DE10020049A1 - Preparation of catalyst useful for hydroconversion of hydrocarbons comprises using group VIII metal and additional metal added in form of water soluble organometallic compound - Google Patents

Abstract

The incorporation of the additional metal as a promoter element improves the activity of the resulting catalyst, and the means of introduction of the metal is advantageous. Process for the preparation of a catalyst comprises using a binder support, a group VIII metal and an additional element M, chosen from Ge, Sn, Pb, Re, Nb, Ga, In or Tl. The element M is introduced in the form of an organometallic compound in aqueous solution at a pH less than 10, the compound comprising at least one carbon-M bond. Independent claims are also included for the catalysts obtained and its uses.

Description

Technical part

The present invention relates to a new manufacturing process for a catalyst that has at least one support, at least a metal from group VIII of the periodic table of the Elements (Handbook of Physics and Chemistry, 63rd edition, 1982-83) and at least one additional element M, which under Germanium, tin, lead, rhenium, niobium, gallium, indium and Thallium, gold and silver was chosen. This catalyst can also include at least one other element that comes from the Group consisting of the alkaline metals selected was, and / or a non-metal such as sulfur and / or any other chemical element such as a halogen or a have halogenated compound. The invention relates also a catalyst according to the invention Process was made, as well as the use of said Catalyst in conversion reactions from organic Compounds such as hydrocarbons.

Current state of the art

Numerous patents and publications prove that the addition of promoters to a starting metal the Improved catalyst quality. These elements are in various forms, for example as salts or organometallic compounds, added. The result is usually a more effective or selective, sometimes more stable Catalyst as the corresponding monometal catalyst. The Way in which these modifiers are initiated is not without importance as it has the catalyst properties strongly shape.  

The formulation of catalysts that are used in Find hydrocarbon conversion processes especially the formulation of catalysts for catalytic reforming and selective hydrogenation would be in very many writings. They are acidic catalysts which in addition to a carrier is a precious metal from the platinum range and at least one additional metal M such as tin, germanium, lead, Contain rhenium, gallium, indium, gold or silver. she were u. a. in US 3,998,900 and FR-A-2 495 605 described. These catalysts are bifunctional in that they two functions essential for achieving good performance combine in itself: a hydrating-dehydrating function, those for the naphthene dehydrogenation and the hydrogenation of the Coke precursor, and has an acidic function Isomerization of naphthenes and paraffins as well as Cyclization of the long paraffins. Platinum has one hydrogenolysing activity that affects gasoline and / or aroma yields that occur during catalytic reforming or are desired in the flavoring process, adversely affects. By adding the additional metal M can this hydrogenolysing activity is greatly reduced and consequently, the catalyst selectivity can be increased. Moreover can by adding the element M, the hydrating Properties of the platinum are strengthened, whereby the Hydrogenation of the coke precursors and therefore the Catalyst stability are favored. This Two-metal catalysts therefore show greater effectiveness and / or Selectivity performances than the catalysts that only the main metal (palladium, platinum or nickel) contain. The metals contained in the catalyst are in various forms, as mineral salts or organometallic Connections, added. The way like this Modifiers being introduced is important as they  strongly influenced the catalyst properties. This is how it is done advantageously the introduction of the additional metal M via the Initiation of an organometallic connection of said Metalls M. The introduction technique for the metal M would be in Patent specification US 4,548,918 of the applicant and in Patent US 3,531,543 discloses.

Patent US 5,128,300 describes the manufacture of a Catalyst by peptizing the inorganic oxide with Introduction of the metal from group IVA as halogenated organic connection.

The processes already described describe the manufacture a catalyst by using at least one organometallic connection of the element M. The element M is considered to be at least one organometallic compound found in selected from the group consisting of the complexes, especially the carbonyl, polyketone complexes of the metals M and the metal hydrocarbylene of element M like that Metal alkyls, -cycloalkylene, -arylene, -alkylarylene and the Metallarylalkylen is introduced. Patent specification US 4,727,216 discloses the manufacture of Dehydrogenation catalysts using organometallic Tin compounds such as the halogenated organometallic Tin compounds.

The introduction of the additional element M as an organometallic Compound produces more powerful catalysts, but requires the use of an organic Solvent. The impregnation solvent, which according to the Technology is described in US Pat. No. 4,548,918, is made up of the group consisting of the oxygen-enriched organic solvents with 2 to 8  Carbon atoms per molecule, the paraffin-containing, naphthenic or aromatic hydrocarbons predominantly 6 to 15 carbon atoms per molecule, the organic and halogenated oxygen-enriched Compounds with 1 to 15 carbon atoms per molecule, select. These solvents can be used alone or as a mixture find use between them.

Patent applications FR 97 / 13.684, FR 97 / 13.685, FR 97 / 13.686 and FR / 9713.687 of the applicant describe the introduction of the additional element M as a water-soluble organometallic connection of the element M in one hydrous solvent and the use of the generated Catalyst for paraffin dehydration, the Hydroreformation and selective dehydration of the unsaturated compounds.

Summary of the invention

With the present invention it was discovered that the element M in an aqueous solvent with a pH of less than 10 can be introduced. Thus concerns the present Invention a new manufacturing process for a Catalyst, the at least one carrier, at least one Metal from group VIII of the periodic table Elements and at least one additional element M contains that the group consisting of germanium, tin, lead, rhenium, Niobium, gallium, indium, thallium, gold and silver, was selected, the said method thereby is characterized in that said additional element M as at least one organometallic compound with at least a carbon-M compound in an aqueous solvent is initiated with a pH of less than 10.  

The present invention also relates to the use of the prepared by the inventive method Catalyst in a hydrogenation process for unsaturated Compounds as well as in a catalytic hydroforming and manufacturing process of flavorings.

advantage

The present invention represents a significant advance towards simplifying catalyst production Use of organic solvents in industrial Quantities are of great disadvantage in terms of Safety (flammability, toxicity) and costs. Moreover improves the solubility of the organometallic Compounds of element M in solutions with a pH between 0 and 10 clearly, which makes it possible to use much smaller amounts of solvent than in the processes state of the art to work.

description

The one produced by the process according to the invention Catalyst contains at least one carrier. The carrier points at least one fireproof oxide, which is usually among the Oxides of metals from groups IIA, IIIB, IVA or IVB the periodic system of the elements such as the Magnesium, aluminum, silicon, titanium, zirconium and Thorium oxides are selected alone, as a mixture between them or as a mixture with the oxides of others Elements of the periodic system of elements occur. Carbon can also be used.

In the hydrocarbon conversion reactions, alumina is the preferred carrier, the surface area index of which is advantageously between 5 and 400 m ² per gram, preferably between 50 and 350 m ² per gram. Zeolites or molecular sieves of type X, Y, such as mordenite, faujasite, ZSM-5, ZSM-4, ZSM-8, MFI, EUO, mazzite and oxide mixtures of the metals of groups IIA, IIIA, IIIB, IVA and IVB and zeolite material, in particular oxide mixtures of aluminum oxide and zeolite, are used. The preferred carriers for the conversion of organic functions are silica, carbon and aluminum oxide.

In addition to the carrier, the catalyst according to the invention contains the following:

• a) At least one Group VIII metal, which is under iridium, Nickel, palladium, platinum, rhodium and ruthenium selected has been. Platinum and palladium are the preferred metals for the hydrocarbon conversion reactions. Rhodium and Ruthenium are the preferred metals for the change of functional molecules. The weight percentage in Ratio to total catalyst weight, for example between 0.01 and 10 percent, preferably between 0.05 and 5 percent selected. In the selective hydrogenation of unsaturated compounds are palladium, nickel and platinum the preferred metals. In this case the Weight percentage in relation to Total catalyst weight between 0.01 and 50 percent, preferably selected between 0.05 and 1 percent, if the metal is a precious metal, and between 5 and 30 Percent if the metal is nickel. In which Hydro-reforming is preferred with platinum and iridium Metals. In this case, the weight percentage  between 0.01 and 10 percent, preferably between 0.05 and 5 percent selected; and
• b) at least one additional element M which is selected from the group, consisting of germanium, tin, lead, rhenium, niobium, Gallium, indium, thallium, gold and silver, selected and as an organometallic compound in an aqueous Solvents with a pH between 0 and 10 was initiated. In the selective hydrogenation of unsaturated compounds are tin, germanium, silver and Gold the preferred elements. When hydroforming are Tin and germanium are the preferred elements. The Weight percentage in relation to Total catalyst weight is, for example, between 0.01 and 10 percent, preferably between 0.02 and 5 percent select. Advantageously, one can in certain cases use at least two elements of this group, the each initiated as an organometallic compound become.

Depending on the area of use, the catalyst may additionally, for example, 0.1 to 3 percent by weight of one Halogen or a halogenated compound. He can also 0.1 to 3 weight percent of an alkaline or alkaline earth metal. He may be able to also 0.01 to 2 percent by weight of an element such as Contain sulfur. It can also be 0.01 to 3 Weight percent of at least one other element M included that in the catalyst by means of everyone per se known method and in any form known per se can be initiated.  

The precursor of the element M can be selected from the group of the halogenated compounds, the hydroxides, oxides, carbonates, carboxylates, nitrates and sulfates of the organometallic compounds of the element, without this list being considered restrictive. These compounds have at least one carbon-M compound. For example, the precursor of element M can be selected from the polyalkyl halides, for example trimethyl (Me ₃ MX), triethyl halides (Et ₃ MX), dimethyl (Me ₂ MX ₂ ), diethyl (ET ₂ MX ₂ ), Diisopropyl (iPr ₂ MX ₂ ), di-n-propyl dihalides (n-Pr ₂ MX ₂ ), the methyl (MeMX ₃ ), ethyl (EtMX ₃ ), isopropyl (iPrMX ₃ ), n-propyl trihalides (n -PrMX ₃ ), the polyalkyhydroxides, for example the trimethyl (Me ₃ MOH), triethyl hydroxides (Et ₃ MOH), the dimethyl (Me ₂ M (OH) ₂ ), diethyl (Et ₂ M (OH) ₂ ), Diisopropyl (iPR ₂ M (OH) ₂ ), di-n-propyl dihydroxides (n-Pr ₂ M (OH) ₂ ), methyl (MeM (OH) ₃ ), ethyl (EtM (OH) ₃ ), Isopropyl (iPrM (OH) ₃ ), n-propyl trihydroxide (n-PrM (OH) ₃ ), the polyalkyl acetates, for example the trimethyl (Me ₃ MOC (O) Me), triethyl (Et ₃ MOC (O) Me) ), Tributyl acetates (Bu ₃ MOC (O) Me), the polyalkyl oxides, for example the bis-trimethyl- ([Me3M] ₂ O), bis-triethyl- ([Et ₃ M] ₂ O), bis-tripropyl- ([ Pr ₃ M] ₂ O), bis- Tr ibutyl oxides ([Bu ₃ M] ₂ O), the polyalkyl sulfates, for example the bis-trimethyl ([Me ₃ M] ₂ SO ₄ ), bis-dimethyl sulfates ([Me ₂ M] SO ₄ ), the methyl trioxides (MeMO ₃ ) in which X represents a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine. The precursor of the element M can also be selected from the compounds with the overall formula (R1) _x M (R2) _y (R3) _z with x + y + z = valence of the metal M, in which R1 from the group of alkyl, Cycloalkyl, nitrile (CN), carbonyl (CO), aryl, alkylaryl and arylalkyl radicals have been selected, and R2 is a function of the form C _a H _b R ' _c in which R' is a hydroxide, halide , Carboxylate function, PO ₃ H or SO ₃ H and R3 represents an aqua, oxo (MO), alkoxide (O-alkyl), hydride, hydroxyl, alkyl sulfonate, alkyl sulfate, thioalkyl group, N (SO ₃ R ") ₂ , Pr" ₂ and PR " ₃ , in which R" is an alkyl group and P represents phosphorus (Handbook of Physics and Chemistry, 63rd edition, 1982-83).

Alkyl groups are groups which are linear, branched or cyclic, saturated carbon and Contain hydrogen atoms. Aryl groups are those aromatic groups.

It is also possible among the precursors like those above were defined, at least one alkyl group by a Alkenyl group d. H. through an unsaturated, linear, branched or cyclic group to replace the carbon and contains hydrogen atoms, for example an allyl group, to replace.

When the metal is M tin, the preferred precursors are polyalkyl halides such as Me ₃ SnCl, Me ₂ SnCl2, MeSnCl ₃ , Et ₃ SnCl, Et ₂ SnCl ₂ , EtSnCl ₃ , iPrSnCl ₂ and the hydroxides Me ₃ SnOH, Me ₂ Sn (OH ) ₂ , Et ₃ SnOH, Et ₂ Sn (OH) ₂ , the oxide [Bu ₃ Sn] ₂ O, the acetate Bu ₃ SnOC (O) Me.

When the Group M metal is germanium, the preferred precursor is the oxide [EtGeO] ₂ O.

When the metal M is niobium, the preferred precursors are the niobium dibromide-bis-cyclopentadienylhydroxyl p (C ₅ H ₅ ) ₂ Nb (OH) Br ₂ , the niobium dichloride-bis-cyclopentadienylhydroxyl (C ₅ H ₅ ) ₂ Nb (OH) Cl ₂ , the niobium tribromide-bis-cyclopentadienyl (C ₅ H ₅ ) ₂ NbBr ₃ , the niobium trichloride-bis-cyclopentadienyl (C ₅ H ₅ ) ₂ NbCl ₃ .

If the metal is rhenium, the preferred precursor is methyltrioxorhenium MeReO ₃ .

When the metal M is lead, the preferred precursors are the halides Me ₂ PbCl ₂ , Et ₂ PbCl ₂ and the hydroxides Et ₂ Pb (OH) ₂ and Me ₂ Pb (OH) ₂ .

According to the inventive method, it is possible Metal from group VIII, the additional element M as Organometal, possibly the halogen or the halogenated Compound, possibly the alkaline or alkaline earth Metal, possibly the non-metal, possibly the other metal M, simultaneously or in succession in any order initiate.

According to the invention is the introduction of the organometallic Elements M characterized in that the element in one aqueous solvent is introduced. The pH of the Solution containing element M varies from 0 to 10. The pH is preferably strictly below 10. The others Elements can be created using any method known per se be initiated.

In a method according to the invention, the additional metal M can be introduced via a sol-gel technique during the carrier synthesis. In the case of a carrier containing aluminum oxide and / or silica, for example, a mixed gel of metal M and aluminum oxide and / or of metal M and silica can be produced by using an organic solution of Al (OR ') ₃ or of Si (OR ') ₄ hydrolyzed in a solvent such as ROH with an aqueous solution of an organometallic compound of element M with a pH between 0 and 10. R and R 'can be an alkyl group of the methyl, ethyl, isopropyl, n-propyl, butyl type or even a heavier group such as n-hexyl. The alcoholic solvent must be highly dehydrated before the aluminum alcoholate and / or silicon alcoholate can be introduced. After the hydrolysis, a thermal treatment of the resulting gel takes place at a temperature between 200 and 800 ° C, preferably between 300 and 700 ° C and in a more preferred embodiment between 400 and 500 ° C, in order to achieve a complete reaction of the water-soluble organometallic compound Elements M with the gel, which causes the formation of the mixed oxide Al ₂ O ₃ -MO _x and / or SiO ₂ -MO _x .

In another process, element M can be added to an alumina sol. US Pat. No. 3,929,683 discloses the introduction of tin as a salt, for example SnCl ₂ , into an aluminum oxide sol. According to the present invention, it is possible to introduce an organometallic compound of element M in an aqueous solvent with a pH between 0 and 10 into an alumina hydrosol, said alumina hydrosol being prepared, for example, by using an acidic AlCl ₃ solution with a pH falls from 4-5 and then supports the reaction of the compound of element M with the alumina hydrosol, for example under the action of heat or a base.

In another embodiment of the invention, the Additional element M during the carrier production according to the Carrier design process from the previous state of the Technology, such as by extrusion (US 3,917,808) or be introduced by drop gelling (US 3,558,508).  

In catalyst production according to the drop gelation Invention (oil-drop) are preferably water-soluble organometallic precursors of element M used, the below the oxide or carboxylate compounds, for example of tin such as tin tributyl bis-oxide or Tin tributyl carboxylate are selected. A watery Solution of at least one connection of the element M with a pH below 10 is directly in the Alumina suspension introduced before going through Drop gelling or extrusion is formed. This connection is then dried and exposed to air annealed between 350 and 700 ° C. The way manufactured oxide carrier, which contains the element M. then with an aqueous or organic solution of at least one compound of a metal from group VIII impregnated, the solution volume preferably greater than the retention volume of or equal to the wearer. To The product obtained is a few hours of impregnation dried and exposed to air at one temperature annealed between 300 and 600 ° C, preferably some Purged with air for hours. In another Embodiment it is also possible to have at least one water-soluble organometallic compound of compound M and at least one compound of the metal from Group VIII during the stage of shaping the wearer simultaneously initiate.

In this particular embodiment, precursors of the element M are preferably used, which are among the polyalkylacetates, the polyalkyloxides, the polyalkylcarbonates, the polyalkylsulfates, the compounds with the overall formula (R1) _x M (R2) _y (R3) _z with x + y + z = Valence of the metal M is selected in which R1 was selected from the group of alkyl, cycloalkyl, nitrile (CN), carbonyl (CO), aryl, alkylaryl and arylalkyl functions, and R2 is a function of the form C. _a H _b R ' _c , in which R' represents a hydroxide, carboxylate function, PO ₃ H or SO ₃ H and R3 is an aqua, oxo (MO), alkoxide (O-alkyl), hydride, hydroxyl - represents alkyl sulfonate, alkyl sulfate, thioalkyl function, N (SO ₃ R ") ₂ , Pr" ₂ and PR " ₃ , in which R" is an alkyl group.

For example, it is also possible to use the moist powder serves as a carrier to knead with the catalyst precursors and then shape, dry and glow them.

In another process, the catalyst can be different impregnation methods of the element M are produced and the invention is not limited to a specific impregnation process. If multiple solutions Intermediate drying and / or can be used Impregnation processes take place.

In a preferred technique according to the invention, the Catalyst by carrier impregnation using at least one aqueous or organic solution of at least one Connection of at least one metal from Group VIII manufactured. The impregnated support is then filtered, possibly washed with distilled water and dried. Then he is exposed to hydrogen a temperature usually between about 200 and about 600 ° C, preferably between about 300 and about 500 ° C. A Intermediate annealing under the influence of air can occur between the Drying and the reduction stage can be switched. The product obtained is then by means of an aqueous solution of at least one tin, germanium, lead, rhenium, Niobium, gallium, indium, thallium, gold or  Impregnated silver compound. The volume of the watery Solution is equal to the retention volume of the carrier, or preferably larger than this. The pH of the watery Solution is between 0 and 10. After the contact between the support impregnated with the Group VIII metal and the aqueous solution containing at least one compound of the Elements M contains, for example, a few minutes to After several hours, the product filtered, possibly washed with water and dried. This process sees a reduction in one Temperature between 300 and 600 ° C before, preferably by purged with hydrogen for a few hours. It is also possible after the drying stage with a Glow level under air purge at a temperature between 300 and complete at 600 ° C.

In one embodiment of the invention, element M and the group VIII metal can be introduced simultaneously during a carrier impregnation step using an aqueous solution containing at least one element M and at least one metal from group VIII, the solution volume being equal to or greater than the carrier retention volume than this is. In a particularly advantageous embodiment, an aqueous solution of a halogenated organometallic compound of the element M such as Me ₃ MX or Me ₂ MX _{2 is used} , in which X is a halogen such as chlorine, for example Me ₃ SnCl or Me ₂ SnCl ₂ or an oxide compound of the element M represents the tributyl bis-oxide compound of the element M, for example the tin tributyl bis oxide compound. The pH of the solution is between 0 and 10. The catalyst is then dried and thermally activated according to, for example, one of the methods described above.

Before use, the catalyst is exposed to hydrogen, for example between 20 and 600 ° C, reduced to one to get active metal phase. The treatment process looks for example before that the temperature under hydrogen flow up to the maximum reduction temperature, for example between 20 and 600 ° C, preferably between 90 and 500 ° C lies, slowly increases and then, for example 1 to For 6 hours.

This reduction can happen immediately after a glow or to a later at the user. It exists also the possibility of directly drying the dried product at Reduce users.

It is also possible to find the one in solution Compound of Group VIII metal by organic Molecules with a reducing effect like formic acid in Reduce apron. The connection of the additional element M can then be introduced simultaneously or successively. The Catalyst can be used directly if the catalytic reaction an aqueous solvent requires what, especially in the conversion area organic functions is applicable. Another possibility consists in filtering the catalyst obtained and then dry. It can then be annealed and among the conditions described above can be reduced. The reduction can also be done directly on the dried product.

If the catalyst according to the invention contains sulfur, the sulfur on the shaped, annealed catalyst that the or contains the above metal (s), either in-situ applied before the catalytic reaction or ex situ. The any sulfurization takes place after the reduction. in the  In the case of in-situ sulfurization, the reduction takes place before Sulfurization if the catalyst has not previously been reduced has been. In the case of an ex situ reduction, this is done first Reduction and then sulfurization. The sulfurization takes place in Presence of hydrogen using everyone in itself known sulfurizing agents such as dimethyl sulfide or hydrogen sulfide. The catalyst is, for example, in Presence of hydrogen treated with an insert that Contains dimethyl sulfide and has such a concentration that the sulfur / metal atomic ratio is 1.5. The The catalyst is then at about 3 hours Temperature of about 40 ° C kept under hydrogen flow, before the mission is launched.

The catalyst prepared according to the invention can be in one Hydrocarbon conversion processes in the field of Refining and pertochemistry are used. He can also in a process in the chemical field Find use.

The catalyst prepared according to the invention can be used, for example, in a dehydrogenation process of saturated aliphatic hydrocarbons and in particular in the dehydrogenation processes of C ₃ -C ₂₂ paraffins. The dehydrogenation processes of light paraffins make it possible to refine the low boiling point aliphatic hydrocarbons such as butanes and isobutanes, pentanes and isopentanes which are collected after extraction of the unsaturated portions of the steam cracking fractions or the fractions from the catalytic cracking. The dehydration process of longer paraffins is a commercially important process due to the currently increasing demand for monoolefins for the production of, for example, biodegradable detergents or pharmaceutical products.

When using the catalyst according to the invention in The dehydration process of the paraffins is underneath the metal M. Germanium and tin and the metal from group VIII, preferably selected from platinum and palladium.

These different procedures differ in that Choice of working conditions and the composition of the Use. Adjustment of working conditions under Consideration of the type of application to be treated is done in such a way that you get the best possible ratio between Pressure, temperature, yield and effect according to known Methods achieved. The dehydration reaction usually takes place at a pressure between 0.02 and 2 MPa, preferably between 0.1 and 1 MPa, and at a temperature between 400 and 800 ° C each depending on the type of application.

The temperature is advantageously between 400 and 550 ° C for an application that mainly contains isopentane. The Temperature is advantageously between 450 and 550 ° C in the case of an application which predominantly contains paraffins, the 9 to Have 22 carbon atoms per molecule. The use can also unsaturated hydrocarbons with 3 to 22 Contain carbon atoms per molecule. The mass flow of the treated use per catalyst mass unit usually between 0.5 and 100 kg / kg / h. It can be an advantage Use hydrogen as a diluent. The Molar ratio between hydrogen and hydrocarbon usually between 0 and 20, preferably between 0 and 6.  

According to the invention, the one previously found advantageously described catalyst in selective hydrogenation processes of fractions using the acetylene or diene compounds contain. Thanks to the selective hydrogenation processes, the highly unsaturated compounds removed in the Fractions occur which are catalytic or thermal cracking or steam cracking stem from these fractions either as Polymerization inserts or as a product that as a basis can be used to refine a fuel.

The stakes that are typically to be dealt with are the C2, C3 or C4 fractions from the steam cracking, the Gasoline fractions from steam cracking, the C3, C4 and C5 Fractions or petrol from catalytic cracking. The Use is usually with the catalyst of the invention brought into contact at a temperature between 20 and 200 ° C. The mass flow of the treated insert per Catalyst mass unit can range from 0.1 to 10 kg / kg / h vary. Working pressure can be between atmospheric pressure and 6 MPa can be set.

According to the invention, the catalyst described above can be used in Gasoline reforming and flavoring manufacturing processes Find use. The reforming process can Octane number of gasoline fractions from crude oil distillation and / or from other refining processes. The Flavor manufacturing processes provide those in the petrochemical industry usable bases (benzene, toluene and xylenes). This Procedures are of additional interest by going to Production of significant amounts of hydrogen for the hydrogenation and water treatment processes in the Refining are essential. These two procedures  differ in the choice of working conditions and the Insert composition.

The typical use dealt with using these procedures contains paraffinic, naphthenic and aromatic Hydrocarbons with 5 to 12 carbon atoms per molecule. This use is u. a. by its density and its Weight composition defined. The stake is with the inventive catalyst at a temperature between 400 and 700 ° C brought into contact. The mass flow of the treated use per catalyst mass unit can from Vary from 0.1 to 10 kg / kg / h. The working pressure can be between atmospheric pressure and 4 MPa. A part of the generated hydrogen is equivalent to one molar Return rate between 0.1 and 10. That rate corresponds to the molar ratio between the returned Hydrogen flow and the feed flow.

The present invention will now be more apparent from the following Meaning non-limiting examples explained in more detail.

A - CATALYST PRODUCTION AND THEIR USE FOR PARAFFINDEHYDRATION example 1

Two catalysts A and B are produced, each containing 0.6 percent by weight of platinum and 0.3 percent by weight of tin in relation to the total catalyst weight. The carrier is a Degussa silica with a surface area index of 200 m ² per gram.

Catalyst A (comparison)

Catalyst A is produced using the methods from the prior art. The support is calcined at 500 ° C. under the influence of dry air for 5 hours and then brought into contact with an ammonia-containing solution (1 N) for 15 hours under a nitrogen bubble. The platinum is then deposited by introducing a tetramine platinum hydroxide solution. The suspension is then filtered, washed with distilled water and dried at 110 ° C. under a nitrogen flow. Then 10 grams of the solid, containing 0.6 percent by weight of platinum, are reduced for 4 hours at 450 ° C. under a hydrogen flow. The catalyst is then loaded into a reactor under the action of hydrogen, which contains 300 cm ^{3 of} an aqueous ammonia-containing solution (pH 11) which has 30 mg of tin in the form of a tin tributyl acetate (Bu ₃ SnOC (O) CH ₃ ). After 24 hours of contact under a hydrogen atmosphere, the reaction mixture is filtered, washed and dried at 80 ° C. The catalyst is then reduced at 550 ° C. for 4 hours under a stream of hydrogen.

Catalyst B (according to the invention)

Catalyst B is made based on 10 grams of the solid with 0.6 weight percent platinum and reduced for 4 hours at 450 ° C under a stream of hydrogen. The catalyst is then loaded with hydrogen into a reactor which contains 100 cm ^{3 of} an aqueous nitrite acid solution (pH 1) which contains 30 mg of tin in the form of a tin tributyl acetate (Bu ₃ SnOC (O) CH ₃ ). After 24 hours of contact under a hydrogen atmosphere, the reaction mixture is filtered, washed and dried at 80 ° C.

The catalyst is then 4 Reduced for hours at 550 ° C.

Results

The solubility of the tin tributyl acetate is at a pH of 1 much higher than at pH 11, which makes aqueous solutions with a higher Tin tributyl acetate concentration can be used. In the Preparation of the catalyst B according to the invention is that Volume of the aqueous solution 3 times less than that Catalyst A, which according to the prior art was produced. Accordingly, the tin deposit takes place in smaller amounts of aqueous solution, which is not a denying advantage for the industrial manufacture of these Represents catalysts.

Example 2

Catalysts A and B are subjected to an isobutane dehydrogenation test in an isothermal tube reactor. 1 g of catalyst is reduced for 2 hours at 550 ° C. under a hydrogen flow of 2 liters per hour. After the start of use, the temperature is stabilized at 550 ° C. The analysis of the gas discharges is carried out in a continuous process using gas phase chromatography. The working conditions are as follows:
Application: iC4 liquid air N35
Temperature: 550 ° C
Pressure: 0.1 MPa
H ₂ / iC ₄ (molar ratio): 1
Mass flow rate per hour:
liquid iC ₄ / catalyst mass: 500 h ^-1

The results obtained under these conditions are in Table 1 summarized:

Table 1

The performance of catalyst B, the better Solubility conditions of the tin precursor was established are at least as good as that of catalyst A, which follows the previous state of the art was produced.

Example 3

5 catalysts C, D, E, F and G are produced, each containing 0.6 weight percent platinum, 0.2 weight percent tin, 1 weight percent chlorine and 1 weight percent potassium in relation to the total catalyst weight. The carrier is a γ-aluminum oxide with a surface area index of 200 m ² per gram.

Catalyst C (comparison)

Catalyst C is produced according to the techniques from the prior art. 150 cm ^{3 of} an aqueous solution of hydrochloric acid and tin chloride with 0.10 g of tin content are added to 50 g of aluminum oxide support. The contact lasts for 3 hours. Then it is spun. The solid is then brought into contact with 150 cm ^{3 of} a solution of platinum (IV -) - hydrochloric acid with 0.3 g of platinum content. The contact lasts for 3 hours, then it is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours. Then an aqueous solution of potassium carbonate with 0.5 g potassium content is added, the sample is then dried at 120 ° C. and annealed at 500 ° C. for 2 hours.

Catalyst D (according to the invention)

The catalyst D is produced by impregnation with tin before the platinum. 100 cm ^{3 of} an aqueous solution with a pH of 8 are added to 50 g of aluminum oxide support by adding NH ₃ , which contains 0.1 g of tin in the form of tin dimethyl dichloride ((CH ₃ ) ₂ SnCl ₂ ). The reaction takes place for 3 hours at room temperature. The solid is then filtered, dried at 120 ° C. for 1 hour and annealed at 500 ° C. for 2 hours. 50 g of this solid are then brought into contact with 150 cm ^{3 of} an aqueous solution of hydrochloric acid and platinum (IV-) hydrochloric acid with 0.3 g of platinum content. The contact lasts for 3 hours, then it is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours. Then 30 cm ^{3 of} an aqueous solution of potassium carbonate with 0.5 g of potassium content are added, the sample is then dried at 120 ° C. and annealed at 500 ° C. for 2 hours.

Catalyst E (according to the invention)

Catalyst E is produced by simultaneous impregnation with platinum and tin. 50 g of the aluminum support are in contact with 30 cm ^{3 of} a solution containing 0.1 g of tin, which is originally in the form of Me ₃ SnCl, 0.3 g of Pt in the form of platinum (IV) hydrochloric acid (H ₂ PtCl ₆ ) and contains hydrochloric acid in such an amount that the pH of the solution is 1. The solid is then dried at 120 ° C. for one hour and annealed at 500 ° C. for 2 hours. Then 30 cm ^{3 of} an aqueous solution of potassium carbonate with 0.5 g of potassium content are added, the sample is then dried at 120 ° C. and annealed at 500 ° C. for 2 hours.

Catalyst F (according to the invention)

Catalyst F is produced on the basis of 50 grams of aluminum oxide with 0.6 percent by weight of platinum and reduced for 4 hours at 450 ° C. under a stream of hydrogen. After this reduction stage, the catalyst is loaded without air contact into a reactor containing 100 cm ^{3 of} an aqueous solution of Me ₃ SnCl with a pH of 4, which has enough tin to deposit 0.2 percent by weight of tin on the support. After 24 hours of contact, the reaction mixture is filtered, washed and dried at 80 ° C. The catalyst is then dried at 120 ° C for one hour and annealed at 500 ° C for 2 hours. Potassium is then introduced by contacting 50 g of this catalyst with 30 cm ^{3 of} an aqueous solution of potassium carbonate with 0.5 g of potassium content, then the sample is dried at 120 ° C. and annealed at 500 ° C. for 2 hours.

Catalyst G (according to the invention)

Catalyst G is produced by dry impregnation of the tin and excess impregnation of the platinum. 50 g of the alumina carrier is brought into contact with 30 cm ^{3 of} an aqueous solution of tin trimethyl chloride ((CH ₃ ) ₃ SnCl) with a pH of 4, which contains 0.1 g of tin. The contact lasts for 3 hours, then the solid is dried at 120 ° C. for 1 hour and annealed at 500 ° C. for 2 hours. The solid is then brought into contact with 150 cm ^{3 of} an aqueous solution of platinum (IV -) - hydrochloric acid with 0.3 g of platinum content. The contact lasts for 3 hours, then it is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours. Then 30 cm ^{3 of} an aqueous solution of potassium carbonate with 0.5 g of potassium content are added, the sample is then dried at 120 ° C. and annealed at 500 ° C. for 2 hours.

Example 4

The catalysts C, D, E, F and G become one Isobutane dehydrogenation test in an isothermal Tube reactor subjected. 1 g of catalyst is left for 2 hours at 550 ° C under a hydrogen flow of 2 liters per Hour reduced. After initiation of the operation, the Temperature stabilized at 550 ° C. Analysis of gas exits is carried out in a continuous process using gas phase chromatography.

The working conditions are as follows:
Application: iC4 liquid air N35
Temperature: 550 ° C
Pressure: 0.1 MPa
H ₂ / iC ₄ (molar ratio): 1
Mass flow rate per hour:
liquid iC ₄ / catalyst mass: 725 h ^-1

The results obtained under these conditions are in Table 2 summarized:

Table 2

These results show that catalysts D, E, F and G, the invention, d. H. based on a organometallic precursor of element M in aqueous Solution that have been prepared have catalytic performances, that are at least as good and even slightly better than that of the Catalyst C, according to the prior art was produced.

Example 5

Three catalysts H, I and J are produced which contain 0.4% by weight of platinum, 0.3% by weight of tin, 0.1% by weight of indium and 0.6% by weight of lithium. The carrier is a γ-aluminum oxide with a surface area index of 200 m ² per gram.

Catalyst H (comparison)

Catalyst H is produced according to the prior art. 30 cm ^{3 of} an aqueous solution of lithium acetate with 0.3 g of lithium content are added to 50 g of aluminum oxide support. The contact lasts for 3 hours. The solid is then dried at 120 ° C. for one hour and annealed at 350 ° C. for 2 hours. The solid is brought into contact with 200 cm ^{3 of} an aqueous solution of indium nitrate with 0.05 g indium content. The contact lasts for 3 hours, then the solid is dried at 120 ° C. for one hour and annealed at 530 ° C. for 2 hours. This is followed by contact between the solid and 30 cm ^{3 of} an n-heptane solution with 0.15 g of tin in the form of tin tetrabutyl. The contact lasts for 3 hours, then the solid is dried at 120 ° C. for one hour and annealed at 530 ° C. for 2 hours. Platinum is then introduced by adding 200 cm ^{3 of} a toluene solution which contains 0.2 g of platinum in the form of platinum acetylacetonate. The contact is made for 24 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 530 ° C for 2 hours.

Catalyst I (according to the invention)

Catalyst I is produced by the drop gelation method ("oil drop"). 0.88 g of tin acetate tributyl (C ₄ H ₉ ) - ₃ SnOCOCH ₃ ) in 282 g of an aqueous nitrite acid solution are introduced at 1.1 percent by weight, then 100 g of boehmite powder are added with stirring. The suspension is then drained by flowing through calibrated tubes with an internal diameter of 1 mm and made to gel by passing it through an ammonia-containing solution at 3% by weight. The carrier balls thus formed are dried at 120 ° C. for 2 hours and annealed at 600 ° C. for 2 hours. Then there is contact between 50 g of this solid and 30 cm ^{3 of} an aqueous lithium acetate solution with 0.3 g of lithium content. The contact lasts for 3 hours, then the solid is dried at 120 ° C. for one hour and annealed at 350 ° C. for 2 hours. Then the solid is brought into contact with 200 cm ^{3 of} an aqueous indium nitrate solution with 0.005 g indium content. The contact lasts for 3 hours, after which the solid is dried at 120 ° C. for 1 hour and annealed at 530 ° C. for 2 hours. The platinum is then introduced by adding 200 cm ^{3 of} a toluene solution which contains 0.2 g of platinum in the form of platinum acetylacetonate. The contact is made for 24 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 530 ° C for 2 hours.

Catalyst J (according to the invention)

Catalyst J is produced using the sol-gel method. The support is produced by hydrolysis of an aluminum isopropylate solution Al (OiPr) ₃ in isopropanol by means of an aqueous tin trimethyl chloride solution ((CH ₃ ) ₃ SnCl) with a pH value of 4 and subsequent heat treatment at 450 ° C. Then lithium is introduced through the contact between 50 g of this support with 30 cm ^{3 of} an aqueous lithium acetate solution with 0.3 g of lithium content. The contact lasts for 3 hours. The solid is then dried at 120 ° C. for one hour and annealed at 350 ° C. for 2 hours. The solid is then brought into contact with 200 cm ^{3 of} an aqueous solution of indium nitrate with 0.05 g indium content. The contact lasts for 3 hours, then the solid is dried at 120 ° C. for one hour and annealed at 530 ° C. for 2 hours. Platinum is then introduced by adding 200 cm ^{3 of} a toluene solution which contains 0.2 g of platinum in the form of platinum acetylacetonate. The contact is made for 24 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 530 ° C for 2 hours.

Example 6

Catalysts H, I and J are subjected to an n-dodecane dehydrogenation test in an isothermal tube reactor. 2 g of catalyst are reduced for 2 hours at 450 ° C. under a hydrogen flow of 4 liters per hour. The working conditions are as follows:
Use: n-dodecane
Temperature: 450 ° C or 470 ° C
Pressure 0.2 MPa
H ₂ / nC ₁₂ (molar ratio) 5
Mass flow rate per hour: liquid nC ₁₂ / catalyst mass 80 h ^-1

The results obtained under these conditions are summarized in Table 3. The nC ₁₂ conversion and yield values are given as weight percent of the use.

Table 3

The catalysts I and J, according to the invention in aqueous Environment based on the organometallic Sn precursors were produced, show olefin yields that are at least are equal to those of the catalyst H, which after the prior art was produced.

B - CATALYST PRODUCTION AND THEIR USE IN THE ISOPRENE HYDRATION Example 7

Four catalysts K, L, M and N are produced which contain 0.4 percent by weight of palladium and 0.4 percent by weight of tin. The carrier is an aluminum oxide with a surface area index of 70 m ² per gram.

Catalyst K (comparison)

Catalyst K is produced using the methods from the prior art. 40 cm ^{3 of} an aqueous palladium nitrate solution are added to 50 grams of aluminum oxide support. The catalyst is dried at 110 ° C, annealed at 450 ° C under the influence of air and reduced at 450 ° C under a stream of hydrogen. The catalyst is then loaded into a reactor containing toluene without air contact. The amount of tin tetrabutyl required is then introduced at 20 ° C. in order to deposit 0.4 percent by weight of tin on the support. After 24 hours under these conditions, the catalyst is filtered, washed, dried and reduced at 450 ° C.

Catalyst L (comparison)

Catalyst L is produced using the methods from the prior art. The palladium is initially deposited via the contact between the aluminum oxide support and a palladium nitrate solution. The catalyst is then dried at 110 ° C, annealed at 450 ° C under the influence of air and reduced at 450 ° C under a stream of hydrogen. 10 g of this catalyst are loaded into a reactor without air contact, which contains 400 cm ^{3 of} an ammonia-containing solution (pH 10.5) which contains 40 mg of tin in the form of tin tributyl acetate (Bu ₃ SnOC (O) CH ₃ ). The pressure is increased to 4 MPa and the temperature to 100 ° C. After 1 hour under these conditions, the reaction mixture is filtered, washed, dried and reduced at 450 ° C.

Catalyst M (according to the invention)

The catalyst M is produced using 10 g of the solid with 0.4 percent by weight of palladium and is reduced at 450 ° C. for 4 hours under a stream of hydrogen. This catalyst is loaded without air contact into a reactor which contains 150 cm ^{3 of} a nitrite acid solution (pH = 1) which contains 40 mg of tin in the form of tin tributyl acetate (Bu ₃ SnOC (O) CH ₃ ). The pressure is increased to 4 MPa and the temperature to 100 ° C. After 1 hour under these conditions, the reaction mixture is filtered, washed, dried and reduced at 450 ° C.

Catalyst N (according to the invention)

In the case of catalyst N, 50 g of the aluminum oxide support are brought into contact with 40 cm ^{3 of} an aqueous palladium nitrate solution. The catalyst is then dried at 110 ° C, annealed at 450 ° C under the influence of air and reduced at 450 ° C under a stream of hydrogen. After this reduction stage, 50 g of this catalyst with 0.4% by weight of palladium without air contact are loaded into a reactor which contains 150 cm ^{3 of} an aqueous solution of Me ₃ SnCl (pH = 4) which has the required amount of tin in order to To deposit 4 percent by weight of tin on the carrier. After 24 hours of contact, the catalyst is filtered, washed and dried at 80 ° C.

Example 8

The catalysts are then tested in a reactor with careful stirring and under the following working conditions in the isoprene hydrogenation reaction:
Use: n-heptane + isoprene
Temperature: 65 ° C
Pressure: 1 MPa

The results obtained under these conditions are the following table. The yields are as Molar percentage given after one working hour.  

The solubility of the tin tributyl acetate is at a pH of 1 much higher than at pH 11, which makes to get aqueous solutions with higher ones Tin tributyl acetate concentrations can use. The Production of the catalyst M according to the invention is shown in FIG Use a volume of the aqueous solution that is 2.5 times less than the volume of the catalyst L, the after the previous state of the art was prepared. Therefore the tin is deposited in smaller amounts of the aqueous Solution, which is an undeniable advantage in the represents industrial production of these catalysts.

The catalysts M and N, according to the invention, i. H. on the Foundation of an organometallic precursor in water Milieu produced have performances that are similar are as good as those of the prior art manufactured catalysts K and L and even slightly better, the advantage being that they are in an aqueous environment better solubility of the tin precursors than in the processes be manufactured according to the prior art.

C - CATALYST PRODUCTION AND ITS USE IN THE HYDROCARBON CONVERSION Example 9

9 catalysts P, Q, R, S, T, U, V, W and X are produced, which contain 0.4 weight percent platinum, 0.25 weight percent tin and 1.2 weight percent chlorine. The carrier is a γ-aluminum oxide with a surface area index of 200 m ² per gram.

Catalyst P (comparison)

Catalyst P is produced using the processes from the prior art. The carrier is a γ-aluminum oxide with a surface area index of 210 m ² per gram. 150 cm ^{3 of} an aqueous solution of hydrochloric acid and tin chloride with 0.125 g of tin content are added to 50 g of the aluminum oxide support. After a 3-hour contact, it is spun. The solid is then brought into contact with 150 cm ^{3 of} an aqueous solution of platinum (IV) hydrochloric acid with 0.2 g of platinum. The contact is 3 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours.

Catalyst Q (comparison)

Catalyst Q is produced using the processes from the prior art. 10 g of the aluminum oxide support is brought into contact with 250 cm ^{3 of} an aqueous ammonia-containing solution (pH 11), which contains 0.025 g of tin in the form of tin tributyl acetate (Bu ₃ SnOC (O) CH ₃ ). After a 3-hour reaction at room temperature, the solid is filtered, dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours. 10 g of this solid are then brought into contact with 100 cm ^{3 of} an aqueous solution of hydrochloric acid and platinum (IV-) hydrochloric acid with 0.04 g of platinum content. The contact is 3 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours.

Catalyst R (according to the invention)

10 g of the aluminum oxide support are brought into contact with 100 cm ^{3 of} an aqueous ammonia-containing solution (pH 1), which contains 0.025 g of tin in the form of tin tributyl acetate (Bu ₃ SnOC (O) CH ₃ ). After a 3-hour reaction at room temperature, the solid is filtered, dried at 120 ° C. for 1 hour and annealed at 500 ° C. for 2 hours. 10 g of this solid are then brought into contact with 100 cm ^{3 of} an aqueous solution of hydrochloric acid and platinum (IV-) hydrochloric acid with 0.04 g of platinum content. The contact is 3 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours.

Catalyst S (according to the invention)

The catalyst S is the contact between 50 g of the alumina support with 150 cm ^{3 of} an aqueous solution with a pH of 8 by adding NH ₃ , which contains 0.125 g of tin in the form of tin dimethyl dichloride ((CH ₃ ) ₂ SnCl ₂ ) , manufactured. The reaction takes place for 3 hours at room temperature. The solid is then filtered, dried at 120 ° C. for 1 hour and annealed at 500 ° C. for 2 hours. 50 g of this solid are then brought into contact with 150 cm ^{3 of} an aqueous solution of hydrochloric acid and platinum (IV-) hydrochloric acid with 0.2 g of platinum content. The contact lasts for 3 hours, then it is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours.

Catalyst T (according to the invention)

Catalyst T is produced by contact between 50 g of the aluminum support and 30 cm ^{3 of} a hydrochloric acid solution (pH = 1), the 0.125 g of tin, which is originally in the form of Me ₃ SnCl, and 0.2 g of Pt in the form of platinum (IV-) hydrochloric acid (H ₂ PtCl ₆ ) contains. The solid is then dried at 120 ° C. for one hour and annealed at 500 ° C. for 2 hours.

Catalyst U (according to the invention)

Catalyst U is prepared by the drop gelation method by introducing 0.56 g of tin tributyl acetate Bu ₃ SnOC (O) CH ₃ into 282 g of an aqueous nitrite acid solution at 1.1 percent by weight; then 100 g of boehmite powder are added while stirring. The suspension is then drained by flowing through calibrated tubes with an internal diameter of 1 mm and made to gel by passing it through an ammonia-containing solution at 3% by weight. The carrier balls thus formed are dried at 120 ° C. for 2 hours and annealed at 600 ° C. for 2 hours. This is followed by contact between 50 g of this solid and 150 cm ^{3 of} an aqueous platinum (IV) hydrochloric acid solution with 0.2 g of platinum content. The contact lasts for 3 hours, then the sample is dried at 120 ° C for 1 hour and annealed at 500 ° C for 2 hours.

Catalyst V (according to the invention)

The catalyst V is produced using 50 g of the solid with 0.4% by weight platinum content, which was reduced at 450 ° C. for 4 hours under a stream of hydrogen. Platinum was applied to the alumina support by contact with 150 cm ^{3 of} an aqueous platinum (IV) hydrochloric acid solution containing 0.2 g of platinum. The solid is then dried at 120 ° C. for 1 hour and annealed at 450 ° C. for 2 hours. The catalyst is then loaded, without air contact, into a reactor containing 200 cm ^{3 of} an aqueous tin trimethyl chloride (CH ₃ ) ₃ SnCl with a pH of 1, which contains enough tin to deposit 0.2 percent by weight of tin on the support. After contact for 24 hours, the reaction mixture is filtered, washed, dried at 80 ° C. and reduced at 500 ° C. for 2 hours.

Catalyst W (according to the invention)

30 cm ^{3 of} an aqueous tin trimethyl chloride solution (CH ₃ ) ₃ SNCl with a pH of 4 and a tin content of 0.125 g are added to 50 g of aluminum oxide support. The contact lasts for 3 hours, then the solid is dried at 120 ° C. for 1 hour and annealed at 500 ° C. for 2 hours. The platinum is deposited in the amount of 0.4% by weight of platinum in relation to the annealed support by excess impregnation using a platinum (IV) hydrochloric acid solution. After annealing at 450 ° C for 12 hours, the catalyst is reduced at 500 ° C for 4 hours under a stream of hydrogen.

Catalyst X (according to the invention)

Catalyst X is prepared according to the sol-gel result. The carrier is produced by hydrolysis of an aluminum isopropylate solution Al (OiPr) ₃ in isopropanol using an aqueous tin trimethyl chloride solution (CH ₃ ) ₃ SNCl with a pH of 4 and subsequent heat treatment at 450 ° C. The platinum is deposited in the amount of 0.4% by weight of platinum in relation to the annealed support by excess impregnation using a platinum (IV) hydrochloric acid solution. After annealing at 450 ° C for 12 hours, the catalyst is reduced at 500 ° C for 4 hours under a stream of hydrogen.

Example 10

The samples of the catalysts, the preparation of which was described above, are tested when converting an insert with the following characteristics:
Volume-related mass at 20 ° C: 0.753 kg / dm ³
Research octane number: ≈ 60
Paraffin content: 49.4 percent by volume
Naphthane content: 35.1 volume percent
Flavor content: 15.5 percent by volume

The conversion takes place in the presence of hydrogen under the following working conditions:
Temperature: 490 ° C
Total pressure: 0.30 MPa
Flow rate: 2.0 kg per kg of catalyst per hour

The catalysts are left for 2 hours before starting the application activated under the influence of hydrogen at 450 ° C. The after 24 Hours of operation are shown in the table below summarized.

The catalysts R, S, T, U, V, W and X, which according to the invention, ie on the basis of an organometallic precursor in an aqueous medium, either by impregnating the support with the compounds Me ₃ SnCl, Me ₂ SnCl ₂ or Bu ₃ SnOC ( O) CH ₃ or by introducing tin tributyl acetate during the carrier shaping have better performances than catalyst P, which was produced according to the prior art.

The solubility of the tin tributyl acetate is at a pH of 1 much higher than at pH 11, which makes to make aqueous solutions with higher tin tributyl acetate can use concentrations. The production of the Catalyst R according to the invention provides for the use of a Volume of the aqueous solution that is 2.5 times less than the volume of the catalyst Q is that after the previous one State of the art was prepared. Accordingly, the Tin deposit in smaller amounts of the aqueous solution what an undeniable advantage at  represents industrial production of these catalysts. In addition, the performance of the catalyst R, the under prepared better solubility conditions of the tin precursor was at least as good as the performance of the Catalyst Q, according to the prior art was made, and even better.

Claims (38)

1. Production process for a catalyst which contains at least one support with at least one binder, at least one metal from group VIII of the periodic system of the elements and at least one additional element M which consists of the group consisting of germanium, tin, lead, rhenium, Niobium, gallium, indium, thallium, gold and silver was selected, characterized in that said additional element M is introduced into an aqueous solvent with a pH of less than 10, said element M being in the form of at least one water-soluble organometallic compound with at least one carbon element M compound occurs. 2. The method of claim 1, wherein the pH of the aqueous Solution of element M is strictly below 10. 3. The method according to any one of claims 1 or 2, in which a alkaline or alkaline earth metal also in the Catalyst is introduced. 4. The method according to any one of claims 1 to 3, in which a Non-metal is additionally introduced into the catalyst. 5. The method according to any one of claims 1 to 4, in which at least one halogen or a halogenated compound is additionally introduced into the catalyst. 6. The method according to any one of claims 1 to 5, in which the Group VIII metal under iridium, nickel, palladium, Platinum, rhodium and ruthenium is selected.   7. The method according to any one of claims 1 to 6, in which the Introduction of the element M in the form of an organometallic Compound selected from germanium and tin he follows. 8. The method according to any one of claims 1 to 7, in which at least 1 element M under any form known per se is additionally initiated. 9. The method according to any one of claims 1 to 8, in which the precursor of the element M is selected from the group consisting of the polyalkyl halides, the polyalkyl hydroxides, the polyalkyl oxides, the polyalkyl carboxylates, the polyalkyl carbonates, the polyalkyl nitrates, the polyalkyl sulfates, the compounds with of the overall formula (R1) _x M (R2) _y (R3) _z with x + y + z = valence of the metal M, in which R1 consists of the group of alkyl, cycloalkyl, nitrile (CN), carbonyl (CO), aryl, alkylaryl and arylalkyl radicals have been selected, and R2 is a function of the form C _a H _b R ' _c , in which R' represents a hydroxide, halide, carboxylate function, PO ₃ H or SO ₃ H and R3 represents an aqua, oxo (MO), alkoxide (O-alkyl), hydride, hydroxyl alkyl sulfonate, alkyl sulfate, thioalkyl group, N (SO ₃ R ") ₂ , Pr" ₂ , and PR " ₃ in which R "is an alkyl group. 10. The method according to claim 9, in which at least one Alkyl group by an alkenyl or an aryl group is replaced. 11. The method according to any one of claims 1 to 10, in which the Additional element M during the carrier synthesis by means of a Technology of the SOL-GEL type is initiated.   12. The method according to any one of claims 1 to 10, in which the Additional element M in the form of an organometallic Compound in a solution with a pH between 0 and 10 is introduced into an alumina hydrosol. 13. The method according to any one of claims 1 to 10, in which the Additional element M initiated by a drop gelling technique becomes. 14. The method according to claim 13, in which the organometallic compound of the element M among the polyalkylacetates, the polyalkyloxides, the polyalkylcarbonates, the polyalkylcarboxylates, the polyalkylsulfates, the compounds having the overall formula (R1) _x M (R2) _y (R3) _z x + y + z = valence of the metal M is selected, in which R1 was selected from the group of alkyl, cycloalkyl, nitrile (CN), carbonyl (CO), aryl, alkylaryl and arylalkyl functions, and R2 is a function of the form C _a H _b R ' _c , in which R' represents a hydroxide, carboxylate, PO ₃ H or SO ₃ H and R3 is an aqua, oxo (MO), alkoxide (O-alkyl) Represents hydride, hydroxyl alkyl sulfonate, alkyl sulfate, thioalkyl group, N (SO ₃ R ") ₂ , Pr" ₂ and PR " ₃ in which R" is an alkyl group. 15. The method according to any one of claims 1 to 10, in which the Group VIII metal, the element M in organometallic form in an aqueous solvent with a pH of less than 10, possibly the halogen, possibly the alkaline or alkaline earth metal, possibly the non-metal, possibly another element M by simultaneous or successive impregnation on the Carrier are applied.   16. The method according to claim 15, in which a carrier by means of a aqueous or organic solution of at least one Group VIII metal impregnated, filtered, dried, annealed under the influence of air and under the influence of hydrogen is reduced. The product is created with a aqueous solution of an organometallic compound of Elements M impregnated with a pH below 10, then filtered, dried, possibly reduced and annealed. 17. The method according to claim 15, in which a carrier by means of a aqueous solution of an organometallic compound of Additional element M impregnated with a pH below 10, dried, annealed. The solid obtained is with an aqueous or organic solution of at least impregnated with a Group VIII metal, then dried and annealed. 18. The method according to claim 17, in which the organometallic Compound of element M is a polyalkyl halide compound of M or a polyalkyl oxide compound of M. 19. The method according to claim 18, in which the organometallic Compound of element M is a halide trimethyl of M or is a dihalodimethyl of M. 20. Catalysts according to one of claims 1 to 19 were manufactured. 21. Use of the catalysts according to claim 20, or the were produced according to one of claims 1 to 19, in Conversion reactions of organic compounds.   22. Use of the catalysts according to claim 21 in Aliphatic dehydrogenation reactions Hydrocarbons that are saturated at corresponding have olefinic hydrocarbons. 23. Use according to claim 22 at a temperature of 400 up to 800 ° C, a pressure of 0.02 to 2 MPa, a Mass flow of the treated insert per Unit of catalyst mass from 0.5 to 100 kg / kg / hour and a molar ratio between hydrogen and Hydrocarbon from 0 to 20. 24. Use of the catalysts according to claim 21 in catalytic reactions of hydroforming and Flavoring. 25. Use according to claim 24, in which the use with the Catalyst at a temperature between 400 and 700 ° C, a mass flow of the treated insert per Unit of catalyst mass between 0.1 and 10 kg / kg / hour and a pressure between atmospheric pressure and 4 MPa in Is brought into contact. 26. Use according to one of claims 24 to 25, in which at least part of the hydrogen generated with a Molar recycle rate between 0.1 and 10 is recycled. 27. Use according to one of claims 24 to 26, in which the Use of paraffinic, naphthenic and aromatic Hydrocarbons with 5 to 12 carbon atoms per Molecule exists.   28. Use of the catalysts according to claim 21 in selective Hydrogenation reactions of unsaturated compounds like that Acetylene compounds or the diolefins. 29. Use according to claim 28, in which the metal of the group VIII in the catalyst under nickel, palladium, platinum, Rhodium, ruthenium and iridium, preferably under platinum, Palladiun and nickel is selected. 30. Use according to one of claims 28 to 29, in which the Element M in the catalyst under germanium, tin, silver and Gold is selected. 31. Use according to one of claims 28 to 30, in which the Precursor of element M in the catalyst from the group of Carboxylates of organic compounds of the element M is selected. 32. Use according to one of claims 28 to 31 in one Procedure in which the insert to be treated at a pressure between atmospheric pressure and 6 MPa, one temperature between 20 and 200 ° C, a mass flow of the treated Use per unit of catalyst mass between 0.1 to 10 kg / kg / h is brought into contact with the catalyst. 33. Use according to one of claims 28 to 32, in which the Inserts to be treated C2 or C3 steam cracking fractions are. 34. Use according to one of claims 28 to 33, in which the insert to be treated is a C4 steam cracking fraction.   35. Use according to one of claims 28 to 34, in which the Inserts to be treated C5-C8 gasoline fractions from the Steam cracks are. 36. Use according to one of claims 28 to 35, in which the use to treat the C3 fraction from the catalytic Cracking is. 37. Use according to one of claims 28 to 36, in which the to be treated use the C4 fraction from the catalytic Cracking is. 38. Usef according to one of claims 28 to 37, in which the inserts to be treated the C5-C8 fractions from the are catalytic cracking.