GB2134536A - Treatment of hydrocarbons in the presence of a catalyst with a base of alumina balls shaped by oil drop - Google Patents

Abstract

Hydrocarbons are treated in the presence of a solid catalyst containing (a) a carrier with at least alumina as basic material and (b) an active phase containing at least one noble metal from group VIII of the periodic classification of elements and at least one additional metal, the alumina being at least partly shaped as balls whose manufacture involves a shaping by oil drop of an aqueous suspension or dispersion of alumina, or of a solution of a basic alumina salt, in which the aqueous alumina suspension or dispersion or the basic aluminium salt solution is an emulsion of the oil-in-water type, the emulsion viscosity being from 100 to 800 centistokes and the emulsion, formed of an organic phase, an aqueous phase and a surfactant or emulsifier, being such that the proportion of organic phase in the aqueous phase (or "hydrocarbon/free water ratio") ranges by volume, between 1 and 10%.

Description

SPECIFICATION Process for the treatment of hydrocarbons in the presence of a catalyst with a base of alumina balls shaped by oil drop This invention relates to various hydrocarbon treatments, in heterogeneous phase, in the presence of a catalyst containing (a) a matrix or carrier with alumina as basic material and (b) an active phase having as basic substances a noble metal of the VIlIth group and at least one other metal used as promoter.

At least a portion ofthe alumina matrix or carrier is used as balls manufactured according to a specific method of the invention. The so-prepared catalysts can be used for conducting such reactions as dehydration, hydrosulfuration, hydrodenetrogenation, desulfu ration, hydrodesulfu ration, dehydrohalogenation, reforming, steam-cracking, cracking, hydro-cracking, hydrogenation, dehydrogenation, isomerization, dismutation, oxychlorination, dehydrocyclization of hyd rocarbons or other organic compounds, oxidation and/or reduction reactions, the Claus reaction, the treatment of exhaust gases from internal combustion engines and demetallation.

Particularly noticeable are the catalytic reforming processes, as well as the catalytic processes for manufacturing aromatic hydrocarbons, said processes being conducted, for example, at a temperature from 400 to 600"C, under an absolute pressure from 0.1 to 5 MPa (0.1 MPa # 1 kg/cm2), at a hourly velocity ranging from 0.1 to 10 volumes of liquid charge per volume of catalyst, the hydrogen/hydrocarbons molar ratio being from 1 to 20.

There will also be mentioned, in particular, the hydrocracking reactions, generally conducted at a temperaturefrom about 260 to 530"C and under a pressure from about0.8 to 25 MPa.

The catalysts can also be used for the isomerization of aromatic hydrocarbons (e.g. xylenes) generally conducted at a temperature from about 200 to 6000C, under a pressure between about 0.005 and 7 MPa, the hourly flow rate by volume being from 0.1 to 10 times the catalyst volume.

The catalysts are further useful for the isomerization, under hydrogen atmosphere, of hydrocarbons comprising 4to 7 carbon atoms, at a temperature from 50 to 250"C.

The catalysts are also useful for the hydrodealkylation of aromatic hydrocarbons or the steam-dealkylation of aromatic hydrocarbons, said reactions being conducted under known operating conditions, usually from 300to 600"C,forexample for manufacturing benzenefromtolueneorfrom other alkyl benzenes.

The catalysts used in the above-mentioned reactions are formed of a matrix or carrier of alumina base whereon orwherein has been introduced an active phase basically consisting of a least one metal ofthe periodic classification and more frequently, since about twenty years, at leasttwo metals or more.

The catalysts with an alumina carrier base and containing a single metal, forexamplefrom group VIII, and without metal promoter, do not have their properties substantially improved when prepared according to the method disclosed in this patent. Thus, the catalysts specifically convenientforthe process according to the invention arethe catalysts comprising an alumina carrier and critical contents of various adequate metal elements (metals or metal compounds).Thus, the specific catalysts forth reforming or the production, generally contain, expressed by weight with respect to the alumina matrix or carrier (the generic term of "carrier" will be used hereinafter): a) 0.02 to 1 % of at least one first metal selected from platinum, palladium, iridium, ruthenium, rhodium and osmium (preferably platinum and/oriridium) and b) 0.01 to 2 % of at least are additional metal or promoter and, optionally, c) 0.1 to 10 % ofatleastone halogen,forexample chlorine orfluoine, for such reactions as reforming, production of aromatic hydrocarbons, certain isomerizations etc...

Particularly preferred catalysts according to the invention are those containing: - platinum - platinum and iridium - platinum and at least one metal selected from the group consisting of titanium, rhenium, tin, germanium, indium, thallium, manganese, nickel, iron, cobalt, zinc, copper, gold, silver, niobium, lanthanum, cerium, samarium, zirconium, thorium, hafnium, lead, gallium, vanadium, technetium, uranium and selenium.

- platinum, rhenium and at least one of the various metals listed above, - platinum, iridium and at least one ofthe above-listed metals, - platinum, germanium and at least one ofthe above-listed metals, - platinum,tin and at least one of the above-listed metals, - platinum, indium and/orthallium and at least one ofthe above-listed metals etc...

Table I shows in particularthe advantage ofthe process of the invention whereby the pore volume of the manufactured balls can be increased.

According to the invention,the alumina balls used as carrier are shaped by oil drop, under particular conditions which will be explained hereinafter.

It is known from the European patent application N 15801 to prepare alumina balls of double porosity by the so-called "oil drop" or"coagulation in droplets" technique.

The process described in said European patent application uses a mixture, at a pH lowerthan 7.5, of a sol of uitra-fine boehmite or pseudo-boehmite with spheroidal alumina particles (alumina proportion ranging from 30 to 95 % by weight, boehmite proportion from 5to 25 %).

The spheroida shaping and the gelation of the mixture drops are effected by dropping the mixture drops in a column containing an upper oil phase and a lower aqueous phase consisting ofan ammonia solution.

The shaping is effected in the upper phase and the gelation essentially in the lower phase. The oil temperature is generally close to room temperature, the pH ofthe ammonia solution being maintained ata value higherthan about 9.

The residence time ofthe drops in ammonia is a few minutes, generally lessthan about 15 minutes. In these conditions the resultant bal Is are sufficiently strong and are not deformed by subsequent handling.

It will be apparent that the process for manufacturing alumina according to the present invention is an important ofthe processes for manufacturing alumina balls shaped by oil drop, giving balls whose loss by attrition is very low and which are of particular interest in the catalytic processes operated with a moving or ebullated bed or with catalyst recycling.

Moreoverthe balls obtained by the process according to the invention have an increased pore volume without suffering from a substantially reduced strength. This property makes of particular interest their use as catalyst or catalyst carrier since the lightness ofthe balls reduces theirthermal inertia so thattheirtemperature of use may be attained more quickly.

According to the present invention, the process for manufacturing alumina balls comprises the shaping by oil drop of an aqueous alumina suspension or dispersion or of a solution of an aluminum basic salt, followed by the recovery oftheformed balls, drying and calcination.

The invention is characterized in that the suspension,the alumina aqueous dispersion orthe aluminum salt solution is of the oil-watertype emulsion.

The total alumina proportion by weight ofthe aqueous alumina suspension or dispersion or ofthe aluminum salt solution is, in most cases, between 5 and 30%.

This emulsion must have a viscosity from 100 to 800 centistokes (1 cSt = 1 mm2/s), preferably from 300 to 400 centistokes. Elsewhere, in the application we use the word "centipoise".

The total porevolume increase seems to be obtained as a result ofthe emulsion which generates porosity inside the ball after calcination.

A brief description ofthe main methods of the prior art using alumina shaping by oil drop, 1-from an aqueous alumina suspension ordispersion and 2-from an aluminum basic salt solution, is given hereinafter.

1/ The processes for manufacturing alumina balls comprising the oil drop shaping of an alumina suspension or dispersion, the recovery ofthe resultant balls, their drying and calcination, may be classified in three separate categories: a) Thefirstcategoryconcerns processes wherein the gelation of the drops is achieved by increasing the pH ofthe aqueous alumina suspension or dispersion.

Such processes which use either suspensions or aqueous dispersions of alumina have been extensive ly described in the literature, particularly in US patents 2 435 379,2 620 314,3 346 336,3 096 295,3 600 129,3 943 071,3 979 334,4 116 882 and in european patents No 1023 and 15 The preferred techniques are those already mentioned with reference to the euro pean patent No 15801.

b) The second category concerns processes based on the water removal from the drops of the aqueous alumina suspension or dispersion by drying or by introducing or suspending the drops in a non-miscible liquid adapted to remove water. Gelation ofthe drops then takes place. The drying orthe non-miscible liquid extract water from the drops and result in the gelation thereof in spheroidal shape.

An example of a non-miscible liquid is 2 ethyl -1hexanol or a long- chainaliphatic alcohol. The main steps ofthese processes have been described particularly by P.A. Haas, F.G. Kitts and H. Bentler in Chemical Engineering Progress Symposium series 1967,63, No 80, P.16-27, and by I. Amato and D. Martorana in Rev.

Int. Hautes Temp. et Refract. 1972, t: 9, p 197-204, c) The third category concerns pr:esses based on thecross-linking of a polymer which , Foducesthe gelation of the drops. According to these princesses, the aqueous alumina suspension or dispersion is admixed with at least one hydrosoluble monomer whose non cross-linked polymer is water soluble or forms a gel; the resultant mixture is then dispersed as drops in a hot fluid medium wherein a substantial polymerization of the monomer (e.g. ofthe acrylic type) takes place.

The main steps of this type of process have been mainly described in French patents No 2261 056 and 2 261 057.

Forthesethree categories of processes described above, is should be emphasized that the aqueous alumina suspension or dispersion usedforcarrying outthe invention must be gelatable or coagulable.

The aqueous alumina suspensions or dispersions which can be used are in particularthefine or ultra-fine aqueous boehmite suspensions or dispersion formed of particles of convenient size in the colloidal domain, i.e. lowerthan about 2000 .

The fine or ultra-fine boehmite dispersions or suspensions may be obtained by peptization in water or acidified water of these products, and particularly by the process described in French patents No 1 261 182 and 1 381 282 or in the european patent application No 15 196. The French patent No 1 261182 describes a process for manufacturing fine or ultra- fine boehmite by heating an aqueous alumina disper sioninthepresenceofa monovalentacid radical.

The French patent No 1 381 282 describes a process for manufacturing fine or ultra-fine boehmite by subjecting a suspension or cake of amorphous hydrated alumina to a temperature between 60 and 150"C, said hydrated alumina containing up to 35 % by weight of A1203 and, in proportion to said Al203 alumina, an amount of monovalent acid ions from 0.05 to 0.5.

The european patent application No 15196 describes in particular a process for manufacturing boehmite, at least partially as ultra-fine boehmite, by treating, in an aqueous medium having a pH lower than 9, a powder of active alumina obtained by quick dehydration of hydrargillite in a stream of hot gas.

It is also possible to use aqueous suspensions or dispersions of amorphous alumina gels, aluminum hydroxide or ultra-fine hydrargillite gels obtained from pseudo-boehmite.

Pseudo-boehmite may have been prepared by the process described in the US patent 3630670 by reacting an alkali metal aluminate solution with an inorganic acid solution. It may also have been prepared as described in the French patent 1.357 830 by precipitation at pH 9, at a temperature slightly above room temperature, of reactants at such concentrations asto obtain about 50 g/l of alumina in the dispersion.

The amorphous alumina gels may have been prepared in particular by the processes described in the article "Alcoa Paper N" 19 (1972) pages 9-12", more particularly by aluminate and acid reaction or by reaction of an aluminum salt with a base or of an aluminatewith an aluminum salt or by hydrolysis of aluminum alcoholates or by hydrolysis of basic aluminum salts.

The aluminum hydroxide gels may advantageously be those prepared according to the process described in the US patents No 3268295 and 3245919.

The ultra-fine hydrargillite may have been prepared in particular according to the process described in the French Patent No 1 371 808, by subjecting to a temperature between room temperature and 60"C alumina gels as a cake containing 0.10 monovalent acid ions per molecule ofAl2O3.

The aqueous suspensions or dispersions of ultrapure boehmite or pseudo-boehmite used according to the invention may be prepared according to a process performed by reacting an alkali metal aluminate with carbon dioxide to form an amorphous aluminum hydrocarbonate precipitate, the resultant precipitate being separated byfiltration and washed (such a process is described in US patent 3 268 295).

When it is desired to manufacture catalyst carriers of very pure alumina, there is preferably used ultra-pure boehmite or pseudo-boehmite aqueous suspensions or dispersions, prepared according to the above-described processes, or peptizized aluminium hydroxide gels prepared by hydrolysis of aluminu m alcoholates according to a process ofthetype described in US patent 2892858.

Thus aluminum hydroxide gels ofthe boehmite type are obtained as by-products in the manufacture of alcohol by hydrolysis of an aluminum alcoholate or alkoxide (Ziegler synthesis).

The Ziegleralcohols synthesis reactions are described in particular in US patent 2892858. According to this process triethyluminum is first prepared from aluminum, hydrogen and ethylene, the reaction being conducted in two steps with partial recycling of triethyluminum.

Ethylene is added during the polymerization step and the resultant product is then oxidized to alumi num alcoholate, the alcohols being obtained by hydrolysis.

The aluminum hydroxide paste, optionally dried and roasted, leads to appropriate alumina.

the hydrated alumina obtained as by-product in the Ziegler reaction is described in particular in a paper of the CONOCO NUT Company dated January 19,1971.

The products described in said paper are sold on the trade under the trade mark CATAPAL R, CON DEA CHEMIE Co also sells such products underthe trade marks PURAL Rand DISPURAL R.

When these hydrated aluminas are in the form of a gel, they are peptized by water or an acidified solution.

2/ The processes for manufacturing alumina balls comprising the shaping by oil drop of a solution of a basic aluminum salt, use basic salts ofthe general formula Al2 (OH)XAy, wherein 0 < x and n < y < 6, n being the number of charges ofthe anion A, the anion A being selected from : the nitrates, chlorides, sulfates, perchlorates, chloroacetates, dichloroace- tates, trichloroacetates, bromoacetates, dibromoacetates and the anions ofthe general formula:

wherein R is a radical selected from the group consisting for example of H, CH3, C2H5, CH3CH2CH2 and (CH3)2 CH.

Aluminum hydroxychlorides are generally preferred.

These basic aluminum salts may be obtained, in particular, by digestion of aluminum metal in a HA acid or in a AIA3 solution, by electrolysis of an aluminum salt solution, by neutralization of a more or less basic aluminum salt and removal of the resultant salt, by reaction of an aluminum salt with an electron donor such as ethylene oxide and removal of the reaction product, by contacting an aluminum salt with a solvent, non-miscible with water and containing a long chain aliphatic amine, followed by the recovery ofthe aqueous phase containing the basic salt and concentration thereof, by peptization of a freshly precipitated alumina gel, by attacking an aluminum oxide or hydroxide with a HA acid.

In accordance with the present invention, catalysts with an alumina base have been discovered. These catalysts, which have a good behavior in various hydrocarbon treatmeents are prepared from an aqueous alumina suspension or dispersion orfrom a solution of a basic aluminum salt, said aqueous alumina suspension or dispersion or said solution of a basic aluminum salt being used under specific conditions, as an emulsion of the oil-in-watertype, which emulsion will be subsequently poured, in orderto obtain said shaping by oil drop, into a column containing an upper organic phase and a lower aqueous phase.

It must be added that the technique according to the invention makes it possible to avoid the use of a detergent (or hydrosoluble surfactant) in the lower aqueous layer during the shaping by oil drop.

This technique is based particularly on the selection of an emulsifying agent whose H.L.B ("Hydrophilic- Lipophylic Balance") has a value differentfrom those indicated, for a similartechnique, in the French patent No 1 492326.

As it is well known, an emulsion ofthe aqueous type (orthe oil-in-watertype is heterogeneous, as it is formed by dispersing fine droplets of a liquid (hereinafter called "organic phase") into water, so that water forms a continuous phase in the presence of a surface-active agent or emulsifier, the surface-active agent or emulsifier providing for a good dispersion of the organic phase in the continuous phase (water) by modifying the properties ofthe interface between the two liquids.

According to the process ofthe invention, the dispersion, in order to form the emulsion, is effected by stirring the aqueous alumina dispersion or suspen sion orthe solution of basic aluminum salt in the presence ofthe surface-active agent oremulsifier. The so-obtained emulsion must have a viscosity between about 100 and about 800 centipoises, preferably between 300 and 400 centipoises. The above viscosi ties are measured by the so-called "Couette" method with aviscosimeterhaving co-axial cylinders (1cSt= 1 mm2/s).

The proportion by volume ofthe organic phase in the aqueous phase (the aqueous phase consisting of the free water present in the emulsion) ranges from about 1 % to about 10 %, preferably from about 4 % to about9 %; this proportion has an effectonthe mechanical strength ofthe alumina balls manufactured by the process ofthe invention. In the following disclosure the term "hydrocarbon/free water ratio" is used to express the proportion, in percent by volume, of the organic phase in the aqueous phase.

The organic phase ofthe emulsion must consist of materials not completely miscible with water, removable by combustion and liquid at room temperature. It may be selected from the dispersed phases the more frequently used industrially, pertaining to thefollow- ing categories: oils, inorganic greases and waxes, fatty substances (glycerides or cerides) and the usual solvents. But it is preferred to use petroleum materials (i.e any hydrocarbon charge of petroleum origin, for example: an oil cut) and/or kerosene, having densities close to 0.78.

The surfactant or emulsifier is so selected asto stabilizethe emulsion; it must also be removable by combustion and be liquid at room temperature and, since an oil-in-watertype of emulsion isto beformed, a surfactant having hydrophilic properties will be selected. The selection of this agent will be effected according to techniques well known in the art and described in particularinthe book"Emulsions: Theory and Practice by Paul Becher 1957-Reinhold Publishing Corporation". However it is essential that the H.L.B ("Hydrophilic- Lipophylic Balance") ofthe selected surfactant be close to that of the organic phase to be dispersed, i.e. generally in the range from 11 to 20, preferably between 12 and 18.

This particular HLB selection is importantforthe catalysts containing at least two active metals (in particular bimetallic and trimetallic catalysts). The HLB number is determined as described, for example, in the article of W.C GRIFFIN (official Digest 28, 1965, N 377446).

The proportion by weight of emulsifying agent with respect to the organic phase ranges between 2 and 8 %, preferably between 5 and about8 %.

The shaping by oil drop ofthe aqueous alumina suspension or dispersion or of the solution of a basic aluminum salt as an emulsion ofthe oil-in-water type, is then achieved according to known techniques as above indicated. The balls are then recovered, dried and calcined.

The alumina suspensions or dispersions orthe solutions of basic alumina salts, as used, may contain an alumina charge.

The proportion of charge in the solution, dispersion or suspension may be as high as 90 % byweight, expressed as Al2O3. with respect to the total alumina amount.

The size ofthe alumina particles forming the charge may vary within wide limits. Itis usuallyfrom 1 to 50 microns.

The alumina charge may be any alumina compound. It may consist, in particular, of hydrated alumina compounds such as: hydrargillite, bayerite, boehmite, pseudo-boehmite and the amorphous or essentially amorphous alumina gels. There can also be used the dehydrated or partially dehydrated forms of these compounds which consist of the transition aluminas and which comprise at least one ofthe phases selected from the group consisting of rho, chi, meta, gamma, ka^sa, that, delta and alpha aluminas.

When it is desired to manufacture catalyst carriers of very pure alumina, the preferred alumina charges arethoseobtained by dying and calcining ultra-pure boehmite or pseudo-boehmite aqueous suspensions or dispersions obtained by the above-described processes, or aluminum hydroxide gels as prepared by hydrolysis of aluminum alcoholates.

According to an embodimentofthe invention it is possible to replace a portion ofthe alumina suspen sion or dispersion or of the initial basic aluminum salt solution, by solos of other elements such as, for example, elementsfrom groups IB, IIIB, IVB,VIB, IIIA, IVA, VA, VIA,VIII ofthe periodic classification of elements; it is also possible to mixthe initial suspension or dispersion or solution with various salts, in particularthose formed with metals from groups Ig, IIB, Ills, IVB, VB, IIIAT IVA, VA, VIVA, VIII and elements from group VIB of the periodic classifica tion.

It is possible to mix the initial suspension or dispersion or solution with any compound either catalytically active or not; among the letter are to be mentioned the powders of metalsfrom groups Is, IIB, Ills, IVB, V5, Vile, IA, IIA IIIA, IVA, VA, VIA, VIIA, VIII and elements from group VIB, these powders being optionallythe metals or the elements themselves, their oxides, their insoluble salts, the solid solutions and the mixed oxidesthereof.

The characteristics ofthe balls which can be obtained by the above-described techniques are very large. These balls may, in particular, have a mono modal orbimodal pore structure with atotal pore volume ranging from 0.30 cc/g to 3 cc/g and a specific surface which may be as high as 350 m2/g and a resistance to attrition higherthan 95% and generally higherthan 98 %.

When the balls are manufactured from suspen sions or dispersions of ultra-pure alumina in the optional presence of an ultra-pure alumina charge, said balls are particularly efficient as carrier of catalysts for reactions of hydrodesu lfu rization, re forming, hydro-cracking,isomerization and steam reforming.

The following examples given in a non-limitative manner, illustrate the invention without limiting the scope thereof.

In the examples, the packed filling density (PFD) is measured as follows : a given weight of conglomer ates is introduced into a bu ret with a volume graduation. Then the buret is subjected to vibrations until the conglomerates are completely packed and theirvolume remains constant. Then the conglomer ate weight pervolume is determined.

The total pore volume (TPV) is measured as follows: the values of the grain density and of the absolute density are determined : the grain density (Gd) and absolute density (Ad) are measured bythe pic nometry method respectively with mercury and helium;theTPV is given bytheformula: 1 1 TPV = Gd Ad The specific surface (SBE) is measured bythe B.E.T method.

The mechanical strength (EGG) is measured by the grain-to-grain crushing method. It consists of measuring the maximum compression strength which can be withstood bya granule before breaking, when the product is placed between two planes moving at a constant velocity of 5 cm/mn. In the particularcase of sheres, the compression force is expressed in kilograms.

The mechanical strength (E G G) is related to the total volume (TPV) bytheSchillerlaw: B E G G = A Log Gd x TPV wherein A and B are constant. Thus, when the porosity ofthe product (T P V) increases, the E G G value decreases; it is therefore difficu It to manufacture products both porous and strong.

The resistance to attrition (A IF) is measured as the per cent of product not worn by friction according to the following method: a given volume (60 cc) of conglomerate is introduced into an overturned erlen meyerflaskofparticularconstructionwhich is connected to a metal inlet orifice. The bottom ofthe erlenmeyerflask is provided with a large outlet port (2.54 cm) covered with a sieve with openings of 1.168 mm; a strong stream of dry nitrogen is fed to the inlet orificewith the double purpose of pushing the conglomerates against each other, thus generating theirwear by friction, and of causing the impact ofthe conglomerates against the erlenmayer flask, resulting in their degradation in proportion to the impact force. The production is tested for five minutes and the remaining conglomerates are weighed.The weight decrease aftertest, expressed in percent of the initial charge, is representative ofthe resistance to attrition Al F.

The catalysts, as prepared according to the invention, are convenient for being used in a moving bed, with regeneration ofthe catalyst withdrawn from the reactors and feed back ofthe regenerated catalyst to said reactors; a preferred process makes use of several moving bed reactors and operates as follows: The charge successively passes through each reactor or reaction zone in axial or radial flow (radial meaning a direction of flow from the center to the periphery orfrom the periphery to the center). The reaction zones are arranged in series, per exemple side-by-side or superposed. Preferably the reaction zones axe placed side-by-side.The charge flows successively through each of said reaction zones, with intermediary heating there between; the fresh catalyst and the fresh charge are introduced at the top ofthefirstreaction zone; the catalystthen flows progressively downwardlythrough said zone ans is progressively withdrawn from the bottom thereof, and,through any convenient means (lift, particularly in the case of side-by-side reactors) it is conveyed to the top ofthe next reaction zone,wherethrough it flows also progressively downwardly, and soon till the last reaction zone from the bottom of which the catalyst is also progressively withdrawn and then conveyed to a regeneration zone. The catalyst recovered at the output of said regeneration zone is progressively reintroduced at the top of the first reaction zone.The various catalyst withdrawals are effected "progressively" as above indicated, i.e.

either periodically or continuously. Continuous with drawalsare preferred to periodic withdrawals.

Example 1 In a tank containing 130 liters of demineralized water are successively introduced, under strong stirring: - 2.71of63% nitricacid - 33.3 kg of aluminum hydroxide gel of the boehmitetype with a 75 % A1203 content, obtained as by-product in the manufacture of alcohol by Ziegler synthesis and sold by Condéa Company under the trade mark PURALR SB at 75 % of Al203.

- 9 kg of an alumina charge formed of the preceding gel calcined and crushed to an average diameter of the particles between 4 and 5 microns, - 7 kg of a C10 - C13 paraffinic hydrocarbon sold by BP Company, under the name"SOLARR 195-230" admixed with 450 cc of Galoryl EM 1 OR, a non-ionic emulsifying agent of H.L.B 14.

The viscosity of the suspension after 4 hours of slow stirring is 350 centipoises (1 cSt = 1 mm2/s).

The suspension contains 18.5 % of Al2O3; the proportion or percent of calcined alumina charge with respect to the total alumina is 26.5 %.

The proportion of organic phase in the aqueous phase, which is called hereinafter "hydrocarbon/free water ratio", is 5 % (byvolume).

The proportion of emulsifying agentwith respectto the hydrocarbon is 6.4 %.

The suspension falls as drops through a calibrated tube of 1.3 mm inner diameter and 1.8 mm external diameter, into a column containing an upper phase of oil of 6 cm thickness and a lower phase of ammonia solution containing 20 g/liter of NH3.

The recoyered hydrogel balls are dried and calcined at 550 C.

The caracteristics of the balls are indicated in table I.

Example 1A(comparative) The preparation of the suspension and the drops gelation are effected as in example 1.

However only 1 kg of hydrocarbon and 225cm3 of Galoryl EM 1 OR are introduced into the suspension.

The hydrocarbon/free water ratio is reduced to 0.75 %.

The caracteristics of the bnalls dried and calcuned at 500 C, are given in table I.

Example 2 The suspension is prepared and the drops gelation effected as in example 1.

No alumina charge is introduced.

In these conditions the suspension contains 15 % of Al2O3.

The hydrocarbon/free water ratio is 5 % by volume and the proportion of emulsifying agent with respect to the hydrocarbon is 6.4%.

The charcteristics ofthe dried and calcined balls are given in Table I.

Example 3 The preparation ofthe suspension as well as the gelation of the drops are effected as in example 1 but with the use of: - 2litersof63% nitricacid; - 40 kg of aluminum hydroxide gel Pural R SB, - 21.2 Kg of alumina charge - 10 kg ofthe hydrocarbon "SolparR 195-230" admixed with 500 cm3 of Galoryl EM 1 OR (H.L.B 14).

After4 hours of gentle stirring, the viscosity ofthe solution is 350 centipoises.

In these conditions, the suspension contains 25 % of Al2O3, the percent of calcined aluminium charge with respect to the total alumina amount is 40 the hydrocarbon/free water ratio is 8 % and the proportion of emulsifying agent with respect to the hydrocarbon is 5 %.

The characteristics ofthe dried and calcined balls are indicated in Table 1.

Example 4 Afiltered sodium aluminate solution, at equivalent Al203 concentration of 81 g/l and equivalentNa2O concentration of 61.6 g/l, is introduced into a glass reactor equipped with a mechanical stirrer, a thermo meter and a pH measuring electrode. Understrong stirring, a CO2 gas stream under atmospheric press ure is passedtherethrough at such a rate that a slight excess escapes from the reactor. The temperature is allowed to decrease to 400C and is maintained at said value by external cooling with cold water.

The CO2 stream is discontinued when, after 11 mn, the pH volume has decreased to 9.5 and the stirring is then continued for 5 additional minutes. The precipitate is separated by filtration and washed on a filter with permuted water at 30 C up to the obtainment of a filtrate having a resistivity of 3.1 o5 ohms.cm. A sample ofthefiltration cake dried in air at 30 c was subjected to X-ray diffraction analysis and no crystalline structure was detected. The calcination residue at 1000 C (Al203) is 51.3 % by weight.

The washed hydroxycarbonate precipitate as obtained is admixed at 200 with an aqueous ammonia solution in a sufficient amount to obtain a mixture having a resultant concentration of aluminum compound, expressed as Al2O3, of 50 g/l and a molar ratio of the NH4+ ion concentration (calculated on the assumption of a complete ionisation of ammonia, or ofthe product resulting from its reaction with the hydroxycarbonate) to the aluminium compound concentration, expressed as A12O3, 0.20.

This mixture is prepared by progressively pouring the ammonia solution into the aqueous hydroxycar bonatesolution, under strong stirring. The pH of the so-obtained aqueous medium is 10.2.

In a second step, the treatment medium from the first step is heated to 85 for 4 hours under atmospheric pressure.

In a third step, the treatment medium from the second step is heated to 150 C for 6 h. There is obtained a boehmite suspension which is filtered, washed and dried at 1000C.- In atankcontaining 9.3 liters of demineralized water are successively added, under vigorous stirring - 150cm3of63 % nitric acid, - 2160 g ofthe boehmite obtained atthe end of the above-described operations.

~ 1440 g of alumina charge obtained by calcination at 600 C of the above-described boehmite, - 720 g ofthe hydrocarbon "SolparR 195-230" admixed with 36 cm3 of Galoryl EM 10R (H.L.B.14).

The viscosity is of the same order as in the preceding examples.

In these conditions there is obtained a suspension containing 25 % ofAl2O3with a proportion of alumina charge, with respectto total alumina, of40 %, a hydrocarbon/free water ratio of 8 % and a proportion of 5 % of emulsifying agent with respect to the hydrogen.

The gelation of the drops is effected as in example 1.

The characteristics ofthe dried and calcined balls are given in Table I.

Example 5 (comparative) The suspension is prepared and the drop gelation effected as in example 1.

No hydrocarbon or emulsifying agent is added.

The hydrocarbon /free water ratio is zero.

The viscosity ofthe suspension after 4 hours of gentle stirring is 250 centipoises.

The characeristics ofthe dried balls after calcination at 550 C are indicated in Table I.

TABLE I CHARACTERISTICS OF THE BALLS

Surface BET TPV Type of pore Average diameter DRT EGG AIF Examples m/g cm /g distribution of the pore in Kg % 1 210 0.63 monomodat 90 0.650 5.2 99.9 1A 200 0.50 monomodat 90 0.810 7.1 99.9 2 200 0.56 monomodat 90 0.670 5 99.9 3 200 0.66 monomodat 90 0.620 4.8 99.9 4 220 0.62 monomodat 80 0.645 5 99.9 5 210 0.40 monomodat 90 0.850 8 99.7 (comparative) Example 6 Several catalysts are prepared with an alumina carrier, each containing, by weight, 0.4% platinum, 0.5% iridium and 1.12% chlorine.Thealumina carriers are successively each of the 5 alumina carriers prepared according to examples 1,2,3,4 and 5,there are thus obtained respectively 5 catalysts A1 to A5, which are prepared as follows: To 100 g of each alumina prepared according to examples 1 to 5 is added 100 cm3 of an aqueous solution containing: - 1.96 g of concentrated HCI (d = 1.19), - 17cm3 of a chloroplatinic acid aqueous sol u- tion containing 2.35% byweightof platinum, and - 14.5cm3 of a chloroiridic acid aqueous solution containing 2.3% byweightoriridium.

The contact is maintained for 5 hours and, after water removal and drying for one hour at 100 C, the remaining product is calcined for4 hours at 5300C in actived alumina).

Then a reduction is effected by means of a dried (with activated alumina) hydrogen streamfortwo hours at 450 C.

The specific surface and pore volume ofthe so-obtained catalysts A, to A5 are as follows: Specific surface Pore volume (m/g) (cm /g) A1 205 0.60 A2 195 0.53 A3 195 0.63 A4 215 0.59 A5 205 0.37 Example 7 In orderto obtain gasoline having a clear octane number of 103, a naphtha is used which has the following characteristics: - ASTMdistillation :80-1600C - Composition: Aromatic hydrocarbons:7% by weight Naphthenic hydrocarbons:27% by weight Paraffinic hydrocarbons:66% by weight - "Clear research" octane number: about 37 - Average molecular weight:110 - Density at 20 C:0.782 This naphtha is passed with recycle hydrogen over catalysts A1 to A5.

The operation is continuous and performed in a moving bed reactor.

The operating conditions are asfollows: - pressure :1 MPa - temperature:530 C - H2/Hydrocarbons molar ratio :8 naphtha volume/catalyst volume/hour:1.65 Table II hereinafter indicates, after 200 hours, the C5+ yield and the hydrogen content in percent of the recycle gas.

A significant increase ofthe yield and of the recycle hydrogen is observed when the catalyst is prepared according to the invention (A1 to A4) as compared with a catalyst not prepared according to the inven tion (A5).

Table II

CATALYST YIELD C5+ RECYCLE GAS % H2 (WEIGHT) (molar) A1 76.3 75.9 A2 76.4 75.8 A3 76.5 76.1 A4 76.4 76.0 A5 . 75.2 74.8 Example 8 A new series of catalysts having the same platinum and chlorine contents as catalysts A1 to A5 of example 6 is prepared.

These catalysts are manufactured from carriers prepared according to the technique of examples 1 to 5. Instead of iridium they contain 0.5 by weight of another metal promoter. Thus: The catalysts B1 and B5 contain 0.5 % of rhenium, B1 having the carrier of example 1 and B5 that of example 5. The 100 cm3 ofthe aqueous solution poured over 100 grams of alumina contain (in addition to 1.96 g concentrated HCl of density 1.19 and 17 cm3 of chloroplatinic acid aqueous solution at 2.35 % by weight of platinum), 51 cm3 of a perrhenicacid solution at 0.98% by weight of rhenium.

The catalysts C1 and C5 contain 0.5 % of tin, C1 having the carrier of example 1 and C5that of example 5.

The 100 cm3 of aqueous solution, poured in the alumina, contain 2.5 grams of a tin acetate solution at a 20 % by weight tin concentration.

The catalysts D1 and D5 contain 0.5 % ofthallium, the catalyst D1 having the carrier of example 1 and D5 that of example 5. The 100 cm of the aqueous solution, poured in the alumina, poured in the TABLE III alumina, contain 2.5 grams of a thallium acetate solution at a 20 % by weightthallium concentration.

The catalysts E1 and E5 contain 0.5% of indium, the catalyst E1 having the carrier of example 1 and the catalyst E5that of example 5. The 100 cm3 of the aqueous solution, poured in the alumina, contain 1.87 g of indium nitrate.

The catalysts F1 and F5 contain 0.5% oftitanium, the catalyst F1 having the carrier of example 1 and the catalyst F5 that of example 5. The 100 cm of the aqueous solution, poured in the alumina,contain 10.75 grams of titanium trichloride solution.

The resultant catalysts are dried, calcined and reduced as indicated for catalyst A1-A5. All the catalysts have a specific surface of 205 m/g. The pore volume of catalysts B1, C1, D1, E1 and F1 is 0.60 cm3/g, that of catalysts B2, C2, D2, E2 and F2 being 0.37 cm3/g.

Example 9 The catalysts prepared in example 8 are used for obtaining gasoline of clear octane number equal to 103 charge and the operating conditions are those of example 7. The results are given in Table Ill.

The catalysts with index 5, not conforming with the invention, give results not so good as those obtained with catalysts having index 1.

CATALYST PRECIOUS METAL METAL PROMOTER YIELD RECYCLE GAS C5+ (weight) % H2 (molar) B1 platinum rhentium 76.2 76.3 B5 platinum rhenium 74.9 75.3 C@ platinum tin 77.4 77.0 C5 platinum tin 76.5 76.1 D1 platinum thallium 77.8 77.1 D5 pLatinum thallium 76.6 76.1 E1 platinum indium 76.7 76.3 platinum indium 75.5 75.2 F1 platinum titanium 77.9 77.3 F5 platinum titanium 76.7 76.2 Example 10 The catalysts D1 and D5, E1 and E5 and F1 and F5, prepared in example 8 are used in a process for producing aromatic hydrocarbons. There is passed over these catalysts a charge whose composition by weight is asfollows:: - 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 TABLE IV The operating conditions are: - pressure:1MPa - temperature:550 C - liquid charge hourly flow rate : 3 times the catalystvolume - hydrogen/charge molar ratio : 6 The results are reported in Table IV where are indicated, in relation with the age of the catalyst, the contentbyweightof benzene,toluene, benzene + toluene in proportion to the initial charge, as well as the C5+ yield byweight. It is observed in particular that catalysts D1, E1 and F1, conforming to the invention are more stable than catalysts D5, E5 and F5 respectively.

By weight Age of Ca- CATALYST composition of talyst in 30H 200 H 400 H the product hours x |x |x - benzene 24.6 23.9 23.2 - toluene 30.2 29.5 29.1 D1 - benzene + toluene 54.8 53.4 52.1 - - C5 yield by weight 59.7 60.3 60.9 - benzene 23.9 Z2.5 19.5 -- toluene 30.4 29.1 Z7.3 - ~ benzene + toluene 54.3 51.6 46.8 - C5 yield by weight 58.9 59.9 61.4 - benzene 23.9 23.5 22.7 - toluene 32.1 31.6 30.9 E1 - benzene + toluene 56.0 55.1 53.6 - C5 yield by weight 62.1 62.5 63.2 - benzene 23.t 21.3 19.1 5 - toluene 31.3 29.8 27.8 - - benzene + toluene 54.4 51.1 46.9 - C5+ yield by weight 60.3 61.4 63.5 - benzene Z6.Z 25.7 25.1 - toluene 34.6 34.2 33.5 F1 - benzene + toluene 60.8 59.9 58.6 -C5+ yield by weight 70.9 71.1 72.0 ~ benzene 25.9 23.4 21.0 - toluene 34.2 32.6 30.3 - ~ benzene + toluene 60.1 56.0 51.3 - C5 yield by weight 70.3 72.3 74.1 Example 11 This example relates to the use of catalysts D1 and D5, E1 and E5 and F1 and F5 of example 8 for the hydrocracking of a cut distilling between 330 and 610 C, obtained by hydrotreatment of a vacuum distilate (400-650 C) of crude oil. This cut has the following characteristics: - d415:0.870 - nitrogen:5 ppm In orderto obtain a 160-340 C cut which constitutes a good "Diesel" fuel, the conditions of the reaction were thefollowing: ~ temperature:420 C - total pressure: 12 MPA - velocity (vol/vol/hour):1 - hydrogen flow rate (vol/vol of hydrocarbons: 1000 With catalyst D1 the effluent consists of: - fraction C3- 1 605C: 23.6% of the charge weight.

- fraction 1 60-3400C :48.1 % ofthe charge weight.

- fraction above 340 C: 28.3 % of the charge weight.

The 1 60-3400cfraction is an excellent "Diesel" fuel: - "Diesel" number: 73 - Cloud point lowerthan - 300C - Freezing point lower than-63 C With catalyst D5, the effluent consists of: - fraction C3- 160 C: 23.4 % of the charge weight.

- fraction 160-340'C: 47.6 % ofthe charge weight.

~ fraction above 340 C:29% of the charge weight.

The 160-3400Cfraction is a "Diesel" fuel of the same characteristics as that obtained with catalyst D1, but in this case the amount of said fraction is less than that obtained with catalyst D1.

With catalyst E1, the effluent consists of: - fraction C3- 160 C: 23.5 % ofthe charge weight.

- fraction 160-340 C:48.0 % of the charge weight.

fraction above 340 C: 28.5 % ofthe charge weight.

The 160-340 C is a "Diesel" fuel having the same characteristics as that obtained with catalyst D1.

With catalyst E5, the effluent consists of: fraction C3-160 C:23.2% of nthe charge weight.

- fraction 160-340 C: :47.9% of the charge weight.

- fraction above 340 C: 28.9 % ofthe charge weight.

The 1 60-340'C fraction is a "Diesel" fuel of the same quality asthat obtained with catalyst E1, but is obtained in a slightly loweramountthan that obtained with catalyst E1.

With catalyst F1 the effluent consists of: - fraction C3-160 C: 23.5 % of the charge weight.

- fraction 160-340 C: :48.2ofthecharge weight.

- fraction above 340ss C;28.35 of the charge weight.

The 1 60-340'Cfraction is a "Diesel"fuel of the same quality as that obtained with catalyst D1.

With catalyst F5, the effluent consists of: - fraction C3- 1 600C : 23.1 % ofthe charge weight.

- fraction 160-3400C 47.8 % of the charge weight.

- fraction above 340 C: 29.1 % of the charge weight.

The 1 60340eCfraction is a "Diesel" fuel of the same quality as those obtained with the proceding catalysts but in a slightly lower amount than the fraction obtained with catalyst F1.

Example 12 This example relates to the use of modified catalysts E1, E5, F1 and F5, for isomerizing saturated hydrocarbons.

The modification of each of these four catalysts is effected as follows. In a stainless steel reactor are placed, in fixed bed, 100 g of each catalyst E1, E5, F1 and F5 previously calcined for one hour in air at 400C.

The reactor, forthe treatment of each of these catalysts, is then scavenged with a dry hydrogen stream at a rate of 50 liters of hydrogen per liter of catalyst and per hour, at a temperature of 50 C and under an absolute pressure of 200 KPa.

After that, by means of a pump, one liter of solution containing 0.2 mole/liter of AICI2 (C2H5) in normal heptane, is introduced at a rate of 500 cm3/hour, the reactor effluent being recycled.

After eight hours of circulation, the pump is stopped, the solvent is discharged and the solid is dried under hydrogen atmosphere.

The analysis, effected on each halogenated solid, shows that each modified catalyst contains 11.7 % of chlorine and 0.34 % of platinum. Moreover, each of the modified catalysts E1 and E5 contains 0.43 % of indium and each of the modified catalysts F1 and F5 contains 0.43 % oftitanium.

The previously used tubular reactor is charged with 50 cm3 of each modified catalyst E1, E5, F1 and F5 in fixed bed in 4 successive experiments. The reactor is maintained under hydrogen stream at 150 C and 2MPa and a hydrocarbon charge containing 50 % by weight of normal pentane and 50 % by weight of normal hexamewith an additional amount of 1000 ppm by weight of carbon tetrachloride, is introduced.

The charge is fed at a rate oftwo liters per liter of catalyst and per hour, the hydrogen hourly feed rate being such as to maintain a hydrogen/hydrocarbons ratio of 3 moles/mole.

The reactor effluent has the composition reported Table V.

TABLE V

Effluent Catalyst mod:ied E E5 F1 F weight % difi d mod1fied mod1fied modiSied isopentane 28.5 27.9 28.6 27.9 normal pentane 21.5 21.9 21.5 22.1 isohexanes 43.6 43.3 43.8 43.4 normal hexane 6.4 6.9 6.1 6.6 i C5 57.0 56.0 57.1 55.8 ZC i C6 87.2 86.3 87.8 86.8 LC6 Example 13 This example relates to the use of catalysts D 1, D 5, E'1, E'5, F'1 and F'5 for reactions of aromatic hydrocarbons isomerization.Catalysts D 1 to F'5 are identical to catalysts D1 to F5, exceptthatthey have been prepared by using hydrofluoric acid instead of hydrochloric acid and that they contain 10 % by weight of fluorine. The so-prepared catalysts are used for isomerizing a metaxylene charge to paraxylene : the operation is conducted at 4300C, under a pressure of 1.2 MPa (weight of charge per weight of catalyst and per hour = 5; molar ratio hydrogen/ hydrocarbons= 5).

For a xylenes yield by weight of 99.9 % the conversion rate, to the corresponding paraxylene amountsto: - 95.3%ofthethermodynamicequilibriumwith catalyst D 1.

- 95.2 % ofthethermodynamic equilibrium with catalyst D 5.

- 95.1 % ofthethermodynamic equilibrium with catalyst E'1.

- 94.9 % of the thermodynamic equilibrium with catalyst E 5.

- 95.2 % of the thermodynamic equilibrium with catalyst F'1.

- 95.0% of nthe thermodycnamic equilibrium with catalyst F 5.

Claims (12)

1. A process for the treatment of hydrocarbons in the presence of a solid catalyst containing (a) a carrier with at least alumina as basic material and (b) an active phase containing at least one noble metal from group VIII ofthe periodic classification of elements and at least one additional metal ofthe periodic classification of elements, the alimina being at least partly shaped as balls whose manufacture involves a shaping by oil drop of an aqueous suspension or dispersion of alumina, or of a solution of a basic alumina salt, the recovery ofthe formed balls, their drying and calcination, this manufacture being characterized in that the aqueous alumina suspension or dispersion or the basic aluminum salt solution is an emulsion ofthe oil-in-water type, the emulsion viscosity being from 100 to 800 centipoises (1 cSt = 1 mm2/s), said emulsion, formed of an organic phase, an aqueous phase and a surfactant or emulsifier, being such that the proportion of organic phase in the aqueous phase (or "hydrocarbon/free water ratio") ranges byvolume, between 1 and 10% and that the proportion by weight of emulsifying agent with respect to the organic phase ranges from 2 to 8 %, said organic phase being selected from the group consisting of at least one oil cut and one kerosene, said surfactant or emulsifier having an H.L.B from 11 to 20.

2. A process according to claim 1, characterized in thatthe alumina suspension or dispersion or the basic aluminum salts solution further contains an aluminacharge,the proportion ofthecharge being up to 90 % by weight, expressed as Al2O3, with respect to the total alumina amount.

3. A process according to claim 2, characterized in that the alumina charge is selected from : hydrargil lite, bayerite, boehmite, pseudo-boehmite and amor phous or essentially amorphous alumina gels, the dehydrated or partially dehydrated forms of said compounds consisting of transistion aluminas or comprising at least one ofthe phases selected from the group consisting of rho, chi, meta, gamma, kappa, that, delta and alpha aluminas.

4. A process according to one of claims 1 to 3, characterized in that the total weight alumina concentration ofthe aqueous alumina suspension ordisper sion orofthe basic aluminum salt solution is from 5to 30%.

5. Aprocessaccordingto oneofclaims 1 to4, characterized in that the viscosity of the emulsion is from 300 to 400 centipoises (1cSt= 1mm/s).

6. A process according to one of claims 1 to 5, characterized in thatthe H.L.B of the surfactant is from 12to 18.

7. A process according to one of claims 1 to 6, wherein the catalyst contains 0.02 to 1 % of platinum and 0.02 to 1 % of iridium with respect to the alumina matrix or carrier.

8. A process according to one to claims 1 to 6, wherein the catalyst contains, by weight with respect to the alumina matrix or carrier, (a) 0.02 to 1 % of at least one precious metal of the platinum family and 0.01 to 2 % of at least one additional metal.

9. A process according to claim 8, wherein the one or more additional metal(s) is (are) selected from the group consisting of titanium, rhenium, tin, germanium, indium, thallium, manganese, nickel, iron, cobalt, zinc, coppr, gold, silver, niobium, lanthanum, cerium, samarium, zirconium, thorium, hafnium, lead, gallium, vanadium, technetium, uranium and selenium.

10. A process according to one of claims 1 to 9, applied to reactions selected from catalytic reforming, production of aromatic hydrocarbons, isomrization of paraffinic and aromatic hydrocarbons, hydrocracking, hydrodealkylation, steam-dealkylation of aromatic hydrocarbons, dehydration, hydrosulfuration, dehydrohalogenation, steam-reforming, cracking, hydrogenation, dehydrogenation, dismutation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation and/or reduction reactions, Claus reaction, the treatment of exhaust gases from internal combustion engines and demetallation.

11. A process according to Claim 1, in which the catalyst is substantially as hereinbefore described in any one ofthe foregoing Examples.

12. Hydrocarbons treated by a process according to any one of the preceding claims.