FR2537889A1 - PROCESS FOR TREATING HYDROCARBONS IN THE PRESENCE OF A CATALYST BASED ON ALUMINUM BALLS FORMED BY DROP-COAGULATION - Google Patents

Abstract

THE PRESENT INVENTION CONCERNS A PROCESS FOR TREATMENT OF HYDROCARBONS IN THE PRESENCE OF A SOLID CATALYST CONTAINING AN ALUMINA-BASED SUPPORT AND AN ACTIVE PHASE CONTAINING AT LEAST ONE NOBLE METAL OF THE PLATINUM FAMILY. AT LEAST PART OF THE ALUMINA IS USED IN THE FORM OF BALLS WHICH ARE OBTAINED BY DROP-COAGULATING A SUSPENSION OR AQUEOUS DISPERSION OF ALUMINUM OR A SOLUTION OF A BASIC SALT OF ALUMINUM IN FORM OF AN OIL-IN-WATER EMULSION. THE CATALYZERS THUS OBTAINED CAN BE USED TO PERFORM IN PARTICULAR THE REACTIONS CHOSEN FROM REFORMING, STEAM REFORMING, CRACKING, HYDROCRACKING, HYDROGENATION, DEHYDROGENATION, ISOMERIZATION, HYTERRIDDISMUTATION OR HYDRODROBIDATION AND DEHYDROGENATION. ORGANIC COMPOUNDS.

Description

The present invention relates to various treatments of hydro-

  carbides, in a heterogeneous phase, in the presence of a catalyst containing (a) an alumina matrix or support and (b) an active phase based on at least one metal of the periodic table of elements; At least a part of the alumina matrix or support is used in the form of beads, the manufacture of which is a characteristic of the invention. The catalysts thus prepared are suitable for carrying out the reactions chosen from: dehydration, hydrosulfuration, hydrodenitrification, desulphurisation, hydrodesulfurization,

  dehydrohalogenation, reforming, steam reforming, cracking,

  hydrocracking, hydrogenation, dehydrogenation, isomerism,

  disinfection, oxychlorination, dehydrocyclization of hy-

  hydrocarbons or other organic compounds, oxidation reactions

  and / or reduction, the Claus reaction, the treatment of

  exhaust of internal combustion engines, the demetallation.

  The present invention relates more particularly to reactions

  conversions of hydrocarbons and in particular hydroconversions of hydrocarbons. In particular, reforming processes (or reforming)

  catalytic processes and catalytic processes for the manufacture of

  aromatic hydrocarbons, processes carried out for example at a temperature of

  between 400 and 6000 ° C., under an absolute pressure of between

  between 0.1 and 5 M Pa, (0.1 M Pa # Ikg / cm 2) with a combined hourly speed

  between 0.1 and 10 volumes of liquid charge per volume of catalyst

  the hydrogen / hydrocarbon molar ratio being between

I and 20.

  The catalysts are also suitable for hydrocracking reactions.

  which are usually carried out at a temperature between

  The conversion conditions comprise a liquid hourly space velocity, or LHSV, or volume per hour of liquid charge at 15 ° C. per volume of catalyst, at about 260 ° C. and 53 ° C. and at a pressure of between about 0.8 and 25 ° C. from about 0.1 to 10.0, having

  preferably an upper limit of about 4.0 and a flow rate of

  hydrogenation of about 1 to 20 moles / mole of filler.

  The catalysts are also suitable for

  aromatic hydrocarbons (eg xylenes), reactions

  which are usually carried out at a temperature between

  200 and 600 ° C, at a pressure of between about 0.005 and 7 M Pa, the hourly volumetric flow being between 0.1 and 10 times

the volume of catalyst.

  The catalysts are also suitable for isomerizations, in a hydrogen atmosphere, of hydrocarbons comprising 4 to 7 carbon atoms, at a temperature of between 50 and 250 ° C., for example 100-200 ° C. The reaction is preferably carried out under a pressure of 0 ° C. , 5 to 10 M Pa, with a space velocity of 0.2 to 10 liters of charge per liter of

  catalyst and per hour The molar ratio H 12 / hydrocarbons is

  taken, for example, between O, O 01: and 10: 1 o

  The catalysts are also suitable for hygrothermal reactions.

  drodealkylation of aromatic hydrocarbons or dealkylation at

  aromatic hydrocarbon vapors, these reactions being carried out

  killed under the known operating conditions, generally between 300 and 600 C, to manufacture for example benzene from toluene

  or from other alkylbenzenes.

  The catalysts used in the reactions listed above

  consist of a matrix or a support based on alumina on the

  which or in which was introduced a so-called active phase based on

  least a metal of the periodic table and most often

  then twenty years, at least two metals and more.

  Thus, the specific catalysts suitable for the process according to the invention are catalysts containing an alumina support and critical contents of various suitable metallic elements (metals

  or metal compounds) Thus, the specific catalysts for reforming

  ming or production of aromatic hydrocarbons or other

  mentioned above, usually contain by weight

  relative to the matrix or support of alumina: (subsequently we use

  will be the general term "support") a) 0.02 to 1% of at least one first metal selected from platinum,

  palladium, iridium, ruthenium, rhodium and osmium (and of.

  preferably platinum, iridium, ruthenium and rhodium), and optionally b) 0.01 to 2% of at least one additional metal or promoter chosen

  for example, among titanium, rhenium, tin, germanium,

  dium, thallium, manganese, nickel, iron, cobalt, zinc,

  copper, silver, gold, niobium, lanthanum, cerium, salt,

  marium, zirconium, thorium, hafnium, lead, selenium, 1 o gallium, vanadium, technetium and uranium, and possibly also c) 0.1 to 10% of at least one halogen , for example chlorine or

  for reactions such as reforming, hydrocarbon

  Examples of preferred catalysts for the present invention are catalysts containing platinum, platinum and iridium, platinum and, if desired, at least one of the metals 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, iridium and tin, -

  platinum, iridium and germanium, platinum, iridium and selenium, platinum, iridium and thallium, platinum, iridium and indium, platinum, iridium and titanium, platinum, iridium and rhenium, platinum, iridium and manganese, platinum, iridium and copper or gold or silver,

  platinum, rhenium and at least one of the various metals

  above (for example selenium or any other promoter), platinum, germanium and at least one of the various metals listed above,

  platinum, tin and at least one of the various metals

  platinum, indium or thallium and at least one of the

  various metals listed above.

  Table I shows in particular the interest of the process according to the invention.

  which makes it possible to increase the pore volume of the balls produced.

  According to the invention, the alumina balls used as support

  are shaped by coagulation into drops.

  It is known from European Patent Application No. 15801 to prepare double porosity alumina beads by the technique known as

  "dripping in oil" or "dripping coagulation".

  The process described in this application comprises a mixture at a pH less than 7.5 of an ultra-fine boehmite sol or pseudo-boehmite with spheroidal particles of alumina in a proportion of

  between 30 and 95% by weight The boehmite sol has a concentration of

  between 5 and 25% The spheroidal particles of alumina are under-

  at least one of the phases included in the group consisting of

  eta, gamma, theta, delta They have a microporous volume

  taken between 0.4 and 1 cm 3 / g, their specific surface is between 350 m 2 / g and their diameter is between 1 and 50 microns, spheroidal shaping and gelling of the drops of the mixture, the recovery gelled beads, their drying and their calcination

  at a temperature for example between 550 and 1100 C.

  The spheroidal shaping and gelation of the drops of the mixture used in the process is carried out by draining the drops of the mixture into a column containing an upper phase consisting of petroleum and a lower aqueous phase constituted by a solution of ammonia. formatting is done in the

  upper phase and gelation essentially in the

  The temperature of the oil is generally close to room temperature. The ammonia solution having its pH maintained at a value greater than about 9. The residence time of the drops in ammonia is a few minutes and generally less than about 15 minutes. Under these conditions, the collected beads are sufficiently solid and are not deformed during subsequent manipulations. In the present invention, the process for producing alumina beads shaped by drop coagulation makes it possible to obtain

  balls with a very low loss of attrition and whose

  flow in catalytic processes operating in moving bed or bubbling bed or catalyst recirculation is particularly interesting.

  In addition, the beads obtained according to the process of the present invention

  feel a total increased pore volume without unduly harming their strength.

  This characteristic makes their use as catalyst or catalyst support particularly interesting because the lightness of the balls

  decreases their thermal inertia and thus makes it possible to reach

  temperature of use.

  In the present invention, the process for producing alumina beads comprises forming, by dropwise coagulation, an aqueous suspension or dispersion of alumina, or of a solution

  of a basic aluminum salt, recovery of the formed beads, drying

  ge and calcination and is characterized in that the suspension, the dis-

  aqueous alumina persion or the aluminum salt solution is in the form of an oil-in-water emulsion The total alumina concentration in the aqueous alumina suspension or dispersion or the basic salt solution of aluminum is usually between 5

and 30% in grams / liter.

  The increase in the total pore volume seems to be obtained thanks to

  to the emulsion that creates porosity inside the ball after

  cination. Processes for producing alumina beads of the type comprising shaping by drop coagulation of an aqueous suspension or dispersion of alumina, recovering the formed beads, drying and calcining are methods well known in the art. Man of Art and have been widely described in the literature One can, for example,

  classify them into three distinct categories.

  (a) The first concerns processes based on increasing

  p H of the suspension or the aqueous dispersion of alumina which pro-

is the gelation of the drops.

  Such processes which use either suspensions or aqueous alumina dispersions or solutions of basic aluminum salts have been widely described in the literature and, in particular in US Pat. Nos. 2,435,379, 2,620,314, 3,346,336, 3,096,295, 3,227,234, 3,600,129, 3,943,071, 3,979,334, 4,116,882, and

  European Patent Nos. 1023 and 15801.

  According to a preferred embodiment of the invention, the implementation

  in the form of dropwise coagulation of a suspension or dispersion

  aqueous alumina solution is operated by introducing the drops into a column containing an upper phase consisting of petroleum

  and a lower aqueous phase consisting of an ammonia solution

  The shaping takes place in the upper phase and the gelation

  mainly in the lower phase.

  oil is generally close to ambient temperature.

  The residence time of the drops in ammonia is a few minutes and generally less than about 15 minutes. Under these conditions,

  the logs collected are sufficiently strong and are not deformed

  during subsequent manipulations.

  (b) The second category concerns processes based on

  removal of water from the drops of the suspension or the aqueous dispersion

  of alumina by drying or by introduction or suspension of the drops in an immiscible liquid, capable of removing the water.

  gelling of the drops then occurs. Drying or liquid

  immiscible extract the water drops and cause gelation thereof in spheroidal form; it is possible to use, as immiscible liquid, for example 2-ethyl-1-hexanol or a long-chain aliphatic alcohol sold under the trademark Octylol.

  steps and a device for carrying out the gelling process

  cation by contacting with an immiscible liquid are in particular described in the articles by HA Haas, FG Kitts and H Bentler in Chemical Engineering Progress Symposium series 1967, 63, n 80, p 16-27.

  and I Amato and D Martorana in Rev Int High Temp and Refract.

  1972 t: 9 p 197-204 When operating by drying, the drops are usually generated in a stream of hot gas at a temperature

between 100 and 1200 C.

  (c) The third category concerns processes based on

  crosslinking of a polymer which produces the gelling of the drops.

  According to these methods, the aqueous suspension or dispersion of alumina is mixed with at least one water-soluble monomer whose non-crosslinked polymer is soluble in water or forms a gel, the mixture obtained is then dispersed in the form of drops in a medium. hot fluid o se

  produces a substantial polymerization of the monomer.

  The main stages of this type of process have notably been

  described in French patents Nos. 2 261 056 and 2 261 057.

  The beads obtained are then separated from their medium of

  lification then dried and calcined.

  For the three processes above, it will be specified that the suspension

  or the aqueous dispersion of alumina used according to the invention.

  must be gelable or coagulable.

  The aqueous suspensions or dispersions of alumina that can be used include suspensions or dispersions

  aqueous solutions of fine or ultra-fine boehmites which are composed of

  particles having dimensions in the colloidal domain, that is to say

less than about 2000A.

  The aqueous dispersions or suspensions of fine or ultrafine boehmites can be obtained as is well known in the art.

2537889-

  those skilled in the art by peptization in water or the acidulated water of these products The fine or ultra-fine boehmites used according to the

  In particular, the present invention may have been obtained according to the

  described in French Patent Nos. 1,261,182 and 1,381,282 or in European Patent Application No. 15,196. French Patent No. 1,261,182 discloses in particular a method of

  manufacture of fine or ultra-fine boehmite by heating a dispersion

  aqueous solution of alumina in the presence of a monovalent acid radical, the aqueous alumina dispersion having been obtained from chloride

  basic aluminum, basic aluminum nitrate, aluminum hydroxide

  minium, alumina gel or colloidal alumina solutions.

  French Patent No. 1,381,282 describes, in particular, a process for producing fine or ultra-fine boehmite by

  at a temperature between 60 and 150 C a suspension or a

  water of amorphous hydrated alumina salt containing up to 35% by weight of alumina counted at A 1203, and with respect to this alumina counted in molecules of A 1203, a quantity of monovalent acid ions varying from 0.05 at 0.5, for a period of 15 hours to 10 days; the cake having

  was obtained by spinning, washing and filtration of alumina gel preci

  continuously at a pH between 8 and 9 from a solution of sodium aluminate and nitric acid The specific surface of these

  products generally varies between 200 and 600 m 2 / g.

  European Patent Application No. 15,196 discloses, in particular, a

  process for the manufacture of boehmite at least partially in the form of ultra-fine boehmite by treatment in an aqueous medium having a pH of less than 9 of an active alumina powder obtained by dehydration

  rapid hydrargillite in a stream of hot gases.

  It is also possible to use the suspensions or dispersions

  aqueous solutions obtained from pseudo-boehmite, amorphous alumina gels,

  phlie, aluminum hydroxide gels or ultra-fine hydrargillite.

  The pseudo-boehmite may in particular have been prepared according to the process described in US Pat. No. 3,630,670 by reaction.

  of a solution of an alkali aluminate with a solution of a half

  It may also have been prepared as described in

  French Patent No. 1,357,830 by precipitation at pH 9, at a temperature of

  slightly lower than ambient from con-

  centrations such that about 50 g / l of alumina is obtained in the dispersion. Amorphous alumina gels may in particular have been prepared

  according to the methods described in the article "Alcoa Paper No. 19 (1972)

  9 to 12 "and in particular by reaction of aluminate and acid, or an aluminum salt and a base or an aluminate and an aluminum salt

  or by hydrolysis of aluminum oxides or by hydrolysis of salts of

aluminum alloys.

  The aluminum hydroxide gels may especially be those which have been prepared according to the processes described in the US patents

Nos. 3,268,295 and 3,245,919.

  In particular, ultra-fine hydrargillite may have been prepared separately.

  the process described in French Patent No. 1,371,808, by way of

  at a temperature between room temperature and 60 C

  of alumina gels in the form of cake and containing in relation to the aluminum

  mine counted in molecules of A 1203, 0.10 monovalent acidic ions.

  It is also possible to use the aqueous suspensions or dispersions of ultra-pure boehmite or pseudo-boehmite prepared according to a process in which the reaction of an alkaline aluminate is carried out.

  with carbon dioxide to form a hydroxycarbon precipitate

  amorphous aluminum oxide, the precipitate obtained is filtered off and then washed (the process is described in particular in US Pat. No. 3,268,295).

  a) in a first step, the washed precipitate of hy-

  amorphous aluminum hydroxycarbonate with a solution of an acid, a

  base or salt or their mixtures; this mixture is carried out in ver-

  the solution on the hydroxycarbonate, the middle fold thus constituting

  in a second step, the reaction medium thus formed is heated to a temperature of less than 90 ° C. for a time of at least 5 minutes, and c) in a third step, the medium resulting from

  the second step at a temperature between 90 C and 250 C.

  The dispersions or suspensions of boehmite and pseudo-boehmite obtained according to this process have a lower alkali content

  0.005% expressed as the weight ratio of alkali metal oxide to

Lin / A 1203.

  When it is desired to manufacture catalyst supports in

  very pure alumina, the suspensions or dispersions are preferably used.

  Aqueous boehmite or ultra-pure boehmite

  prepared according to the process described above, or the hydroxyl gels

  of peptized aluminum which have been prepared from the hydrolysis of aluminum alkoxides by a process of the type described in US Pat.

U.S. Patent No. 2,892,858.

  The following is a brief description of the manufacturing process which

  leads to such boehmite type aluminum hydroxide gels obtained as a by-product in the manufacture of the alcohol by hydrolysis of an alkoxide or aluminum alkoxide (Ziegler synthesis) Ziegler alcohol synthesis reactions are described in particular in the patent

  US Pat. No. 2,892,858. According to this method, the triturate is first prepared.

  ethylaluminium from aluminum, hydrogen and ethylene, the

  reaction being carried out in two stages with partial recycling of

  ethyl aluminum. Ethylene is added to the polymerization step and the resulting product is then oxidized to aluminum alcoholate, the alcohols

being obtained by hydrolysis.

  The aluminum hydroxide paste obtained can be optionally

  after drying and calcination, used according to the process of the invention.

  The hydrated alumina obtained as a by-product in the Ziegler reaction is described in a bulletin of the CONOCO Company dated January 19, 1971. The products described in this bulletin are marketed under the trade name CATAPAL. Moreover, CONDEA CHEMIE also sells such products under the brand names PURAL and DISPURAL O When these hydrated aluminas are in the form of a gel, they are

  peptized with water or an acidulated solution.

  2) The processes for producing alumina beads comprising shaping, by dropwise coagulation, with a solution of a basic aluminum salt using basic salts of general formula A 12 (OH) x Ay in which O x 5 and N y 6, N representing the

  number of charges of the anion A, the anion A being chosen from:

  traps, chlorides, sulphates, perchlorates, chloroacetates, dichloro-

  tate, trichloroacetates, bromoacetates, dibromoacetates and anions of general formula o

R C O

  in which R represents a radical taken from the group comprising

  H, CH 3, C 2 H 5, CH 3 CH 2 CH 2, (CH 3) 2 CH

  It is generally preferred to use aluminum hydroxychlorides. These basic aluminum salts can be obtained in particular by digestion of aluminum metal in HA acid or in a solution of A 1 A 3, by electrolysis of a sodium salt solution. aluminum, by neutralization of a more or less basic aluminum salt with a base and elimination of the salt formed; by reacting an aluminum salt with an electron donor such as ethylene oxide and removing the reaction product, by contacting an aluminum salt with a water-immiscible solvent containing a long-chain aliphatic amine then recovery of the aqueous phase containing the basic salt and concentration, by peptisation of a freshly precipitated alumina gel, by etching an oxide-or hydroxide

of aluminum by HA acid.

  3) The concentration expressed in A 1203 of the suspension, dispersion or solution is generally between 5 and 6%, it must generally be such that its viscosity is

  between 100 and 800 centipoises.

  4) According to a variant of the process of the invention, the suspensions or dispersions of alumina or solutions of basic aluminum salts used may contain a charge of alumina. The proportion of filler in the solution, dispersion or suspension can be up to 90% by weight, expressed as A 1203 by

compared to total alumina.

  The size of the alumina particles constituting the charge can vary within wide limits It is generally understood

between 1 and 50 microns.

  The alumina charge used can be any alumina compound. In particular, it is possible to use hydrated alumina compounds such as: hydrargillite, bayerite, boehmite, pseudo-boehmite and alumina gels. The amorphous or essentially amorphous forms can also be used for the dehydrated or partially dehydrated forms of these compounds which consist of transition aluminas and which comprise at least one of the phases taken from the group consisting of rh S, chi, eta, gamma, kappa,

theta, delta, alpha.

  In particular, it will be possible in particular to use aluminum charges

  obtained according to one of the processes described after possible grinding and sieving of the particles, in US Pat. No. 3,520,654, in French Patent 2,221,405, in GB 888,772, in US Pat. No. 3,630,670, in US Pat. French Patent No. 1,108,011 and in the patent

European Union No 15 196.

  It is also possible to use as feedstock alumina any

  particle of alumina obtained by grinding alumina body previously

fashioned.

  When it is desired to manufacture very pure alumina catalyst supports, it is preferable to use alumina feeds obtained by drying and calcining the aqueous suspensions or dispersions of ultra-pure boehmite or pseudo-boehmite which have been obtained according to described above, or aluminum hydroxide gels which have been prepared from hydrolysis

alcoholates of aluminum.

  According to a variant of the invention, it is possible to replace part of the suspension or dispersion of alumina or of the starting basic aluminum salt solution with soils of other elements such as, for example those, when they exist, elements of groups 'B' IIIB 'IVB, VB, VIBI III A' VA, VA, VIA, VIII of the Periodic Table; it is also possible to mix the suspension or dispersion or starting solution with various salts and in particular those consisting of the metals of groups IB 'IIB' III'B IV Be VBD IIIA 'IVA, V As VIA, VIIA, VIII and elements of

  group VIB of the Periodic Table.

  It is also possible to mix the suspension or dispersion or starting solution with any catalytically active or non-catalytic compound, among these there may be mentioned in particular: the powders of the metals of the groups IB 'IIB' III Be IVBD VB, VIIB, 'IA' " IV, VI, VIIA, VIII and Group VI elements, these powders being the metals or the elements themselves, their oxides, their salts

  insoluble solutions, solid solutions and mixed oxides thereof.

  6) According to the process of the invention, the suspension, the aqueous dispersion of alumina or the basic aluminum salt solution optionally containing a charge of alumina, is in the form of a

oil type emulsion in water.

  As is well known, an aqueous-type or oil-in-water emulsion is a heterogeneous system consisting of the dispersion of fine globules of a liquid (which will be hereinafter referred to as the "organic phase") in water in such a way that the water forms a continuous phase in the presence of a surfactant or emulsifier, the surfactant or emulsifier providing a good dispersion of the organic phase in the continuous phase (water) by

  modification of the properties of the interface between the two liquids. According to the process of the invention, the dispersion to form the emulsion is

  by stirring the dispersion or the aqueous suspension of alumina or the basic aluminum salt solution optionally containing a filler in the presence of the surfactant or emulsifier. The emulsion thus produced must

  have a viscosity of from about 100 to about 800

  tipoises and preferably between 300 and 400 centipoises Viscosities

  indicated are measured by the so-called "Couette" method, which is a

  cosimeter with coaxial cylinders (1 c St = 1 mm 2 / s).

  The volume proportion of the organic phase in the aqueous phase (the aqueous phase being represented by the free water present in the emulsion) is from about 0.5 to about 40% and preferably from about 1 to about 10%. %; this proportion, although not critical according to the process of the invention, influences the solidity

  mechanical alumina beads made by the process of the invention.

  tion. The organic phase of the emulsion must consist of products that are not completely miscible in water, that can be eliminated by combustion and that are liquid at room temperature. This can be chosen from the dispersed phases that are the most frequently encountered industrially and which are in the following categories: minerals, greases and waxes; fatty substances: glycerides or

  cerides and the usual solvents The description of these products is

  particular given in the book "The Aqueous Dispersions" Jean Poré edited by the Publications Society "Le Cuir" We will implement preferably the oils and kerosene whose density is

close to 0.78.

  The surfactant or emulsifier is chosen so as to ensure the stability of the emulsion, it must also be removable by combustion and liquid at room temperature and since it is desired to produce an oil-in-water emulsion, A choice of a surfactant with hydrophilic tendency The choice of this agent will be carried out according to the techniques well known to those skilled in the art and which are described in particular in the book "Emulsions Theory and Practice by Paul Becher 1957 Reinhold Publishing Corporation" When an organic phase such as oil or kerosene is used, the HLB ("HydrophileLipophyle-Balance") of the surfactant chosen should preferably be close to that of the organic phase to be dispersed. to be understood

* generally between 8 and 20 and more particularly from 10 to 14.

  The weight ratio of emulsifier / hydrocarbon varies widely

between 2 and 8%.

  According to the process of the invention, the drop-shaped coagulation shaping of the aqueous suspension or dispersion of alumina in the form of an oil-in-water emulsion is carried out according to the well-known methods of the invention. Those skilled in the art and who were recalled above The balls obtained are then

  recovered then dried and calcined.

  The characteristics of the beads that can be obtained according to the process of the invention are very extensive. These beads may, in particular, have a monomodal or bimodal pore structure with a total pore volume which may vary from 0.1 to 30 cm 3 / g at 3 cm 3 / g and a specific surface area of up to 350 m 2 / g and an attrition resistance greater than 95% and generally

greater than 98%.

  When the beads are manufactured from suspensions or dispersions of ultrapure alumina optionally in the presence of a charge of ultrapure alumina, these beads are particularly effective as a catalyst support for the hydrodesulfurization, reforming, hydrocracking reactions ,

  isomerization and steam reforming.

  The following examples, given in a non-limiting way, illustrate

  the invention without limiting its scope.

  In the examples, the packed filling density (DRT) is measured as follows: a given weight of agglomerates is introduced into a graduated test tube to contain the agglomerates in a given volume. The test specimen is then vibrated until at the end of any settling and until a constant volume is obtained. The weight of agglomerate which occupies a

unit volume.

  The total pore volume (VPT) is measured in the following way the value of the grain density and the absolute density are determined: the grain density (Dg) and absolute density (Da) are measured by the method of picnometry respectively with mercury and helium; the VPT is given by the formula

VPT, 1 1

  Dg -Da The specific surface area (SBE) is measured by the BE T method. The mechanical fastness (EGG) is measured by the grain-to-grain crushing method. It consists in measuring the maximum compressive force that can withstand its rupture, when the product is placed between two planes moving at the constant speed of 5 cm / min In the particular case of spheres, the

strength is expressed in kilograms.

  The mechanical fastness (EGG) is related to the total pore volume (VPT) by Schiller's law EGG = A Log BD x VPT g where A and B are constants Thus, when the product porosity (VPT) increases, the EGG decreases, so it is difficult to

  make products that are both porous and solid.

  The attrition resistance (AIF) is measured as the percentage of product not rubbed off according to the following method: a given volume (60 cm 3) of agglomerate is introduced into an inverted Erlenmeyer flask of particular construction which is connected to a metal inlet port On the bottom of the Erlenmeyer flask is placed a large outlet (2.54 cm) covered with a sieve of 1. 168 mm aperture; a strong flow of dry nitrogen is sent through the opening opening, which has two functions, on the one hand to circulate the agglomerates against each other, which leads to their wear by friction, on the other hand to cause the agglomerates clash against the Erlenmeyer flask, resulting in their degradation according to the intensity of the shock The product is tested for 5 minutes and the weight of the remaining agglomerates is weighed down The weight reduction after the test expressed as a percentage of the initial charge represents resistance to

attrition AIF.

EXAMPLE 1

  In a 250 liter tank containing 130 liters of demineralised water, 33.3 kg of boehmite-type aluminum hydroxide gel, obtained as a result of stirring strongly, with 2.700 l of 63% nitric acid, are introduced successively. by-product in the manufacture of alcohol by Ziegler synthesis and marketed by Condéa under the brand name

75% PURAL'Q @ SB at 1203,

  9 kg of an alumina feedstock consisting of the preceding gel which has been calcined at 650 ° C. and ground in such a way that the average particle diameter is between 4 and 5 microns, 7 kg of a C 10 C paraffinic hydrocarbon 13 marketed by the company BP under the name "SOLPAR 195 230" mixed with 450 cm 3 of Galoryl EM 10, a non-emulsifying agent.

ionic of H L B 14.

  The viscosity of the suspension after 4 hours of low agitation

  is 350 centipoise (1 c St = 1 mnm 2 / s).

  The suspension contains 18.5% of A 1203, the load ratio

  calcined alumina on total alumina is 26.5%.

  The proportion of the organic phase in the aqueous phase which will be called thereafter: "hydrocarbon / free water ratio" is

of 5%.

  The emulsifier / hydrocarbon ratio is 6.4%.

  The suspension, by the use of the calibrated tube of inner diameter 1.3 mm and outer diameter 1.8 mm, drops into drops in a column containing an upper phase consisting of oil to a thickness of 6 cm, and of a lower aqueous phase

  constituted by an ammoniacal solution containing 20 g / liter of NH 3.

  The hydrogel beads collected are dried and calcined at

550 C.

  The characteristics of the balls are gathered in the

Table I.

EXAMPLE 2

  The preparation of the suspension as well as the gelling of

  drops are made as in Example 1.

  There is no introduction of a charge of alumina.

  Under these conditions, the suspension contains 15% of A 203. 2 3 '

  The hydrocarbon / free water ratio is 5% and the emul-

oil / hydrocarbon is 6.4%.

  The characteristics of the dried and calcined balls are

in Table I.

EXAMPLE 3

  The preparation of the suspension as well as the gelling of

  drops are made as in Example I but by implementing

  vre: -2 liters of 63% nitric acid, 40 kg of Pural PSB aluminum hydroxide gel, 21.2 kg of alumina feed, kg of hydrocarbon "Solpar O 195-230" mixed with 500 cm 3 of

Galoryl EI 10.

  Viscosity of the suspension after 4 hours of low agitation

350 centipoises.

  Under these conditions, the suspension contains 25% of A 1203, the ratio of calcined alumina charge to total alumina is 40%, the

  hydrocarbon / free water ratio is 8% and the ratio of emulsifier

The most important hydrocarbon is 5%.

  The characteristics of the dried and calcined balls are

in Table I.

EXAMPLE 4

  A filtered solution of sodium aluminate having a concentration equivalent to A 1203 81 g / l and Na 61.3 g / 1 is introduced into a glass reactor with mechanical stirrer thermometer and measuring electrode of p H With strong stirring, a stream of gaseous CO 2 is passed at atmospheric pressure, such that a slight excess escapes from the reactor. The temperature is allowed to change to 40 ° C. and then it is fixed at this value by external circulation of cold water. the CO 2 stream when, after 11 min, the pH was lowered to -9.5, and the mixture was stirred for a further minute. The precipitate was filtered off and washed with a 30.degree. of a resistivity filtrate 3.105 ohms cm On a sample of the filter cake dried in air at 30 ° C., no diffraction X was detected

  Crystalline The calcination residue at 1000 (A 1203) is 51.3%.

  The precipitate of washed hydroxycarbonate obtained is mixed with an aqueous solution of aqueous ammonia in sufficient quantities to obtain in the mixture, on the one hand, a resulting concentration of aluminum compound expressed in A 1203 of 50 g / l and, on the other hand, a molar ratio between the concentration of NH 4 + ion (calculated by assuming the complete ionization of the ammonia or the product resulting from its reaction with the hydroxycarbonate) and the concentration of aluminum compound expressed in At 1203 of 0.20 To carry out this mixing, the ammoniacal solution is gradually poured into the aqueous suspension of hydroxycarbonate, with vigorous stirring.

  the aqueous medium thus obtained is 10.2.

  In a second step, the treatment medium from the first step is heated to a temperature of 85 for one

  time of 4 h under atmospheric pressure.

  In a third step, the treatment medium from the second step is heated at a temperature of 150 C for 6 h. A suspension of boehmite is obtained which is filtered, washed

water and dry at 100 C -

  9.3 g of nitric acid, 2160 g of the boehmite obtained from the operations described above, 1440 g of feedstock are introduced into a tank containing 9.3 liters of demineralised water, successively and with a strong stirring of 63% nitric acid. alumina obtained by calcination at 600 C of the boehmite described above, 720 g of hydrocarbon "Solpar 195-230" mixed with 36 cm 3 of

Galoryl EM l O od '.

  Viscosity of the same order as in the previous examples.

  Under these conditions, a suspension containing 25% of A 203 is obtained with a ratio of alumina feedstock to total alumina of 40%.

  a hydrocarbon / free water ratio of 8% and an emulsifying

sizing / hydrocarbon 5%.

  The gelling of the drops is carried out as in Example 1.

  The characteristics of the dried and calcined balls are

  Table 5 EXAMPLE 5 (Comparative) Preparation of the suspension and gelation of

  drops are made as in Example 1.

  There is no introduction of hydrocarbon or agent

emulsifier.

  The hydrocarbon / free water ratio is 0.

  The viscosity of the suspension after 4 hours of gentle stirring is

of 250 centipoises.

  The characteristics of the balls dried and calcined at 550 ° C. are collated in Table I.

TABLE I

CHARACTERISTICS OF BL LLES

I I I ", TI

  Surface BET VPT Type of average O of Examples m 2 / g cm 3 / g Pore distribution in A DRT EGG AIF of pores kg% I 210 0.63 monomodal 90 0.650 5.2 99.9 2200 0.56 monomodal 90 0.670 5 99.9 3200 0.66 monomodal 90 0.620 4.8 99.9 4,220 0.62 monomodal 80 0.645 5 99.9 (comparative) 210 0.40 monomodal 90 0.850 8 99.7 No. Co

EXAMPLE 6

  Several catalysts are prepared whose support is alumina and containing, by weight, each 0.4% of platinum, 0.5% of iridium and 1.12% of chlorine. As alumina supports, each of the 5 alumina supports prepared in Examples 1 to 5 to thereby obtain 5 catalysts Al to A 5, respectively, which are prepared as follows: To 100 g of each alumina prepared in Examples I to 5, 100 cm 3 of an aqueous solution containing 1.96 g of concentrated HCl (d = 1.19), 17 cm 3 of an aqueous solution of chloroplatinic acid containing 2.35% by weight of platinum, and 14.5 cm 3 of aqueous solution of 2.3% chloroiridic acid

in weight of iridium.

  The mixture is left in contact for 5 hours, filtered off and dried for one hour at 100 ° C. and then calcined for 4 hours at 5 ° C. in the air.

  dry (drying with activated alumina).

  Then it is reduced under a current of dry hydrogen (activated alumina)

for two hours at 450 C.

  The specific surfaces and porous volumes of the catalysts A 1 to A 5 thus obtained are as follows: Surface area Porous volume (m 2 / g) (cm 3 / g)

A 1 205 0.60

A 2 195 0.53

A 3 195 0.63

A 4,215 0.59

A 5 205 0.37

EXAMPLE 7

  In order to obtain a gasoline having a clear octane number (or

  103), it is proposed to treat a naphtha having the characteristics

  following characteristics: distillation AS-r I 80 160 C Composition: aromatic hydrocarbons 7% by weight naphthenic hydrocarbons paraffinic hydrocarbons number of octane "clear research" Molecular weight average density at 20 C 27% by weight 66% by weight ca 37 0.782 Ce naphtha goes on with recycled hydrogen on the catalysts

A to A 5.

  The operating conditions are as follows: pressure I M Pa temperature 5300 C molar ratio H 2 / hydrocarbons 8

  volume of naphtha / volume of catalyst / hour 1,65 -

  The following Table II shows, after 200 hours, the return

  obtained in C 5 and the percentage of hydrogen contained in the gas

recycling.

  There is a significant gain in yield and hydrogen

  cycling when the catalyst is prepared according to the invention (A 1 to A 4) relative to a catalyst not prepared according to the invention (As).

TABLE II

  CATALYST RECYCLING C GAS% H

2

(weight) (molar) Al 76.3 75.9

A 2 76.4 75.8

A 3 76.5 76.1

* A 3

A 76.4 76.0

A 75.2 74.8

EXAMPLE 8

  A new series of catalysts containing the same

  my platinum and chlorine contents than the catalysts A 1 to A 5 prepa-

res in Example 6.

  These catalysts are made from the prepared substrates.

  In the technique of Examples 1 and 5, instead of iridium, these catalysts

  The catalysts B and B contain 0.5% of rhenium, B having the support of Example I and B of Example 5. of the aqueous solution poured on 100 grams of alumina contain, (in addition to 1.96 g of concentrated HCl density 1.19 and 17 cm 3 of aqueous solution of chloroplatinic acid at 2.35% by weight of platinum. ), 51 cm 3 of a

  perrhenic acid solution at 0.98% by weight of rhenium.

  Catalysts C 1 and C 5 contain 0.5% tin, C 1 having the support of Example 1 and C 5 that of Example 5 The 100 cm 3 of the

  aqueous solution, poured into the alumina, contain 2.5 grams of

  tin acetate with 20% tin.

  The catalysts D 1 and D 5 contain 0.5% of thallium, the catalyst

  Dl having the support of Example 1 and D that of Example 5 The 100 cm 3 of the aqueous solution, poured into the alumina, contain 2.5 grams of a solution of thallium acetate containing 20 ml. % by weight of thallium. Catalysts E and E contain 0.5% indium, the catalyst

  E 1 having the support of Example I and the catalyst E 5 that of the example

  The 100 cm 3 of the aqueous solution, poured into the alumina, yields

  ferment 1.87 g of indium nitrate -

  Catalysts F and F contain 0.5% titanium, the catalyst

I 5

  F 1 having the support of example I and catalyst F 5 that of the example

  The 100 cm 3 of the aqueous solution, poured into the alumina, yields

  ferment 10.75 grams of a solution of titanium trichloride.

  We know, calcine and reduce the catalysts obtained as indi-

  The catalysts obtained all have a specific surface area of 205 m 2 / g. The pore volume of the catalysts B 1, C 1, D 1, E 1 and F 1 is 0.60 cm 3 / g. , that of catalysts B 2, C 2, D 2, E 2 and

F 2 being 0.37 cm 3 / g.

EXAMPLE 9

  The catalysts prepared in Example 8 are used to obtain a gasoline with a clear octane number of 103. The charge and the operating conditions are those of Example 7. The results are given in Table III. 'index, not in accordance with the invention, give results lower than those

assigned index 1.

TABLE III

PERFORMANCE GZRECYCLAGE

  PRECIOUS METAL METAL CATALYST PROMOTER GAS RECYCLING

  C '(weight): (molar) Bl platinum rhenium 76.2 76.3 platinum rhenium 74.9 75.3 C 1 platinum tin 77.4 77.0 C 5 platinum tin 76.5 76.1 D 1 platinum thallium 77.8 77.1 D 5 thallium platinum 76.6 76.1 E 1 platinum indium 76.7 76.3 E 5 platinum indium 75.5 75.2 F 5 F 5 platinum titanium 77.9 77.3 F 5 platinum titanium 76.7 76.2

EXAMPLE 10

  The catalysts D 1 and -D, E 1 and E 5 and F and F 5, prepare

  res in Example 8 are used in a production process of hy-

aromatic hydrocarbons.

  These catalysts are passed over with hydrogen with a charge of the following weight composition: isopentane + n pentane 1.59% isohexanes + n hexane 24.22% isoheptanes + n heptane 42.55% cyclopentane 0.13% methylcyclopentane 6 , 72% cyclohexane 5.50% C 7 naphthenes 15.81% C 8 enaphtenes 0.14% benzene 1.68% toluene 1.66% The operating conditions are as follows: pressure: M Pa temperature: 550 C flow rate liquid load schedule: 3 times the volume of the catalyst molar ratio hydrogen / charge: 6 The results are presented in tab 1 water IV where is indicated

  depending on the age of a catalyst, the benzene

  ne, toluene, benzene + toluene, relative to the initial charge, as well as the C 5 + weight yield.

  catalysts D 1, E 1 and F 1 according to the invention with respect to

  to the catalysts D 5, E and F 5.

TABLE IV

Composition Age of the cata-

  CATALYST weight in 30 H 200 H 400 H of the product hours%%% benzene 24.6 23.9 23.2 D toluene 30.2 29.5 29.1 1 benzene + toluene 54.8 53.4 52.3 weighted yield C 5 59.7 60.3 60.9 benzene 23.9 22.5 19.5 toluene 30.4 29.1 27.3 D 5 benzene + toluene 54.3 51.6 46.8 weighted yield C 58.9 59.9 61.4 benzene 23.9 23.5 22.7 E toluene 32.1 31.6 30.9 benzene + toluene 56.0 55.1 53; 6 weighted yield C 5 + 62.1 62.5 63, 2 benzene 23.1 21.3 19.1 E toluene 31.3 29.8 27.8

  E 5 benzene + toluene 54.4 51.1 46.9.

  weighted yield C 5 + 60.3 61.4 63.5 benzene 26.2 25.7 25.1 F toluene 34.6 34.2 33.5 1 benzene + toluene 60.8, 59.9 58.6 yield weighting C 5 + 70.9 71.1 72.0 benzene 25.9 23.4 21.0 toluene 34.2 32.6 30.3 F 5 benzene + toluene 60.1 56.0 51.3 + weight yield C 70.3 72.3 74.1

7037.37,

EXAMPLE 11

  This example relates to the use of catalysts D 1 and D 5, E 1 and E 5, and F 1 and F 5, of Example 8 for the hydrocracking of a distilling cup.

  between 330 and 610 C, obtained by hydrotreating a distillate under

  -of (400 650 C) of crude oil This cut has the following characteristics: d 4: 0.870 nitrogen: 5 ppm

  In order to obtain a 160-340 C fraction, constituting a good

  "Diesel", the reaction conditions are as follows: temperature: 420 C total pressure: 12 M Pa speed (vol / vol / hour): 1 flow of hydrogen (vol / hydrocarbon flight): 1000 With the catalyst D 1, an effluent is obtained consisting of: fraction C 3 160 C, 23.6% of the weight of the feed fraction 160 340 C, 48.1% of the weight of the feed fraction greater than 340 C, 28.3% of the weight of the filler The 160-340 C fraction constitutes an excellent "diesel" fuel: index "Diesel: 73 cloud point, less than 30 ° C." freezing point, lower than 63 ° C. With the catalyst D 5, an effluent is obtained consisting of: fraction C 3 160, 23.4% of the weight of the feed fraction 160 340 C, 47.6% of the weight of the feed fraction 160 greater than 340 C, 47.29% of the feed weight fraction greater than 340 C, 29% of the weight of the feed The 160340 C fraction constitutes a "Diesel" fuel of the same

  characteristic as that obtained with the catalyst D 1.

  With the catalyst E 1, an effluent is obtained consisting of: fraction C 3 160 C, 23.5% of the weight of the feed fraction 160 340 C, 48.0% of the weight of the feed fraction greater than 340 C, 28, 5% of the weight of the load The 160-340 C fraction constitutes a "Diesel" fuel of the same

  characteristics than that obtained with the catalyst D 1.

  With the catalyst E 5, an effluent is obtained consisting of: fraction C 3 160 C, 23.2% of the weight of the feed fraction 160-340 C, 47.9% of the weight of the feed fraction greater than 340 C, 28 The fraction 160-340 C constitutes a "Diesel" fuel of the same quality as that obtained with the catalyst D 1 '. With the catalyst F 1, an effluent consisting of a C 3-160 C fraction is obtained. 23.5% of the weight of the feedstock fraction 160-340 C, 48.2% of the weight of the feedstock fraction greater than 340 C, 28.3% of the weight of the feedstock 160-340 C constitutes a diesel fuel "likewise

  quality than that obtained with the catalyst Dl.

  With the catalyst F 5, an effluent is obtained consisting of: fraction C 3160 C, 23.1% of the weight of the feedstock fraction 160-340 C, 47.8% of the weight of the feedstock fraction greater than 340 C, 29, 1% of the weight of the load The 160-340 C fraction is a "Diesel" fuel

  quality (read those obtained with the previous catalysts -

EXAMPLE 12

  This example relates to the use of catalysts El, E 5, F 1 and F 5

  for isomerization reactions of saturated hydrocarbons.

  In a stainless steel tubular reactor, 100 g of the catalyst A prepared in Example 1 and beforehand are placed in a fixed bed.

  calcined one hour under air at 400 C.

  The reactor is then flushed with a stream of dry hydrogen at the rate of fifty liters of hydrogen per liter of catalyst and

  hour, at a temperature of 50 C and a pressure of 200 K Pa absolute.

  After which, one pump of solution is injected

  0.2 mol / l of A 1 C 12 (C 2 H 5) in normal heptane, at the rate of

  500 cm 3 / h and recycling the reactor effluent.

  After eight hours of traffic, we stop the pump, we evacuate

  the solvent and the solid is dried under hydrogen.

  The analysis carried out on the halogenated solid shows that it contains 11.7% by weight of chlorine, 0.34% by weight of platinum, 0.17% by weight of

  weight of tantalum and 0.26% by weight of iron.

  In the tubular reactor previously used, it has, in

  fixed bed, 50 cm 3 of catalyst The reactor being kept under control

  hydrogen at 150 ° C. and 2 ° C., a hydrocarbon feedstock is injected.

  containing 50% by weight of normal pentane and 50% by weight of normal hexane

  to which was added 1000 ppm by weight of carbon tetrachloride.

  The feedstock is injected at the rate of two liters per liter of catalyst per hour while maintaining an hourly flow of hydrogen such as the

  hydrogen / hydrocarbon ratio of 3 moles / mole.

  The reactor effluent has the following composition given in

table V.

TABLE V

EXAMPLE 13

  This example concerns the use of catalysts D'-, D'5, E'1, E'5,

  F'1 and F'5 for isomerization reactions of aromatic hydrocarbons

  The catalysts D 'to F' 5 are identical to the catalysts D 1 to F 5; however, they were prepared using hydrofluoric acid at

  instead of hydrochloric acid and they contain 10% fluorine by weight.

  The catalysts thus prepared are used to isomerize in parax-

  binds a charge of metaxylene: one operates at 430 C, under a pressure of 1.2 M Pa (weight of filler / weight of catalyst and per hour = 5;

  ratio in moles hydrogen / hydrocarbons = 5) -

  For a yield by weight of xylenes of 99.9%, a corresponding para-xylene conversion is obtained: Effluent Catalyst EEFF% by weight I 5 1 5 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 norma I hexane 6,4 6,9 6,1 6,6 i C 5 i O s 57,0 56,0 57,1 55.8 C. c 5 i C 6 87.2 86.3 87.8 86.8 .6

Z 04 6

% Z 4 6

  % 6 'i 76% 1 e 96 L here% Z 4 6 Q cl inesKlequv al Dms onb Tmuu powaqq aÉqîlnbgl -a P% ú' 6 i ze

Claims (4)

R E V E N D I C A T IO N S   1. Process for treating hydrocarbons in the presence of a catalyst   solid containing (a) a support based on alumina and (b) - an acuminate phase.   containing at least one metal of the periodic table of the elements, the alumina being used at least partly in the form of beads, the manufacture of which comprises the shaping by drop coagulation of an aqueous suspension or dispersion of alumina, or a solution of a basic aluminum salt, the recovery of the beads   formed, their drying and their calcination, this production being   characterized in that the suspension, the aqueous dispersion of alumina or the basic aluminum salt solution is in the form of an emulsion of oil type in water.   2) Process according to claim I characterized in that the suspensions or dispersions of alumina or basic aluminum salt solutions further contain an alumina filler, the proportion of filler can be up to 90% by weight expressed in A 1203 by compared to total alumina.   3) Process according to claim 2 characterized in that the alumina filler is selected from: hydrargillite, bayerite, boehmite, pseudo-boehmite and amorphous or essentially amorphous alumina gels, dehydrated or partially dehydrated of these compounds which consist of transition aluminas and which comprise at least one of the phases taken from the group consisting of rh S, chi, Jta, gamma, kappa, theta, delta, alpha. 4) Process according to claim 1 characterized in that the total concentration expressed in A 1203 of the suspension, of the   dispersion or solution is between 5 and 30%.   Method according to one of the preceding claims   characterized in that the viscosity of the emulsion is between   100 and 800 centipoise (1 c St = Imm 2 / s).   6) Process according to any one of the preceding claims   characterized in that the oil-in-water emulsion consists of an organic phase, an aqueous phase and a surfactant or emulsifier, the proportion of the organic phase in the aqueous phase being between 1 and 40%.   7) Process according to claim 6 characterized in that the phase or-   and the surfactant or emulsifier can be removed by   bust and liquids at room temperature.   7) Catalysts obtained according to one of claims I to 6 and containing   mantle in weight with respect to the 0.02 to 1% alumina matrix or support   platinum, 0.02 to 1% iridium and 0.1 to 10% of at least one halogen.   8) Catalysts obtained according to one of claims I to 6 and containing   by weight relative to the alumina matrix or support (a) 0.02 to 1% of at least one precious metal of the platinum family, 0.01 to 2%   at least one additional metal and (c) 0.1 to 10% of at least one halogen.   9) Catalysts according to claim 8 wherein the additional metal or metals are selected from the group consisting of titanium, rhenium, tin, germanium, indium, thallium, manganese,   nickel, iron, cobalt, zinc, copper, gold, silver, nickel,   bium, lanthanum, cerium, samarium, zirconium, thorium, hafnium, lead, gallium, vanadium, technetium, uranium and selenium.   ) Use of the catalysts according to claims 7 to 9 or   compounds according to one of claims I to 6, in the reactions chosen   catalytic reforming, the production of aromatic hydrocarbons   isomerization of paraffinic and aromatic hydrocarbons, hydrocracking, hydrodealkylation, steam-alkylation of aromatic hydrocarbons, dehydration, hydrosulphurization,   hydrodenitrification, desulphurisation, hydrodesulfurization, dehydration   droheating, steam reforming, cracking, hydrogenation,   dehydrogenation, disproportionation, oxychlorination, dehydrocyclization   hydrocarbons or other organic compounds, reactions of   xydation and / or reduction, the Claus reaction, the treatment of   exhaust gas from internal combustion engines and demetallation.