BE632455A - - Google Patents

Description

       

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 catalyst and process for converting organic compounds *
The invention relates to an improved catalyst which is useful in converting organic compounds, as well as a process for preparing it. A subject of the invention is also a process for the conversion of hydrocarbons in the presence of these catalysts. More particularly, the subject of the invention is the composition, the preparation and the application of active, selective and stable catalysts consisting of a finely divided crystalline aluminosilicate in which the molar ratio is @:

   alusnine is greater than 3 t 1, which is

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 distributed and kept in suspension in a matrix of a suitable binder, and in which the negative electrovalence
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 of the silica and alumina of the aluminosilioate is balanced by ions of one or more types selected from the croup which includes the metals Lower than sodium in the electromotive series, calcium, ammonium and hydro- ions.
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 gene, and organic nitrogen ions such as quaternary amino ions, those of guanlne salts and amine salts.



  A preferred embodiment of the in-
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 The invention resides in the preparation and application of collectors in which the aforesaid crystalline aluminoillicate is a Y-type zeolite.



   It has already been pointed out that it is possible to advantageously carry out various chemical reactions by a ca-
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 talrae by contact, using crystalline solites of the metallic aluminosilicate type as catalysts exhibiting a rigid three-dimensional network consisting of unit cells characterized by the almost total absence of variation in the distensions of the unit cell when it is is dehydrated and rehydrated, and by a very uniform homogeneous porous structure. The above conditions are satisfied by certain crystalline zeolites called molecular sieves.

   The effective body catalyzed reactions include, for example, cracking
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 hydrocarbons, alkylation, dealkylation, deletion, isomerination and polyaerinatlon. Since these catalysts have the property of influencing and directing the course of chemical conversion, they have a remarkable degree of catalytic selectivity.

   In short, there are two types of selectivity on the one hand, selectivity
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 geometry which depends on the relation between the diameter of the pores of the crystal structure of the aluainoel zeolite

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   lieate and the diameter of the reactant and product molecules
 EMI3.1
 On the other hand, there is the intrinsic catalytic selectivity which depends on the choice of cation present on the internal surfaces of crystalline metallic isalitolotilicate.



  A wide variety of zeolites of natural and synthetic origin are known, for example ohabasite, gmeli. nite, mesollte, mordenite, natrolite, sodalite, scapolite, lazurite, loucrite and cancrinitte Synthetic zeolites may be type A, type Z, type Y or other well known forms of chipmunk molecular. The preparation of the above synthetic zeolites is
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 described in the literature, for example that of zeolite A in United States patent of America no. 2,882,243 of April 14, 1959, that of zeolite X in the state patent.
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  States of America nb 2.882.2 of 7 ,. April 1959 and that of zeolite Y in Belgian Patents Nos. 577.6x and 598.582. Under the volume initially prepared, the metal of 18 & luminoui. lioate is an alkali metal, usually sodium. This alkali metal can undergo base exchange with a wide variety of others. metal ions. The molecular sieves thus obtained are remarkably porous, the pores exhibiting very uniform molecular sizes, generally between about 3 and 15 in diameter. Each crystal of molecular chipmunk contains an extremely large number of tiny cavities or cages interconnected by channels of invariable diameter.

   The size and proportion of the metal ions contained in the crystal determines the effective diameter of the communication channels.
 EMI3.4
 According to the invention, it has been discovered that one obtains ,; a very active and selective catalyst for the conversion of organic compounds, preferably replacing almost all the alkali ions of a crystalline alkali aluminosilicate in which the silica: alumina molar ratio

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 is greater than 3 8 1 4. nreferenes of an alWB.1nol1l1oat. crystalline alkali of the Y type, by ions of one or more
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 type. ehoJLflf in! # croup * which includes 1..¯.'tAUX infriturM
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 au aoolua ama ia series 8.1.eOUOIllOU10., m O & J.01W1, ammonium and hydrogen ions.

   Particularly preferred replacement ions are those of aloallno-earth metals, those of rare earth metals, the manganese ion, the ammonium ion, and combinations thereof * Before or after the exchange of ion., llaluminouili is mixed intimately. crystalline cate, all finely formed,. a suitable binder, under conditions such that the aluminuilicate distributes intimately and is suspended in a matrix of the binder.

   In cases where the alkali aluminosilicate is initially mixed with the binder, the ion exchange is then carried out on the composition obtained, to replace the
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 alkali metal ions by one or more ions of the above group Unexpectedly, the obtained aluminum catalyst was found to exhibit greater activity and greater efficiency.
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 leotivltd than comparable catalysts prepared from other synthetic aluminosilicates such as those of type X in which the molar ratio of allice: alumina
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 is inside 3 t 1.



   Unlike previously usual cracking catalysts, the catalyst of the invention is prepared from a crystalline Y-type aluminosilicate exhibiting a rigid three-dimensional network structure characterized by uniform pores with a diameter of 6-15 and in. wherein the original alkali metal has been replaced, preferably substantially all, by a metal lower than sodium in the electromotive series, by calcium, ammonium and hydrogen ions, separately or together.

   Uniform pore openings in the mentioned gazas occur
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 in all dimensions and allow access to the eurface

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 of the catalyst of all the hydro- reactant molecules
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 carbide and allow easy release of the molds from the product. In addition, unexpectedly, the o, .tIl1..ur possessed remarkable stability when in the form of hydrogen aluminoeilicate or l-type acid, which has been exchanged1 in a hydrate oxide matrix *. The high stability of such a catalyst is due to the apparent synorgic action between the acid aluminosilioate and the hydrated oxide pitch which results in it.



   In one embodiment, the invention provides a process for the preparation of a remarkable catalytic composition which consists in intimately combining with a suitable binder a finely divided crystalline aluminosilicate of type Y, the cation of which consists, separately or separately.
 EMI5.2
 Threshold t, by metal ions lower than sodium in the electromotive series, calcium, ammonium or hydrogen ions, the composition obtained having, after drying and calcination, an exchangeable alkali metal content of less than 3% by weight.



   In another embodiment, the invention
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 provides a process for the preparation of a remarkable cracking catalyst * which consists in dispersing in a suitable matrix a finely divided aluminosilicate Y in which at least 70% of the initial alkali metal content has
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 been replaced by 1 = 3 or more tlP "chosen from the group which includes metals interior to sodium in
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 the electromotive series, calcium, aaxoniua and hydrogen ions, this alumlnosillcate having unitoMl pore openings of between 6 and 15 A approximately, then drying the composition obtained,

   in calcining it and in treating it with water vapor at a temperature of 200-790 "C for a time greater than approximately 2 hours.



  In another embodiment, the invention

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 Privoit a process for the preparation of a catalyst intended * for the conversion of hydrocarbons which eonslste to disperse in an inorganic oxide sol an alwl1ftO.l11oat .. 1 finmont divided given by releasing * of ions described above, a etteo - killing the 1'11tloat1on of the soil containing the finely divided balwainouilicate, washing the composition obtained for ridding of soluble matter, licking, calcining and treating the calcined * composition with 4'.au steam.



   In another embodiment, the invention
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 provides a catalytic competition which comprises an aluainosilicate its uniformly distributed suspension * in a matrix, the cation of alumino.l11oat. being constituted by one or more ions of the group which includes the metals lower than sodium in the electromotive series, calcium,
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 ammonium and hydrogen ions. In yet another embodiment, the Yto- tion provides a cracking catalyst of exceptional activity and selectivity essentially consisting of
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 by 1-90;

  C by weight of a crystalline T-type aluminosilicate resulting from the mentioned ion exchange, the particle size of the aluminum oxide being less than 40 microns and preferably less than 15 microns in diameter, and ll The aluminoeilicate being in suspension distributed in a matrix of a hydrated oxide which can be drilled from clay or Binerai oxide gels.



   In another torii, embodiment of the invention, there is provided a catalyst composition comprising
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 essentially forced spheroidal exiles of 1-50% by weight of an aluminoeilicate resulting from ion exchange such as o1- <1 ... u "having an average particle diameter of 2-7 will bind, in suspension uniformly distributed in a matrix of mineral oxide gel which can kill alumina, alloy * or compounds formed by silica with au

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 minus one metal from troops 11A 111B and IVA of the Periodic Classifi cation.



   Another embodiment of the invention resides in a process for the catalytic conversion of organic compounds, particularly a process for the catalytic cracking of hydrocarbon oils in the presence of the above catalyst and under cracking conditions, according to which process an increased conversion of the raw material into useful products is achieved.



   Catalytic cracking is commercially carried out by contacting a hydrocarbon feedstock, in the vapor state or in the liquid state, with a catalyst of the above type, under the desired temperature conditions, pressure. tion and time to achieve the near total conversion of the feed to lower boiling point hydrocarbons.



  The reaction which has been produced is essentially a cracking with the formation of lighter hydrocarbons but it is accompanied by several complex side reactions such as armotization, polymerization, alkylation, etc.



  As a result of these complex reactions, a carbonaceous deposit, commonly known as coke *, forms on the catalyst.



  The deposition of coke tends to seriously decrease the efficiency of the catalyst for the main reaction, and then the conversion stops once the coke has accumulated on the catalyst in the amount of a few wt% units.



  The surface of the catalyst is then regenerated by burning the coke in a stream of oxidizing gas and the catalyst is returned to the conversion stage of the cycle.



   As will be appreciated, coke and other undesirable products are formed at the expense of useful products such as gasoline. It is evident that during the regeneration time the catalyst is not efficiently used for the conversion. As a result, it is very de-

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   desirable not only to achieve a high global conversion
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 bal * of the hydrocarbon feed, a '.. t..A-4iJ "to adopt a catalyst of high activity, but also to obtain a
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 increased yield of useful product such as esaence while keeping undesirable products such as coke to a minimum. The ability to have a cracking catalyst to thereby direct the course of the conversion is called selectivity.

   Thus, a very useful and highly sought-after characteristic for a cracking catalyst is high selectivity and also high vapor stability, so that it withstands the treatment with the vapor which comes out to regenerate the catalyst. In a particular cracking process of the invention, the catalyst is essentially formed of a crystalline hydrogen aluminosilicate of type Y having a structure with rigid three-dimensional networks characterized by uniform pores with a diameter of 6-15 A.
Still according to the invention, it has been discovered that
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 It is possible to efficiently carry out the catalytic conversion of hydrocarbons in the presence of a very active and very selective catalyst essentially consisting of a crystalline hydrogen aluminosilate of type Y.

   We get the latter
 EMI8.4
 alumlnosilicate by replacing preferably almost all the alkali ions * of a crystalline alkali alu: nino8il1cate of the Y type with hydrogen ions. In order to effect this replacement, the crystalline alkaline alkali aluminoilicate of the Y type can be contacted with a fluid containing hydrogen ions, under conditions such that the zeolite structure of the aluminosilicate is not destroyed. Another effective way to
 EMI8.5
 replacing the alkaline ions involves bringing the alkali aluminoailicate into contact with a fluid containing ions. & m: 1Onlum, then heating the ammonium aluminosilicate obtained to effect the decomposition of the ions. ammonium with the release of 1m3 'long hydrogen replacing alkaline ions

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 EMI9.1
 initials.

   It was found that a cracking executed the tidw of the 81wt1no.ll1cat. of crystalline Y-type hydrogen thus obtained gives a high yield of useful product.



  The alkali metal aluainosilicates used in the preparation of the catalyst of the invention are those called in the art zeolites Y. The latter are particularly described in Belgian patents n-577,642 pr6064e "ent described and n8,598,582 pr'o4d.ent describedpet
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 they can be advantageously prepared by the process of and $ patents @ The molar composition of these zeolites comes within
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 the formula, 61balfl t 0.9 + 0.2 ..2. A1, 203 3-6.3 8102 9 Duo.

   The above seolito, used in the preparation
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 of the present catalyst having a uniform pore structure
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 comprising openings characterized by an etteotif pore diameter 4. 6-15 1.
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 The catalysts used in the process are prepared
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 by subjecting the crystalline alkali aluminosilicate 1 o1.-des-! seen us exchange of bases with ions of the type already mentioned, so as to replace at least 70% and preferably more da N0% of the initial alkaline ions. i a * series 4l.otl'OlIO- trtc * B of which one speaks lot is that which is defined in the eüanabook of Chaalttry and Ph7.1c .., 43bae edition, edited by Chaalcal Rubbar Publithini Company.

   We can prepare the $ catal1'.ur. of the invention by int1JatCIent mixing, on the one hand a crystalline alkali alurainosilicate 1 having a structure with rigid three-dimensional networks characterized by an effective diameter and a pore size of 6-15 2, in a finely divided form in which the particles generally have an average diameter of less than about 0 microns and preferably less than about 15 microns, on the other hand a suitable binder such as an aetallic powder, an ar-
 EMI9.8
 wing or an inorganic oxide gel, then subjecting the resulting composition to a base exchange with virtually elimination.

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   complete with alkali metal,

   by treatment with a solution containing ions of one or more types selected from the group which includes the metals interior to sodium in the
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 electromotive series # calcium # tmatoniun and hydrochloride ions and then, om hnnt, drying and calcining the resulting composition. Alternatively, preferably, the alkali luminoillicate can be subjected to a berry exchange as above before mixing it with the binder.

   In this method, the mixture formed by the finely divided aluminosilioate is washed pr "lab1e.lI8nt under the exchange of bases, distributed and maintained in a suspension in a matrix of the binder,
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 an exchange of bases is carried out where necessary to remove the non-political alkali metal from the binder, it is dried and calcined
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 retort above * The content of exchangeable alkali u5ta1 in the catalyst compositions obtained by the above processes is preferably within 1 3% and more especially in
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 less than 2% by weight.



   The maximum alkali metal content that can be tolerated in the final catalyst composition depends in part on the nature of the cation. So when the cation is a rare earth metal or a combination of ions
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 metal and hydrogen ions, up to 3% by weight of exchangeable alkali metal can be tolerated. In the case of man- genesis and alkaline earth metals such as calcium, the residual amount of exchangeable alkali metal is hampered.
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 groove maintained below: 1.1 and preferably below 1.5% by weight.



  To get the intimate blend of s. wa1.n.o1111oat. finely d.1 rt "and a binder such as a metal powder, a clay or an inorganic oxide hydrogel, the two materials can be passed together in the ball mill for an extended time, preferably in the presence of water, under the conditions required to reduce the size of

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 i'sluminoaüioate particles having an average diameter of less than 40 microns and preferably less than 81% OR. luis 00 mixing process is less interesting than that which CCID81I- te to disperse 1 il alumjmo silicate any drill * finely divided in a hydrated mineral oxide, for example a hydrosol or
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 a hydrogel.

   According to this process, the divided alWR1nosilicate can be dispersed in a hydrogel or hydrosol already prepared, or, which is preferable when the hydrosol is characterized by a gelation time: Lon short, the hydrogel or hydrosol can be added. finely divided aluminosilicate with one or more of the reagents which serve to form the hydrosol, or else mixed,
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 as a separate stream, to hydrosol-forming reactant * streams, in a mixing nozzle or other device in which the reactants are contacted in time.

   As noted above, it is desirable that the aluminoailicate introduced into the hydrosol have an average particle diameter of less than about 40 microns and preferably less than 15 microns, and between 2 and 7 microns when we break up large particles. It has been found that the use of an aluminoailicate having an average particle diameter greater than 40 microns results in a phy-
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 sically low, whereas the use of an aluminoailicate having an average particle diameter of less than 1 micron gives a product of low diffusibility.



   The inorganic oxide hydrosol containing the powder sets into a hydrogel after a suitable time and the resulting hydrogel is subjected to base exchange if zeolite alkali metal has been introduced due to the use. of an alkali silicate, and then washed, dried in a
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 gel and thermally activated at a temperature above the melting point of the incorporated aluminosilicate powder.



  It has been found that the product obtained, which is essentially formed of an aluminosilicate of type T, the cation of which is constituted by
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 tube, separating or jointly by a metal less than

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 sodium in the electromotive series or by calcium, ammonium or hydrogen ions, and which is suspended uniformly distributed in a matrix of mineral oxide gel, has remarkable properties. as a catalyst for hydrocarbon vapors.



     In addition to the aluminosillicate Y described above, it has been found desirable in certain cases to include in the catalyst matrix a secondary solid additive also in finely divided form, generally with an average particle diameter of between 1 and 40 microns, capable of making the composition more diffusible. This additive may be inert or it may contribute to the overall catalytic activity of the final catalyst composition. The amount of this additive can be up to 40% of the weight of the composition.



     Generally, when the catalyst is in the form of gel beads, the average particle diameter of the additive is less than 10 microns. Suitable additives for the above use are, for example, clay alumina, zircon, barite, charcoal, wood powder, silica, recycled fine particles of catalyst, magnesia, fine particles. used cracking catalyst, and various natural minerals and rocks. These additives can remain in the final composition, or in the case of combustible materials such as charcoal or wood powder, they can be removed beforehand as a result of a preparatory treatment applied to the catalyst, or as a result of its use at high temperature.



   The binder which constitutes the matrix of the catalyst must be thermally stable under the conditions in which the conversion reaction is carried out. Thus, it is contemplated to use solid porous adsorbents and carriers of the type previously employed in catalytic operations, in conjunction with crystalline aluminosilicate of

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 EMI13.1
 typt Ï describes d, .dütï.

   These materials may be catalytically inert or they may have intrinsic catalyst activity or activity attributable to * close association * or reaction with the crystalline aluminolllate of type Y * These materials include, for example, gels. dried * mineral oxide and the gelatinous precipitates of alne, silica, zircon * # of mmtndsia, hafnium oxide, thorium oxide, titanium oxide, boric anhydride and mixtures. of these oxides with each other and with other constituents. Other suitable binders include premium metal powders, charcoal, mulllte, kieselguhr, activated charcoal, bauxite, silicon carbide, sintered alumina * and various clays.

   Preferably
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 a1wnino81l1oatt is intimately associated with a hydrated oxide such as an inorganic oxide hydrogel or an ergil, as indicated above.



   Although mineral oxide gels can be used as gangue in general, it is preferable that the mineral gel
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 ral is an oogel of silica and an oxide of at least one metal of groups IIA, IIIB and IVA of the Periodic Table. These constituents include, for example, alloy * systems - alumina, silica-magnesia, silica-zirconia, silica-haf oxide.
 EMI13.4
 niua, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, as well as ternary combinations such as millee-maum systems: Lne-oxido de thorium, garlic * - alumlne-tlrcone, .111ct- alumina-mané.le and .111ct- # ané.le- zirccnt.

   In the above gels, silica is generally present as the main constituent and the oxides of the salts are present as a result. Thus, the silica content of these gels is generally between 55 and 100% by weight. metal oxide content varying from 0 to 45% and weight. Laws
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 erase oxide hydrochloride used herein and the hydrogelas derived therefrom can be prepared by any method well known in the art, for example ortho-hydrolyzate can be hydrolyzed.

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 ethyl silicate, acidify an alkali silicate which may contain a compound of a Metal which is desired COI'lts .... the oxide with silica, etc ...

   The relative proportions of finely divided crystalline luminouillest and gangue can vary widely, with crystalline aluainosilicate being about 1-90, and most common are about 1-50% of the weight of the composition, particularly when the latter is. prepared in the form of pearls.



   The catalyst of the invention can be prepared in any physical form desired. Preferably, it is used in the form of small fragment of the size most suitable for the job under the particular conditions.
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 lières in question. So the catalyst can be the whole tome of finely divided powder or we form it
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 grains of 1.6-3.2 m in size, which are obtained for example by agglomeration, molding or extrusion according to well-known techniques *. We can leave a hydrosol
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 with the addition of crystalline aluminoailicate powder, it solidifies into a hydrogel which is then dried and which is divided into pieces of the desired size.

   The gel pieces thus obtained are generally of irregular shape, It is possible to obtain pieces of gel of uniform shape by
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 extraditing or granulating the hydrocel containing the aluminosilicate. It is also possible to introduce the hydrosol into the perforations of a perforated plate and hold it there until the soil has set into a hydrogel, after which the pieces of hydrogel formed are removed from the plate.

   A particularly practical method consists in preparing the catalyst in any form of spheroidal particles dispersed therein.
 EMI14.6
 alustinosillcate powder in a hydrosol and by introducing globules of the hydrosol obtained in a manna of liquid immiscible with eru, for example in a medium
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 oily in which the hydrosol globules take in hydrogel and then arrive in a lower layer.

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 from which they are removed for subsequent processing operations such as bass exchange, water washing, drying and alkination.

   The larger spheres are usually between 0.4 and 6.4 m in diameter while the smaller spheres generally called micorospheres and formed by spray drying or other well-known techniques have a diameter of between 20 and 300. micron oar. It is particularly advantageous to use particles of spheroidal shape in hydrocarbon conversion processes. where the catalyst is subjected to continuous movement, such as the moving compact layer process, the fludified layer process, etc.



  In the case of the immobile layer, the spherical catalyst particles ensure effective contact between the reactants and the catalyst by avoiding pathways.



   While the initial formation of a hydrosol which sets in a short time to give a hydrogel in the form of beads is an essential point in the manufacture of a spheroidal catalyst, it is also possible, particularly when The catalyst is prepared in any form other than spheroidal using a matrix comprising a gelatinous precipitate of hydroxide at varying degrees of hydration or a mixture of a hydrogel and a gelatinous precipitate gel. The word "gel" as used herein denotes hydrogels, gelatinous precipitates and mixtures of both. On the other hand, the gangue may consist wholly or partially of a clay, particularly a clay of the genus. montmorillonites or kaolinites, crude or treated with an acid.



   Another class of materials useful as gangues includes powdered metals not subject to oxidation under the reaction conditions. Suitable metal powders include, for example, aluminum and iron alloys such as stainless steel and various

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 other metals characterized by their stability under working conditions.

   Other materials suitable for gangue in the catalyst composition of the invention include charcoal, graphite, bauxite and other binder compatible with the crystalline metal alumosilicate and thermally stable in the conditions. ditions of temperature where the catalyst is used As we said above, 1 JI crystalline alkali aluminc silicate Y is subjected to an exchange of bases, Among the metals which little-will be used ,, we will mention manganese, alkaline metals earth metals such as calcium and magnesium, rare earth metals such as cerium, praseodymium, lanthanum, neodymium, samarium, gadolinium and their mixtures.

   The base exchange is carried out so as to replace at least 70% and preferably more than 80% of the initial alkaline ions by ions of the group already mentioned, and to reduce the content of the catalyst below 3%. 6changeable alkali metal finish. The alumnosilicate in finely divided form bound in all aggregate particle form with a suitable binder or gangue, can undergo the base exchange before or after intimate mixing with the binder. The base exchange is carried out by treating the product with a solution containing the ions which it is desired to introduce into the aluminosilicate. It is envisaged to use for the base exchange any innisable compound providing hydrogen ions, ammonium or the metals mentioned above. Generally, an aqueous solution of these compounds is used.

   A particularly effective base exchange solution is one which contains one or more metals interior to sodium in the electromotive series and ammonium ions, including complex ammonium ions, the ratio of metal ions and
Ammonium ions being between 10: 1 and 1: 100 so as to replace the alkaline ion by the metal ions in question and the ammonium ions. The exchangeable alkali metal content

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 EMI17.1
 of the finished strength should be less than about z and preferably within about 2% by weight. The 4chcl8 solution of bases can be contacted with crystalline aluml-ODdleate in any form of fine powder, pellet. Compr1 .., extruded dough, opheroidal bead or particles of * other shape.

   It has been found that the desired base exposure can most easily be achieved if the alkali lumi- nosilicate subjected to the treatment has not been subjected to a temperature or greater than about 315 "C. The temperature at which the exchange is effected.
 EMI17.2
 The base can vary widely and generally from the temperature of sandblasting * to a temperature elevated but below the boiling point of the treatment solution. Although the volume of the base exchange solution can vary widely, generally an excess is used and this excess is subtracted on contact with the crystalline aluminosilicate after an appropriate contact time.

   The contact time between the base exchange solution and the crystalline aluminosilicate,
 EMI17.3
 in all cases of s-accidental contact, is calculated so as to replace the alkali ions to an extent such that the exchangeable alkali metal content of the final catalytic composition is within 1 3% by weight. It will be understood that this contact time can vary widely depending on the temperature of the solution and the compound of the bases. Thus the contact tempo can range from a few hours for small particles to longer times of the order of several days for large particles.



   After the basas exchange treatment, we remove
 EMI17.4
 the product of the solution of tr & .1t8Q81t. If desired or necessary, the anions can be removed. Introduced following the treatment with the base exchange solution by washing the treated composition for the time required so that it is free * of these anions . We then dry the

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 EMI18.1
 product washed, usually in air, to remove all of the water. Although drying can be carried out at room temperature, it is more satisfactory to facilitate the removal of moisture by maintaining the
 EMI18.2
 produced between 65 and 315'OC for 4-48 hours.



  It is then possible to subject the dried material to calcination by heating it in an inert atmosphere, ie under an atmosphere which has no harmful influence on the catalyst such as air, nitrogen, hydrogen, flue gases, helium or other inert gases. * General-
 EMI18.3
 However, the dried material is aired at a temperature of about 26O-820 ° C for at least about 1 hour, usually 1-48 hours.



   It has also been found that the catalytic selectivity of the above composition is greatly improved if it is
 EMI18.4
 subjected to a moderate treatment with water vapor. Steam catalyst expansion is a very desirable operation in order to obtain a product capable of giving increased gasoline yield. We can lead the treatment to
 EMI18.5
 steam between 200 and 790 ° C approximately, for at least approximately 2 hours. Usually, steam is used at about
 EMI18.6
 510-760C with a treatment time of about 2-100 hours.



  On the other hand, one can use an atmosphere comprising a significant amount of vapor, for example at least about 5% by volume, mail containing air or other convenient gas.
 EMI18.7
 they are inert to the composition to be treated and such mixtures may be desirable in certain cases, with relatively high temperatures, in order to avoid possible deactivation of the catalyst. The steam treatment can be carried out at pressures varying from the level
 EMI18.8
 atmospheric to about 35 kg / cm. 2.

   The purpose of the above-mentioned steam treatment is to reduce the specific surface area of the calcined composition. So . it is particularly preferable to subject the calcined composition

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 to steam treatment to reduce its specific surface area by at least about 20%, without exceeding about 75%.



   The reactions catalyzed by the crystalline lumniosilicate compositions described herein include the transformation of catalytically convertible organic compounds in the presence of acidic groups of the catalyst. Typical of these reactions include the cracking of paraffinic, aromatic lefomic and npathenic hydrocarbons. and mixtures thereof, for example of petroleum fractions, such as those which have the gas oil boiling range; the disproportionation of aromatic compounds, the dehydration of alcohols with the formation of olefins and ethers; hydration of olefins to alcohols, isomerization and polymerization of olefins, iaomerization of terpenes, alkylation of iaoparaffinea and dealkylation of aromatic hydrocarbons.



   The storming of hydrocarbons represents a particularly advantageous application of the catalyst of the aluminosilicate type described here, since the nature of the products can easily be regulated. In this process, the catalyst can be used as a seed in a fixed bed operation, or in a moving compact bed or fluidized bed operation. The general working conditions cover a wide range given the wide utility of catalysts.



   It is generally desirable to conduct these processes at a temperature of between about 260 and 650 and at a pressure varying from a subatompheric level to several hundred atmospheres. In any case, the contact time of the oil with the catalyst is adjusted according to the conditions, the particular raw material and the particular results which are desired, in order to obtain a notable cracking with the formation of products with an internal boiling point.



   The cracking activity of the catalyst gives the lean 4% its ability to catalyze various conversions

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 of hydrocarbon and is expressed here as the percentage of
 EMI20.1
 conversion of a United Mats * gas oil which has a boiling range of 2-S1Q "C to = 9 gasoline which has an end boiling point of 210C, when vapors of gas oil through the catalyst at 468,482 ° Ct at approximately atmospheric pressure, with a flow rate of 0.6-16 volumes of liquid hydrocarbon per volume of catalyst per hour, with 10 minute times between regenerations .



   It has been found desirable, in order to analyze the results obtained * with the catalysts described here, to compare them with the results obtained with a commercial cracking catalyst formed from silica and alumina gel and containing about 10% alumina by weight, L The activity, the stability and the exceptional selectivity of the catalyst of the invention are revealed by the comparison of the product yields obtained with this catalyst and the product yields obtained with
 EMI20.2
 the usual silica-alumina catalyst, at the same level of conversion.



   The following examples illustrate the invention without limiting it.



    EXAMPLE 1
A crystalline sodium aluminosilicate of type Y is prepared from the following reagents!
 EMI20.3
 A - Solution d. s11ge 1551 cm3 (1870 s) of colloidal silica containing 0.361 g of 8io2 per cm3.



  Bu sodium alumDte solution 75 g of NaAlO2 (4l, 7 by weight of Al2O3, 30% by weight of A20) 330 g of NaOH (77.5 by weight of Hz0) 1345 cm3 of g20.



  The gol4tto g ot-4 are mixed. to about 2790 by pouring solution a into the iqlutiqp 4, 9 fool sharp-

 <Desc / Clms Page number 21>

 
 EMI21.1
 8M1 \ b slang * PlncSab \ #ntlron 1/2 hour .. Leaks OA'8 'l' there boils Obtained at a tben1que trfclteaent at'93 for 42 hours. We then separate * by tlltrat10D: ', -. solid liquid that floats. We lare 1 tourt.au mifÊèw; .,, gold. ?: ../, voltunt of water per volume of boiling Initial * for '1.' ,:, -, 1! , .....- ;. } .çr ':: 4' ,, t ;.



  1 * cMttiqu <Hbr <. 4 & ± É $ ai To pr4p * r r the competition d * c t .xep1! F:,!: '' '.S <:'. .:., t ',, x..3 disperses 101 by weight d. the doUte Y prepared * oo.:f: a <.rxy ",, ¯c'f, r" 'T'. '' above in a * pitch d * .l tilioe-elumint Qontaap ',' '; ..t. ; ..-. '¯¯, Tir on 9 .'-' 4th silioe and 6% alumina by weight. ¯ ::, t =, k;, - We use the following * r6aatives: .. 'fr. (:;:.' ¯yli: c ^ tCTy'2 1 a ..



  ǯ Solution d. tilicat. , '.-' t- '1) .4.,' 4 kC sodium silicate (281 '.'. VIII r: 8.9 di 'a20, 62.6 d * B20 in weight: - :; : - 2) tI, here d'ttu; <ç: '"i.,' ;, r- = 2) 2.24 KI of water '' .. u, <. - ',' u '; ts,. ::. wr.r. é, 2.24 d * au '....; (11} \ ... ""' 0.30 IcC of aluminosilicate. 4. sodium X -, # '"(54.3 by weight 4. solids) On add solution 2 to solution 18Q while stirring frequently, to obtain a * solution which *. Vv! 1 * half d * 1.182 at 16 ° C.



  D - Acid solution '"': '.' :: i'i, - 25.90 xI of water!> -.: fi: '* 1.92 kg of III2 (SO) 3.1.8 Ii20' -V bzz .. ".., ... rt 0.90 kg d * B2BOI. (at 97) dmsitd at 25 C i 1.056. .Y.,%:,:, - We pass the solutions above j pass the solutions, ", '.' ';)':;: 'F .r..Jf a t1st. of 394 cm3 / min of 801utl9fi. # ', -tSa?' - 'for 374 cm3 / min of solution C. The hydrosol obtained. pe h. 4âpgt,' '"7t ..... -f {- s {1 - pH 8.5; we introduce it under your own. of .1obu1 "-, ::," <>:;: i '.'. ' .. =,. 'i,: yG'v: s'' -r ..

   F. <=, mass of oil where it takes in beads 4'h7dro & !, j (.. '\.:; Seconds at 17 C.'. ':,. (".; 3: W-j' j The hydrogel in beads is subjected to a .Ch8nIé ''.: "bases with an aqueous solution. to 2 d (by weight 4. chïoTUSpM,

 <Desc / Clms Page number 22>

 rare earths containing 0.63% etium chloride, 0.33% lanthanum chloride, 0.06% praseodyne chlorurt 0.23% neodymium chloride and traces of samarium chloride, gadolinium chloride and other rare earth chlorides. The base exchange is carried out using 12 contacts (9 contacts of 2 hours chreun and 3 contacts of 20 hours each) with 1/2 volume of solution to 1 volume of hydrogel parles. .

   The hydrogel is washed which. undergone the exchange to free it from soluble union, it is dried for 24 hours in air at 132 ° C., conditioned in air for 10 hours at 538 ° C. and treated with water vapor at 1, 05 kg / cm2 and 1649 C losing 30 hours and for 60 knocks *.



   The finished composition contains 0.21% by weight of sodium and its content of rare earth oxides is 10.8% by weight. The specific surface area of the product steamed for 30 hours is 195 m2 / g and that of the product steamed for 60 hours is 167 m2 / g.

 <Desc / Clms Page number 23>

 
 EMI23.1
 WLEAU 1
 EMI23.2
 ¯ ..1 pucrlDtlQD.



  OanBue S1 / J.1! (9U6) Partlcultt finti ia / U / 8i (13X) Concentration 10 s Ide% go of buet solution RRC136H C
 EMI23.3
 
<tb> Concentration <SEP> 2
<tb>
<tb>% <SEP> in <SEP> weight
<tb>
<tb> composition
<tb>
 
 EMI23.4
 ! ta.% by weight 0.21 (RE) 20,. by weight 10, $ Phyalouei properties Specific surface area 2 / t harsh treat 1 la iq (i) 167 (2) Tapeur treat 3'95 (1) 16'7) yaluat1on catalvt1au8 Conversion% enllole 63.0 bzz relative flow. h. 53.7 10 RVP gaa-oi, in flight. 55, z 53.7 excess C4 '.. by volume 10.2 batches C5 + gasoline,% daytime 52 # 5 51.1 total C408% approx volume 12.9 13.3 gas 88C,: C by weight 6 # 4 5.1 coke,% by weight vt erBqnge T * l 10 RVP Il in "f01Ut! 8 + 8, e 5 excess b4 'by volume - 4.8,. 2.9 C- + gasoline,% by volume + 8.4. + $ 5 total, '% by volume 4.2 -3r2 ¯If .. place% weight 1 8 ....:

  2 # 6, wt% - $ 1 -2 coke, wt% - 2.7 eurerott yield of C5 + gasoline compared to 6i02 / A1z03AFX (###) # 2.2; 24
 EMI23.5
 (.) EZ earth metals Taret M coùrc1al silica-alumina catalyst containing about 90% of 8i02 and lO of A120, (...) zeolite lJxay & nt rub1 a cutout 4.b ....... 0 ohlo Te of rare terrt and n1um, and contained in a gel matrix 8102- Al20)

 <Desc / Clms Page number 24>

 (1) treated for 30 hours at 649 * C and 1.05 kg / cm2 with 100% water vapor (2) treated 60 hours at 649 C and 1.05 kg / cm2 with 100% water vapor.



   As can be seen, the data for the catalyst of Example 1 is compared, with the results obtained using a commercial silica-alumina cracking catalyst at the same conversion, and also with the results of a catalyst. comprising 10% by weight of type X sodium aluminosilicate dispersed in a gel matrix comprising 94% silica and 6% alumina by weight, the catalyst having undergone base exchange with combined solutions of sodium chloride. rare earths and ammonium, down to a low residual sodium content.



   The data in Table 1 demonstrate the catalytic advantages of gangue type Y exchanged aluminosilicate over the comparable type X aluminosilicate, as well as the very significant improvement in activity and selectivity over usual commercial silica-alumina catalyst, EXAMPLE 12-3
The compositions of these examples are prepared in the same manner as that of Example 1, except that the base exchange of the beaded hydrogel is carried out with an ammonium chloride solution.



   Thus, the exchange of the hydrogel in beads for these two examples is carried out by contact with an aqueous solution containing 1% by weight of ammonium chloride, using 12 contacts of 2 hours each with 1/2 volume of solution per hydrogel volume. The hydrogel is then washed, dried and conditioned as in Example 1. The composition of Example 7 is steamed for 30 hours at 1.065 kg / cm2 and 649 C while the composition of Example 7 is steamed for 30 hours. Example 8 is treated for 24 hours under the conditions
Indicated $.

 <Desc / Clms Page number 25>

 



  EXAMPLE A
The composition of this example was prepared by both base exchange 200 g of the Y zeolite prepared cocus in Example 1 with a 5% by weight aqueous ammonium chloride solution. The base exchange at 82 ° C was carried out using 12 contacts of 2 hours each with 1/2 volume of solution per volume of slurry. The exchanged material is washed, dried and conditioned as in Example 1, then treated with water vapor at atmospheric pressure for 20 hours at 663 ° C.



   The composition thus obtained contains 1.19 sodium and 27.0% alumina by weight and it has a specific surface area of 66 m2 / G EXAMPLE 5
The composition of this Example is prepared in the same manner as for Example 2, except that the sodium aluminosilicate is of type X and is present in an amount corresponding to 25% by weight.



   A base exchange of the hydrogel beads of this example was carried out with a 2% by weight aqueous solution of ammonium chloride at room temperature, using 8 contacts of 2 hours each with 1/2 volume. of solution by volume of hydrogel beads. The exchanged hydrogel is then washed to rid it of chloride, dried in air at 110 ° C, conditioned in air at 538 ° C for 10 hours and it is treated with water vapor at 1.05 and 649 C for 24 hours.



   The cracking activity of the composition of Examples 2-5 was tested as described above, and the results are shown !! in Table II.

 <Desc / Clms Page number 26>

 



    TABLE II
 EMI26.1
 Example no 2 3; pescri.ption 8i / Al (94/6) Si / Al (94/6) Si / Al (94/6) gangue s1 / ll (9416) s1 / .u (9416) S1 / ll (9416)
 EMI26.2
 
<tb> gangue <SEP> is
<tb>
 
 EMI26.3
 atièrea tinea: Avsi type JalJ1! S1 (13I) lalAl / S1 (1)!) t'll / S1 (13I) laIS1 (1JI) concentratign 10 100 E Solution h of baaca IR, 4C '1H4C1 liH4Cl IIR4cl Solution IR4Cl
 EMI26.4
 
<tb> Concentration, <SEP>% <SEP> in <SEP> weight <SEP> 1
<tb>
 
 EMI26.5
 Ç01tlDOS 0.3 Na, by weight z 0.3 1.19 1 * 1 09 Al203 'by weight 8.1 27 # 0 1316 fr911 hyslaues g 0.96 0.82 0.66 o, if r;): & . <13 apparent pec1f1que :. g / c: a Os 0.82 0.66 0.81 specific surface area, m, 2 / g after treatment with the Tapeur 137 136 Evaluation c8t¯lyt1 61 53.2 30.0 Conversion, in volua. 43.2 60.3 51.3 .3.3 6119 53.2 30.0 Relative flow rate h'1 4 2 3 10 Relative RVP, volume sorting 38.3 49.4 43.7 37.9 50.7 47.2 2''S Excess C4,;

   by volume, 6 12.7 10.5 7.5 13.1 9 # 3 4.2 CS + gasoline, by volume 36.3 .7.1 41.7 36.0 4g, i, 7 25'a. total C4 ':' in voli, - 9.6 1.4.9 12.4 9.4 lS, 4 n, 'S, a Dry gas,% by weight 4.5 7.4 5.7, 4 7.4 5.2 3.1 Coke, wt% 0.9 1.7 1.1 1.2 r 0.99 1.0

 <Desc / Clms Page number 27>

 TABLEAO II (sote)
 EMI27.1
 O M C- * # ir? f? f? ² $> "9,. M <C <0 i i? I <i t r-1 r1 f1 no h s? -F * f #? 1 '
 EMI27.2
 
<tb> cont
<tb>
 
 EMI27.3
 <f \ t- CIL + q + -5, H.



  T T? #ri N '13 y? ? T? T 0
 EMI27.4
 
<tb> yseut <SEP> usual
<tb> e
<tb> a
<tb> volme
<tb> ume
<tb> s
<tb>
<tb>
<tb>
<tb> lmerclal <SEP> closed <SEP> from <SEP> c
<tb>
 
 EMI27.5
 s. mi 5 S. S c '3 w P4 nitC "*' '] 44 Û It a'0 93 ti tgU4.



  1 * fi r

 <Desc / Clms Page number 28>

 
The catalytic data in the table above show that the aluminosilcates Y are active cracking catalysts which have better selectivity than the usual silica-alumina catalyst. In order to make a direct comparison between the catalysts of Examples 2 and 3 and the rare earth catalyst of Example 1, the former must be operated under conversion conditions at a fine relative flow rate 2 h-1 At this flow rate, the activities of the catalysts of Examples 2 and 3 are respectively brought to 60.3 and 61.9% conversion by volume.

   These acid catalysts exhibit good selectivity at this level of conversion, the selectivity being improved to the detriment of the cone and with dry gas, with a low loss on the total C4
The data in Table 11 further show that the catalyst of Example 2, containing 10% by weight of sodium aluminosilicate Y approximates the activity of pure material, which is the catalyst of Example 4, then even that it was steamed much harsher. These data show that when a type aluminosilicate is incorporated into a silica-alumina matrix and then base exchange is carried out with an ammonium chloride solution, the stability of the alumosilicate is increased.

   Although the reason for this strained natural increase is not known with certainty, it appears to be due to the synergy between the acid aluminosilicate type I and the matrix which contains it.



   It is also seen from the data in Table II that the catalyst of Example 5 prepared from type X aluminosilicate is much less active than the catalyst of Example 12 which contains less of the aluminosilicate. but of type Y.



   The following examples serve to demonstrate that hydrated alumina and hydrated clay can be used as gangue to prepare dilute Y-type rare earth aluminosilcate catalysts exhibiting exceptional catalytic properties.

 <Desc / Clms Page number 29>

 tional EXAMPLE 6
The crystalline sodium aluminosilicate Y was prepared as in Example 1. 230 g of this product were subjected to base exchange with a combined aqueous solution containing 55 by weight of LaC13.6H20 and 2 by weight of BH4C1 for 48 hours. continuously, using the equivalent of 24 2-hour changes, with one volume of solution per volume of Douillie. Wash the exchanged way to rid it of soluble anions and dry it.



    Mixing 30 g of the dried powder with 90 g of hydrated alumina containing bb.5 of solids at 538 C causes the mixture to be mixed in a mixer by adding 150 cm3 of water to dilute the mixture into a homogeneous mass. The mixture is dried in air at 110 C for 24 hours, then granulated and sieved into 4.8 x 2mm particles. The particles are calcined for 10 hours at 538 C and then treated with steam for 24 hours at 649 C and $ 10.5 kg / cm2
The resulting composition contained 0.35 wt. Sodium, 4.25 wt.% La 2 0 and had a specific surface area of 172 m / g after steam treatment.



  EXAMPLE 7.-
One prepares the composition as in Example 6, if so! is that the exchange solution ae boxes contains 5% by weight of rare earth metal chloride (RC13.6H20) and 2% by weight of ammonium chloride and that a hydrated clay is used as diluting gangue.



   In this example 22 g of the exchanged and dried material are mixed with 76 g of crude clay (88% solids) at 538 ° C. The dry mixed product is then granulated, calcined and treated with water. steam as in the previous example.



   The final composition contains U.44 wt. Sodium, 4.0 wt.% Rare earth oxide and has a specific surface area of 105 m2 / g after steaming.

 <Desc / Clms Page number 30>

 



   The characteristics and the results obtained in the test of the compositions of Examples o and 7 with regard to their cracking activity as indicated in Table III;
TABLE III
 EMI30.1
 
<tb> Example <SEP> 6 <SEP> 7
<tb>
<tb> Description
<tb>
<tb> gangue <SEP> 75% <SEP> alumina <SEP> 75% <SEP> clay
<tb> hydrated <SEP> hydrate *
<tb>
<tb> Material <SEP> finea
<tb>
 
 EMI30.2
 Type La.i1x RETIE
 EMI30.3
 
<tb> Concentration <SEP> 25 <SEP> 25
<tb>
<tb> Composition
<tb>
<tb> Ma, <SEP>% <SEP> in <SEP> weight <SEP> 0.3 <SEP> 0.44
<tb>
 
 EMI30.4
 (RE) 20), z. Weight, 25 4.0
 EMI30.5
 
<tb> Property, <SEP> physics
<tb>
<tb> Specific <SEP> surface <SEP> after
<tb> treatment <SEP> has <SEP> the <SEP> steam,

  
<tb> m2 / g <SEP> 172 <SEP> 105
<tb>
 
 EMI30.6
 Catalan evaluation
 EMI30.7
 
<tb> Conversion, <SEP>% <SEP> to <SEP> volume <SEP> 64.5 <SEP> 77.2 <SEP> 66.8
<tb>
<tb>
<tb> Dedit <SEP> relative, <SEP> h-1 <SEP> 4 <SEP> 4 <SEP> 8
<tb>
<tb>
<tb>
<tb>
<tb> 10 <SEP> Rvp <SEP> diesel, <SEP>> <SEP> en
<tb>
<tb> volume <SEP> 59.2 <SEP> 60.6 <SEP> 65.1
<tb>
 
 EMI30.8
 Excess C4 'by volume 8.9 16.2 11.8 C5 + Eence,% by volume 55.9 58.1 551 Total C4' by volume 12.2 lts, 8 bzz
 EMI30.9
 
<tb> Gas <SEP> dry,% <SEP> in <SEP> weight <SEP> 5.6 <SEP> 10.1 <SEP> 6.3
<tb>
<tb> Coke, <SEP>% <SEP> in <SEP> weight <SEP> 2.0 <SEP> 4.4 <SEP> 2.6
<tb>
 

 <Desc / Clms Page number 31>

 TABLE III (continued)
 EMI31.1
 
<tb> Example <SEP> 6 <SEP> 7
<tb>
<tb> Advantage <SEP> over <SEP> the <SEP> catalyst
<tb>
 
 EMI31.2
 ;

   Q: fttitY8r 10 RVP, volume% +12.2 +8.6 +10.1 Excess C4 'in volume - &, 5 S, 4 -Â, 7 C5 + gasoline,> in volume +11.1 +7, 7 +9.1
 EMI31.3
 
<tb> Total <SEP> C4,% <SEP> in <SEP> volume <SEP> -5.4 <SEP> -4.4 <SEP> -3.7
<tb> Gas <SEP> dry,% <SEP> in <SEP> weight <SEP> -2.9 <SEP> 0.9 <SEP> -2.6
<tb>
<tb> Coke, <SEP>% <SEP> en <SEP> polo shirts <SEP> -3.4 <SEP> 3.6 <SEP> -3.2
<tb>
<tb> <SEP> advantage of <SEP> yield
<tb>
 
 EMI31.4
 C5 + gasoline compared to 6102 / Al20) -REHX (**) +5.1 ¯¯- +3.2 (x) commercial silica-alumina catalyst containing approx.
 EMI31.5
 9u> de 8io2 and 1u dJÀ1293 (XX) 13% zeolite having undergone an exchange of bases with chlorides! of rare earth and ammonium and contained in a gel matrix
 EMI31.6
 8102-A1203.

   PLEMPLE 6? -
This example demonstrates that a catalyst with good activity and selectivity can be prepared using
 EMI31.7
 reading a rare earth aluminosilioate Y which has undergone a prior exchange, together with additional pulverized material to increase diffusibility. The fines consist of 5% by weight of rare earth aluminosilicate X and 24% by weight of ar-. gile which has an average particle diameter of 4-5 microns. The resulting beaded hydrogel is subjected to a base exchange, washed, dried, conditioned and steamed.



   The final composition contains 0.18 wt. Sodium, 0.95 wt. Rare earth oxide and 16.bwt.% Alumina.



  The specific surface of the composition after steam treatment is 126 m2 / g
Table IV shows the results given by the cracking activity test of the composition of this example!

 <Desc / Clms Page number 32>

 TABLE IV
 EMI32.1
 
<tb> Example
<tb>
 
 EMI32.2
  e, çr1 \? t1on Gangues bi / Al (94 8102-6 À'2 "3)
 EMI32.3
 
<tb> Fine <SEP> materials
<tb>
 
 EMI32.4
 Type 5% KEX 24% clay Concentration Bebange Oe bageai
 EMI32.5
 
<tb> Solution <SEP> NH4C1
<tb> Concentration, <SEP>% <SEP> in <SEP> weight <SEP> 1
<tb>
<tb> Contacta <SEP> 1-24 <SEP> hours <SEP> continuous <SEP> to <SEP> the <SEP> tem
<tb> ambient <SEP> temperature, <SEP> equivalent
<tb> pera <SEP> <SEP> changes of <SEP> 2 <SEP> hours
<tb>
 
 EMI32.6
 CompoaitiQn
 EMI32.7
 
<tb> ba, <SEP>% <SEP> in <SEP> weight <SEP> 0.18
<tb>
 
 EMI32.8
 (HE) 203,% by weight 0.95 Au by weight read,

   b roprlété5 physiouea
 EMI32.9
 
<tb> Apparent specific <SEP> <SEP> weight <SEP> g / cm3 <SEP> 0.78
<tb>
<tb>
<tb>
<tb> Specific <SEP> surface <SEP> after <SEP> treatment
<tb>
<tb>
<tb> to <SEP> the <SEP> steam, <SEP> m2 / g <SEP> 126
<tb>
 
 EMI32.10
 CaliilytIQ33.1 Rating
 EMI32.11
 
<tb> Conversion, <SEP>% <SEP> to <SEP> volume <SEP> 51.6
<tb>
<tb> Relative <SEP> flow, <SEP> h-1 <SEP> 4
<tb>
 
 EMI32.12
 10 HVP gas-Oil, i by volume 46.4
 EMI32.13
 
<tb> Excess <SEP> C4,% <SEP> in <SEP> volume <SEP> 7.0
<tb>
 
 EMI32.14
 C5 + essetice,> in volume 43.6
 EMI32.15
 
<tb> Total <SEP> C4,% <SEP> in <SEP> volume <SEP> 9.9
<tb>
<tb> Gas <SEP> sec, <SEP>% <SEP> in <SEP> weight <SEP> 5.0
<tb>
<tb>
<tb> Coke, <SEP>% <SEP> in <SEP> weight <SEP> 1,2
<tb>
 

 <Desc / Clms Page number 33>

 
 EMI33.1
 f1àiAü IV (him you)

   
 EMI33.2
 
<tb> Example <SEP> 8
<tb>
 
 EMI33.3
 Advantage over the usual catalyst d9..craaM <: <... t) '!).



  1OHVP,% by volume +509 Excess c 4 '.,. by volume -4.0 C5 + easenoe,.,. by volume + 5 # 4 Total (,; 4 'by volume -3, I, Dry gas,' j. by weight -1, 2
 EMI33.4
 
<tb> Coke, <SEP> in <SEP> weight <SEP> -1.9
<tb>
 (X) commercial silica-alumina catalyst containing about 905
 EMI33.5
 of 510 and 10% of Al2U3.



  EXAMPLE 9. -
This example demonstrates the use of a powdered metal as gangue for the above catalysts.



   A Y zeolite was prepared as in Example 1 and subjected to base exchange with an aqueous solution containing 2% by weight of ammonium chloride and 5% by weight of mixed rare earth chlorides having the following composition : 1.57% of cerium chloride, 0.83% of lanthanum chloride, 0.17 of praseodymium chloride, 058 of neodymium chloride and traces of samarium chloride, gadolinium chloride and d other rare earth chlorides. The base exchange was carried out continuously for 48 hours at 82 ° C. using the equivalent of 24 2 hour changes with 1 volume of solution per volume of slurry.

   The exchanged material is then washed to rid it of chloride, it is then
 EMI33.6
 dried 24 hours at 11U C, conditioned at 5380C for 10 hours in air and finally brought into contact with 1005 water vapor at atmospheric pressure and 663 C for 20 hours.
 EMI33.7
 The residual sodium content of the exchanged material is 1.32% by weight, a mixture of the aluminosilicate exchanged with aluminum powder, at a rate of 50 g of the aluminosilicate and 150 g of powder.

 <Desc / Clms Page number 34>

 of metallic aluminum, in a ball mill for 4 hours.



  The mixture is then granulated, sieved into 4.8 x 2mm particles, conditioned for 10 hours at 538 C in air and finally treated with steam for 24 hits * at 649 C and 1, 05 kg / cm2
The composition obtained contains 0.09% by weight of sodium and 2.76% by weight of rare earth oxides. The specific surface of the composition after steam treatment is 76 m2 / g
Table V shows the results obtained by checking the cracking activity of the composition of this example.

 <Desc / Clms Page number 35>

 



  TABLE V
 EMI35.1
 
<tb> Example <SEP> n * <SEP> 9
<tb>
<tb>
<tb> Description
<tb>
<tb>
<tb>
<tb> uangue <SEP> alumina <SEP> metallic <SEP> in <SEP> powder
<tb>
<tb>
<tb> Fine <SEP> materials
<tb>
<tb>
<tb>
<tb> Type <SEP> REHY
<tb>
<tb>
<tb> Concentration <SEP> 2 <SEP> If '<SEP>
<tb>
<tb>
<tb>
<tb> Composition
<tb>
 
 EMI35.2
 Ua,;

  4 wt 0.09 (RE) 2O3, wt% 2.76
 EMI35.3
 
<tb> Physical <SEP> properties
<tb>
<tb>
<tb> Apparent specific <SEP> <SEP> weight, <SEP> g / cm3 <SEP> 0.76
<tb>
<tb>
<tb> Specific <SEP> surface <SEP> after <SEP> treatment
<tb>
<tb>
<tb> to <SEP> the <SEP> steam, <SEP> m2 / g <SEP> 76
<tb>
 
 EMI35.4
 at1Qn atalyt1Q '
 EMI35.5
 
<tb> Conversion, <SEP>% <SEP> to <SEP> volume <SEP> 71.9
<tb>
<tb>
<tb> Relative <SEP> flow, <SEP> n-1 <SEP> 4
<tb>
<tb>
<tb>
<tb>
<tb> 10 <SEP> RVP <SEP> gas oil, <SEP>% <SEP> in <SEP> volume <SEP> 64.3
<tb>
<tb>
<tb>
<tb> Excess <SEP> C4,% <SEP> in <SEP> volume <SEP> 12.0
<tb>
 
 EMI35.6
 c5 + gasoline, by volume 61.1
 EMI35.7
 
<tb> Total <SEP> C4% <SEP> in <SEP> volume <SEP> 15.3
<tb> Gas <SEP> sec, <SEP>% <SEP> in <SEP> weight <SEP> 5.9
<tb>
<tb> Coke, <SEP>% <SEP> in <SEP> weight <SEP> 2.6
<tb>
<tb> H2,

  % <SEP> in <SEP> weight <SEP> 0.02
<tb>
<tb> Advantage <SEP> over <SEP> a usual <SEP> catalyst <SEP>
<tb>
 
 EMI35.8
 ae cracking
 EMI35.9
 
<tb> 10 <SEP> RVP, <SEP>% <SEP> in <SEP> volume <SEP> +14.2
<tb>
 
 EMI35.10
 Excess C 4 '"by volume -6.9 C5 + gasoline; 6 by volume +12.8
 EMI35.11
 
<tb> Total <SEP> C4,% <SEP> in <SEP> volume-5.5
<tb>
<tb> Gas <SEP> sec, <SEP>% <SEP> in <SEP> weight-3.9
<tb>
<tb>
<tb> Coke, <SEP>,. <SEP> in <SEP> weight <SEP> -4.2
<tb>
 
 EMI35.12
 (*) commercial catalyst containing approximately 90% 61 2 and 10% Al e3.

 <Desc / Clms Page number 36>

 



   It can be seen from the data above that the catalyst obtained, containing 25% by weight of rare earth aluminosilicate and hydrogen, has superior catalytic properties. The catalytic data summarized in Table V show that this catalyst is extremely selective and gives an Advantage of about 1.2.8% by volume of C5 gasoline over the usual silica-alumina catalyst.



    EXAMPLE 10.-
To prepare the composition of this example, a sodium aluminosilicate Y is subjected to a continuous base exchange with a combined solution comprising 5 by weight of CaCl2 and 2% by weight of NH4Cl at 82 ° C. for 72 hours, using the solution. total equivalent to 36 changes of 2 neurons with 1 volume of solution per volume of slurry.



   The exchanged product is washed, dried, conditioned and steamed for 24 hours at 649 ° C and 1.05 kg.
 EMI36.1
 cm The composition, characteristics and results of
 EMI36.2
 the cracking activity test are shown in Table VI.



  TABLE VI
 EMI36.3
 Ezemp3q n 10
 EMI36.4
 
<tb> Description <SEP> sodium aluminosilicate <SEP> <SEP>
<tb>
 
 EMI36.5
 Type HA / Al / 81 (131)
 EMI36.6
 
<tb> Concentration <SEP> 100
<tb>
 
 EMI36.7
 basic pchangg Solution aul2; dH4c: 1
 EMI36.8
 
<tb> Concentration, <SEP>% <SEP> in <SEP> weight <SEP> 5 <SEP> 2
<tb>
<tb> Contacts, <SEP> 3x24 <SEP> hours <SEP> continuous, <SEP> equivalent
<tb> a <SEP> 36 <SEP> <SEP> changes of <SEP> 2 <SEP> hours
<tb>
 

 <Desc / Clms Page number 37>

 
 EMI37.1
 Abatl Vt ('U1t &> "1 ¯M. ,,
 EMI37.2
 Zz = L2-n- 10
 EMI37.3
 
<tb> Composition
<tb>
<tb> Na,% <SEP> a <SEP> weight <SEP> 0.82
<tb>
<tb> ca <SEP>% in <SEP> weight <SEP> 6.8
<tb>
 
 EMI37.4
 -emprl4téo ohy3ia3de5
 EMI37.5
 
<tb> Specific <SEP> surface <SEP> after <SEP> treatment
<tb> to <SEP> the <SEP> steam,

   <SEP> m2 / g <SEP> 187
<tb>
 
 EMI37.6
 Catalytic evaluation Con'Yer: 11on,:, by volume 61.8 Relative flow rate, h-l read 10 hVP oli-gas, by volume,) 7, U Excess \ .: 4 ',. in volume V, 5
 EMI37.7
 
<tb> C5 <SEP> gasoline, <SEP>% <SEP> in <SEP> volume <SEP> 54.0
<tb>
<tb> Total <SEP> C4,% <SEP> in <SEP> volume <SEP> 12.5
<tb> Gas <SEP> dry,% <SEP> in <SEP> weight <SEP> 4.8
<tb>
<tb> Coke, <SEP> in <SEP> weight <SEP> 1.5
<tb>
 
 EMI37.8
 4 go & this on a usual catalyst
 EMI37.9
 
<tb> of <SEP> crackers <SEP> (s)
<tb>
<tb> lu <SEP> RvP <SEP> in <SEP> volume <SEP> +11.2
<tb>
 
 EMI37.10
 Excess 1,; 4 '> in volume -4.8, + en3ence,; i in volume +10.4 Total 1 ,;

  4 '% by volume -4.1 Gas <ee, anpoida -3.2
 EMI37.11
 
<tb> Coke, <SEP> in <SEP> weight <SEP> 3-3
<tb>
 
 EMI37.12
 Advantage of efficiency C 5 + gasoline at r hkàtx (u) +2.4
 EMI37.13
 (*) commercial catalyst containing approximately SruG biU2 and 1 (! x A1203 (XX) 13X zeolite having undergone a base exchange with a solution of rare earth chlorides and ammonium.

 <Desc / Clms Page number 38>

 



   The following example serves to illustrate that an effective catalyst composition can be prepared by subjecting sodium aluminosilicate Y to base exchange with a solution containing manganese and ammonium cations.



  EXAMPLE 11.-
The composition is prepared by subjecting to a continuous base exchange 300 g of sodium aluminosilicate X with an aqueous solution containing 2% by weight of manganese chloride and 1% by weight of ammonium chloride. Base exchange is equivalent to 36 contacts of 2 hours with 1 volume of solution per volume of slurry. The product is then washed with water to remove chloride ions, dried for 20 hours in air at 132 C and steamed for 24 hours at 649 C and 10 5 kg / c2m.
The compositions thus obtained have a sodium content of 1.49 by weight and a specific surface area after steam treatment of 52 m2 / g.
Table VII shows the results given for testing the cracking activity of this composition.

 <Desc / Clms Page number 39>

 



  TABLE VII
 EMI39.1
 USOVII il, \, v..crlpt1oJ1 1,, 1 1-1 alwdnOa11cat. de .oua .1011'8 1 J9hange bJI. ' bolution MnC12 + h4 '
 EMI39.2
 
<tb> Concentration, <SEP>) <SEP> in <SEP> weight
<tb>
<tb> Contacts <SEP> equivalent <SEP> to <SEP> 36 <SEP> changes
<tb> Contact <SEP> of <SEP> 2 <SEP> hours
<tb>
 
 EMI39.3
 npo:

  ! 1 ton a, by weight the 'rronrl, jA8 mi C [Ute
 EMI39.4
 
<tb> Specific <SEP> surface <SEP> after <SEP> line -
<tb>
<tb> ment <SEP> to <SEP> the <SEP> steam, <SEP> m2 / g
<tb>
 
 EMI39.5
 vlu8t19P oatalvtiQUq
 EMI39.6
 
<tb> Conversion, <SEP> $ <SEP> to <SEP> volume <SEP> 34.7
<tb> Relative <SEP> flow, <SEP> h-1 <SEP> 10
<tb>
 
 EMI39.7
 10 RVP petrol,> by volume 33.3 Excess C, 9 by volume 4.0 cS + petrol,% by volume 31,
 EMI39.8
 
<tb> Total <SEP> C4,% <SEP> in <SEP> volume <SEP> 6.0
<tb>
<tb> Gas <SEP> sec <SEP>% <SEP> in <SEP> weight <SEP> 2.8
<tb>
<tb> Coke, <SEP>% <SEP> in <SEP> weight <SEP> 0.02
<tb>
 
 EMI39.9
 Advent, 4;

  , e.-gur un- 9atalYeur usu! À de cra (iuege 10 liVP, by volume +2.8
 EMI39.10
 
<tb> Excess <SEP> C4 <SEP>% <SEP> on <SEP> volume <SEP> -2.4
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> C5 + gasoline, <SEP>% <SEP> in <SEP> volume <SEP> +3,0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Total <SEP> C4, <SEP>% <SEP> in <SEP> volume <SEP> -2,
<tb>
 
 EMI39.11
 Dry gas, J6 by weight -0.9 Coke,% by weight -1.2 commercial oatalyst containing about 9U> 61 2 and 10% II


    

Claims (1)

EMI40.1 x v u x c I u b. --t: -rwt-.rw.t ... ww-.ww 1. Catalytic composition of the type der alum1111oate .. o1.t.111n., characterized in that 1 # aluminoàiillcate has a molar ratio a111061A1umJn greater than 3sl and contains CI * Metal Ions in the electromotive series, calcium ions, ammonium ions, byarogen ions or organic nitrogen ions, alone or in combination. 2. Composition according to claim 1, characterized in that the negative electrovalence of the silica and of the alumina is compensated for by these ions. 3. Composition according to claim 1 or 2, character- EMI40.2 This is because the aluminosilioate is a type Y aluminosilicate. 4. Composition according to claim 1, 2 or 3, characterized in that the aluminosilicate contains an exchangeable alkali metal in an amount of less than 3% by weight. 5. Composition according to either of the preceding claims, characterized in that the aluminosilicate is fine. EMI40.3 is divided and is agglomerated by a binder into an articular aggregate. 6. Composition according to one or the other of the preceding claims, characterized in that the aluminosilicate is finely divided and kept in suspension and distributed in a matrix. 7. Composition according to Claim 6, characterized in that the matrix is formed of a hydrated oxide, of an inorganic gel, of a metal or of a clay. 8. Composition according to claim b or 7, characterized in that the matrix is an inorganic oxide gel chosen from the class formed by alumina, silica and compounds formed by silica with at least one oxide d. 'a metal chosen from among metals EMI40.4 of the JIA, Illa and IvA groups on the periodic table. 9. A composition according to claim 6, 7 or 8 charac- EMI40.5 terized in that only the hydrogen ion or the ammonium ion is comoined <Desc / Clms Page number 41> aluminosilicate in the lu gangue composition according to claim 5, 6 7 8 or 9, characterized in that the alumminosilicate is present in an amount of 1 to 90 by weight. 11. Composition according to either of the preceding claims, characterized in that it comprises, in addition to the aluminallcate, a secondary solid additive capable of increasing the diffusibility of the composition. 12. A composition according to claim 11, characterized in that the solid additive is thinned by a clay or fines of the composition. 13. Composition according to either of the preceding claims, characterized in that the ions are ions of a rare earth metal, a combination of ions of a rare earth metal and Hydrogen ions, ions of an alkaline earth metal, lanthanum ions or a combination of lantnane ions and hydrogen ions 14. Composition according to either of claims 1 to 8, 10, 11 or 12, characterized in that the ions are magnesium or manganese ions. 15. Composition according to one or the other of claims 1 to 8, 10, 11 or 12, characterized in that these organic nitrogen ions are present and are quaternary ammonium ions or ions derived from guanidine salts or amine salts. 16. Composition according to either of claims 1 to 8, 10, 11 or 12, characterized in that the ions present comprise calcium ions combined with ammonium ions and the ratio of metal ions to ions. ammonium is between 10: 1 and 1: 100 17. Process for preparing the composition according to claim 1, characterized in that a crystalline alkali aluminosilicate is subjected in which the silica: dumina ratio is Dupe. <Desc / Clms Page number 42> 3: 1 basis exchange with a solution containing metal ions internal to sodium in the electromotive series, calcium ions, ammonium ions, hydrogen ions or organic nitrogen ions, alone or in combination. 18. The method of claim 17, characterized in that the exchange of bases is conauit so as to replace at least 70% of the initial alkaline ions. 19. The method of claim 18, characterized in that the content of exchangeable alkali ions is real at less than 3% by weight. ; 20. A process according to claim 17, 18 or 19, characterized in that the aluminosilcate is finely divided and intimately mixed with a binder before or after the base exchange. 21. Process according to Claim 20, characterized in that the binder is a gangue for the aluminosilcate. 22. A method according to claim 21, characterized in that the solution contains only hydrogen or ammonium ions so that an aluminosilicate appears in its hydrogen form in a matrix. 23 A method according to claim 20, 21 or 22, characterized in that the composition obtained is dried and calcined. 24 A method according to claim 23, characterized in that the composition is freed from soluble matter by washing before drying. 25. The method of claim 23 or 24, characterized in that the calcined composition is treated with steam at a temperature of about 200 to 820 ° C for at least about 2 hrs. 28 Method according to either of the claims 17 to 25, characterized in that the aluminosilcate is a type 1 aluminosilicate 27, Process according to either of the claims <Desc / Clms Page number 43> 17 to 26, characterized in that the diffusibility of the composition 18 is increased by adding to it a finely divided solid 28. A method according to any one of claims 17 to 27 characterized in that the base exchange solution contains metal ions and ammonia ions and the ratio of metal ions to ammonium ions is between 10 : 1 and 1; 100 29. Process for converting organic compounds capable of catalytic conversion in the presence of acidic catalytic sites by contacting these compounds with the catalyst composition according to either of Claims 1 to 16 30. Process according to Claim 29, characterized in that a hydrocarbon feedstock is subjected to cracking by bringing it into contact with this catalyst under these oatalytic storming conditions. 31. A process for cracking a hydrocarbon feed characterized in that the feed is brought into contact with a catalyst of the crystalline aluminosilcates type of type I hydrogen forms under catalytic cracking conditions. 32. Crystalline aluminosilicate catalyst having a silica: alumina molar ratio greater than 3: 1 and containing cations, substantially as described above 3j. A catalyst preparation process according to any of claims 1 to 1b or 32, substantially as described above.