NL8304355A - PROCESS FOR THE TREATMENT OF HYDROCARBONS IN THE PRESENCE OF A CATALYST BASED ON ALUMINUM BULBS, WHICH ARE FORMED BY COAGULATION INTO DROPS. - Google Patents

Description

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Brief designation: Process for the treatment of hydrocarbons in the presence of an aluminum spheres catalyst formed by coagulation into droplets.

The invention relates to the treatment of various hydrocarbons, in heterogeneous phase, in the presence of a catalyst comprising (a) a matrix or a support based on aluminum oxide and (b) an active phase based on a noble metal from group VIII and based on at least one other metal used as a promoter.

At least a portion of the alumina matrix or support is used in the form of spheres the manufacture of which falls within the scope of the invention. The catalysts thus prepared are suitable for carrying out the reactions selected from the dehydration, hydrosulfation, hydronitri- fication, desulfurization, hydrodesulfurization, dehydrohalogenation, reforming, vapor reforming, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, dismutation, oxychlorination, dehydro-cyclization of hydrocarbons or other organic compounds, oxidation and / or reduction reactions, Claus reaction, treatment of exhaust gases from internal combustion engines, demetallization.

In particular, the catalytic reforming processes as well as the catalytic processes for the preparation of aromatic hydrocarbons, which can be carried out, for example, at a temperature of 400 to 600 ° C, under an absolute pressure of 0.1 to 5MPa, (0 (1 MPa, 1 kg / cm) at an hourly rate of 0.1 to 10 parts by volume of liquid feed per part by volume of catalyst, the hydrogen / hydrocarbon molar ratio being between 1 and 20.

Particular mention may also be made of the hydrocracking reactions which are generally carried out at a temperature of from about 260 to 530 ° C and under a pressure of from about 0.8 to 8304355 - 2 - *** * 25 ΜΡα.

The catalysts are also suitable for the isomerization reactions of aromatic hydrocarbons (eg, xylenes), which are generally conducted at a temperature of from about 200 to 600 ° C under a pressure of from about 0.005 to 7 MPa, the volumetric flow rate per hours is between 0.1 and 10 times the volume of the catalyst.

The catalysts are furthermore suitable for the isomerization in hydrocarbon atmosphere of hydrocarbons with 4 to 7 hydrocarbon atoms at a temperature of 50 to 250 ° C.

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

The catalysts used in the above-mentioned reactions consist of a matrix or an aluminum oxide-based support on which or in which a phase, called active phase, is applied on the basis of at least one metal from the periodic system and usually for about twenty years, at least two or more metals.

The alumina supported catalysts containing a single metal, for example, Group VIII, and without a promoter metal, have not been particularly improved in their properties when prepared in accordance with the present process.

The specific catalysts which are suitable in the process of the invention are therefore those which contain an alumina support and critical contents of various suitable metal elements (metals or metal compounds). The specific catalysts for the reforming or formation of aromatic hydrocarbons or other reactions mentioned above, 8304355-3 -C, therefore generally include in parts by weight with respect to the matrix or with respect to the alumina support: (in the following the following will be used the general term "support"): a) 0.02 to% of at least one first metal selected from platinum, palladium, iridium, ruthenium, rhodium and osmium (and preferably platinum and / or iridium) and b) 0.01 to 2% of at least one added metal or promoter and optionally also 10 c) 0.1 to 10% of at least one halogen, for example chlorine or fluorine, for reactions such as reforming, the formation of aromatic hydrocarbons, certain isomerizations and so on.

Particularly preferred catalysts for the present invention are those which include: platinum-platinum and iridium-platinum and optionally at least one of the metals selected from titanium, rhenium, tin, germanium, indium, thallium, manganese, nickel, iron, cobalt, zinc, copper, gold, silver, niobium, lanthanum, cerium, samarium, zircon, thorium, hafnium, lead, gallite techium urn, vanadium, uranium and selenium, platinum, rhenium and at least one of the various other metals mentioned above - platinum, iridium and at least one of the various metals mentioned above - platinum, germanium, and at least one of the various metals mentioned above - platinum, tin and at least one of the different metals mentioned above, 30. contain platinum, indium and / or thallium and at least one of the various metals mentioned above and so on.

Table A shows in particular the importance of the method 8304355 - 4 -

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according to the invention, whereby the pore volume of the spheres formed can be increased.

According to the invention, the aluminum oxide spheres used as a support are formed by coagulation into droplets, under special conditions which will be explained below.

From European patent application no. 1 5801 it is known to prepare aluminum oxide spheres with a double porosity according to the technique called "dripping in oil" or "coagulation to droplets".

The process described in this European patent application requires a mixture having a pH less than 7.5 of an ultrafine boehmite or pseudo-boehmite sol with spherical alumina particles (amount of alumina between 30 and 95% by weight, amount of boehmite between 5 and 25%).

Forming into spheres and gelling the drops of the respective mixture are effected by dripping the drops of the mixture 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 gelling mainly in the lower phase.

The temperature of the petroleum is generally about room temperature, while the ammonia solution has a 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 spheres are sufficiently firm and are not deformed during the subsequent treatments.

From the following, it can be seen that the alumina manufacturing process of the present invention is an improvement over the methods of producing alumina spheres coagulated by droplets and allows spheres to be obtained which have a very low loss by abrasion. and the flow of which is particularly interesting in the catalytic processes performed in a moving bed or bubbling bed with catalyst recycle.

Moreover, the spheres obtained according to the method of the invention have a total pore volume that is larger without much detracting from the firmness thereof. This property makes their use as a catalyst or catalyst support particularly interesting because the lightness of the spheres reduces their heat inertia and thus allows to reach operating temperatures very quickly.

In the present invention, the method of making alumina spheres comprises forming by coagulation into droplets an aqueous suspension or dispersion of aluminum oxide or a solution of a basic aluminum salt, then recovering the spheres formed, drying and calcining; the invention is characterized in that the aqueous suspension, the alumina dispersion or the aluminum salt solution is present in the form of an oily emulsion in water. The total concentration of aluminum oxide in the aqueous suspension or dispersion of aluminum oxide or the solution of the basic aluminum salt is generally between 5 and 30 / E in grams / liter.

This emulsion should be such that its viscosity is between 100 and 800 centipoises (1c St = 1 mm / S) and preferably between 300 and 400 centipoises.

The enlargement of the total pore volume seems to be achieved by the emulsion which forms a porosity in the bead after calcination.

The most important known methods for forming aluminum oxide by coagulation into droplets are briefly described below.

1) Starting from an aqueous suspension or dispersion of 8304355 - 6 -

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aluminum oxide and 2) starting from a solution of a basic aluminum salt.

1) The processes for making alumina spheres including molding by coagulation to droplets of an aqueous suspension or dispersion of alumina, recovering the spheres formed, drying and calcining can be classified into three separate groups.

(a) The first group relates to the methods based on increasing the pH of the aqueous suspension or alumina dispersion which promotes the gelling of the drops.

Such methods using either aqueous suspensions or dispersions of alumina have been extensively described in the literature and, in particular, in U.S. Pat. Nos. 2,435,379, 2,620,314,336,366,3,096,295,327,234 , 3 600 129, 3 943 071, 3 979 334, 4 116 882 and European Patent Nos. 1023 and 15 801. The preferred techniques are those already mentioned above with respect to European Patent 15 801.

(B) The second group relates to the methods based on withdrawing water from the drops of the aqueous suspension or dispersion of alumina by drying and by adding or suspending the drops in an immiscible liquid which can extract water. The drops then gel 25. Drying or the immiscible liquid extracts water from the drops and gels them into spheres; as immiscible liquid, for example, 2-ethyl-1-hexanol or a long chain aliphatic alcohol can be used. The main steps of such methods are specifically described in the articles of P.A. Haas, FG. Kitts and H. Bentler in Chemical Engineering Progress Symposium series 1967, 63, no. 80, pp. 16-27 and of I. Amato and D. Martorana in Rev. Int. Hautes Temp.

8304355 «« - 7 - i c et Refract. 1972 t 9, biz. 197-204.

(c) The third group relates to the methods based on the cross-linking of a polymer which results in the gelation of the drops. According to these methods, the aqueous suspension or dispersion of alumina is mixed with at least one water-soluble monomer, the polymer of which is not cross-linked and is soluble in water or forms a gel; the mixture obtained in the form of drops is then dispersed in a warm liquid medium in which an important polymerization of the monomer (for example of the acrylic type) takes place.

The main steps of this process are described, for example, in French Patents 2 261 056 and 2 261 057.

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For the above three groups of processes, it has been indicated that the aqueous suspension or dispersion of alumina used in accordance with the invention must be gellable or coagulable.

The aqueous alumina suspensions or dispersions that can be used are, for example, aqueous suspensions or dispersions of fine or ultrafine boehmites, which consist of particles of suitable sizes in the colloidal region, i.e., less than about 2000%.

The aqueous dispersions or suspensions of fine or ultra-fine boehmites can be obtained by peptization in water or weakly acidified water of these products and are obtained, for example, according to the method described in French patents 1 261 182 and 1 381 282 or in the European patent application no. 15 196.

French Patent No. 1,261,182 describes a process for producing fine or ultrafine boehmite by heating an aqueous dispersion of alumina in the presence of a group of a monovalent acid.

Hpt French Patent No. 1 381 282 discloses a process for the production of fine or ultra-fine boehmite in which a suspension or cake of amorphous hydrated alumina salt containing up to 35% by weight is used at a temperature between 60 and 150 ° C. Alumina, counted as Al 2 O 2, and with respect to this aluminum oxide, counted as molecules A 2 O 2, contains an amount of ions of monovalent acids ranging from 0.05 to 0.5.

In particular, European patent application no. 15 196 describes a process for the production of boehmite which is at least partly present as ultrafine boehmite, by treatment in an aqueous medium with a pH below 9 of an active aluminum oxide powder obtained by rapid dehydration of hydrargillite in a stream of warm gases.

The aqueous suspensions or dispersions obtained from pseudo-boehmite, gels of amorphous aluminum oxide, gels of aluminum hydroxide or ultra-fine hydrargillite can also be used.

In particular, the pseudo-boehmite may have been prepared according to the method described in U.S. Pat. No. 3,630,670 by reacting a solution of an alkali metal aluminate with a solution of an inorganic acid. It can also be prepared as described in French Patent 1 357 830 by precipitation at pH 9, at a temperature slightly above room temperature, starting from the reaction constituents at such concentrations that about 50 g / l of alumina is dispersed in the dispersion obtains.

The amorphous alumina gels can be prepared, for example, according to the methods described in the article "Alcoa Paper No. 19 (1972), pp. 9 to 12" and, for example, by reaction of aluminate and acid, or of an aluminum salt and a base or of an aluminate and an aluminum salt or by hydrolysis of aluminum aluminates or by hydrolysis of basic aluminum salts.

The aluminum hydroxide gels may be, for example, the gels, 8 3 0 4 3 5 5-9 prepared according to the methods described in U.S. Pat. Nos. 3,268,295 and 3,245,919.

For example, the ultra-fine hydrargillite can be prepared following the method described in French Patent No.

5 1 371 808, by conversion at a temperature between room temperature and 60 ° C of alumina gels in the form of a cake which, with respect to alumina, counted in molecules of AlgO 0.10.10 of monovalent acids.

It is also possible to use aqueous suspensions or dispersions of ultra-pure boehmite or of pseudo-boehmite, prepared by a process in which an alkali metal aluminate is reacted with carbon dioxide to form a precipitate of amorphous aluminum hydroxycarbonate, then the resulting precipitate is filtered off. (the method is described, for example, in U.S. Patent No. 3,268,295).

If it is desired to manufacture catalyst supports of high-purity alumina, it is preferred to use aqueous suspensions or dispersions of ultra-pure boehmite or of pseudo-boehmite, prepared according to the above-described processes, or peptized aluminum hydroxide gels, prepared by hydrolysis of aluminum alkanates according to a method as described in U.S. Patent 2,892,858.

Aluminum hydroxide gels of the boehmite type are also obtained as by-products in the preparation of alcohol by hydrolysis of an aluminum alkoxide (ziegler synthesis). Ziegler alkanols reactions are described, for example, in U.S. Pat. No. 2,892,858. This process produces first triethyl aluminum from aluminum, hydrogen, and ethylene, which reaction is conducted in two stages with partial return of triethyl aluminum.

Ethylene is added in the polymerization step and then the product obtained is oxidized to aluminum alkoxide, while 8304355 K-10 alcohols are obtained by hydrolysis.

The paste of optionally dried and calcined aluminum hydroxide results in a suitable aluminum oxide.

The hydrated alumina obtained as by-product in the Ziegler reaction was described, for example, in a report by CONOCO dated January 19, 1971. The products described in this report are marketed under the trade mark CATAPAL0. CONDEA CHEMIE also markets such products under the brand names PURAl® and DISPURAl®. When present in the form of a gel, these hydrated alumina are peptized by water or a weakly acidified solution.

2) In the methods of making alumina spheres, comprising molding by coagulation to 15 drops of a solution of a basic aluminum salt, basic salts of general formula A1 "(0H) A are used, wherein z x y

. 0 <x <5 and n <y <6, where n is the number of charges of the anion A.

wherein the anion A is selected from the nitrates, chlorides, sulfates, perchlorates, chloroacetates, dichloroacetate, trichloroacetates, bromoacetates, dibromoacetates and the anions of general formula n R - C - 0 "wherein R represents a group selected from for example h, ch3, c2h5, ch3ch2ch2, (ch3) 2ch.

Preferably, the aluminum hydroxy chlorides are generally used. These basic aluminum salts can be obtained, for example, by leaching metallic aluminum in an acid HA or in a solution of Al A3, by electrolysis of a solution of an aluminum salt, by neutralization of a more or less basic aluminum salt with a base and removal of the salt formed, by reacting an aluminum salt with an electron donor such as ethylene oxide and removing the reaction 8304355 I * - η product, by contacting an aluminum salt with a water-immiscible solvent containing a long chain aliphatic amine followed by recovering the aqueous phase containing the basic salt and concentration, by peptizing a gel of freshly precipitated alumina, by attacking an alumina or hydroxide with the acid HA. In accordance with the present invention, various hydrocarbon treatment reactions have observed the good performance of alumina-based catalysts prepared from an aqueous suspension or dispersion of alumina or from a solution of a basic aluminum salt, which aqueous suspension or dispersion of alumina or solution of basic aluminum salt under special conditions is formed into an oily emulsion in water, which is then poured, molding, by coagulation to droplets, takes place in a column containing an upper organic phase and a lower aqueous phase contains.

It is noted that one can sometimes work according to the method of the invention in the absence of a surfactant (or water-soluble surfactant) in the bottom water layer during molding by coagulation into drops.

In particular, this technique is based on the selection of an emulsifier whose HLB ("Hydrophilic-Lipophilic Equilibrium") has a value different from the% values shown for a neighboring technique in French Patent 1,492,326.

It is also known that an aqueous type of emulsion (or oil in water) is a heterogeneous system consisting of the dispersion of fine spheres of a liquid (which will hereinafter be referred to as "organic phase") in water such that the water forms a continuous phase in the presence of a surfactant or emulsifier, whereby a good distribution of the organic »304355 I« - 12 - phase in the continuous phase (water) is obtained by changing the properties of the interface between the two liquids.

According to the method of the invention, the dispersion to form the emulsion is formed by stirring the aqueous dispersion or suspension of aluminum oxide or the solution of the basic aluminum salt in the presence of the surfactant or the emulsifier. The emulsion thus formed should have a viscosity between about 100 and about 800 centimeters. i poises and preferably between 300 and 400 centipoises. The displayed viscosities are measured according to the method called "Couette" which is a viscometer with coaxial cylinders (1 c St = 1 mm / s).

The volume ratio of the organic phase in the water phase (where the water phase is represented by the water freely present in the emulsion) is between about 1 and about λ0% and at. preferably between about 4% and about 9%} this ratio affects the mechanical strength of the aluminum oxide spheres formed by the process of the invention (hereinafter, the term "Hydrocarbon / Free Water Ratio" 20 is used to determine the ratio of the organic phase in express the water phase, in parts by volume, as a percentage).

The organic phase of the emulsion should be formed from incompletely water-miscible products that can be removed on burning and are liquid at room temperature.

They can be selected from the dispersed phases which are mostly used on an industrial scale and form the following categories: oils, lubricants and mineral waxes, fats (glycerides or cerides) and conventional solvents. Preferably, however, the gasolines are used (ie any hydrocarbon-containing petroleum feed, for example: petroleum fraction) and / or kerosene whose densities are about 0.78.

The surfactant or emulsifier is chosen to ensure the stability of the emulsion, it must also be able to be removed by combustion and be liquid at room temperature, because one wishes to use an oily type emulsion in water. one will choose a surfactant 5 with hydrophilic properties. The choice of this agent is made using techniques known to those skilled in the art and described, for example, in the book "Emulsions: Theory and Practice by Paul Becher 1957 Reinhold Publishing Corporation". However, it is primarily important that the HLB ("Hydrophilic Lipophilic 10 "Balance") of the selected surfactant approximating the organic phase to be dispersed, ie generally between Π and 20 and preferably between 12 and 18.

This particular choice of the HLB is important for the catalysts containing at least two active metals (bimetal catalysts and especially trimetal catalysts). The HLB index is determined in accordance with, for example, the article by W.C. GRIFFIN (Official Digest 28, 1965, no. 377 446).

The weight ratio of the emulsifier to the organic phase varies between 2 and 8%, preferably between about 5% and 8%.

The molding by coagulation to drops of the aqueous suspension or dispersion of alumina or of the solution of a basic aluminum salt in the form of an oily emulsion in water then takes place according to known techniques which have been presented above. The spheres obtained are then collected, then dried and calcined.

The alumina suspensions or dispersions or solutions of basic aluminum salts used may contain a dose of aluminum oxide.

The amount of the dose in the solution, dispersion or suspension may be up to 90 wt.% Expressed as A 2 Og relative to the total amount of alumina.

8304355 r - Η -

The size of the alumina particles of this dosage can vary within wide limits. It can generally be between 1 and 50 microns.

The dose of alumina used can be any compound of alumina. In particular hydrated alumina compounds can be used such as: hydrargillite, bayerite, boehmite, pseudo-boehmite and the gels of amorphous or substantially amorphous aluminum oxide. It is also possible to use the dehydrated or partially dehydrated forms of these compounds, which consist of transition aluminum oxides and which contain at least one of the phases rho, chi, eta, gamma, kappa, theta, delta, alpha.

If it is desired to manufacture catalyst supports of high purity alumina, it is preferable to use dosages of alumina obtained by drying and calcining aqueous suspensions or dispersions of ultra-pure boehmite or pseudo-boehmite obtained according to the above-described processes, or Aluminum hydroxide gels prepared by hydrolysis of aluminum & anolates.

According to a variant of the invention, it is possible to replace part of the starting suspension or dispersion of alumina or of the solution of the basic aluminum salt with sols of other elements such as, for example, those of the elements of the groups Ig, Illg, IVg, Vg, VIg, III ^, IV ^, VA 'VI ^, VIII of the Periodic Table; it is also possible to mix the starting suspension or dispersion on solution with various salts and in particular those formed with the metals of the groups Ig, lig, Illg, IVg, Vg, III ^, IV ^, V ^ , VI ^, VII ^, VIII and the elements of group VIg of the Periodic Table.

It is also possible to mix the starting suspensions or dispersions or solution with any other catalytically active or non-catalytically active compound, in particular the powders of the metals of the 8304355-15 groups Ig, Hg, IHg, IVg »Vg, 11, 11 ^, III ^, V ^, VI ^, VII ^, VIII and the elements of group VIg can be mentioned, which powders include the metals or the elements themselves, their oxides, their insoluble salts, their solid solutions and the mixed oxides thereof may be 5.

The properties of the spheres that can be obtained according to the techniques described above are very extensive. In particular, these spheres may have a structure of monomodal pores or bimodal pores with a total pore volume that can vary from 0.30 on / g to 3 cm / g and a specific surface area 2 which can be up to 350 m / g and an abrasion resistance greater than 95% and generally greater than 98%.

When the beads are prepared from suspensions or dispersions of ultra-pure alumina, optionally in the presence of a dose of ultra-pure alumina, these beads are particularly effective as a catalyst support for hydrodesulfurization, reforming, hydrocracking, isomerization and reforming reactions with vapor.

The following non-limiting examples further illustrate the invention.

In the examples, the pile-filling density (DRT) is measured as follows: a certain amount of agglomerates by weight is placed in a graduated test tube to contain the agglomerates in a certain volume. The test tube 25 is then allowed to vibrate until the end of settling and until a constant volume is obtained. The agglomerate weight, which takes up a volume unit, is then calculated.

Total pore volume (VPT) is measured as follows:

The value of the grain density and of the absolute density is determined: the grain density (Dg) and absolute density (Da) are measured according to the picnometric method, with mercury respectively. with helium; where the VPT is represented by the formula: 8304353 - 16 - νρτ _ J_ _ ι_

Dg Da

The specific surface area (SBE) is measured according to the B.E.T. method.

The mechanical strength (EGG) is measured according to the 5 grain-grain crushing method. It includes measuring the maximum compression force that a grain can tolerate before breaking when the product is placed between two planes moving at a constant speed of 5 cm / min. In the special case of spheres, the force is expressed in kilos-10 grams,

The mechanical firmness (EGG) is linked to the total pore volume (VPT) according to Schiller's law: EGG = A Log * _

15 DgxVPT

where A and B are constant. Therefore, as the porosity of the product (VPT) increases, the EGG decreases; it is therefore difficult to manufacture products that are both porous and sturdy.

The abrasion resistance (AIF) is measured as the percentage of the product not worn by rubbing according to the following method: A certain volume (60 cm) of agglomerates is introduced into a tilted conical flask of special construction which is connected to a metal feed opening . A large discharge opening (2.54 cm) covered with a sieve with an opening of 1.168 mm is placed on the bottom of the conical flask; a powerful stream of dry nitrogen, which has two functions, is passed through the inlet opening, on the one hand circulating the grains with respect to each other, which leads to their wear by friction, on the other hand preventing the grains from colliding with the conical flask, 8304355 - 17 - which, depending on the intensity of the collision, leads to its disintegration. The product is tested for five minutes and the weight of the remaining grains is weighed. The weight reduction after the test, expressed as percentage 5 of the original amount, reflects the abrasion resistance AIF.

The catalysts prepared according to the invention are particularly suitable for use in a moving bed, with regeneration of the catalyst withdrawn from the reactor vessels and returning to the reactor vessels of the regenerated catalyst; a preferred method comprises using multiple moving vessel vessels which operates as follows:

The feed circulates successively in each reaction vessel or reaction zone with an axial or radial flow (radial means a flow from the center to the circumference or from the circumference to the center). The reaction zones are placed in series, for example next to each other or one above the other. Reaction zones which are placed next to each other are preferably used. The feed flows successively through each of these reaction zones, with heating of the feed between the reaction zones; the fresh catalyst is placed at the top of the first reaction zone where the fresh feed is fed; it then flows gradually from top to bottom in this zone from which it is gradually withdrawn at the bottom and by any suitable means (in particular an elevator in the case of reactor vessels placed side by side), it is led to the head of the next reaction zone in which it also flows gradually from top to bottom, and likewise thereafter to the last reaction zone from which the catalyst is also gradually withdrawn at the bottom, and then sent to a regeneration zone. When the regeneration zone is discharged, the catalyst is again gradually introduced into the top of the first reaction zone. The extraction of the catalyst several times is carried out as shown above. given in "gradual" fashion, i.e., either periodically or continuously. Continuous extraction is preferable to periodic extraction.

Example I.

5 Into a vessel containing 130 liters of demineralized water, successively, with vigorous stirring, are added: - 2700 liters of 63% nitric acid, - 33.3 kg of boehmite aluminum hydroxide gel, obtained as a by-product in the preparation of alcohol according to the Ziegler synthesis and marketed by the company Condéa under the designation PURAl® SB with 75 $ A ^ O ^ 9 kg of a dose of aluminum oxide consisting of the above gel which has been calcined at 650 ° C and crushed that the average diameter of the particles is between 4 15 and 5 microns, 7 kg of a paraffinic hydrocarbon with 10-13 carbon atoms sold by BP under the designation "SOLPAi ^ 195-230", mixed with 450 ml of Galoryl EM 1 (^, a non-ionic emulsifier with H.L.B. 14.

The viscosity of the suspension after 4 hours of gentle stirring is 350 centipoise (1cSt = 1mm / s).

The suspension contains 18.5% by weight, the ratio or percentage of dosage of calcined alumina to total alumina is 26.5%.

The amount of organic phase in the water phase which will hereinafter be referred to as "hydrocarbon / free water ratio" is 5 vol.

The emulsifier to hydrocarbon ratio is $ 6.4.

Using the calibrated tube 30 with an internal diameter of 1.3 mm and an external diameter of 1.8 mm, the slurry falls as drops into a column containing an upper phase, consisting of 6 cm thick petroleum, and a lower aqueous phase, consisting of an ammonia solution containing 20 g / l NH 4, 8304353-19.

The collected hydrogel spheres are dried and calcined at 550 ° C.

The properties of the spheres are shown in Table A. Example 1A (comparative example).

The preparation of the suspension as well as the gelling of the drops was carried out according to example I.

However, only 1 kg of hydrocarbon and 225 cm3 of Galoryl EM 10® are introduced into the suspension.

10 The hydrocarbon / free water ratio is not more than 0.75%,

The properties of the dried spheres calcined at 550 ° C are shown in Table A.

Example II.

The preparation of the suspension as well as the gelling of the drops were carried out as in example I.

A dose of aluminum oxide has not been added

Under these conditions, the suspension contains 15% A 2 O 2.

The hydrocarbon / free water ratio is 5% by volume and the amount of the emulsifier relative to the hydrocarbon is 6.4%. 20 The properties of the dried and calcined spheres are shown in Table A.

Example III.

The preparation of the suspension as well as the gelling of the drops was carried out as in example I, but using: - 2 liters of 63% nitric acid,

- 40 kg gel of aluminum hydroxide Pural ^ SB

- 21.2 kg aluminum oxide dosage, - 10 kg of the hydrocarbon "Solpar® 195-230", mixed with 500 30 cm3 Galoryl EM 10® (H.L.B. 14).

The viscosity of the suspension after light stirring for 4 hours: 350 cP. Under these conditions, the slurry contains 25% by weight, the per 8304335

I I

- 20 percent of the dosage of calcined alumina to the total alumina is 40 $, the hydrocarbon / free water ratio is 8 $, and the percentage of the emulsifier to the hydrocarbon is 5%.

5 The properties of the dried and calcined spheres are shown in Table A.

Example IV.

A filtered solution of sodium aluminate at a concentration corresponding to 81 g / 1 A ^ O ^ and 61.3 g / 1 Να2 © is placed in a glass reaction vessel equipped with a mechanical stirrer, thermometer and electrode for measuring the pH . With vigorous stirring, a gaseous (X 2) stream is passed through at atmospheric pressure, so that a small excess escapes from the reaction vessel. The temperature is allowed to rise to 40 ° C, then it is maintained at this value by external circulation with cold water. The (X 2) stream is stopped when, after 11 minutes, the pH is lowered to 9.5, and the mixture is stirred for an additional 5 minutes. The precipitate is filtered off and washed on the filter with water permuted at 30 ° C until obtain a filtrate 5 with a resistivity of 3.10 ohm.cm. In a sample of the filtered cake dried in air at 30 ° C, no crystalline state is detected by X-ray diffraction. The residue obtained after calcination at 1000 ° C (A ^ O ^) is 51.3 wt.%.

The resulting precipitate of washed hydroxycarbonate is mixed at 20 ° C with an aqueous ammonia solution in sufficient quantities to give in the mixture, on the one hand, a final concentration of the aluminum compound, expressed in A ^ Og, of 50 g / l and, on the other hand, a molar ratio between the concentration of NH ^ + ions (calculated by the full ionization of ammonia or the product obtained by assuming its reaction with hydroxycarbonate) and the concentration of aluminum compound, expressed in A ^ Og, of 0.20 to to gain. To obtain this mixture, the ammonia solution is gradually poured into the aqueous suspension of hydroxycarbonate, with vigorous stirring. The pH of the aqueous medium thus obtained is 10.2.

In a second stage, the treatment medium from the first stage is heated for 4 hours, under atmospheric pressure, at a temperature of 85 °.

In a third stage, the treatment medium from the second stage is heated at a temperature of 150 ° C for 6 hours. A boehmite suspension is obtained which is filtered off, washed with water and dried at 100 ° C.

Into a vessel containing 9.3 liters of demineralized water, one is charged successively with vigorous stirring: 3 - 150 cm of 63% nitric acid, - 2160 g of the boehmite obtained from the operations described above, - 1440 g of aluminum oxide dosage obtained by calcination at 600% of the boehmite described above, 3 - 720 g of hydrocarbon "Solpar ^ 195-230", mixed with 36 cm of Galoryl EM 10® (HLB 14).

The viscosity is of the same order of magnitude as in the previous examples.

Under these conditions, a slurry containing 25% AlgOg with an amount of the alumina dosage to the total alumina of 40%, a hydrocarbon / free water ratio of 8% and a percentage of the emulsifier to the hydrocarbon of 5 $.

The gelling of the drops was carried out as in example I.

i

The properties of the dried and calcined spheres are shown in Table A.

30 Example V (comparative),

The preparation of the suspension as well as the gelling of the drops was carried out as in example I.

3304355 - 22 -

No hydrocarbon or emulsifier is added.

The hydrocarbon / free water ratio is equal to 0.

The viscosity of the suspension after 250 hours of gentle stirring is 250 centipoise.

The properties of the dried spheres calcined at 550 ° C are shown in Table A.

- TABLE A - 8304355 - 23 -

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Example VI.

Several catalysts are prepared, the support of which is aluminum oxide, each containing 0.4 wt.% Platinum, 0.5 wt. Iridium and 1.12 wt.% Chlorine. As alumina support, 5 of each of the five alumina supports prepared in Examples I, II, III, IV and V are used in succession, so as to obtain 5 catalysts to Ag, respectively, prepared as follows:

To 100 g of each alumina prepared in Examples 3 I to V is added 100 cm 3 of an aqueous solution containing: 10 1 1 96 g concentrated HCl (d = 1.19), 3 - 17 cm of a aqueous solution of chloroplatinic acid with 2.35 wt.% platinum, 3 and 14.5 cm. of an aqueous solution of chloriridic acid with 2.3 wt.% iridium.

This is allowed to contact each other for 5 hours, aspirated and dried at 100 ° C for 1 hour, then calcined at 530 ° C for 4 hours with dry air (dried with activated alumina).

It is then reduced for 2 hours at 450 ° C under a stream of dry hydrogen (activated alumina).

The specific surfaces and pore volumes of the catalysts Aj to Ag thus obtained are as follows:

Specific surface area Pore volume (m / g) (cm / g) A1 205 0.60 25 A2 195 0.53 A3 195 0.63 A4 215 0.59

Ag 205 0.37

Example VII.

30 To obtain a gasoline with an octane number "clair" of 103, treat a light tar oil with the following properties: 8304355

----- J

* I

- 25 -

- distillation A5 ™: 80-160 ° C

- composition: aromatic hydrocarbon I

fabrics: 7 wt%

naphthenic hydrocarbons: 27 wt% I

5 paraffinic hydrocarbons: 66 geu,% I

- octane number "dear research": approximately 37 I.

- average molecular weight: 110 I.

density at 20 ° C: 0.782

This light tar oil is fed with recycled hydrogen I.

10 on catalysts A-j to Ag. I

It is operated continuously in a moving bed reactor. The export I

ring conditions are as follows: I

- pressure: 1 M Pa I.

- temperature: 530 ° C]

15 - molar ratio Hg / hydrocarbons; 8 I

- parts by volume of light tar oil / parts by volume I.

catalyst / hour: 1.65 I.

Table B below lists the yield of Cg + obtained after 200 hours and the percentage of hydrogen present in I.

20 the return gas.

Significant gains in yield and in the hydrogen recycle are observed when the catalyst is prepared according to the invention (Aj to A ^) over a catalyst.

lyser not prepared according to the invention (Ag).

- TABLE B - 8304333 - 26 -

TABLE B

Catalyst Yield Cg + $ Hg in recycle gas (wt.) (Molar) A1 76.3 75.9 A2 76.4 75.8 A3 76.5 76.1 5 A4 76.4 76.0

Ag 75.2 74.8 Ί —.................................. I ...... .......................... {....... .....——

Example VIII.

A new series of catalysts containing the same amounts of platinum and chlorine as the A 10 to Ag catalysts prepared in Example 6 are prepared.

These catalysts were prepared from the supports prepared by the process of Examples I and V. Instead of iridium, these catalysts contained 0.5 wt.% Of another metal promoter:

Catalysts B 2 and Bg contain 0.5% rhenium, B 15 containing the support of Example I and Βς that of Example V. The 100 ml of the aqueous solution poured onto 100 g of aluminum oxide contains (in addition to 1.96 concentrated HCl with a density 3 of 1.19 and 17 cm of an aqueous chloroplatinic acid solution containing 2.35 3 wt.% Platinum) 51 cm of a perrhenic acid solution with 0.98 wt.

20 $ rhenium.

The catalysts and Cg contain 0.5% tin, the support of Example I and Cg containing that of Example V. The 100 ml of the aqueous solution poured onto the aluminum oxide contains 8304355 ______________ ....... __1 - 27 -

2.5 g tin acetate solution with 20 µl tin. I

The catalysts and contain 0.5 ^ thallium, with I.

the catalyst D. the support of example I and D_ that of example I.

3 ° I

V contains. The 100 cm of the aqueous solution poured on the I

Aluminum oxide, contains 2.5 g of a thallium acetate solution containing I.

20 wt. Thallium. I

The catalysts and contain 0.5 ^ indium, the I

catalyst E. the support of example I and the catalyst E- which I.

3 ° I

of example V. The 100 cm of the aqueous solution, from I

10 cast on the alumina, contains 1.87 g of indium nitrate. I

The catalysts contained 0.5j titanium, the 1

Catalyst F- the support of Example I and Catalyst F1 which is I.

3 ° I

of example V. The 100 cm of the aqueous solution, from I

cast on the alumina, contains 10.75 g of a titanium tri-I

chloride solution. I

The resulting catalysts are dried, calcined and reduced as shown for catalysts A-j-A, .. The I obtained

catalysts all have a specific surface area of 205 ml / g.

The pore volume of the catalysts B ^, C ^, D ^, Ey and F ^ is 0.60 cm ^ / g, that of the catalysts BE-2 and I

cmVg.

Example IX. I

The catalysts prepared in Example VIII are used to obtain a gasoline having an octane "clear" equal to 103. The feed and operating conditions are those of Example VII. The results are shown in Table C.

The catalysts bearing the number 5, not according to the invention, give results lower than those I.

which have the number 1.

- TABLE C - 8304353 30 - 28 -

TABLE C

Catalyst Precious Metal Metal Yield # Hg in back promoter Cg + (wt.) Feed gas (molar) B.j platinum rhenium 76.2 76.3 5 Bg platinum rhenium 74.9 75.3

Cj platinum tin 77.4 77.0

Cg platinum tin 76.5 76.1 D. platinum thallium 77.8 77.1

Dg platinum thallium 76.6 76.1 10 Eg platinum indium 76.7 76.3

Eg platinum indium 75.5 75.2

Fj platinum titanium 77.9 77.3

Fg platinum titanium 76.7 76.2

Example X.

The catalysts D 1 and D g, E 2 and Eg and F 2 and F g, prepared in Example 8, have been used in a process for the preparation of aromatic hydrocarbons.

These catalysts, with hydrogen, are passed over a feed of the following weight composition; 20 - isopentane + n. pentane ................. 1.59 # - isohexanes + n. hexane ................. 24.22 # - isoheptanes + n. heptane ................. 42.55 # - cyclopentane ................. 0.13 # 8304355 '... ..— 'II' · '- 29 - - cyclohexane 5.50% - methylcyclopentane .. ·····. ··. ·. ···· 6.7 ^ - af naphthenes with Cy .... ............. 15.81j - 21 toes with Cg ................. 0.14% 5 - benzene .... ............. 1.68% - toluene 1.66 ^ 100%

The operating conditions are as follows: - pressure: 1 MPa

- temperature: 550 ° C

10 - flow rate of the liquid feed per hour: 3 times the volume of the - hydrogen / feed molar ratio: 6 catalyst in which,

The results are shown in Table D / as a function of the age of a catalyst, the weight amounts of benzene, toluene, benzene + toluene, relative to the original feed, and the weight yield Cg + are shown. In particular, a better stability of the catalysts D.j, E.j and according to the invention with respect to the catalysts Dg, Eg and Fg is observed.

- TABLE D - 8304355 - 30 -

TABLE D

Catalyst Weight composition - 30 h 200 h 400 h 400 h The catalyst in%%% product in hours - benzene 24.6 23.9 23.2 - toluene 30.2 29.5 29.1 D1 - benzene + toluene 54 .8 53.4 52.3 - weight yield Cg + 59.7 60.3 60.9 - benzene 23.9 22.5 19.5 - toluene 30.4 29.1 27.3 ^ 5 - benzene + toluene 54, 3 51.6 46.8 - weight yield C ^ + 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 - weight yield Cj- + 62.1 62.5 63.2 - benzene 23.1 21.3 19.1 - toluene 31.3 29.8 27.8 E5 - benzene + toluene 54, 4 51.1 46.9 - weight yield C ^ + 60.3 61.4 63.5 - benzene 26.2 25.7 25.1 - toluene 34.6 34.2 33.5 E1 - benzene + toluene 60, 8 59.9 58.6 - weight yield Cg + 70.9 71.1 72.0 - benzene 25.9 23.4 21.0 - toluene 34.2 32.6 30.3 E5 - benzene + toluene 60.1 56 , 0 51.3 - weight yield 0ς + 70.3 72.3 74.1 3304355 - '--------- »ï - 31 -

Example XI.

This Example relates to the use of the catalysts Dj and D, f and Eg, and and Fg, of Example VIII for hydrocracking a fraction distilling between 330 and 610 ° C, obtained by hydrotreating under vacuum (400 -650 ° C) of a crude oil distillate. This fraction has the following properties: - d] 5: 0.870 - nitrogen: 5 ppm 10 To obtain a fraction of 160-340 ° C, which forms a good "Diesel" fuel, the reaction conditions are as follows:

- temperature: 420 ° C

- total pressure: 12 MPa - speed (vol / vol / hour): 1 15 - hydrogen flow (vol./vol.hydrocarbons): 1000

With catalyst Dj, an effluent consisting of: - fraction C 1 -10 6, 23.6 wt. / C of the feed, - fraction 160-340 ° C, 48.1 wt. Of the feed, - fraction higher than 340 ° C, 28.3 wt.% of the feed.

The fraction 160-340 ° C forms an excellent "Diesel" fuel: - "Diesel" index: 73

cloud point, below -30 ° C

- freezing point, below -63 ° C.

With catalyst Dg, an effluent consisting of: 25 - fraction C 1 - 10 10 ^ 23.4 wt.% Of the feed - fraction 160-340 ° C, 47.6%,% of the feed - fraction higher than 340 ° C, 29 wt.% Of the feed.

The fraction 160-340 ° C forms a "Diesel" fuel with the same characteristic as that obtained with catalyst D4, but this fraction is somewhat less important here than that obtained with catalyst Dj.

With catalyst Ej, an effluent consisting of: 8304355 ir - 32 - - fraction C3-160 ° C, 23.5 wt.% Of the feed - fraction 160-340 ° C, 48.0 wt. # Of the feed - fraction higher than 340 ° C, 28.5 wt.% of the feed.

The fraction 160-340 ° C forms a "Diesel" fuel with the same properties as that obtained with catalyst Dj.

With catalyst Eg, an effluent consisting of: - fraction C3 -160 ° C, 23.2% by weight of the feed - fraction 160-340 ° C, 47.9% by weight of the feed - fraction higher than 340 ° C, 28.9 wt.% Of the feed.

The fraction 160-340 ° C forms a "Diesel" fuel of the same quality as that obtained with catalyst Ej, but is present in a slightly minor amount compared to that obtained with catalyst Ej.

With catalyst Fj, an effluent consisting of: 15 - fraction C3-160 ° C, 23.5% by weight of the feed - fraction 160-340 ° C, 48.2% by volume of the feed - fraction higher than 340 ° C, 28.3% by weight of the feed.

The 160-340 ° C fraction forms a "Diesel" fuel of the same quality as that obtained with catalyst Dj.

With catalyst Fg, an effluent consisting of: - fraction C3-160 ° C, 23.1 wt.% Of the feed - fraction 160-340 ° C, 47.8 wt.% Of the feed - fraction higher than 340 ° C, 29.1 wt.% Of the feed.

The 160-340 ° C fraction forms a "Diesel" fuel of the same quality as that obtained with the previous catalysts, but is slightly less important than the fraction obtained with catalyst Fj.

Example XII.

This example relates to the use of the catalysts Ej, Eg, Fj, and Fg, which have been modified for the isomerization reactions of saturated hydrocarbons.

To carry out the modification of each of these four catalysts, one successively charges 100 g of each catalyst Ej, Ε ^, Fj and Fg into a tubular stainless steel reaction vessel in a fixed bed. calcined under air at 400 ° C for hours.

Before the treatment of each of these catalysts, the reactor is purged with a stream of dry nitrogen in an amount 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. Then, with the aid of a pump, 1 liter of solution containing 0.2 mol / 3 10 liters of AlC (Hg) in n-heptane is injected in an amount of 500 cm / h and by returning the effluent from the reactor.

After circulating for 8 hours, the pump is stopped, the solvent is extracted and the solid is dried under hydrogen.

Analysis 15 carried out with each halogenated solid shows that each of the modified catalysts contains 11.7 wt.% Chlorine and 0.34 wt.% Platinum; in addition, the modified catalysts E 1 and Eg each contain 0.43 $ indium and the modified catalysts F 1 and F g each contain 0.43 $ titanium.

In the previously used tubular reaction vessel, 50 cm 2 of each modified catalyst E.j, Eg, Fj and Fg are introduced in four successive fixed bed runs. A hydrocarbon feed containing 50 wt.% N-pentane and 50 wt.% N-hexane to which 1000 wt.% Carbon tetrachloride has been added is injected into the reactor which is maintained under a circulation of hydrogen at 150 ° C and 2 MPa. The feed is injected in an amount of 2 liters per liter of catalyst and per hour and by maintaining an hydrogen flow rate per hour such that the hydrogen / hydrocarbon ratio is equal to 3 mol / mol.

The reactor effluent has the composition shown in Table E.

- TABLE E - 83043 = - 34 -

TABLE E

•

Effluent catalyst E ^ Eg Fj Fg ^ ew *% Modified Modified Modified Fied Fied Fied Isopentane 28.5 27.9 28.6 27.9 n-pentane 21.5 21.9 21.5 22.1 isohexanes 43.6 43.3 43.8 43.4 5 n-hexane 6.4 6.9 6.1 6.6 i C- - 57.0 56.0 57.1 55.8

Sc5 i C * - 87.2 86.3 87.8 86.8 Z * 6 ____ 10 Example XIII.

This example relates to the use of the catalysts D'j, D'g, E'y E * g, F * ^ and F'g for the isomerization reaction of aromatic hydrocarbons. Catalysts D '^ to F'g are the same as catalysts Dj' to Fg; however, they have been prepared by using hydrofluoric acid in place of hydrochloric acid and they contain 10% by weight of fluorine. The catalysts thus prepared are used to isomerize to paraxylene a methaxylene feed; The operation is carried out at 430 ° C, under a pressure of 1.2 MPa (parts by weight of the feed per part by weight of catalyst and per hour = 5; molar ratio of hydrogen / hydrocarbons = 5).

For a yield of xylenes of 99.9% w / s, a conversion to paraxylene corresponding to: 8304355 4 - 35 - - to 95.32 of the thermodynamic equilibrium with catalyst D '- - to 95.2 * "is obtained. "" D'g - up to 95.12 "HHE * 1 - up to 94.92" "" e'5 5 - up to 95.22 "" "F'l - up to 95.02" "" ρ, 5 - conclusions - 8304355

Claims (10)

A process for the treatment of hydrocarbons in the presence of a solid catalyst containing (a) a support, at least based on aluminum oxide, and (b) an active phase comprising at least one Group VIII noble metal of the periodic table and at least another metal of the periodic table, aluminum oxide being used at least in part in the form of spheres, the manufacture of which comprises shaping by coagulation into droplets an aqueous suspension or dispersion of aluminum oxide, or a solution of a basic aluminum -10 nium salt, recovery of the spheres formed, drying and calcination thereof, the manufacture of which is characterized in that the aqueous suspension, dispersion of alumina or the solution of the basic aluminum salt is present as an oily emulsion in water, the viscosity of the emulsion being between 100 and 800 2 15 centipoise (IcStslmm / s), which emulsion consists of an organic fa se, an aqueous phase and a surfactant or emulsifier, such that the amount of the organic phase in the water phase (or ratio "hydrocarbon / free water") is between 1 and 10 vol # and the weight ratio of the emulsifier to 20 of the organic phase is between 2 and 8 #, the organic phase being selected from at least one petroleum fraction and a petroleum fraction, and the surfactant or emulsifier an HLB owns between 11 and 20, 2. A method according to claim 1, characterized in that the suspension or dispersion of aluminum oxide or the solution of basic aluminum salts additionally contains a dose of aluminum oxide, the amount of the dose being up to 90% by weight, expressed in A A og relative to of the total amount of alumina. S3 04 3 5 5 s i '• m' fc r - - ~ - 37 - Method according to claim 2, characterized in that the dosage of alumina is selected from: Hydrargillite, x-bayerite, boehmite, pseudo-boehmite and the gels of amorphous or almost amorphous aluminum oxide, the dehydrated or partially dehydrated forms of these compounds consisting of transition aluminum oxides and containing at least one of the phases rho, chi, êta, gamma, kappa, theta, delta, alpha. 4. Process according to any one of claims 1-3, characterized in that the total concentration of aluminum oxide in the aqueous suspension or dispersion of aluminum oxide or the solution of the basic aluminum salt is between 5 and 30 # in grams per liter. Method according to any one of claims 1-4, characterized in that the viscosity of the emulsion is between 300 and 15 centipoise (1 c St = 1 mm / s). A method according to any one of claims 1 to 5, characterized in that the H.L.B. of the surfactant is between 12 and 18. 7. Process according to any one of claims 1-6, characterized in that the catalyst contains 0.02 to 1 # platinum and 0.02 to 1 # iridium in parts by weight relative to the matrix or support of aluminum oxide. 8. Process according to any one of claims 1-6, characterized in that the catalyst relative to the matrix or the support of aluminum oxide (a) is 0.02 to 1% by weight of at least one platinum group precious metal and 0 .01 to 2 wt. # Of at least one other metal. Process according to claim 8, characterized in that the or the other metals is or are selected from the group 8304355 -% * * * * - 38 - formed by titanium, rhenium, tin, germanium, indium, thallium, -Λ manganese, nickel, iron, cobalt, zinc, copper, gold, silver, niobium, 'lanthanum, cerium, samarium, zircon, thorium, hafnium, lead, galium, vanadium, technetium, uranium and selenium. 5 10. Process according to any one of claims 1-9, used in the reactions selected from the catalytic reforming, the formation of aromatic hydrocarbons, the isomerization of paraffinic and aromatic hydrocarbons, the hydrocracking, the hydrodealkylation, the water vapor dealkylation of aromatic hydrocarbons, 10 dehydration, hydrosulfuration, dehydrohalogenation, vapor 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 the demetallization. 8304355 __i