alumina matrix of at least one doping metal selected from the group consisting of alkali and alkaline earth metals has the effect, in particular, of preserving the alumina or alumina matrix from its loss of specific surface area during the different regenerative treatments undergone by the catalyst while at the same time the catalytic performances are substantially maintained, in particular in the reforming reactions and in the production of aromatics.

A preferred catalyst of the invention comprises
a matrix consisting of 0 to 100% by weight of transition alumina, the complement at 100% by weight of the matrix being y transition alumina, and
relative to the catalyst,
from 0.001 to 8% by weight of at least one doping metal selected from the group of alkali and alkaline earth metals,
from 0.10 to 15.0% by weight of at least one halogen chosen from the group formed by fluorine, chlorine, bromine and iodine,
from 0.01 to 2.00% by weight of at least one noble metal of the platinum family,
from 0.005 to 10% by weight of at least one promoter metal chosen from the group formed by tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese , chromium, molybdenum and tungsten.

A further preferred catalyst according to the invention comprises
a support consisting of a matrix of alumina, n-alumina or a mixture of alumina and alumina, of one or more metal or doping metals chosen from the group consisting of alkali and alkaline earth metals,
at least one halogen,
a catalytic metal providing the dehydrogenation function of the catalyst, consisting of one or more noble metals or metals of the platinum family, and
at least one promoter metal chosen from the metals mentioned above.

 According to the invention, the matrix of alumina or alumina is modified by at least one doping metal selected from the group consisting of alkali and alkaline earth metals. The group consisting of alkali and alkaline earth metals comprises the elements of group la such as lithium, sodium, potassium, rubidium and cesium and those of group 2a such as beryllium, magnesium, calcium, strontium and barium.

 According to the invention, the catalyst may comprise one or more of these doping metals and their total content in the catalyst, expressed in percentages by weight relative to the catalyst, is from 0.001 to 8% by weight, preferably from 0.005 to 3% by weight. and more preferably from 0.01 to 0.3% by weight.

 Preferably, the doping metal is potassium and / or magnesium.

 The halogen (s) used to acidify the support may represent in total 0.1 to 15% by weight, preferably 0.2 to 10% by weight of the catalyst.

Preferably, a single halogen is used, in particular chlorine.

 The catalyst also comprises one or more promoter metals which have the effect of promoting the dehydrogenating activity of the platinum group noble metal and of limiting the dispersion loss of the noble metal atoms at the surface of the matrix, which is partly responsible deactivation of the catalyst.

 The promoter metals are selected according to the mode of use of the catalyst.

 Thus, when the catalyst is to be used in a fixed bed process, the promoter metal is preferably selected from the group consisting of rhenium, manganese, chromium, molybdenum, tungsten, indium and thallium. .

 When the catalyst is to be used in a moving bed process, the promoter metal is preferably selected from the group consisting of tin, germanium, indium, antimony, lead, thallium and gallium.

 Of these, rhenium is more preferred for fixed bed processes and tin for moving bed processes, since these provide the best effects of promoting catalyst activity.

 The total content of metal (metals) promoter (s) is, relative to the catalyst, from 0.005 to 10.00% by weight, preferably from 0.01 to 1.00% by weight.

 When the catalyst contains only one promoter metal, for example rhenium or tin, it is preferably present in an amount of from 0.005 to 0.9% by weight and more preferably from 0.01 to 0.8% by weight. by weight relative to the catalyst.

 The catalyst of the invention further comprises at least one platinum family noble metal at a level of from 0.01 to 2.00% by weight, preferably from 0.10 to 0.80% by weight.

 The noble metals that can be used are platinum, palladium and iridium; platinum is preferred.

 The catalyst of the invention may be prepared by depositing its various constituents on the alumina matrix. The deposition of each component may be carried out, in whole or in part, on one or both aluminas of the matrix before or after shaping thereof. Constituents may be deposited separately or simultaneously in any order.

 Thus, when a mixture of aluminas is used as the matrix, the constituents of the catalyst can be deposited on the two aluminas or on one of them, preferably on the alumina n before mixing the two. aluminas and their shaping.

 It is also possible to partially or completely deposit one or more constituents on the two aluminas or one of them before mixing them, then to make the other deposits after mixing the two aluminas, either before or after the in the form of the mixture. When depositing one or more constituents before mixing the two aluminas, the deposition of doping metal on the transition alumina is preferably carried out.

 However, according to the invention, it is generally preferred to mix the two aluminas before depositing the metal components and the halogen or halogen.

Also, the invention also relates to a process for preparing the catalyst of the invention, which comprises the following steps
a) preparation optionally by mixing and then shaping a transition alumina matrix y, transition alumina, or a mixture of transition alumina n and transition alumina y,
b) deposition on at least one of the transition aluminas y and n of the following components, in the percentages by weight given below, which relate to the total weight of the catalyst,
from 0.001 to 8%, preferably from 0.005 to 4% and better still from 0.01 to 3%, by weight of at least one doping metal selected from the group consisting of alkali and alkaline earth metals,
from 0.1 to 15%, preferably from 0.2 to 10%, by weight of at least one halogen chosen from the group consisting of fluorine, chlorine, bromine and iodine,
from 0.1 to 2% and preferably from 0.10 to 0.80% of at least one noble metal of the platinum family, and
from 0.005 to 10% and preferably from 0.01 to 1.00% by weight of at least one promoter metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten; the steps a) and b) can be performed in any order, but preferably step a) is performed before step b) and the deposits of step b) can be made in part only before step a) and can be performed in any order.

 According to a preferred embodiment of this method, a support formed of the alumina matrix and at least one doping metal is first prepared, then the promoter metal or metals is deposited thereon. or halogens, and the noble metal (s) of the platinum family.

 In this case, the doping metal or metals can be deposited on the alumina or the alumina mixture, before or after shaping.

 Preferably, depositing the doping metal or metals after shaping of the alumina matrix.

 Also, the subject of the invention is also the support obtained in the first stage of this preferred process, which consists of a matrix comprising from 0 to 100% by weight of transition alumina, the complement at 100% by weight being transition alumina y, and at least one doping metal selected from the group consisting of alkali and alkaline earth metals, the amounts of doping metal representing in percentages by weight relative to the support of 0.001 to 11%, preferably from 0.005 to 4% and more preferably from 0.011 to 0.4% by total weight of doping metal relative to the support.

 The deposition of the various constituents of the catalyst can be carried out by conventional techniques, in the liquid phase or in the gas phase, from appropriate precursor compounds. When the deposition is carried out on the formed alumina matrix, the techniques employed may be, for example, dry impregnation, impregnation with excess solution or ion exchange. This operation is followed if necessary by drying and calcination at a temperature of 300 to 900 ° C., preferably in the presence of oxygen.

 The deposition of the metal or metals selected from the group consisting of alkali and alkaline earth metals can be carried out by any technique, for example dry impregnation, impregnation with excess solution or ion exchange and intervene at any stage of the catalyst preparation process. When this deposition is carried out after forming the alumina matrix, it is preferable to use the impregnation in aqueous medium by excess of solution, followed by drying to remove the impregnating solvent and calcination under air at a temperature of, for example, between 300 and 9000 ° C.

 These doping metals may be deposited via compounds such as, for example, oxides, halides, oxyhalides, nitrates, carbonates, acetates, sulphates, cyanides or oxalates of said elements. In the case of zirconium, alcoholates and acetylacetonates are also usable.

 The deposition of the noble metal (s) of the platinum family can also be carried out by conventional techniques, in particular the impregnation from an aqueous or non-aqueous solution containing a salt or a noble metal compound. By way of example of salts or compounds that may be used, mention may be made of chloroplatinic acid, ammonia compounds, ammonium chloroplatinate, platinum dicarbonyl dichloride, hexahydroxyplatinic acid, palladium chloride and palladium nitrate. .

In the case of platinum, the ammonia compounds may be, for example, the hexamines IV platinum salts of formula Pt (NH 3) 6X 4, the platinum IV halopentamine salts of formula (PtX (NH 3) 5) X 3, the platinum tetrahalogenodiamine salts of formula
PtX4 (NH3) 2X, platinum complexes with halogen-polyketones and halogenated compounds of formula H (Pt (aca) 2X) in which element X is a halogen selected from the group consisting of chlorine, fluorine, bromine and iodine, and preferably chlorine, and the aca group represents the residue of formula CsH702 derived from acetylacetone. The noble metal of the platinum family is preferably introduced by impregnation with an aqueous or organic solution of one of the organometallic compounds mentioned above. Among the organic solvents that can be used are paraffinic, naphthenic or aromatic hydrocarbons, and halogenated organic compounds having, for example, 1 to 12 carbon atoms per molecule. For example, n-heptane, methylcyclohexane, toluene and chloroform may be mentioned. Solvent mixtures can also be used.

 After introduction of the noble metal, drying and calcination are preferably carried out, for example at a temperature of 400 to 7000 ° C.

 The noble metal (s) of the platinum family can be deposited at any time during the preparation of the catalyst. It may be carried out separately or simultaneously with the deposition of other constituents, for example promoter metal (s).

In the latter case, a solution containing all the constituents to be introduced simultaneously can be used for the impregnation.

 The deposition of the promoter metal or metals may also be carried out by conventional techniques from precursor compounds such as the halides, nitrates, acetates, tartrates, citrates, carbonates and oxalates of these metals. Any other salt or oxide of these metals soluble in water, acids, or other suitable solvent is also suitable as a precursor. By way of examples of such precursors, mention may be made of rhenates, chromates, molybdates and tungstates. The promoter metal (s) may also be introduced by mixing an aqueous solution of their precursor compound (s) with the alumina or aluminas before shaping, followed by calcination in air at room temperature. a temperature between 400 and 9000C.

 The introduction of the promoter metal or metals can also be carried out using a solution of an organometallic compound of said metals in an organic solvent. In this case, this deposition is preferably carried out after that of the noble metal (s) of the platinum family and calcination of the solid, optionally followed by a reduction with hydrogen at high temperature, for example between 300 and 5000 ° C. The organometallic compounds are selected from the group consisting of complexes of said promoter metal, in particular polyketone complexes and hydrocarbylmetals such as alkyl, cycloalkyl, aryl, alkylaryl and arylalkyl metals. It is also possible to use organohalogen compounds. In particular, tetrabutyltin may be mentioned in the case where the promoter metal is tin, tetraethylplomb in the case where the promoter metal is lead and triphenylindium in the case where the promoter metal is indium. The impregnating solvent may be selected from the group consisting of paraffinic, naphthenic or aromatic hydrocarbons containing from 6 to 12 carbon atoms per molecule and halogenated organic compounds containing from 1 to 12 carbon atoms per molecule. For example, n-heptane, methylcyclohexane and chloroform may be mentioned. It is also possible to use mixtures of the solvents defined above.

The halogen, for example chlorine, may be introduced into the catalyst together with another metallic constituent, for example in the case where a halide is used as a precursor compound for the platinum-family metal, the promoter metal or alkali or alkaline earth metal. This introduction can also be carried out by impregnation with an aqueous solution containing an acid or a halogenated salt. For example, chlorine can be deposited using a hydrochloric acid solution. It is also possible to carry out the introduction of chlorine by calcination of the catalyst at a temperature ranging, for example, from 400 ° to 900 ° C. in the presence of an organic compound containing halogen, for example CCl 4,
CH2Cl2 and CH3Cl.

 Of course, at least two components of the catalyst can be introduced simultaneously, for example from a solution comprising precursor compounds thereof. We can also introduce the constituents successively in any order, from distinct solutions. In the latter case, dryings and / or intermediate calcinations may be carried out.

 The shaping of the alumina matrix or of an alumina mixture can be carried out using the catalyst shaping techniques known to those skilled in the art, such as, for example: extrusion, coagulation, drop, drageification, spray drying or pelleting.

Preferably, a preparation method according to the invention, which we detail below, comprises the following successive steps
a) shaping of the matrix of alumina or alumina n or a mixture of alumina and alumina tl,
b) depositing on this matrix at least one doping metal selected from the group consisting of alkali and alkaline earth metals,
c) depositing at least one promoter metal selected from tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten ,
d) introducing at least one element selected from the group consisting of fluorine, chlorine, bromine and iodine, and
e) depositing at least one noble metal of the platinum family.

 After forming the matrix and depositing all the constituents, it is possible to carry out a final heat treatment between 300 and 10,000 ° C., which may comprise only one step at a temperature of 400 ° C. to 9 ° C. preferably, and under an atmosphere containing oxygen, and preferably in the presence of free oxygen or air. This treatment generally corresponds to drying-calcination following the deposition of the last component.

 After forming the matrix and depositing all the constituents, a complementary heat treatment is preferably carried out which can be carried out at a temperature of 300 to 1000 ° C., preferably 400 to 7000 ° C., in a gaseous atmosphere containing water vapor and optionally a halogen such as chlorine.

 This treatment can be carried out in bed traversed by a stream of gas or in a static atmosphere. Preferably, the gaseous atmosphere contains water and optionally at least one halogen. The molar content of water is between 0.05 and 100%, preferably between 1 and 50%. The molar content of halogen is between 0 and 20%, preferably between 0 and 1-0%, and more preferably between 0 and 2%. The duration of this treatment is variable depending on the conditions of temperature, partial pressure of water and amount of catalyst. This value is advantageously between one minute and 30 hours, preferably from 1 to 10 hours. The gaseous atmosphere used is for example based on air, oxygen, or an inert gas such as argon or nitrogen.

 The role of this high temperature treatment in the presence of water is important. As shown in the examples described below, the presence of at least one element of the group consisting of alkali and alkaline earth metals, preserves the matrix of alumina or alumina from its loss of specific surface area during different regenerative treatments. Unexpectedly, a severe heat treatment in the presence of water and optionally halogen applied to this type of catalyst containing at least one element of the group consisting of alkali and alkaline earth metals, has the effect, not only to maintain the less loss of specific surface area, but also makes it possible to significantly improve the catalytic performance in the reforming and aromatics production reactions, compared with the catalysts of the prior art prepared according to processes that do not include the final step treatment at high temperature in the presence of water and at least one halogen, preferably chlorine.

 At the end of the preparation according to the invention, the calcined catalyst can advantageously undergo an activation treatment under hydrogen at high temperature, for example between 300 and 5500C.

The hydrogen treatment procedure consists, for example, in a slow rise in the temperature under a stream of hydrogen up to the maximum reduction temperature, generally between 300 and 5500.degree. C. and preferably between 350 and 4500.degree. this temperature for a period generally ranging from 1 to 6 hours.

 The catalyst of the invention can be used in particular in the hydrocarbon conversion reactions, and more particularly in the processes of gasoline reforming and aromatics production.

 The reforming processes make it possible to increase the octane number of the gasoline fractions originating from the distillation of crude oil and / or other refining processes.

 The aromatics production processes provide the bases (benzene, toluene and xylene) that can be used in petrochemicals. These processes are of additional interest in contributing to the production of large quantities of hydrogen essential for the hydrotreatment processes of the refinery.

 These two methods are distinguished by the choice of operating conditions and the composition of the charge.

 The typical feedstock treated by these processes contains paraffinic, naphthenic and aromatic hydrocarbons containing 5 to 12 carbon atoms per molecule. This load is defined, among other things, by its density and its weight composition.

 To carry out these methods, the hydrocarbon feedstock is contacted with the catalyst of the present invention at a temperature of 400 to 700 ° C using the moving bed or fixed bed technique.

 Generally, the mass flow rate of treated feedstock per unit mass of catalyst is from 0.1 to 10 kg / kg.h. The operating pressure can be set between atmospheric pressure and 4 MPa.

 Part of the hydrogen produced is recycled according to a molar recycling ratio ranging from 0.1 to 8.

The rate is the ratio of hydrogen flow recycled to the charge rate.

 Other features and advantages of the invention will appear better on reading the examples which follow, given of course by way of illustration and not limitation.

 The invention will now be described in the following exemplary embodiments given for illustrative and non-limiting.

EXAMPLE 1 Preparation of a Catalyst According to the Invention Comprising a Matrix Comprising a Mixture of Alumina and N-Alumina on Which Potassium, Platinum, Rhenium and Chloride Are Deposited

a) shaping of the alumina matrix
The matrix is prepared by mechanical mixing of an alumina powder r with a specific surface area equal to 220 m 2 / g and an alumina powder 9 with a specific surface area equal to 320 m 2 / g which had been prepared by calcination of bayerite. . The proportion of alumina 8 is 30% by weight. The mixture is then shaped by extrusion. The extruded matrix is calcined under a stream of dry air at 5200C for 3 hours.

b) potassium deposit
After cooling, the matrix obtained in step a) is brought into contact with an aqueous solution of potassium carbonate K2CO3. The concentration of this solution is 12.8 g of potassium per liter. This contact is carried out at room temperature for 1 hour. The impregnated extrudates are then dried at 1200 ° C. for 15 hours and calcined at 53 ° C. under a stream of dry air for 20 hours.

 (c) (d) (e) Deposition of platinum, rhenium and chlorine.

 Platinum deposition of rhenium and chlorine is carried out on part of the support obtained in step b).

Platinum is deposited during a first impregnation of the support with an aqueous solution containing per liter
8.20 g of chlorine in the form of HCl,
1.00 g platinum as H2PtCl6.

The solution is left in contact with the support for 2 hours. After drying and drying for 4 hours at 1200 ° C., the impregnated support is calcined at 53 ° C. for 3 hours under a stream of dry air. Then the rhenium is deposited by a second impregnation with an aqueous solution containing per liter
4.20 G of chlorine in the form of HCl,
1.50 g of rhenium in the form of ReCl3.

 After drying, the impregnated support is calcined at 5300C for 2 h under a stream of dry air.

 f) heat treatment in the presence of water and chlorine.

 The product obtained after steps c) d) e) above is treated at 5100C for 2 h under a current of 2000 dm3 / h of air per 1 kg of solid. This air contains water and chlorine injected into a preheating zone located upstream of the solid bed.

The molar concentrations of water and chlorine are respectively 1% and 0.05%.

EXAMPLE 2 Preparation of a Catalyst According to the Invention Comprising a Matrix of Alumina and N-Alumina on Which Magnesium, Platinum, Rhenium and Chloride are Deposited

a) Formatting the matrix
The alumina matrix is prepared in the same manner as in example 1, step a) by mechanical mixing of a powder of alumina and a powder of alumina n extrusion and calcination.

b) Deposition of magnesium
The matrix obtained in step a) is brought into contact with an aqueous solution of magnesium nitrate hexahydrate Mg (NO3) 2, 6H2O. The concentration of this solution is 8.0 g of magnesium per liter.

This contact is carried out at room temperature for 2 hours. The extrudates are then dried at 1200 ° C. for 15 hours and calcined at 53 ° C. under a stream of dry air for 2 hours.

 (c) (d) (e) Deposition of platinum, rhenium and chlorine.

 The deposition of platinum, rhenium and chlorine is carried out on the product obtained in step b) above in exactly the same manner as in example 1 step c).

 f) Heat treatment in the presence of water and chlorine.

 The product obtained after steps c) d) e) above is treated in exactly the same manner as in Example 2.

Example 3 (comparative)
In this example, the same procedure as in Example 1 is followed, but in step a) only y-alumina is used, no potassium or magnesium is deposited and no treatment is carried out. hydrothermal final.

a) Formatting the matrix
The matrix is prepared by extruding a powder of alumina r whose specific surface area is 220 m 2 / g. The extruded matrix is then calcined in a stream of dry air at 5200C for 3 h.

b) Deposition of platinum, rhenium and chlorine
The deposition of platinum, rhenium and chlorine is carried out on the matrix obtained at the end of step a) above in exactly the same manner as in step "c) d) e)" of Examples 1 ) and 2).

The characteristics of the catalysts thus prepared are summarized in Table I below.
TABLE I

<tb> Catalyst <SEP> Proportion <SEP> content <SEP> in <SEP> content <SEP> in <SEP> content <SEP> in <SEP> content <SEP> in <SEP> content <SEP> in <SEP > surface
<tb><SEP> alumina <SEP> TI <SEP> platinum <SEP> rhenium <SEP> Chlorine <SEP> potassium <SEP> Magnesium <SEP> specific
<tb><SEP> (l <SEP> weight) <SEP> (0 <SEP> ida <SEP> weight) <SEP> (* <SEP> weight) <SEP> {* <SEP> weight) <SEP>(<SEP> weight) <SEP> (* <SEP> weight <SEP> (m2 / 9) <SEP>
<tb><SEP> Ex. <SEP> 3 <SEP> 0 <SEP> 0.23 <SEP> 0.25 <SEP> 1.12 <SEP> 0 <SEP> 0 <SEP> 216
<tb><SEP> Ex. <SEP> 1 <SEP> 30 <SEP> 0.24 <SEP> 0.26 <SEP> 1.16 <SEP> 0.071 <SEP> 0 <SEP> 245
<tb><SEP> Ex. <SEP> 2 <SEP> 30 <SEP> 0.21 <SEP> 0.22 <SEP> 1.11 <SEP> 0 <SEP> O, <SEP> 032 <SEP> 243
<Tb>
Example 4
Catalyst performance
The catalysts prepared above in Examples 1, 2 and 3 have been tested in a charge transformation, the characteristics of which are as follows:
density at 200C 0.742 kg / dm3
research octane number -41
paraffin content 52.2% weight
Naphthenes content 32.4% by weight
aromatic content 15.4% by weight
The following operating conditions were used
temperature 4850C
total pressure 1.5 MPa mass flow rate (in kg.h'l) per kilogram of catalyst 1.5 h ~ 1
The performances of the catalysts are reported in Table II below, and are expressed through the weight yields and the reformate octane number of the reformate.

TABLE II

<tb> Catalyst <SEP> Yield <SEP> Yield <SEP> Yield <SEP> Yield
<tb><SEP> C4
<tb><SEP> reformat <SEP> hydrogen <SEP> into <SEP> into <SEP> C4 <SEP> aromatics
<tb><SEP> (E <SEP> weight) <SEP> (% <SEP> weight) <SEP> aromatic <SEP> (* weight) <SEP>
<tb><SEP> (t <SEP> weight)
<tb> Example <SEP> 3 <SEP> 85.3 <SEP> 3.0 <SEP> 59.3 <SEP> 11.7 <SEP> 0.20
<tb> Example <SEP> 1 <SEP> 86.1 <SEP> 3.2 <SEP> 59.9 <SEP> 10.7 <SEP> 0.18
<tb> Example <SEP> 2 <SEP> 86.8 <SEP> 3.3 <SEP> 59.7 <SEP> 9.9 <SEP> 0.17
<Tb>
If one compares the performance of the catalysts of Examples 1 and 3 on the one hand and those of the catalysts of Examples 2 and 3 on the other hand, it is found that the catalysts of Examples 1 and 2 according to the invention have clear performances. improved compared to the catalyst of Example 3 which represents the prior art.

 Indeed, the yields of light C4 cracking products obtained during the test of the two catalysts of Examples 1 and 2 according to the invention are very significantly lower than those observed on the comparative catalyst of Example 3.

Thus, it can be seen that the ratio of yields of C4 cracking products on the yields of aromatic compounds, referred to as
C4 / aromatics in the table above, is lower for the two catalysts of Examples 1 and 2 according to the invention. The selectivity of the catalysts vis-à-vis the desired aromatic products, will be even stronger than this ratio is low.

 The catalysts of Examples 1 and 2 according to the invention, additionally containing, relative to the comparative catalyst of Example 3, alumina, potassium and magnesium, respectively, and advantageously underwent a heat treatment in the presence of water and of chlorine, have improved characteristics compared to the comparative catalyst of Example 3, in particular selectivities of lower cracking products, and therefore selectivities in improved aromatic products.

Claims (36)

 1. Catalyst comprising  a matrix consisting of 0 to 100% by weight of transition alumina, the complement to 100% by weight of the matrix being transition alumina y, and  at least one doping metal selected from the group consisting of alkali and alkaline earth metals.  at least one promoter metal chosen from the group formed by tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten .  at least one noble metal of the platinum family, and  at least one halogen chosen from the group formed by fluorine, chlorine, bromine and iodine,  The catalyst of claim 1, wherein the matrix comprises from 0 to 84% by weight of transition alumina.  The catalyst of claim 1, wherein the matrix comprises from 3 to 70% by weight of transition alumina.  The catalyst of claim 1, wherein the matrix comprises from 5 to 50% by weight of transition alumina.  5. Catalyst according to claim 1, characterized in that it comprises, expressed in percentages by weight relative to the catalyst  from 0.001 to 8% of at least one doping metal selected from the group consisting of alkali and alkaline earth metals,  from 0.10 to 15% of at least one halogen selected from the group consisting of fluorine, chlorine, bromine and iodine,  from 0.01 to 2.00% of at least one noble metal of the platinum family, and  from 0.005 to 10.00% of at least one promoter metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese , chromium, molybdenum and tungsten.  Catalyst according to any one of claims 1 to 5, wherein the total content of doping metal is more than 0.005 to 3% by weight.  Catalyst according to any one of claims 1 to 5, wherein the total content of doping metal is 0.01 to 0.3% by weight.  Catalyst according to any one of claims 1 to 7, wherein the halogen content is from 0.2 to 10% by weight.  9. Catalyst according to any one of claims 1 to 8, wherein the total content of noble metal is from 0.1 to 0.8% by weight.  10. Catalyst according to any one of claims 1 to 9, wherein the promoter metal is selected from the group consisting of tin, germanium, indium, antimony, lead, thallium, gallium and their mixtures.  11. Catalyst according to any one of claims 1 to 10 wherein the promoter metal is tin.  The catalyst according to any one of claims 1 to 9, wherein the catalyst promoter metal is selected from the group consisting of rhenium, manganese, chromium, molybdenum, tungsten, indium and thallium.  The catalyst of claim 12, wherein the promoter metal of the catalyst is rhenium.  Catalyst according to any one of claims 1 to 13, wherein the total promoter metal content is 0.01 to 1% by weight.  A catalyst according to any one of claims 1 to 13, comprising from 0.005 to 0.9% by weight of a single promoter metal.  The catalyst of claim 15, wherein the promoter metal content is from 0.01 to 0.8% by weight.  Catalyst according to any one of claims 1 to 16, wherein the doping metal is potassium and / or magnesium.  The catalyst of any one of claims 1 to 17, wherein the halogen is chlorine.  19. Catalyst according to any one of claims 1 to 18, characterized in that the noble metal is platinum.  20. A catalyst support consisting of a matrix comprising from 0 to 100% by weight of transition alumina, the 100% complement being transition alumina y, and at least one doping metal selected from the group consisting of the alkali and alkaline earth metals, the amount of doping metal in percentages by weight relative to the support of 0.001 to 11% by weight.  21. Support according to claim 20, characterized in that the amount of doping metal is from 0.005 to 4.0% by weight.  22. Support according to claim 21, characterized in that the amount of doping metal is 0.01 to 0.4% by weight.  23. Process for preparing a catalyst, characterized in that it comprises the following steps  a) preparation optionally by mixing and then shaping an alumina matrix comprising 0 to 100% by weight of transition alumina, the 100% complement being transition alumina y,  b) deposition on at least one of the transition aluminas y and n of the following components, in the percentages by weight given below, which relate to the weight of the catalyst,  from 0.001 to 8% by weight of at least one doping metal selected from the group consisting of alkali and alkaline earth metals,  from 0.1 to 15% by weight of at least one halogen chosen from the group consisting of fluorine, chlorine, bromine and iodine,  from 0.1 to 2% of at least one noble metal of the platinum family,  from 0.005 to 10% by weight of at least one promoter metal selected from the group consisting of tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten the steps a) and b) can be performed in any order and the deposits of step b) can be achieved in part only before step a).  24. The method of claim 23, wherein the deposits are made by impregnation from at least one solution containing at least one precursor compound of a constituent to be deposited, followed by calcination at a temperature of 3000 to 900 ° C. C.  25. Method according to any one of claims 23 and 24, characterized in that it comprises the following successive steps  a) shaping the matrix of alumina or alumina n or a mixture of alumina and alumina,  b) depositing on this matrix at least one doping metal selected from the group consisting of alkali and alkaline earth metals,  c) depositing at least one promoter metal selected from tin, germanium, indium, gallium, thallium, antimony, lead, rhenium, manganese, chromium, molybdenum and tungsten ,  d) introducing at least one element selected from the group consisting of fluorine, chlorine, bromine and iodine, and  e) depositing at least one noble metal of the platinum family.  26. The method of claim 23, characterized in that, in the first step, depositing the doping metal (s) on the y-alumina, the n-alumina or the alumina mixture before forming the alumina. or the mixture of aluminas.  27. Process according to claim 26, characterized in that the support comprises a mixture of aluminas and in that the doping metal (s) is deposited on the transition alumina, and then the alumina is mixed. transition n with the transition alumina y and the shaping of the alumina mixture.  28. The method of claim 23, characterized in that one deposits the doping metal or metals, after forming the alumina or mixture of aluminas.  29. A method according to any one of claims 23 to 28, characterized in that the catalyst is subjected to a complementary heat treatment, carried out for a period of 1 minute to 30 hours, under a gaseous atmosphere comprising water whose molar content is from 0.05 to 100%.  30. The method of claim 29, wherein the molar content of water is from 1 to 50%.  31. The process according to any one of claims 29 and 30, wherein the duration of the heat treatment is from 1 to 10 hours.  32. Process according to any one of claims 29 to 31, characterized in that the gaseous atmosphere further comprises at least one halogen.  33. The method of claim 32, characterized in that the halogen content of the gaseous atmosphere can be up to 20 mol%.  34. Process according to claim 32, characterized in that the halogen content can be up to 10 mol%.  35. Process according to claim 32, characterized in that the halogen content may preferably be up to 2 mol%.  36. Process according to any one of claims 29 to 35, characterized in that the gaseous atmosphere is air, oxygen, argon or nitrogen.