FR2509629A1 - Tri:metallic catalyst for reforming, etc. - contains a platinum group metal, indium, and manganese, molybdenum or technetium on e.g. alumina - Google Patents

Abstract

A catalyst comprises (in wt.% w.r.t. the support): 0.05-0.6 (esp. 0.1-0.5) wt.% of a noble metal of the Pt family; 0.05-4 (esp. 0.2-0.8) In; 0.005-3 of one or more of Mn, Mo and Tc (esp. 0.2-0.5 of Mn and/or Tc); 0.1-15 of a halogen; and a support. Also claimed is the use of the catalyst in isomerisation of aromatics and paraffins, hydrocracking, hydrodealkylation and steam dealkylation of aromatics, and esp. in reforming and aromatics prodn. from gasolines. The catalyst is pref. used as a moving bed. Catalyst activity and life are increased. Under the severe conditions of reforming to high -octane gasoline (min. index 102, clear), hydrogenolysis is reduced.

Description

 The invention relates to novel hydrocarbon conversion catalysts.

 These catalysts contain a support, a platinum family noble metal, indium, at least one metal selected from manganese and technetium and a halogen or a halogen compound.

They are used in particular for a catalytic reforming (or reforming) process as well as for a catalytic process for producing aromatic hydrocarbons, processes carried out for example at a temperature of between 430 and 600 ° C. at an absolute pressure of between 0.degree. 1 and 325 MPa, with a speed of between 0.1 and 10 volutes of liquid charge per volume of catalyst, the molar ratio of hydrogen / hydrocarbons being between 1 and 20. The catalysts according to the invention make it possible in particular to carry out these steps. two processes under severe conditions. Thus the use of the new catalysts applies:
to the reforming reactions with a view to obtaining a gasoline with a clear or higher octane number than 102. The severe conditions of the hydroreforming or catalytic hydroreforming reactions are more particularly the following: the average temperature is between at about 510 and 580 ° C., the pressure is between about 0.5 and 1.8 MPa, preferably 0.6 and 1.3 MPa, the hourly rate is between 1 and 10 volumes of liquid filler per volume of catalyst and the recycling rate is between 6 and 10 moles of hydrogen per mole of filler. The feed is generally a naphtha distilling between about 60 ° C. and about 220 ° C., in particular a straight-run naphtha,
- reactions for the production of aromatic hydrocarbons from unsaturated or unsaturated gasolines (for the production of benzene, toluene, and xylenes). If the charge is unsaturated, ie if it contains diolefins and monoolefins, it must first be removed by selective or total hydrogenation. Subsequently, the charge possibly freed by hydrogenation of substantially all its diolefins and monoolefins, when contained therein, is subjected to a hydrogen treatment in the presence of a catalyst, a temperature of between about 530 and 600. C, at a pressure of between 0.1 and 1.3 MPa, the hourly volumetric flow rate of the liquid feed being of the order of 1 to 10 times the volume of the catalyst, the hydrogen / hydrocarbon molar ratio being of the order of 20. The charge may consist of pyrolysis, cracking, in particular steam-cracking, or catalytic reforming, or may consist of naphthenic hydrocarbons capable of dehydrogenation to be converted into aromatic hydrocarbons.

 The catalysts according to the invention are also suitable for hydrocracking reactions which are generally carried out at a temperature of between approximately 260 and 530 ° C. and at a pressure of between approximately 0.8 and 25 MPa. The conversion conditions include a liquid hourly space velocity, or LHSV, or volume per hour of liquid C load per volume of catalyst, of about 0 to 10.0, preferably having an upper limit of about 4.0, and a flow rate of hydrogen circulation of about 1 molest mol of charge.

 The catalysts of the invention are also suitable for isomerization reactions of aromatic hydrocarbons (eg xylenes) reactions which are generally carried out at a temperature between about 200 and 600 ° C, at a pressure of about 0.005 to 7 MPa. , the hourly volumetric flow rate being between 0.1 and 10 times the volume of catalyst.

 The catalysts of the invention are also suitable for the isobarization in a hydrogen atmosphere of saturated hydrocarbons having 47 carbon atoms, a temperature of between 50 and 250 ° C., for example 100 ° C. and 200 ° C.. 0.5 MPa with a space velocity of 0.2 liters of feed per liter of catalyst per hour. The H 2 / hydrocarbon molar ratio is, for example, between 0.01: 1 and 20: 1.

 The catalysts of the invention are also suitable for reactions of hydrodealkylation of aromatic hydrocarbons or of aromatic hydrocarbons, which reactions are carried out under the known operating conditions, generally between 300 and 600 ° C. for example, to manufacture benzene from toluene or from other alkylbenzenes.

 The catalysts can be used in a moving bed, particularly for the reforming reactions and the production of aromatic hydrocarbons, reactions for which a preferred method consists in using several moving bed reactors.

 The charge flows successively in each reactor or reaction zone following an axial or radial flow (radial meaning a flow from the center to the periphery or from the periphery to the center). The reaction zones are arranged in series, for example side-by-side or superimposed. Preferably, reaction zones placed side-by-side are used. The charge flows successively through each of these reaction zones, with intermediate heating of the charge between the reaction zones; the fresh catalyst is introduced at the top of the first reaction zone where the fresh charge is introduced; it then flows gradually up and down this zone from where it is withdrawn progressively from below, and by any appropriate means (lift especially in the case of reactors arranged side by side), it is transported to the top of the next reaction zone in which it also progressively flows from top to bottom, and so on until the last reaction zone down which the catalyst is also progressively withdrawn and then sent to a regeneration zone. At the exit of the regeneration zone, the catalyst is gradually reintroduced into the top of the first reaction zone. The various catalyst withdrawals are carried out as indicated above "progressively", that is to say either periodically or continuously. Continuous racking is preferred over periodic racking.

 Catalysts containing a metal of the platinum family deposited on a support have been known for a long time. But in spite of the many improvements that have since been made to these catalysts, for example by the incorporation of one, two or even three other metals chosen from among the most diverse groups of the periodic table of elements, we are still endeavoring today to search for new catalysts which, on the one hand, would give even better yields than those obtained hitherto and which on the other hand would also have a longer life than known catalysts.

In addition, efforts are being made to improve the mechanical properties of these catalysts, in particular to enable their use in a moving bed, in the form of agglomerates, for example beads or extrudates, of appreciable size, so as to leave a relatively easy passage to gaseous reactants. The wear of these catalysts results in the formation of much finer grains which gradually obstruct the free space and force to increase the inlet pressure of the reagents or even to interrupt the operation.

 It has now been found that by operating in the presence of very specific catalysts, these specific catalysts have an activity, but especially an increased lifetime, compared to the catalysts of the prior art.

 The specific catalyst used in the present invention contains a support, a platinum family noble metal, indium and a metal selected from manganese and technetium and a halogen, for example chlorine or fluorine. Preferred noble metals of the platinum family are platinum, rhodium and iridium.

The third preferred metal is manganese.

 The catalyst according to the invention contains, by weight relative to the support (a) 0.05 to 0.6% and more particularly 0.1 to 0.5% of noble metal of the platinum family, (b) 0, 0.5 to 4%, preferably 0.07 to 2.5% and more particularly 0.2 to 0.8% indium, (c) 0.005 to 3%, preferably 0.07 to 2% and more particularly 0.2 with 0.5% of manganese and / or technetium and (d) 0.1 to 15% by weight, with respect to the support, of a halogen, for example chlorine or fluorine.

 The supports are generally chosen from the oxides of metals of groups II, III and / or IV of the periodic table of elements, such as, for example, oxides of magnesium, aluminum, titanium, zirconium, thorium or silicon, taken alone or mixed with one another or with oxides of other elements of the periodic classification, such as, for example, boron and / or antimony.

You can also use coal. It is also possible to use zeolites or molecular sieves of the X and Y type, or of the mordenite, faujasite or ZMS-5 type, ZMS-4 type, ZMS-8 type, and the like, as well as mixtures of metal oxides of the groups. II, III and / or IV with zeolite material.

For reforming or aromatic hydrocarbon reactions and for isomerization reactions of paraffinic or aromatic hydrocarbons, the preferred support is alumina; the specific surface area of the alumina may advantageously be between 50 and 600 m 2 per gram, preferably between 150 and 400 m 2.
The catalyst can be prepared by conventional methods of impregnating the support with metal compound solutions that are desired to be introduced. We use either a common solution of these metals, or separate solutions for each metal.

When several solutions are used, dryings and / or intermediate calcinations can be carried out. It is usually terminated by calcination for example between about 500 and 100 ° C., preferably in the presence of free oxygen, for example by conducting an air sweep.

As examples of metal compounds used in the composition of the catalyst, mention may be made, for example, of the nitrates, chlorides, bromides, fluorides, sulphates, ammonium salts or acetates of these metals, or any other salt or oxide of these metals soluble in water, hydrochloric acid or any other suitable solvent
The halogen of the catalyst may come from one of the metal halides, if the metal is introduced by means of one of the halides, or may be introduced in the form of hydrochloric acid or of hydrofluoric acid, of ammonium chloride, ammonium fluoride, chlorine gas, or hydrocarbon halide, for example CCl 2, CH 2 Cl 2 or
CH3Cl etc ...

 A preparation method consists, for example, in impregnating the support with an aqueous solution, for example of indium nitrate, or any other compound containing this element, drying at about 120 ° C. and calcining under air a few hours at a temperature between 500 and 1000 C; then follow a second impregnation with a solution containing the metal and the platinum family and the metal selected from manganese and technetium.

 Another method is for example to impregnate the support by means of a solution containing both the three constituents of the catalyst.

 Yet another method is to introduce the selected promoters by performing as many successive impregnations as there are constituents in the catalyst.

 An important application of the invention is the production of a gasoline of very high octane number which requires operating under very severe conditions that hardly support the catalysts used until today. The use of bimetallic catalysts, however, brings a marked improvement. Numerous attempts at metal combinations have been made and catalytic compositions containing up to 4 and even 5 metals have been seen. These compositions have certainly provided an improvement but generally, if the promoters used provide good stability characteristics. , they also bring, unfortunately, especially in the case of noble metals of the platinum family, a certain tendency towards hydrogenolysis, which ultimately leads to a decrease in yields and a shortening of the duration of the cycle and the possible number of cycles, ie a decrease in the life of the catalyst.

However, the simultaneous use of indium and manganese
(or technetium) together with a noble metal of the platinum family, very significantly attenuates this state of affairs by significantly reducing this hydrogenolysing tendency, and it has been found that the benefits provided by each of the three metals are optimal in the severe operating conditions, especially under low pressures, high temperatures and long operating times.

 The examples below illustrate the invention without limiting it.

Example 1

In order to obtain a gasoline having a clear (or clear) octane number of 103, it is proposed to treat a naphtha having the following characteristics:
- ASTM distillation ...................... 80 - 160 C
- composition
aromatic hydrocarbons ............ 7% by weight
naphthenic hydrocarbons ........... 27% by weight
paraffinic hydrocarbons .......... 66% by weight
- number of octane "clear research" ......... about 37
- average molecular weight .................... 110
- density at 20 C ............................ 0,782
This naphtha passes with recycled hydrogen on two catalysts A and B containing 0.4% of platinum and 0.5% of indium by weight relative to the support which is an alumina having a specific surface area of 240 m 2 / g and a pore volume of 0.57 cm3 / g; the chlorine content of catalysts A and B is 1.12%. Catalyst A also contains 0.3% manganese and catalyst B also contains 0.3% technetium (by weight relative to the support).

Catalysts A and B were prepared by adding to 100 g of alumina 100 cm3 of an aqueous solution containing
1.90 g of concentrated ClH (d = 1.19)
20 g of an aqueous solution of chloroplatinic acid with 2% by weight of platinum
1.7 g of indium nitrate pentahydrate
and 1.37 g of manganese nitrate tetrahydrate for catalyst A
or 30 cc of an aqueous solution containing 1.15 g of (NH4) 2 TC04 for catalyst B.

It is left in contact for 6 hours, filtered off and dried for 2 hours at 100 ° C. and then calcined at 530 ° C. in dry air (drying of the air with activated alumina). Then reduced under a stream of dry hydrogen (activated alumina) for 2 hours at 460 C. The catalysts A and B obtained contain
0.4% platinum
0.5% indium
0.3% manganese (catalyst A) or 0.3% technetium (catalyst B)
1.12% chlorine.

 The catalysts A and B obtained have a surface area of 230 m 2 / g and a pore volume of 0.54 cm 3 / g.

 A continuous operation is carried out in a moving bed in three reactors of substantially identical volumes.

The operating conditions are as follows
pressure: 1 MPa
- temperature: 530 C
- molar ratio H2 / hydrocarbons: 8
- weight of catalyst naphtajpids / hour: 1.65
It is also carried out in the presence of various catalysts of the prior art not according to the invention comprising 1,2 or 3 metal elements. All catalysts contain 1.12% chlorine.

 Table I shows, after 200 hours, the yield obtained in C5 + and the percentage of hydrogen contained in the recycle gas.

 The results obtained in this example 1, with the catalysts according to the invention can be maintained over time, that is to say over very long periods of several months for example, operating as indicated, ie in continuous, in the system with 3 moving bed reactors, the catalyst being withdrawn for example continuously, at a speed adjusted so that the entire catalytic bed of the reactor is gradually renewed by fried catalyst for example in 500 hours.

Table I.

<SEP> Yield <SEP> Gas <SEP> recy
Cata
<tb> Metal <SEP>% <SEP> by <SEP> report <SEP> to <SEP> support <SEP> C5 + <SEP> clage <SEP>% <SEP> H2
<tb><SEP> ly
<tb> of <SEP> Catalyst
<tb><SEP> seur <SEP> (weight) <SEP> (molar)
<tb><SEP> A <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.3 <SEP> Manganese <SEP> 80.2 <SEP> 79.7
<tb><SEP> F <SEP> 0.4 <SEP> Platinum <SEP> - <SEP> - <SEP> 73.4 <SEP> 72.9
<tb><SEP> C <SEP> 0.4 <SEP> platinum <SEP> 0.5 <SEP> indium <SEP> - <SEP> 75.5 <SEP> 75.2
<tb><SEP> D <SEP> 0.4 <SEP> Platinum <SEP> - <SEP> 0.3 <SEP> Manganese <SEP> 77.9 <SEP> 77.6
<tb> B <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.3 <SEP> Technetium <SEP> 80.1 <SEP> 79.8
<tb><SEP> E <SEP> 0.4 <SEP> Platinum <SEP> - <SEP> 0.3 <SEP> Technetium <SEP> 74.9 <SEP> 74.5
<tb><SEP> G <SEP> 0.4 <SEP> Platinum <SEP> 0.2 <SEP> Iridium <SEP> 0.3 <SEP> Manganese <SEP> 79.7 <SEP> 78.3
<tb><SEP> H <SEP> 0.4 <SEP> Platinum <SEP> 0.08 <SEP> Iridium <SEP> 0.3 <SEP> Manganese <SEP> 79.7 <SEP> 78.4
<tb><SEP> I <SEP> 0.4 <SEP> Platinum <SEP> 0.2 <SEP> Iridium <SEP> 0.3 <SEP> Manganese <SEP> 79.3 <SEP> 78.8
<tb><SEP> J <SEP> 0.4 <SEP> Platinum <SEP> 0.08 <SEP> Iridium <SEP> 0.3 <SEP> Technetium <SEP> 79.3 <SEP> 78.8
<tb><SEP> K <SEP> 0.4 <SEP> platinum <SEP> 0.08 <SEP> iridium <SEP> - <SEP> 75.2 <SEP> 74.9
<Tb>
Example 2

 Example 1 was repeated with catalysts containing platinum, indium, manganese or technetium and the levels of indium, manganese or technetium were varied. The metal contents and the results obtained are given in Table II. All these catalysts contain 1.12% chlorine.

TABLE II

<tb> Yield <SEP> Gas <SEP> recy
Cata
<tb> Metal <SEP>% <SEP> by <SEP> report <SEP> to <SEP> support <SEP> C5 + <SEP><SEP>%<SEP> H2
<tb> lydu <SEP> Catalyst
<tb> seur <SEP> (weight) <SEP> (molar)
<tb> A1 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.003 <SEP> Manganese <SEP> 75.5 <SEP> 75.2
<tb> A2 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.02 <SEP> Manganese <SEP> 79.8 <SEP> 78.5
<tb> A3 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.10 <SEP> Manganese <SEP> 80.0 <SEP> 79.4
<tb> A <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.3 <SEP> Manganese <SEP> 80.2 <SEP> 79.7
<tb> A4 <SEP> 0.4 <SEP> platinum <SEP> 0.5 <SEP> indium <SEP> 1.0 <SEP> manganese <SEP> 79.9 <SEP> 79.4
<tb> A5 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 2.5 <SEP> Manganese <SEP> 79.8 <SEP> 78.5
<tb> A6 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 4 <SEP> Manganese <SEP> 74.8 <SEP> 74.9
<tb> B1 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.003 <SEP> Technetium <SEP> 75.5 <SEP> 75.2
<tb> B2 <SEP> 0.4 <SEP> platinum <SEP> 0.5 <SEP> indium <SEP> 0.02 <SEP> technetium <SEP> 79.4 <SEP> 78.9
<tb> B3 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.10 <SEP> Technetium <SEP> 79.6 <SEP> 79.5
<tb> B <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 0.3 <SEP> Technetium <SEP> 80.1 <SEP> 79.8
<tb> B4 <SEP> 0.4 <SEP> platinum <SEP> 0.5 <SEP> indium <SEP> 1.0 <SEP> technetium <SEP> 79.7 <SEP> 79.5
<tb> B5 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 2.5 <SEP> Technetium <SEP> 79.4 <SEP> 79.1
<tb> B6 <SEP> 0.4 <SEP> Platinum <SEP> 0.5 <SEP> Indium <SEP> 4 <SEP> Technetium <SEP> 74.6 <SEP> 75.0
<tb> P1 <SEP> 0.4 <SEP> Platinum <SEP> 0.04 <SEP> Indium <SEP> 0.3 <SEP> Manganese <SEP> 77.9 <SEP> 77.6
<tb> P2 <SEP> 0.4 <SEP> Platinum <SEP> 0.04 <SEP> Indium <SEP> 0.3 <SEP> Technetium <SEP> 74.9 <SEP> 74.5
<tb><SEP> P3 <SEP> 0.4 <SEP> Platinum <SEP> 0.06 <SEP> Indium <SEP> 0.3 <SEP> Manganese <SEP> 79.8 <SEP> 78.5
<tb> P4 <SEP> 0.4 <SEP> Platinum <SEP> 0.06 <SEP> Indium <SEP> 0.3 <SEP> Technetium <SEP> 79.5 <SEP> 78.9
<tb> P5 <SEP> 0.4 <SEP> Platinum <SEP> 0.30 <SEP> Indium <SEP> 0.3 <SEP> Manganese <SEP> 80.0 <SEP> 79.2
<tb> P6 <SEP> 0.4 <SEP> platinum <SEP> 0.30 <SEP> indium <SEP> 0.3 <SEP> technetium <SEP> 79.9 <SEP> 79.6
<tb> P7 <SEP> 0.4 <SEP> Platinum <SEP> 3 <SEP> Indium <SEP> 0.3 <SEP> Manganese <SEP> 80.0 <SEP> 79.3
<tb> P8 <SEP> 0.4 <SEP> Platinum <SEP> 3 <SEP> Indium <SEP> 0.3 <SEP> Technetium <SEP> 79.9 <SEP> 79.6
<Tb>
Example 3

 Catalysts A and B prepared in Example 1 are used in a process for producing aromatic hydrocarbons.

These two catalysts are passed over with hydrogen, a charge of the following composition by weight
- isopentane + n.pentane .................... 1,59%
- isohexanes + n.hexane ...................... 24,22%
- isoheptanes + n.heptane .................... 42.55%
- cyclopentane ............................... 0,13%
- methylcyclopentane ......................... 6.72%
- cyclohexane ................................ 5.50% - # C7 naphthenes ....... ................... 15,81%
- # C8 naphthenes 0.14%
- benzene .................................... 1,68%
- toluene .................................... 1,66%
100
The operating conditions were as follows
pressure: 1 MPa
- temperature: 550 OC
- hourly flow of liquid charge: 3 times the volume of the catalyst
- molar ratio hydrogen / charge: 6
The results are shown in Table III, which indicates, according to the age of the catalyst, the weight contents of benzene, toluene, benzene + toluene, relative to the initial charge, as well as the C5 + ponderal yield.

Table III.

<tb><SEP> Composition \ <SEP> Age <SEP> of <SEP> catal * y
<tb><SEP> Cata- <SEP> CoPosition <SEP> Age <SEP> of <SEP> 30 <SEP> hour <SEP> 200 <SEP> catÙly
<tb><SEP><SEP><SEP><SEP> 30 <SEP> hours <SEP> 200 <SEP> hours <SEP> 400 <SEP> hours
<tb><SEP> of the <SEP> product <SEP> hours
<tb><SEP> - <SEP> Benzene <SEP> .27.3 <SEP> X <SEP> 26.8 <SEP>% <SEP> 26.3 <SEP> X
<tb><SEP> A <SEP> - <SEP> Toluene <SEP> 35.5 <SEP>% <SEP> 35.2 <SEP> X <SEP> 34.7 <SEP> X
<tb><SEP> A <SEP> ~ <SEP> Benzene <SEP> + <SEP> toluene <SEP> 6Z, 8 <SEP> X <SEP> 62.0 <SEP> X <SEP> 61.0 <SEP>%
<tb><SEP> ~ <SEP> + <SEP> 72.3 <SEP> X <SEP> 73, $ g
<tb><SEP> Yield <SEP> weighted <SEP> C5 <SEP>71> 9 <SEP>% <SEP>72> 3 <SEP>% <SEP>73> Ô <SEP>%
<tb><SEP> - <SEP> Benzene <SEP> 27.6 <SEP>% <SEP> 27.3 <SEP> X <SEP> 26.9 <SEP> X
<tb><SEP> - <SEP> .Toluene <SEP> 34.6 <SEP> X <SEP> 34.4 <SEP> X <SEP> 33, <SEP> 9 <SEP> X
<tb><SEP> - <SEP> - <SEP> Benzene <SEP> + <SEP> toluene- <SEP> 62.2 <SEP> X <SEP> 61.7 <SEP> X <SEP> 60, <SEP> 8 <SEP>%
<tb><SEP> - <SEP> Yield <SEP> by weight <SEP> C5 + <SEP> 70.7 <SEP>% <SEP> il, 0 <SEP> X <SEP> 71.6X
<Tb>
Example 4

This example relates to the use of catalyst A of Example 1 for the hydrocracking of a cut distilling between 330 and 610 C, obtained by hydrotreating a vacuum distillate (400 - 650 C) of crude oil. This section has the following characteristics
- d15: 0.870
4
- nitrogen: 5 ppm
The reaction conditions are as follows
- temperature: 380 C
total pressure: 12 MPa
- speed (vol./vol./hour): 1
- Hydrogen flow rate (vol / vol of hydrocarbons): 1000
The conversion to C1 - C2 is equal to 0.30%.

An effluent consisting of
fraction C3 - 160 C, 23.7% of the weight of the charge,
fraction 160 - 340 C, 48.0 of the weight of the charge,
fraction greater than 340 ° C, 2.3 of the weight of the filler.

The fraction 160 - 340 C constitutes an excellent fuel "Diesel"
- "Diesel" index: 73
- cloud point, less than - 30 C,
- freezing point, less than - 63 C.

Example 5

 This example relates to the use of catalysts according to the invention for the isomerization reactions of saturated hydrocarbons.

 In a stainless steel tubular reactor, 100 g of the catalyst A prepared in Example 1 and previously calcined for one hour in air at 400.degree. C. are placed in a fixed bed.

 The reactor is then flushed with a stream of dry hydrogen at the rate of fifty liters of hydrogen per liter of catalyst and per hour, at a temperature of 50 ° C. and at a pressure of 0.2 M Pa. After which, one liter of solution containing 0.2 mole / liter of AlCl 2 (C 2 H 5) in normal heptane is injected with the aid of a pump, at a rate of 500 cm 3 / h, and by recycling the reactor effluent. .

After eight hours of circulation, the pump is stopped, the solvent is removed and the solid is dried under hydrogen.
The analysis carried out on the halogenated solid shows that it contains 11.7% by weight of chlorine, 0.34% by weight of platinum, 0.43% by weight of indium and 0.26% by weight of manganese.

 In the tubular reactor previously used, 50 cm 3 of the catalyst thus prepared is placed in a fixed bed. With the reactor being kept under hydrogen circulation at 150 ° C. and 2 MPa, a hydrocarbon feed containing 50% by weight of normal pentane and 50% by weight of normal hexane is injected to which 1000 ppm by weight of carbon tetrachloride has been added. . The feedstock is injected at a rate of two liters per liter of catalyst per hour while maintaining an hourly flow of hydrogen such that the hydrogen / hydrocarbon ratio is 3 mol / mol.

The analysis of the reactor effluent shows that it has the following composition
- Isopentane: 28.6% by weight
- normal pentane: 21.4% by weight
- isohexanes: 43.8% by weight
- normal hexane: 6.2% wt% iC5 / # C5 = 57.2% and iC6 / # C6 = 87.6%.

Example 6

 This example relates to the use of catalysts according to the invention for isomerization reactions of aromatic hydrocarbons.

 An alumina catalyst containing 0.4% platinum, 0.5% indium, 0.3% manganese and 10% fluorine is prepared. The catalyst is prepared as in Example 1 using hydrofluoric acid instead of hydrochloric acid. The catalyst thus prepared is used to isomerize in paraxylene a charge of metaxylene: one operates at 430 OC, under a pressure of 1.2 MPa (weight of filler / weight of catalyst and per hour: 5, ratio in moles hydrogen / hydrocarbons = 5).

 A conversion to paraxylene corresponding to 95.4% of the thermodynamic equilibrium is obtained with a yield by weight of xylenes of 99.9%.

Claims (9)

CLAIMS. 1 / Catalyst containing a support and, by weight relative to the support, 0.05 to 0.6% of a noble metal of the platinum family, 0.05 to 4% of indium, 0.005 to 3% of at least one metal selected from manganese, molybdenum and technetium and 0.1 to 15 X of a halogen. 2 / Catalyst according to claim 1 containing, by weight relative to the support, 0.1 to 0.5% of a noble metal of the platinum family, 0.07 to 2.5% indium and 0.07 at 2% of at least one metal selected from manganese and technetium. 3 / Catalyst according to claim 1 comprising a support and by weight relative to the support 0.1 to 0.5% of a noble metal of the platinum family, 0.2 to 0.8% of indium and 0, 2 to 0.5% of at least one metal selected from manganese and technetium. 4 / Use of the catalyst according to claim 1 in a hydrocarbon conversion process chosen from reforming reactions, aromatic hydrocarbon production, paraffinic and aromatic hydrocarbon isomerization, hydrocracking, hydrodealkylation and dealkylation water vapor of aromatic hydrocarbons. 5 / A method according to claim 4 wherein one operates with at least one moving bed of catalyst. 6 / The use of the catalyst according to claim 2 in a reforming process or production of aromatic hydrocarbons at a temperature between 430 and 600 C under a pressure between 0.1 and 3.5 M Pa. 7 / Use of the catalyst according to claim 3 in a process for reforming or production of aromatic hydrocarbons at a temperature between 510 and 600 C under a pressure between 0.1 e: 1.8 MPa with a hourly rate of between 1 and 10 volumes of liquid charge per volume of catalyst, the molar ratio of hydrogen / hydrocarbons being between 5 and 20, the method of circulating a charge formed of hydrogen and hydrocarbons through to at least two reaction zones arranged in series, each zone being of the moving catalyst bed type, said charge flowing successively through each reaction zone and the catalyst also flowing successively through each reaction zone flowing from high to high. in each of them, said catalyst being withdrawn from each reaction zone to be sent to the next reaction zone, and the catalyst being withdrawn from the last reaction zone. the reaction zone traversed by the charge and sent to an accumulation zone from which the catalyst is sent to a regeneration zone, then to a production zone, and then gradually reintroduced into the first reaction zone traversed by the charge; .  8. Catalyst according to claim 3, wherein the catalyst contains (a) a support of alumina (b) platinum or iridium (c) indium and (d) manganese. 9 / A catalyst according to claim 3, wherein the catalyst contains (a) a support of alumina (b) platinum or iridium (c) indium and (d) technetium. Process according to Claim 6, in which the operating conditions are chosen so as to produce a gasoline with a clear octane number greater than or equal to 102.