DE102008036109A1 - Method of treating shaped body, preferably e.g. sorbent-shaped body, comprises contacting shaped body comprising tectosilicates with treatment fluid, which is an aqueous fluid, and drying and/or calcining shaped body - Google Patents

Abstract

Method of treating a shaped body, preferably a catalyst-, catalyst carrier-, or sorbent-shaped body, comprises: (a) providing the shaped body comprising one or more tectosilicates; (b) contacting the shaped body with at least one treatment fluid, which is an aqueous fluid and contains one or more compounds (at least 7 mmol/l) soluble in water under anion- and/or cation-formation, and (c) optionally drying and/or calcining the shaped body brought into contact with the treatment fluid. Independent claims are included for: (1) use of an aqueous fluid comprising the compounds, to treat tectosilicates comprising shaped body containing non-calcined- or calcined shaped bodies; and (2) the shaped body, catalyst or catalyst precursor, obtained by the above method.

Description

The Invention relates to a method for treating a shaped body, in particular a catalyst, Katalysatorträger- or Sorbent-shaped body, as well as obtainable by this method Moldings. Furthermore, the present invention relates Uses of an aqueous fluid containing one or more soluble in water with anion and / or cation formation Compounds, for the treatment of a molding.

catalysts are exposed during their use very high loads and must meet ever increasing demands. Particularly high demands are in particular on catalysts or precursor catalysts placed in equipment introduced which after a filling is no longer or only longer can be changed with great effort. This applies, for example, to catalysts used for filling of reactors, in particular tube bundle reactors used become.

Known is that a reduction in activity or selectivity a catalyst bed in a plant, for example can be done by poisoning or coking of the catalyst. A reduction in activity or selectivity However, a catalyst bed can also by a Damage to the catalysts take place at a Filling process or when heated to high temperatures can occur. When cracks occur in a catalyst or a catalyst coating blasted from a catalyst This can lead to a reaction mixture with an uncoated portion of a shaped catalyst body or with chipped pieces of a catalyst coating comes in contact, some of which no longer the desired surface finish exhibit.

In The chemical industry and research is therefore a constant one Need for catalysts with a high mechanical load capacity. A known approach to increase the mechanical strength is based for example, to improve the adhesion of the catalyst coating on the molding or an increase in abrasion resistance the catalyst coating. Such an improvement of the properties however, the catalyst coating is usually associated with high levels of or material costs associated with and may cause deterioration associated with the catalytic properties of the catalyst coating.

task It is therefore an object of the present invention to provide a method which allows catalysts with a high mechanical To obtain resilience, the preparation of such catalysts, but only with a small additional work or Cost of materials should be connected. Such a procedure should also use proven catalyst coatings allow without simultaneously the catalytic properties affect these catalyst coatings or At least this should not worsen significantly.

These The object is achieved by a method for treating a shaped body, in particular a catalyst, Katalysatorträger- or Sorbent-shaped body, solved, which is the following Steps comprises: providing a shaped body, wherein the molding comprises one or more tectosilicates and is selected from the group consisting of non-calcined Shaped bodies and calcined shaped bodies; contacting the shaped body with at least one treatment fluid, wherein the treatment fluid is an aqueous fluid and one or more in water with anion and / or cation formation comprising soluble compounds, and the treatment fluid a content of the one or more in water under anion and / or Cation formation soluble compounds of at least 7 mmol / l; optionally drying and / or optionally calcining of the molded body brought into contact with the treatment fluid.

Farther The present invention teaches uses of an aqueous Fluids containing one or more in water under anion and / or Cation formation comprises soluble compounds, according to one of claims 22 to 24 and relates by the inventive Process obtainable moldings according to claim 25, and catalysts and their precursor according to claim 26. Preferred embodiments are each in the subclaims specified.

During the numerous experiments leading to the present invention, the inventors surprisingly found that by treating a shaped body with an aqueous treatment fluid prior to optional drying, calcining and / or coating, molded articles having high mechanical strength, in particular molded articles having high lateral compressive strength , can be obtained. The inventive method is also feasible without a high additional material or labor cost and allows, if desired, an application of proven catalyst coatings. In addition, it is possible by the inventive method to change the surface of a shaped body and in particular special to reduce the BET surface area of a shaped body and / or the pore volume of a shaped body.

The inventive method for treating a Shaped body, in particular a catalyst, catalyst carrier or sorbent-shaped body, includes a first Providing a non-calcined shaped body, wherein the molding comprises one or more tectosilicates or consists of one or more Tectosilicaten.

Of the Term "shaped body", as in the present Invention comprises any known to a person skilled in the art. For the execution of the invention Method may be particularly advantageous if as a shaped body a granulate, an extrudate or a compact used becomes. In addition, the shaped body but also have other forms and designs known to a person skilled in the art. The term "non-calcined shaped body" comprises that the molding after the molding step, for example by granulating, extruding or pressing, not over about 170 ° C, preferably not more than 140 ° C, preferably not more than 120 ° C, more preferably not over 110 ° C, especially not more than 100 ° C. was heated. In a "non-calcined molding" can it is either a "raw molding" or about act a "dried molding", wherein the term "raw shaped body" shaped body which does not exceed about. after the molding step 59 ° C, preferably not over 40 ° C, preferably not heated above 35 ° C while the term "dried shaped article" shaped article which is greater than about 59 ° C, preferably more heated to 65 ° C. The term "calcined Shaped body "comprises shaped bodies, which after the step of molding heating to greater than about 170 ° C were subjected. Before the step of molding a molding is a heating of one or more of the starting materials of the shaped body, for example, to a temperature above 50 ° C, especially over 100 ° C optionally possible. For example, extrudates are shaped bodies after treatment by the inventive method a very have good mechanical strength.

Preferably has a non-calcined shaped body before contacting with a treatment fluid, a water content of at least 12-16 Wt .-%, preferably of at least 1.5-7 wt .-%, based on the total weight of the non-calcined shaped body, determined by determining the weight difference that a shaped body before and after heating to 1000 ° C to constant weight having.

The contacting of the shaped body with the at least one treatment fluid preferably takes place before the application of a coating, in particular a catalytically active coating, of the shaped body. In particular, it is preferred if the shaped body takes place after its shaping, its optional drying and / or its optional calcination, and / or after an optional step in which an ion exchange, for example a NH ₄ ⁺ ion exchange, takes place and / or an optional washing with water in which subsequent step is contacted with the treatment fluid. In addition, it may be advantageous if, prior to step b) of contacting the shaped body with the at least one treatment fluid, no step of applying a coating, in particular a catalytically active coating, has occurred on the shaped body, and / or if prior to step b) contacting the shaped body With the at least one treatment fluid no drying of the shaped body, for example at a temperature of more than 59 ° C, in particular of more than 100 ° C is carried out. An optional step involving NH ₄ ⁺ ion exchange can be accomplished, for example, by immersion in a solution comprising NH ₄ NO ₃ for, for example, one to two hours, followed by optional water washing. Other techniques known to those skilled in the art for performing ion exchange may also be selected.

As "catalytic active mass "is considered a mass in their presence changed the reaction mechanism of a considered reaction In particular, a reaction will expire faster without that the mass in the reaction, especially in stoichiometric Quantities, is consumed.

The term "tectosilicate" as used in the present invention includes any tectosilicate (skeletal silicate) known to one skilled in the art, and in particular any zeolites. Possible structures and examples of numerous tectosilicates and in particular zeolites are, for example, in "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, p. 776-778 , explained. Tectosilicates, zeolites and their representation are also in the "Rompp Lexicon Chemistry", eds .: J. Falbe, M. Regitz, 10th ed. 1999, Georg Thieme Verlag, ISBN 3-13-107830-8, p 5053ff. explained.

In particular, the term "tectosilicate" includes all compounds in which silicon atoms in the space network structure of the silicon dioxide are partially replaced by other atoms, in particular aluminum. silici dioxides, with the exception of zeolitic silicas, such as silicalite, are not covered by the term "tectosilicate". Preferably, at least 1%, preferably at least 5%, more preferably at least 8%, more preferably at least 12%, of the silicon atoms of the tectosilicate may be replaced by aluminum atoms. Furthermore, a Tectosilicat, in particular a zeolite, cavities and / or channels, which connect the cavities at least partially with each other, having, for example, the cavities may have a diameter of 350 to 1300 pm and the channels, for example, a diameter of 180 to 800 pm. In particular, the one or more tectosilicates may be one or more zeolites or mixtures of zeolite (s) with other tectosilicates.

moreover may according to a preferred embodiment of a Tectosilicat, especially zeolite, the Si / Al atomic ratio of 0.8: 1 to 360: 1, preferably 1: 1 to 110: 1.

Especially For example, the molded article may contain one or more zeolites in addition to optional other tectosilicates, include or from these consist. Moldings with good mechanical strength can For example, be obtained when the molding a or more zeolites, which consists of the group consisting of Fiber zeolites, zeolites, cube zeolites, MFI-type zeolites, beta-structure zeolites, zeolite A, zeolite X, zeolite Y and mixtures thereof are. For example, count among fiber zeolites u. a. natrolite, Laumontite, Mordenite, Thomsonite, to Leaves-Zeolites a. Heulandite, Stilbite, as well as Dice-Zeolithen u. a. faujasite, Chabazite and gmelinite.

Possibilities for the recovery of naturally occurring zeolites, as well as processes for the preparation of synthetic zeolites are known to a person skilled in the art. Processes for the preparation of synthetic zeolites with MFI structure, with an Si / Al atomic ratio of about 8 to 45 are for example in the WO 01/30697 A described.

In particular extent is suitable for carrying out the inventive method a shaped body, a content of Tectosilicaten, in particular of zeolites, of at least 50% by weight, preferably at least 60% by weight, is preferred of at least 70% by weight, more preferably of at least 85% by weight, in particular of at least 90% by weight, based on the total solids content of the shaped body.

In a step of the method according to the invention a contacting of the shaped body takes place with at least a treatment fluid, wherein the treatment fluid is an aqueous Fluid is and one or more in water under anion and / or Cation formation comprises soluble compounds, and that Treatment fluid content of the one or more in Water soluble under anion and / or cation formation Compounds of at least 7 mmol / l may have.

Without that the invention is limited to the correctness of the assumption would, it is believed that by the action of at least a treatment fluid on a shaped body, the structure the molding undergoes a gain and the surface is advantageously changed. In particular, by the method according to the invention the BET surface, for example of extrudates, reduced become. In particular, in the inventive Method of contacting the molding with the at least one treatment fluid carried out such that a reduction the BET surface of the shaped body takes place. Preferably the contacting takes place with the at least one treatment fluid such that in step c) of the invention Process obtained after drying and / or calcining molding has a BET surface area that is at least 5% smaller, preferably 12 to 30% smaller than the BET surface area of the shaped body, in particular of the calcined shaped body is that in step a) of the method according to the invention was provided.

For example, using soda waterglass solutions as the treatment fluid, followed by optional ion exchange with ammonium nitrate and calcining, a decrease in BET surface area of 8% (using a 5% sodium waterglass solution, about 0.04 mol / L based on SiO ₂ Content) to about 25% (when using a 25% sodium silicate solution, about 0.9 mol / l based on SiO ₂ content) with an approximately equal, approximately tripled, lateral compressive strength in both cases.

In addition, the method according to the invention can lead to a decrease in the size of agglomerate crystallites and primary crystallites of a shaped body, which is evident, for example, in moldings treated according to the invention with hydroxide or sodium waterglass solutions, in particular extrudates. Without the invention being limited to the correctness of the assumption, it is presently believed that by the inventive method increased mechanical stability, inter alia, by an additional bond at the molecular level between molded body surface components, for example between primary crystallites, may be caused.

moldings with high mechanical strength, in particular a high lateral compressive strength, can obtained, for example, according to a preferred embodiment when the treatment fluid per gram of molding a content of 0.001 and 100 mmol, preferably from 0.01 to 10 mmol, at the one or more in water under anion and / or Cation formation has soluble compounds. Especially For example, one treatment fluid per gram of molding may require one Content of 0.001 and 100 mmol, preferably from 0.01 to 10 mmol, have potassium cations.

Of the Term "treatment fluid" as used in the present Invention comprises any fluids and in particular, Solutions, suspensions and aerosols, including colloidal solutions or gels. It is preferable in a treatment fluid around a solution or suspension, preferably only other compounds than the one or the more in water with anion and / or cation formation soluble compounds in not completely dissolved Form present.

Of the Term "in water with anion and / or cation formation soluble compounds "includes any in water under anion and / or cation formation at least partially dissociating Compound, such as any of anion and / or Cation formation dissociating salts, any inorganic or organic acid, any inorganic or organic Base and soluble in water with anion and / or cation formation, dissociable complexes. An under anion and / or Cation formation dissociating salt can be both inorganic, as well as organic anions, as well as both inorganic, as well include organic cations.

The salts, inorganic or organic acids, inorganic or organic bases, as well as dissociable complexes can be both compounds which donate protons to water as so-called Brönsted acids or absorb protons as so-called Bronsted bases of water molecules and thus to Formation of hydroxide ions induce cause, as well as act so-called Lewis acids or Lewis bases, which in the presence of water at least partially form an acid-base complex, such as boric acid. The terms Brönsted acids or bases, as well as Lewis acids or bases are known to a person skilled in the art and are described, for example, in US Pat "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, pages 235 to 251 , explained.

The presence of a suitable solubility of the one or more compounds soluble in water with anion and / or cation formation can be determined by one skilled in the art by simple hand experiments. Preferably, at least one of the compounds soluble in water with anion and / or cation formation has a solubility in water at 25 ° C. of at least 0.003 mol / l, preferably of at least 0.007 mol / l, preferably of at least 0.01 mol / l on. The one or more compounds soluble in water with anion and / or cation formation may be in the aqueous treatment fluid, for example after dissociation or addition of OH ^- ions, completely or substantially completely as ions, but may also be substantially not in ionic form. For example, only at least 0.0001% of the amount of the substance in the one or more compounds soluble in water under anion and / or cation formation may be present in the treatment fluid in the form of anions and / or cations.

moldings with high mechanical strength, in particular a high lateral compressive strength, can For example, if the one or more soluble in water with anion and / or cation formation Compounds at least one in water with anion and / or cation formation soluble compound selected from the group consisting of chlorides, hydroxides, nitrates, carbonates, bicarbonates, Bristles, tetralkylammonium compounds, water glasses, Boric acids, platinates, phosphoric acids, sulfates, silicas and their mixtures. Preferably, a treatment fluid comprises besides water, as well as the at least one in water under anionic and / or cation-forming soluble compound from the not more than 10% by weight, preferably not more than 5 wt .-%, in particular not more than 2 wt .-% of a or several other compounds, in particular salts, acids and bases, based on the total weight of the treatment fluid and the total weight of one or more other compounds.

The total content of one or more in water under anion and / or cation image The soluble compounds can preferably be at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably at least 0.007 mol / l to 4.2 mol / l, more preferably 0.007 mol / l to 1.2 mol / l, in particular 0.009 mol / l to 0.8 mol / l.

In particular, moldings having a high mechanical load-bearing capacity, in particular a high lateral compressive strength, can be obtained if the one or more compounds soluble in water with formation of anions and / or cations comprises at least one compound selected from the group consisting of potassium-containing compounds, in particular potassium chloride , Potassium hydroxide, potassium nitrate, potassium carbonate, potassium hydrogencarbonate, potassium borates, potassium waterglasses, sodium and potassium bristles, sodium and potassium containing waterglasses; sodium-containing compounds, especially sodium chloride, sodium hydroxide, sodium nitrate, sodium carbonate, sodium bicarbonate, sodium borates, sodium water glasses; Tetraalkylammonium compounds, especially tetralkylammonium hydroxides; Calcium chlorides; Magnesium compounds, in particular magnesium nitrate, platinates, in particular dihydrogen hexachloroplatinates (IV), zinc compounds, in particular ZnSO ₄ ; Boric acids, in particular H ₃ BO ₃ , phosphoric acids, in particular H ₃ PO ₃ and H ₃ PO ₄ ; Silicas, and mixtures of these compounds.

In especially to an increase of the mechanical Strength of moldings contributes when the Treatment fluid has a high alkali and / or alkaline earth metal content, in particular a high total content of alkali cations, for example one high total content of sodium cations, potassium cations, magnesium cations, Calcium cations, lithium cations and / or rubidium cations has. Particularly advantageous results can be, for example be obtained when the treatment fluid potassium cations and / or Sodium cations, in particular potassium cations comprises.

moldings For example, with very good mechanical strength be obtained when the treatment fluid is a solution is that a total content of alkali and alkaline earth cations, preferably at Lithium, sodium, potassium, magnesium, calcium and rubidium cations, preferably of sodium and potassium cations, in particular a content at potassium cations, of at least 0.007 mol / l, preferably at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably from at least 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l, and / or if the treatment fluid is a suspension and after Separation of the undissolved in the suspension Constituent solution a total level of alkali and alkaline earth cations, preferably of lithium, sodium, potassium, Magnesium, calcium and rubidium cations, preferably on sodium and potassium cations, in particular a content of potassium cations, of at least 0.007 mol / l, preferably of at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably at least 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l.

Preferably the cations comprise potassium cations. The number of particles of potassium cations in the treatment fluid, based on the total particle number For example, cations in the treatment fluid may be at least 50%, preferably at least 70%, preferably at least 85%, in particular at least 90%.

The Separation of the undissolved constituents prior to determination of the Cation and / or anion content may be determined by any one skilled in the art known methods are carried out, in particular by centrifugation.

Very advantageous moldings, for example be obtained when the treatment fluid has an alkali content, the is in particular a content of lithium, sodium, potassium and rubidium, calculated as alkali oxide, between 0.0001 and 20% by weight, in particular between 0.001 and 10% by weight, more particularly between 0.01 and 8 wt .-%, having.

If the treatment fluid is a solution, this may have a total content of anions of at least 0.007 mol / l, preferably at least 0.009 mol / l, more preferably from at least 0.01 mol / l, preferably from at least 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l. If it is the treatment fluid is a suspension, which, after separation in the Suspension undissolved present constituents Solution a total content of anions of at least 0.007 mol / l, preferably of at least 0.009 mol / l, more preferably of at least 0.01 mol / l, preferably at least 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l.

The term "borate" as used in the present invention includes both from Ortho Boric acid derived from boric acid and polyboric acids, as well as any other bristles, such as metaborates, hydroxoborates, in particular borax. Possible structures and examples of bristles are, for example, in "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, p. 851-856 , explained.

The term "tetraalkylammonium compound" includes all tetraalkylammonium compounds known to a person skilled in the art, in particular all compounds which comprise the element (NR ¹ R ² R ³ R ⁴ ) ⁺ , where R ¹ can be any straight-chain or branched alkyl radical having 1 to 30 carbon atoms, R R ² can be any straight or branched chain alkyl radical of 1 to 30 carbon atoms, R ³ can be any straight or branched chain alkyl radical of 1 to 30 carbon atoms, R ⁴ can be any straight or branched chain alkyl radical of 1 to 30 carbon atoms; R ¹ , R ² , R ³ , R ⁴ can be chosen independently. The counterion may be any single or multiple negative-charged anion, preferably a hydroxide, chloride or bromide anion.

Especially advantageous results have been obtained using tetrapropylammonium compounds, in particular of tetrapropylammonium hydroxide.

The term "water glasses" includes any water glasses known to a person skilled in the art. In particular, this term encompasses sodium and / or potassium silicates of the composition M ¹ M ² O.nSiO ₂ , for example with n = 0.8 to 4.2, M ¹ = K or Na, M ² = K or Na, in particular Na ₂ SiO ₃ and K ₂ SiO ₃ . For example, compositions of water glasses and their presentation are described "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, pp. 778-779 , explained.

Moldings of high mechanical resistance are obtained, for example, when the treatment fluid is a potassium chloride, potassium carbonate, potassium hydroxide, potassium nitrate, tetrapropylammonium hydroxide, H ₃ BO ₃ , H ₃ PO ₄ , ZnSO ₄ , magnesium nitrate, calcium chloride, CPA -, sodium-water glass fluid, in particular solution. Preferably, a treatment fluid does not comprise any further compounds soluble in water with anion and / or cation formation, or comprises these only up to a level of up to 1% by weight, based on the total weight of the treatment fluid.

The inventive method is particularly suitable Measures for the treatment of moldings containing a or more zeolites, in particular one or more zeolites of MFI structure type or beta structure type, include or from these consist. Without the invention being limited to the correctness of the assumption would be assumed by the action of a Treatment fluids to an MFI or beta-type zeolite comprehensive moldings, a significant stabilization and Solidification of the molecular structure of the MFI-type zeolite or beta structure type.

Especially can be particularly good mold material properties in a treatment of at least one zeolite from the MFI or Beta structure type comprehensive molding, in particular in the form of an extrudate, with a potassium chloride solution with a content of 0.05 to 0.09 mmol of KCl / g of molding, preferably at a content of 0.06 to 0.08 mmol of KCl / g Shaped body, in particular with a content of about 0.07 mmol of KCl / g of molding can be obtained. Especially good mold material properties can also in a treatment of at least one MFI or zeolite Beta structure type comprehensive molding, in particular in the form of an extrudate, with a tetrapropylammonium hydroxide (TPAOH) solution with a content of 0.15 to 0.20 mmol of TPAOH / g of molding, in particular with a content of about 0.188 mmol of TPAOH / g Shaped body can be obtained.

Further be good mold material properties by the Use of acids, especially with phosphoric acid with a content of 3.0-5.5 mmol of H3PO4 / g of molding, in particular on at least one zeolite of the MFI or beta structure type comprehensive molded body, received.

A treatment fluid can be obtained, for example, if at least one compound soluble in water under anion and / or cation formation is added to an aqueous fluid, in particular water, preferably deionized or distilled water and partially or completely dissolved, for example with stirring. Preferably, the treatment fluid is a solution. A treatment fluid may be generated by one skilled in the art in a variety of ways. In particular, it is also possible to add to the aqueous fluid or water compounds which react with one another or with water after introduction into the water or mixing and give a treatment fluid having a composition suitable for carrying out the method according to the invention. In particular, a One or more acids, for example HCl, and one or more bases, for example KOH, which then react with one another in the aqueous fluid, instead of a salt, for example potassium chloride.

moldings high mechanical load capacity can be obtained in particular when the treatment fluid has a pH above 2, preferably more than 4, more preferably more than 7, preferably greater than 9, more preferably greater than 10, in particular from 4 to 12. In most cases, a pH of 13.8 is not exceeded become.

To achieve a high mechanical strength, the treatment fluid and / or the molded body to be treated may have at least one SiO ₂ source, wherein the SiO ₂ source is water glass, in particular a water glass solution, and / or silica, in particular precipitated silica or colloidal Silica can act.

In particular, the SiO ₂ content of the treatment fluid may be between 0.01 and 40% by weight, in particular between 0.1 and 20% by weight, more preferably between 0.2 and 10% by weight.

Furthermore, the SiO ₂ source in the treatment fluid may have an average particle size (D ₅₀ ) of less than 50 nm, preferably less than 20 nm, particularly preferably less than 10 nm and in particular less than 5 nm. The D ₅₀ value is the value at which half of the particles each have a larger or smaller particle diameter.

The Treatment fluid may include any other optional components, who select a professional based on his general expertise can. However, a treatment fluid preferably contains no or not more than 25% by weight, preferably not more than 5 wt .-%, preferably not more than 1 wt .-% of further, optional Components. It may be advantageous, in particular, if the treatment fluid one or more further solvents, detergents, silanizing agents, for example, colloidal silicon, or metal salts, preferably Salts of catalytically active metals, in particular platinum salts or Contains palladium salts. When using a treatment fluid, containing one or more metal salts, in particular Salts of catalytically active metals, for example copper salts, Nickel salts, platinum salts or palladium salts, is in particular Measures of advantage that after treatment with the treatment fluid a finished catalyst or catalyst precursor can.

The Contacting the molding with the treatment fluid can be done by numerous methods known to a person skilled in the art. From a procedural point of view can advantageously immersing the shaped body in the treatment fluid or spraying the molding with the treatment fluid respectively. Particularly advantageous is when the shaped body introduced into treatment fluid, in particular immersed and for example, 2 minutes to 24 hours, especially 10 to 20 minutes by passing gas, for example air or nitrogen, is circulated.

Very Also advantageous is a step of contacting using the so-called "pore filling method" (also "incipient called "wetness" method). variants These methods are known to a person skilled in the art and, moreover, one is particular advantageous embodiment variant explained in the example sections.

optional For example, the step of contacting the molding with the treatment fluid are repeated one or more times, wherein before a repetition optionally a drying step and / or calcination step can be done.

To contacting the shaped body with the treatment fluid can optionally be washed once or more with water, especially deionized or distilled water. Subsequently the shaped body can optionally be dried and / or calcined become. Drying of the treated with the treatment fluid, as well Optionally washed molding can, for example, in Temperatures from 40 to not more than about 170 ° C, especially between 50 and 80 ° C, in a drying device, for example, a furnace, optionally also with the application of a Vacuum, that is at a relative to the ambient pressure reduced pressure, done. Preferably, drying takes place to constant weight.

Calcining the treated with the treatment fluid, as well as optionally washed and optionally dried shaped body, for example, at temperatures of more than about 170 to 1800 ° C, preferably about 350 ° C to about 650 ° C, in particular about 600 ° C, over a period of about 1 to about 16 hours, in particular about 5 hours.

Furthermore, after the optional steps of washing and / or drying and / or calcination, one or more coatings may be applied to the shaped body. The one or more coatings cover the catalyst at least partially or preferably completely. The coating (s) may comprise at least one component selected from the group consisting of titanium oxides, in particular TiO ₂ , vanadium oxides, silicon oxides, aluminum oxides, phosphorus oxides, metals, metal salts and mixtures thereof. After application of the coating, as well as optional further operations, for example surface treatment steps, washing steps and / or drying steps, a catalyst or catalyst precursor (ie a precursor of a catalyst which is converted into a catalyst in one or more steps, in particular heating) is then converted can be obtained).

to Preparation of catalysts are numerous in the art suitable procedures are described so that a detailed presentation basically not required here. It can all customary and familiar to the expert catalyst forms be chosen, including full catalysts and coated catalysts containing an inert support and at least one layer applied thereto with a catalytic having active mass.

The Tectosilicate catalysts used in the invention, especially those with zeolites are after a possible Embodiment used as catalysts, in particular the zeolites in the H-form (with or without use of base metals and / or precious metals) as catalysts for acid catalyzed Reactions, oxidations, reductions and adsorptions used can be.

These reactions include, among others, catalytic cracking (FCC additive) and hydrocracking (also "dewaxing" by gentle hydrocracking); Alkylations e.g. As of aromatics with olefins, alcohols or with halogenated paraffins; Alkylation of aromatics; Alkylation of isoparaffins with olefins; Transalkylation (of aromatics); Disproportionation (eg, toluene disproportionation, etc.); Isomerization and hydroisomerization (eg of paraffins, olefins, aromatics, xylene isomerization, dewaxing, etc.); Dimerization and oligomerization; polymerizations; Etherification and esterification; Hydration and dehydration; Adsorption; Condensation; Oxidation; acetylation; Dealkylation and cyclization; Alkylation and hydrodealkylation (ethylbenzene to benzene); Emission control. Acid-catalyzed reactions are also for example in the DE-A-4 405 876 in which a catalyst based on a particulate acid-activated phyllosilicate is used whose particles are bound together by a binder.

at their use as catalysts are the invention Products in general in lumpy form (shaped body), z. As extrudates, granules, pellets, spheres, honeycomb body and other shaped bodies.

general may be inorganic, organometallic or organic binders be used. As inorganic binders are used recordable Silica or aluminum hydroxide brine. Furthermore, aluminates, Titanates or phosphates suitable. Particularly suitable are alkaline earth compounds, the sparingly soluble in the reaction with acid Salts form, with strontium and barium compounds compared to the corresponding calcium compounds give better binders.

A binder which leads to particularly high-quality moldings comprises SiO ₂ and TiO ₂ , for example in a molar ratio of 50: 2 to 70: 1, preferably from about 30: 1 to 60: 1.

Other suitable inorganic binders are compounds of the metals of groups IIIA (preferably Y ₂ O ₃ ), IIIB (preferably B ₂ O ₃ , Al ₂ O ₃ or Al (H ₂ PO ₄ ) ₃ ), IVA (preferably TiO ₂ and ZrO ₂ ), IVB (preferably oxides, carbides or nitrides of silicon, lanthanides, preferably LaO ₂ or CeO ₂ ) of the actinides (preferably ThO ₂ ).

As inorganic binders it is also possible to use hydraulic binders, preferably cement or gypsum, bentonite or alumina or the natural silicate binders, such as mullite or talc. In one embodiment, the at least one binder is selected from the group consisting of aluminum silicates, layered silicates, in particular kaolinite and / or montmorillonite, silicas and alumina, SiO ₂ -containing binders or mixtures thereof.

The organometallic binder may be a compound of the formula Me (OR) _n or the formula Me (O-CO-R) _n , where Me is a metal of valency n and R is an organic radical, e.g. Example, represent an alkyl, aryl, aralkyl, alkaryl or heterocyclic radical.

The Organic binders can be a natural, semi-synthetic or synthetic polymer or a precursor thereof, this in terms of processing and / or application conditions Does not lose binding properties. As examples, alkene (Co) Polymers, polycondensates, polyaddition compounds, silicone rubber, Silicone resins, rubber, bone glue, casein, galalith, alginates, Starch, cellulose, guar, carboxymethylcellulose, polyvinyl alcohol, Polyacrylic or polymethacrylic compounds and addition or Called condensation resins. In particular, furan resins can or phenolic resins are used.

The Production of the molding can be carried out by a person skilled in the art known manner. In particular, molded bodies be obtained with advantageous material properties, if a or several tectosilicates, for example in the form of a powder, with optionally at least one binder, and optionally one or more solvents, especially water are and then formed into a shaped body, in particular extruded, and optionally dried and / or washed.

Especially may be a molded article prior to contacting with a Treatment fluid one or more times optionally with water, in particular distilled or deionized water.

According to one In another aspect, the present invention provides moldings and further catalyst or catalyst precursor ready obtainable by the method according to the invention are.

According to In another aspect, the present invention teaches a use an aqueous fluid containing one or more in water comprising compounds capable of forming anions and / or cations, for treating a one or more tectosilicates Shaped body, wherein the content of the one or more soluble in water with anion and / or cation formation Compounds at least 7 mmol / l.

Especially The present invention teaches a use of an aqueous Fluids containing one or more in water under anion and / or Cation formation comprises soluble compounds to increase the mechanical strength, in particular the lateral compressive strength a molding comprising one or more tectosilicates. The term "mechanical strength" as in the used in the present invention comprises both compressive strength, as well as tensile strength, wherein a force of any Directions is possible, and also a resistance against an impact of shear forces.

moreover The present invention teaches a use of an aqueous Fluids containing one or more in water under anion and / or Cation formation comprises soluble compounds for alteration the surface, in particular for reducing the BET surface area and / or pore volume, of one or more tectosilicates comprehensive molded body.

METHODS

to Determination of the parameters of the invention Catalysts are used the following methods:

a) Determination of side pressure resistance

The Side crushing strength was measured with a measuring device of the company Schleuniger, Model 6 D measured according to manufacturer's instructions. Here are the tablets with increasing pressure between two Compression jaws compressed. Upon breakage, a pressure drop occurs and the maximum applied pressure before breakage is recorded. (Quality control according to test equipment number S104.02AA.0043.) Per extrudate, at least 24 pieces (max 50 pieces) of 3-4 mm in length one after the other just aligned in the measuring chamber. The measurement was carried out by the method of the load cell.

b) BET surface area:

The determination is made according to the BET method according to DIN 66131 ; a publication of the BET method can also be found in J. Am. Chem. Soc. 60, 309 (1938) ,

c) particle sizes:

The Determination of the particle sizes took place after the Laser diffraction method with a Fritsch Particle Sizer Analysette 22 Economy (Fritsch, DE) according to the manufacturer, also regarding sample pretreatment: the sample is deionized Homogenized water without the addition of auxiliary agents and 5 minutes treated with ultrasound.

d) Pore radius distribution:

The determination of the pore radius distribution and the pore volume was carried out by means of mercury porosimetry according to DIN 66133 ; maximum pressure: 2,000 bar, Porosimeter 4000 (Porotec, DE), according to the manufacturer.

The Determination of BET surface area, pore radius distribution or the pore volume and the Primärkristallitgrößen and the particle size distribution was carried out in each case at the dried at 150 ° C in vacuum, uncalcined Material.

Of the Active mass fraction (proportion of the catalytically active material, without binder) refers in each case to the proportion (in% by weight) of the catalytic active mass of the total weight of the catalyst including carrier in the respective catalyst layer, measured after conditioning over 4 hours at 400 ° C.

Weight specifications per gram of molded article (unless explicitly stated otherwise) relate in particular to the shaped article which, after its preparation, was treated as follows: The shaped wet extrudates were dried between 60 and 120 ° C. and heated up slowly by 1 ° C. per minute 1000 ° C and while kept under circulating air for 5 h. Fresh air intake of about 3 m ³ / h was given continuously.

The Invention will now be described with reference to the following non-limiting Examples explained in more detail:

EXAMPLES

Example 1: Preparation of a treatment fluid

Several ionic solutions were prepared by dissolving NaCl, NaOH, water glass (Na ₂ SiO ₃ , K ₂ SiO ₃ ), KOH, TPAOH (tetrapropylammonium hydroxide), KCl, KNO ₃ , CaCl ₂ , CPA (dihydrogen hexachloroplatinate (IV)), H ₃ PO ₄ , ZnSO ₄ , Mg (NO ₃ ) ₂ .6H ₂ O or H ₃ BO _{3 was dissolved} in water.

The ionic solutions are placed in a suitable container in the appropriate concentration by stirring in water produced. The used, in particular listed above Compound, the amount of compound used, the used Water volume, the resulting concentration and the Mass of catalyst used are shown in Table 1, 3, 5, and in the following the respective experiments explanatory Tables, indicated in columns 2-5, respectively. column 6 sets the molar amount of compound in relation to the amount of used Catalyst bodies. Partial exotherm occurred during the Solution process; it was therefore taken care that before the experiment, the solutions to 25 ° C. had cooled.

For easier readability, the first column shows the combination of shaped catalyst bodies and the respective aqueous solution used as the treatment fluid in Table 1, as well as in the following tables in which the respective experiments are explained. The following abbreviation is used: "TPAOH" for tetrapropylammonium hydroxide solution, "NWG" for Na ₂ SiO ₃ solution, "CPA" for dihydrogen hexachloroplatinate (IV) solution, "NaCl", "NaOH""KOH","H ₃ BO ₃ "," KOH "," KCl "," KNO ₃ "," CaCl ₂ "," H ₃ PO ₄ "," ZnSO ₄ "," Mg (NO ₃ ) ₂ .6H ₂ O "for a solution of (of) the respectively indicated acid, base or salt (NaCl, NaOH, KOH, H ₃ BO ₃ , KOH, KCl, KNO ₃ , CaCl ₂ , H ₃ PO ₄ , ZnSO ₄ , Mg (NO ₃ ) ₂ .6H ₂ O ). The final digit in the first column indicates the running trial number for a particular tested combination of catalyst body and treatment fluid.

Example 2: Treatment of shaped catalyst bodies with treatment fluid using supernatant solution

a) treatment with treatment fluid under Use of supernatant solution

Catalyst shaped bodies, in particular Cat. 1-4 (Example 2b) and 5 _dried (Example 2c), were in each case brought into contact with the various aqueous ionic solutions (prepared according to Example 1). For this purpose, the catalyst was added rapidly to the ionic solution at 25 ° C, so that the catalyst was completely covered with the ionic solution. The suspension was circulated through nitrogen or air throughflow for about 15 minutes, then decanted off and the supernatant solution discarded. The remaining solids content was dried at 60 ° C for 16 h, then calcined at 600 ° C for 5 h. For comparison, distilled water was also used.

b) Experiments with calcined catalyst moldings

• Kat. 1: H-MFI 90 mit Silizium-haltigem Binder (25 Gew.-% an Binder (kolloidale Kieselsäure), bezogen auf das Gesamtgewicht des Katalysatorformkörpers; Zylindrische Form, Durchmesser 1/16”). Kat. 1 wurde gemäß Beispiel 2 der EP 0 369 364 B1 , sowie dem dort unter Bezugnahme angeführten Beispiel 1 und Vergleichsbeispiel 3 der EP 0 369 364 B1 , hergestellt, wobei jedoch ein Silizium-haltiger Binder (kolloidale Kieselsäure) verwendet wurde.
• Kat. 2: H-MFI 90 mit Aluminium-haltigem Binder (16 Gew.-% Böhmit, bezogen auf das Gesamtgewicht des Katalysatorformkörpers; Zylindrische Form, Durchmesser 1/8”). Kat. 2 wurde gemäß Beispiel 2 der EP 0 369 364 B1 , sowie dem dort unter Bezugnahme angeführten Beispiel 1 und Vergleichsbeispiel 3 der EP 0 369 364 B1 , hergestellt.
• Kat. 3: H-MFI 90 mit Aluminium-haltigem Binder (25 Gew.-% Böhmit, bezogen auf das Gesamtgewicht des Katalysatorformkörpers; Zylindrische Form; Durchmesser 1/16”). Charge 1 und 2 bezeichnen zwei unterschiedliche Ausführungsformen von Kat. 3. Kat. 3 wurde gemäß Beispiel 2 der EP 0 369 364 B1 , sowie dem dort unter Bezugnahme angeführten Beispiel 1 und Vergleichsbeispiel 3 der EP 0 369 364 B1 , hergestellt.
• Kat. 4: H-Beta 25 mit Silizium-haltigem Binder (30 Gew.-% an Binder (kolloidale Kieselsäure), bezogen auf das Gesamtgewicht des Katalysatorformkörpers; NH₄ ⁺-Ausgetauscht; Zylindrische Form; Durchmesser 1/16”). Kat. 4 wurde gemäß Beispiel 2 der EP 0 369 364 B1 , sowie dem dort unter Bezugnahme angeführten Beispiel 1 und Vergleichsbeispiel 3 der EP 0 369 364 B1 , hergestellt und einem NH₄ ⁺Austausch unterzogen, wobei jedoch ein Silizium-haltiger Binder (kolloidale Kieselsäure) verwendet wurde. Die Herstellung von Zeolith Beta 25 ist beschrieben in: ”Verified Syntheses of Zeolitic Materials”, Published an behalf of the Synthesis Commission of the International Zeolite Association, Hrsg.: H. Robson, 2. Aufl.,, 2001, Elsevier Science B. V., S. 115 ). Alle behandelten Katalysator-Formkörper wurden bei 600°C während 5 Stunden kalziniert.

In total, four different calcined shaped catalyst bodies were investigated, namely:

• Cat 1: H-MFI 90 with silicon-containing binder (25 wt .-% of binder (colloidal silica), based on the total weight of the shaped catalyst body, cylindrical shape, diameter 1/16 "). Cat. 1 was according to Example 2 of EP 0 369 364 B1 and Example 1 and Comparative Example 3 cited therein by reference EP 0 369 364 B1 , but using a silicon-containing binder (colloidal silica).
• Cat. 2: H-MFI 90 with aluminum-containing binder (16% by weight boehmite, based on the total weight of the shaped catalyst body, cylindrical shape, diameter 1/8 "). Cat. 2 was according to Example 2 of EP 0 369 364 B1 and Example 1 and Comparative Example 3 cited therein by reference EP 0 369 364 B1 , produced.
• Cat 3: H-MFI 90 with aluminum-containing binder (25 wt .-% boehmite, based on the total weight of the shaped catalyst body, cylindrical shape, diameter 1/16 "). Charge 1 and 2 indicate two different embodiments of Cat. 3. Cat. 3 was according to Example 2 of EP 0 369 364 B1 and Example 1 and Comparative Example 3 cited therein by reference EP 0 369 364 B1 , produced.
• Cat 4: H-Beta 25 with silicon-containing binder (30% by weight of binder (colloidal silica), based on the total weight of the catalyst molding; NH ₄ ⁺ -exchanged; cylindrical shape; diameter 1/16 "). Cat. 4 was according to Example 2 of EP 0 369 364 B1 and Example 1 and Comparative Example 3 cited therein by reference EP 0 369 364 B1 , prepared and subjected to NH ₄ ⁺ exchange, but a silicon-containing binder (colloidal silica) was used. The preparation of zeolite Beta 25 is described in: "Verified Syntheses of Zeolitic Materials", Published on behalf of the Synthesis Commission of the International Zeolite Association, Ed .: H. Robson, 2nd Ed., 2001, Elsevier Science BV, p. 115 ). All treated shaped catalyst bodies were calcined at 600 ° C for 5 hours.

Cat. 1 to 4 were described for a treatment as in Example 2a) subjected and the influence of according to example 1 prepared aqueous ionic solutions the lateral compressive strength of the calcined shaped catalyst bodies was examined.

i) catalyst shaped body cat. 1

Table 1: Overview of the experiments carried out with catalyst bodies Kat. 1 Cat./used solution / numbering Ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat 1 [g] water 0 210 0 - Cat. 1 / NaCl / 2 0.8 210 0.064 40 .3422 Cat. 1 / NaCl / 3b 3.5 236 0.247 40 1.5144 Cat. 1 / NaCl / 4 13.5 210 1.02 40 5,753 Cat. 1 / NaOH / 1 5.1 100 1.2 20 6.38 Cat. 1 / NaOH / 2 10 100 2.25 20 12.5 Cat. 1 / NaOH / 3 20 100 4.12 20 25 Cat. 1 / NaOH / 4 0.38 35 0.26 10 0.94 Cat. 1 / NWG / 2 5 100 0.226 20 1.13 Cat. 1 / NWG / 3 20 80 0.904 20 4.52 Cat. 1 / TPAOH / 1 2.1 100 0.04 40 0.1 Cat. 1 / TPAOH / 2 3.8 100 0.07 40 0.188 Cat. 1 / TPAOH / 3 40 200 0.328 40 1,967 Cat. 1 / TPAOH / 4 50 100 0.66 50 2,459 Cat. 1 / KCl / 1 0.2 240 0.01 40 0.07 Cat. 1 / KCl / 2 10.2 240 0.54 40 3.4 Cat. 1 / _KNO3 / 1 0.22 240 0.009 40 0.05 Cat. 1 / KNO _3/2 11 170 0.6 30 3.63 Cat. 1 / K ₂ CO _3/1 7.5 172 0.3 30 1.81 Cat. 1 / H ₃ BO _3/1 3 180 0.265 30 1.62 Cat. 1 / H ₃ BO _3/2 9 170 0.812 30 4.85 Table 2: Overview of the results obtained with catalyst bodies Kat Cat./used solution / numbering Salt [mmol] / cat. 1 [g] Side pressure resistance [kp / 3-4 mm] Increase lateral crushing strength · cat. 1 [g] / salt [mmol] Cat 1 without treatment 3.4 Cat. 1 / NaCl / 2 .3422 3.8 1.17 Cat. 1 / NaCl / 3b 1.5144 4.6 0.79 Cat. 1 / NaCl / 4 5,753 5.7 0.4 Cat. 1 / NaOH / 1 6.38 3.6 0.03 Cat. 1 / NaOH / 2 12.5 4.8 0.112 Cat. 1 / NaOH / 3 25 6.5 0,124 Cat. 1 / NaOH / 4 0.94 10.4 7.4 Cat. 1 / NWG / 2 1.13 4.5 0.97 Cat. 1 / NWG / 3 4.52 8.4 1.1 Cat. 1 / TPAOH / 1 0.1 4.9 15 Cat. 1 / TPAOH / 2 0.188 4.9 7.97 Cat. 1 / TPAOH / 3 1,967 5.5 1.067 Cat. 1 / TPAOH / 4 2,459 5.9 1.016 Cat. 1 / KCl / 1 0.07 4.6 17.14 Cat. 1 / KCl / 2 3.4 7.3 1,147 Cat. 1 / _KNO3 / 1 0.05 5.2 36 Cat. 1 / KNO _3/2 3.63 8.8 1,487 Cat. 1 / K ₂ CO _3/1 1.81 12.6 5.08 Cat. 1 / H ₃ BO _3/1 1.62 5.5 1,296 Cat. 1 / H ₃ BO _3/2 4.85 5.5 0.43

Table 1 shows that treatment with an ionic solution leads to an increase in lateral compressive strength compared to the untreated catalyst. The highest side pressure strength increases are achieved with the potassium salts. It is striking here that, especially in the experiments "Cat. 1 / KCl / 1 "and" Cat. 1 / _KNO3 / 1 values are achieved ", which are higher by at least an order of magnitude, than for all other experiments. In addition, the highest absolute value of lateral pressure resistance can be achieved by using potassium carbonate. Both salts, which lead to an acid solution when dissolved in water (KNO ₃ ), and salts which lead to a basic solution (KOH) or neutral salts (KCl) show comparably good values.

ii) shaped catalyst body cat. 2

Table 3: Overview of experiments carried out with catalyst bodies Cat 2 Catalyst./used solution / numbering Ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 2 [g] water 0.0 210 0 40 - Cat. 2 / NaCl / 2 15.6 210 1,175 40 6,694 Cat. 2 / NaOH / 4 1.5 140 0.257 40 0.938 Cat. 2 / NWG / 2 10 200 0.214 40 1.13 Cat. 2 / NWG / 3 40 200 0.754 40 4.52 Cat. 2 / KOH / 1 3.5 240 0.25 40 1.52 Cat. 2 / TPAOH / 2 9.07 240 0.072 40 0.446 Cat. 2 / TPAOH / 3 40.0 200 0.328 40 1,967 Table 4: Overview of the results obtained with Cat. 2 Cat./used solution / numbering Salt [mmol] / cat. 2 [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 2 [g] / salt [mmol] Cat 2 without treatment 2.3 water - 2.2 Cat. 2 / NaCl / 2 6,694 2.6 0.0448 Cat. 2 / NaOH / 4 0.938 5.1 2.98 Cat. 2 / NWG / 2 1.13 3.7 1.23 Cat. 2 / NWG / 3 4.52 8.6 1.39 Cat. 2 / KOH / 1 1.52 6.1 2.5 Cat. 2 / TPAOH / 2 0.446 2.5 0,448 Cat. 2 / TPAOH / 3 1,967 2.5 0,101

Also good results with potassium containing ionic compounds, especially KOH solutions achieved.

iii) shaped catalyst body cat. 3

Table 5: Overview of experiments conducted with Cat 3 Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 3 [g] water 0 210 0 40 - Cat. 3 batch 1 / KNO _3/1 4.5 180 0.239 30 1.48 Cat. 3 batch 1 / KNO _3/2 9.0 180 0.446 30 2.97 Cat. 3 batch 1 / K ₂ CO _3/2 6.4 180 0.246 30 1.54 Cat. 3 batch 1 / H ₃ BO _3/1 3 170 0.28 30 1.62 Cat. 3 charge 1 / Mg (NO ₃ ) ₂ · 6H ₂ O 20 180 0,386 30 2.6 Cat. 3 charge 2 / CaCl ₂ .2H ₂ O 20 180 0.673 30 4.53 Cat. 3 charge 2 / KNO ₃ 20 180 0.98 30 6.59 Cat. 3 charge 2 / K ₂ CO ₃ 20 180 0.716 30 4.82 Table 6: Overview of the results obtained with Cat. 3 Cat./inserted solution / numbering Salt [mmol] / cat. 3 [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 3 [g] / salt [mmol] Cat 3 charge 1 without treatment 2.7 Cat 3 charge 2 without treatment 1.7 Cat. 3 batch 1 / KNO _3/1 1.48 2.8 0.0675 Cat. 3 batch 1 / KNO _3/2 2.97 3.7 0,336 Cat. 3 batch 1 / K ₂ CO _3/2 1.54 3.7 0.649 Cat. 3 batch 1 / H ₃ BO _3/1 1.62 3.3 0.37 Cat. 3 charge 2 / Mg (NO ₃ ) ₂ .6H ₂ O 2.6 1.9 0,076 Cat. 3 charge 2 / CaCl ₂ .2H ₂ O 4.53 1.9 0,044 Cat. 3 charge 2 / KNO ₃ 6.59 2.3 0.091 Cat. 3 charge 2 / K ₂ CO ₃ 4.82 2.8 0.228

In this system comparatively low increased lateral compressive strengths are obtained, the potassium salt solutions in the experiments "Cat. 3 / K ₂ CO _3/2 "and" cat. 3 / KNO _3/2 are "beneficial.

iv) catalyst molding cat. 4

• CPA: Dihydrogenhexachloroplatinat (IV) Lösung

Tabelle 8: Übersicht über die mit Kat. 4 erhaltenen Ergebnisse Kat./Eingesetzte Lösung/Nummerierung Salz [mmol]/Kat. 4 [g] Seitendruckfestigkeit [kp/3–4 mm] Erhöhung Seitendruckfestigkeit·Kat. 4 [g]/Salz [mmol] Kat 4 ohne Behandlung 1,8 Kat. 4/CaCl₂/1 1,7 2,7 0,529 Kat. 4/CaCl₂/2 3,4 2,7 0,264 Kat. 4/KCl/1 11,7 4,1 0,196 Kat. 4/Mg(NO₃)₂·6H₂O/1 2,6 2,8 0,384 Kat. 4/CPA/1 1,52 2,3 0,328 Table 7: Overview of experiments conducted with Cat 4 Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 4 [g] water 0 210 0 40 - Cat. 4 / CaCl _2/1 10 240 0,269 40 1.7 Cat. 4 / CaCl _2/2 20 240 0.518 40 3.4 Cat. 4 / KCl / 1 35 205 1,937 40 11.7 Cat. 4 / Mg (NO ₃ ) ₂ .6H ₂ O / 1 20 180 0,386 30 2.6 Cat. 4 / CPA * / 1 10 100 0.55 40 1.52

• CPA: dihydrogen hexachloroplatinate (IV) solution

Table 8: Overview of the results obtained with Cat Cat./inserted solution / numbering Salt [mmol] / cat. 4 [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 4 [g] / salt [mmol] Cat 4 without treatment 1.8 Cat. 4 / CaCl _2/1 1.7 2.7 0.529 Cat. 4 / CaCl _2/2 3.4 2.7 0.264 Cat. 4 / KCl / 1 11.7 4.1 0.196 Cat. 4 / Mg (NO ₃ ) ₂ .6H ₂ O / 1 2.6 2.8 0.384 Cat. 4 / CPA / 1 1.52 2.3 0.328

c) Experiments with dried catalyst moldings

An uncalcined dried catalyst-shaped article cat. 5 is _dried as described in Example 2a) subjected to a treatment with treatment fluid under cover with ionic solution. Catalyst 5 _dried : H-MFI 90 with silicon-containing binder (content of binder (colloidal silica): 25 wt .-%, based on the total weight of the catalyst molding, cylindrical shape, diameter 1/8 ") , Cat. 5 was _dried according to Example 2 of EP 0 369 364 B1 and Example 1 and Comparative Example 3 cited therein by reference EP 0 369 364 B1 , but wherein a silicon-containing binder (colloidal silica) was used. The drying was carried out at 120 ° C for 12 hours. All treated shaped catalyst bodies were calcined at 600 ° C for 5 hours.

The influence of this treatment on the lateral compressive strength of the dried catalyst bodies with treatment fluid was investigated. Table 9: Overview of experiments conducted with Cat 5 Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 5 _dried [g] water 0 210 0 40 - Cat. 5 _dried / H ₃ BO _3/1 9 170 0.812 30 4.85 Cat. 5 _dried / TPAOH / 1 50 100 0.66 30 3,279 Cat. 5 _dried / NWG / 1 20 80 0.904 20 4.52 Cat. 5 _dried / KNO _3/1 20 180 0.98 30 6.59 Cat. 5 _dried / K ₂ CO _3/1 20 180 0.761 30 4.82 Cat. 5 _dried / H ₃ PO _4/2 18 170 0.83 30 5.2 Table 10: Overview of the results _dried with Cat. 5 Cat./inserted solution / numbering Salt [mmol] / cat. 5 _dried [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 5 _dried [g] / salt [mmol] Cat 5 _dried without treatment 5.5 Cat. 5 _dried batch 1 / H ₃ BO _3/1 4.85 6.3 0,165 Cat. 5 _dried / TPAOH / 1 3,279 6.0 0,152 Cat. 5 _dried / NWG / 1 4.52 7.5 0,442 Cat. 5 _dried / KNO _3/1 6.59 11.7 0.94 Cat. 5 _dried / K ₂ CO _3/1 4.82 11.9 1,327 Cat. 5 _dried / H ₃ PO _4/2 5.2 7.5 0.384

Example 3: Treatment of shaped catalyst bodies by pore filling method (also "incipient wetness" method called)

a) Treatment by pore filling method

On the shaped catalyst body, the water absorption is determined by double determination. Approximately up to 10 g of the shaped catalyst body are placed in a beaker and mixed with distilled water in supernatant solution. After 10 minutes, this solution is poured off and the adhering water on the shaped catalyst body quickly removed with a cloth. The back-weighing (determination of the weight difference of the shaped catalyst body before / after absorption of water) and the determination of the volume of water corresponding to this back-weighing takes place immediately. The same volume of ionic solution is then placed in a suitable sealable container, the shaped catalyst body quickly added and homogenized by shaking the container. After a contact time of 10 minutes, the shaped catalyst body is only dried between 60 ° C. and 150 ° C. or brought to 600 ° C. by slow heating at 1 ° C. per minute and kept under circulating air for 5 h. Fresh air intake of about 3 m ³ / h was given continuously.

Of the Influence of a treatment according to "incipient wetness method" on the lateral compressive strength of the calcined shaped catalyst bodies was examined

b) Experiments with calcined catalyst moldings

In total, three different shaped catalyst bodies were investigated, namely:
Cat. 3: H-MFI 90, Cat. 4: H-Beta 25, Cat. 5 _{calc .:} H-MFI 90. Detailed explanations of these _{shaped catalyst bodies} can be found in Example 2b; _calcined in Cat. 5 are: H-MFI 90 with silicon-containing binder (25% by weight of binder (colloidal silica), based on the total weight of the shaped catalyst body, cylindrical shape, diameter 1/8 "). Cat. 5 was _calcined according to Example 2 of EP 0 369 364 B1 and Example 1 and Comparative Example 3 cited therein by reference EP 0 369 364 B1 , manufactured, where however, a silicon-containing binder (colloidal silica) was used. All treated shaped catalyst bodies were calcined at 600 ° C for 5 hours.

Cat. 3, 4 and 5 _calc. were subjected to a treatment as described in Example 3a).

i) catalyst shaped body cat. 3

• n. e. = nicht ermittelt

Tabelle 12: Übersicht über die mit Kat. 3 erhaltenen Ergebnisse Kat./Eingesetzte Lösung/Nummerierung Salz [mmol]/Kat. 3 [g] Seitendruckfestigkeit [kp/3–4 mm] Erhöhung Seitendruckfestigkeit·Kat. 3 [g]/Salz [mmol] Kat 3 charge 2 ohne Behandlung 1,7 Kat. 3 Charge 2/KOH/1 0,45 2,8 2,44 Kat. 3. charge 2/H₃PO₄/1 4,337 2,6 0,2 Table 11: Overview of experiments conducted with Cat 3 Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 3 [g] Cat. 3 lot 2 / KOH / 1 10 ne 0.9 20 0.45 Cat. 3. Charge 2 / H ₃ PO _4/1 10 ne 8.67 20 4,337

• ne = not determined

Table 12: Overview of the results obtained with Cat. 3 Cat./inserted solution / numbering Salt [mmol] / cat. 3 [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 3 [g] / salt [mmol] Cat 3 charge 2 without treatment 1.7 Cat. 3 lot 2 / KOH / 1 0.45 2.8 2.44 Cat. 3. Charge 2 / H ₃ PO _4/1 4,337 2.6 0.2

ii) shaped catalyst body cat. 4

Table 13: Overview of experiments conducted with Cat 4 Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 4 [g] water 0 210 0 40 - Cat. 4./KOH/1 4.5 4.5 0.4 20 0.2 Cat. 4./TPAOH/1 4.5 4.5 0.98 20 0.443 Cat. 4./TPAOH/2 9 ne 1.97 20 0.885 Table 14: Overview of the results obtained with Cat Cat./inserted solution / numbering Salt [mmol] / cat. 4 [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 4 [g] / salt [mmol] Cat 4 without treatment 1.8 Cat. 4./KOH/1 0.2 2.4 3 Cat. 4./TPAOH/1 0.443 3.0 2.7 Cat. 4. / TPAOH / 2 0.885 3.2 1.58

iii) Catalyst Forming Catalyst Cat. 5 Calcined (incipient wetness method)

Table 15: Overview of the experiments carried out with cat. 5 _calcined Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 5 _calcined [g] water 0 0 0 0 - Cat. 5 _calcined / TPAOH / 1 9 1.97 20 0.885 Cat. 5 _calcined / H ₃ PO _4/1 9 0 8.67 20 3,903 Cat. 5 _calcined / K ₂ CO _3/1 5 9 2,559 20 1.81 Cat. 5 _calcined / ZnSO _4/1 9 0 0.1 20 .2787 Cat. 5 _calcined / KOH / 1 9 0 0.9 20 0.4 Table 16: Overview of the results obtained with cat. 5 _calcined Cat./inserted solution / numbering Salt [mmol] / cat. 5 _calcined [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 5 _calcined [g] / salt [mmol] Cat 5 _calcined without treatment 5.5 Cat. 5 _calcined / TPAOH / 1 0.885 6.9 1.58 Cat. 5 _calcined / H ₃ PO _4/1 3,903 20.2 3.76 Cat. 5 _calcined / K ₂ CO _3/1 1.81 19.9 7.95 Cat. 5 _calcined / ZnSO _4/1 .2787 7 5.38 Cat. 5 _calcined / KOH / 1 0.4 6.2 1.75

Also in the experiments using the "incipient wetness Method "and calcined shaped body showed up a very advantageous increase in lateral compressive strength. The "incipient wetness method" also shows the Advantage on that no excess of treatment fluid required is.

c) Experiments with dried catalyst moldings

A non-calcined, dried catalyst-shaped body cat. 5 is _dried as described in Example 3a) subjected to a treatment according to the "incipient wetness" method described therein. Detailed explanations of the shaped catalyst body can be found in Example 2c.

The influence of this treatment on the lateral compressive strength of the dried catalyst bodies with treatment fluid was investigated. Table 17: Overview of the experiments _dried with Cat 5 ("incipient wetness" method) Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 5 _dried [g] water 0 0 0 0 - Cat. 5 _dried / TPAOH / 1 9 1.97 20 0.885 Cat. 5 _dried / H ₃ PO _4/1 9 ne 8.67 20 3,903 Cat. 5 _dried / K ₂ CO _3/1 5 9 2,559 20 1.81 Cat. 5 _dried / KNO _3/1 9 9 4.9 20 4.45 Table 18: Overview of the _dried preserved with Kat 5 results. Cat./inserted solution / numbering Salt [mmol / cat. 5 _dried [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 5 _dried [9] / salt [mmol] Cat 5 _dried without treatment 5.5 Cat. 5 _dried / TPAOH / 1 0.885 6.0 0.564 Cat. 5 _dried / H ₃ PO _4/1 3,903 22.3 4.3 Cat. 5 _dried / K ₂ CO _3/1 1.81 17.3 6.5 Cat. 5 _dried / KNO _3/1 4.45 18.3 2.87

Also in the experiments using the "incipient wetness Method "and a non-calcined shaped body shows a very advantageous increase in lateral compressive strength.

Example 4: Treatment of shaped catalyst bodies with precious metals

• * Dihydrogen hexachloroplatinat (IV) Lösung

Tabelle 20: Übersicht über die mit Kat. 6 erhaltenen Ergebnisse Kat./Eingesetzte Lösung/Nummerierung Salz [mmol]/Kat. 6 [g] Seitendruckfestigkeit [kp/3–4 mm] Erhöhung Seitendruckfestigkeit·Kat. 6 [g]/Salz [mmol] Kat 6 ohne Behandlung 3,2 Kat. 6/CPA/1 0,86295 3,4 0,231 A calcined shaped catalyst article is subjected to a treatment with a noble metal-containing solution using supernatant ionic solution as described in Example 2a). As catalyst shaped body was "Cat. 6 "(designation: Sapo 11, silicon-containing binder (35% by weight of binder based on the total weight of shaped catalyst body, cylindrical shape, diameter: 1/16") US 4,440,871 Example 21. The calcination was carried out according to Comparative Example 3 of EP 0 369 364 B1 , All treated shaped catalyst bodies were calcined at 600 ° C for 5 hours. Table 19: Overview of the supernatant solution experiments conducted with Cat 6 Cat./inserted solution / numbering ionic verb [g] H ₂ O [ml] Conc. in aqueous solution [mol / l] Cat. [G] Salt [mmol] / cat. 6 [g] Cat. 6 / CPA / 1 41.466 1556 0.594 1100 0.86295

• * Dihydrogen hexachloroplatinate (IV) solution

Table 20: Overview of the results obtained with Cat Cat./inserted solution / numbering Salt [mmol] / cat. 6 [g] Side crushing strength [kp / 3-4 mm] Increase lateral crushing strength · cat. 6 [g] / salt [mmol] Cat 6 without treatment 3.2 Cat. 6 / CPA / 1 0.86295 3.4 0.231

at a treatment of a calcined shaped catalyst body with a noble metal-containing solution using the Method of supernatant ionic solution results an increase in the lateral compressive strength of the catalyst molding.

Example 5: Determination of lateral pressure resistance

The Side crushing strength was measured with a measuring device of the company Schleuniger, Model 6 D measured. Each extrudate was 24 Pieces of 3-4 mm in length one after the other just aligned in the measuring chamber. The measurement was carried out by the method of the load cell. The lateral pressure resistance obtained goes from Tables 2, 4 and 6, as well as the other tables the test results, each column 3 ("lateral crushing strength"), out.

Around To be able to determine which under anion and / or cation education soluble compound the highest increase Side pressure resistance was caused, in each case in column 4 of the Tables 2, 4, 6, as well as in the other tables on the test results, the increase in lateral pressure resistance (difference between the lateral compressive strength of the catalyst molding without Treatment and lateral compressive strength of the catalyst molding with treatment) in relation to the amount of under anion and / or Cation formation soluble compound per mass catalyst (Value from column 2).

It shows that with increasing used amount of the respective under anion and / or cation formation soluble compound, the absolute lateral compressive strength often increases. To be as possible To achieve high lateral compressive strengths, should in these cases therefore high levels of soluble under anion and / or cation formation Compounds are added. On the other hand, in some applications too high levels of soluble under anion and / or cation formation To avoid compound in the extrudate, since thereby the proportion of the active component decreases in the extrudate. In some catalysis applications can also be undesirable that one under anion and / or cation formation soluble compound possibly the pores of the occludes active zeolite, and optionally the diffusion of educts and products adversely affected. Furthermore basic ionic salts can be acid-catalyzed reactions, as they are often done with the help of zeolites become difficult. Application-specific can therefore be an advantage be if with the least possible amount of ionic Connection achieved the highest possible lateral pressure resistance becomes.

As the data also show that the different anionic and / or cation-forming soluble compounds a different strong increase in side crushing strength. Here's the direct comparison and under anion and / or cation formation to identify the most soluble compounds increase the lateral compressive strength, the value of column 5 determined (see experiment description). This size is a measure of how strong the lateral compressive strength with the addition of the anion and / or cation formation soluble Connection increases. From this value can be read which compounds the highest increase in lateral compressive strength cause.

Example 6: Lowering of the BET surface area

moreover became the effect of the method according to the invention considered on the BET surface. A use of a 16 wt .-% sodium hydroxide solution leads to a Reduction of BET surface area by more than 30%. A Use of a 6% potassium hydroxide solution (1.06 mol / l) reduces the surface area by up to 20%. A use a 4% potassium chloride solution (0.54 mol / l) to one to 10 and one use of a 6% sodium chloride solution (1.02 mol / L) gives a surface reduction to about 20%.

The decrease in surface area was investigated on the catalyst described above, for example in Example 2, cat. 1: H-MFI 90 with silicon-containing binder (25% by weight of binder (colloidal silica), based on the total weight of the shaped catalyst body; Cylindrical shape, diameter 1/16 "). Table 21: Overview of the results obtained with shaped catalyst bodies Cat Cat./used solution / numbering Salt [mmol] / cat. 1 [9] Surface area [m ² / g] Humiliation of the surface * [%] Cat 1 without treatment 337 Cat. 1 / NaCl / 2 .3422 317 6 Cat. 1 / NaCl / 3b 1.5144 315 6.6 Cat. 1 / NaCl / 4 5,753 269 20.2 Cat. 1 / NaOH / 4 0.94 261 22.6 Cat. 1 / NWG / 3 4.52 231 31.5 Cat. 1 / KCl / 2 3.4 300 11 Cat. 1 / KNO _3/2 3.63 279 17.3 Cat. 1 / K ₂ CO _3/1 1.81 216 36 Cat. 1 / H ₃ BO _3/2 4.85 324 3.9

Example 7: Preparation of a shaped catalyst body in the form of an extrudate with silicon-containing binder (silica binder)

For the shaping or production of a shaped body can ground or unground calcined zeolite powder used become. In the experiments, shaped catalyst bodies, made with ground and calcined powders, used. The binder used was a colloidal silicon source. The zeolite powder used was homogenized by a grinding step and then fed to the kneader. After adding of a binder, both components are mixed for 15 minutes. This mixture can also be done externally and then the kneader separately be supplied. When mixing is complete, if necessary, as long as water is added in portions until a plastic Crowd sets. This plastic mass will also be about 10 minutes remixed and then by drawing the water on extrusion capability brought and then extruded.

Then, the molded shaped catalyst body is dried between 60 ° C-150 ° C for 16 h, after which a dried shaped catalyst body is obtained. Subsequently, a heating takes place at a heating rate of 1 ° C / min to a final temperature of 550 ° C, this final temperature is then held for 5 h. The drying and the further steps at elevated temperature are carried out in air or N ₂ / air.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 01/30697 A [0018]
• - DE 4405876 A [0060]
• - EP 0369364 B1 [0087, 0087, 0087, 0087, 0087, 0087, 0087, 0087, 0096, 0096, 0100, 0100, 0109]
• US 4440871 [0109]

Cited non-patent literature

• - "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, p. 776 to 778 [0014]
• - "Rompp-Lexicon Chemistry", eds .: J. Falbe, M. Regitz, 10th Edition 1999, Georg Thieme Verlag, ISBN 3-13-107830-8, p 5053ff. [0014]
• - "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, pp. 235 to 251 [0027]
• - "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, pp. 851-856 [0038]
• - "Holleman-Wiberg, Textbook of Inorganic Chemistry" by N. Wiberg, 91.-100. Ed., Walter de Gruyter & Co., 1985, ISBN 3-11-007511-3, p. 778 to 779 [0041]
• - DIN 66131 [0076]
• - J. Am. Chem. Soc. 60, 309 (1938) [0076]
• - DIN 66133 [0078]
• - "Verified Syntheses of Zeolitic Materials", Published on behalf of the Synthesis Commission of the International Zeolite Association, Ed .: H. Robson, 2nd Ed., 2001, Elsevier Science BV, p. 115 [0087]

Claims (26)

Process for the treatment of a shaped body, in particular a catalyst, Katalysatorträger-, or Sorbent shaped body comprising the following steps: a) Providing a shaped body, wherein the shaped body one or more tectosilicates; b) bring into contact the shaped body with at least one treatment fluid, in which the treatment fluid is an aqueous fluid and one or several soluble in water with anion and / or cation formation Compounds, and the treatment fluid has a content of the one or more in water with anion and / or cation formation having soluble compounds of at least 7 mmol / L; c) optionally drying and / or optionally calcining the with the treatment fluid brought into contact molding. The method of claim 1, wherein the one or the a plurality of tectosilicates comprise one or more zeolites, wherein preferably at least one zeolite is selected from the group consisting of fiber zeolites, zeolites of leaves, Cube zeolites, MFI-type zeolites, zeolites of the beta-structure type, zeolite A, zeolite X, zeolite Y and theirs Mixtures. Method according to one of the preceding claims, wherein the shaped body has a content of Tectosilicaten, in particular to zeolites, of at least 50% by weight, preferably of at least 60 wt .-%, preferably of at least 70 wt .-%, more preferably of at least 85 wt .-%, in particular of 90 wt .-%, based on having the total solids content of the shaped body. Method according to one of the preceding claims, wherein prior to step b) contacting the molding with the at least one treatment fluid no application step a coating is carried out on the shaped body, and / or wherein before step b) of contacting the molding with the at least one treatment fluid no drying of the molding at a temperature of more than 100 ° C, in particular of more than 40 ° C has occurred. Method according to one of the preceding claims, wherein the treatment fluid per gram of molding a Content between 0.001 and 100 mmol, preferably between 0.01 and 10 mmol, at the one or more in water under anionic and / or cation-forming soluble compounds. Method according to one of the preceding claims, wherein the one or more in water under anion and / or Cation formation soluble compounds at least one Compound selected from the group consisting of chlorides, Hydroxides, nitrates, carbonates, bicarbonates, bristles, tetralkylammonium compounds, Water glasses, platinates, phosphoric acids, sulphates, Boric acids, silicas and mixtures thereof. A process according to any one of the preceding claims wherein the one or more compounds soluble in water with anion and / or cation formation comprises at least one compound selected from the group consisting of potassium containing compounds, especially potassium chloride, potassium hydroxide, potassium nitrate, potassium carbonate , Potassium bicarbonates, potassium borates, potassium water glasses, sodium and potassium containing bristles, sodium and potassium containing water glasses; Calcium Chloride; Magnesium-containing compounds, in particular magnesium nitrate; Sodium-containing compounds, especially sodium chloride, sodium hydroxide, sodium nitrate, sodium carbonate, sodium hydrogencarbonate, sodium borates, sodium waterglasses; Tetraalkylammonium compounds, especially tetralkylammonium hydroxides; Boric acids, in particular H ₃ BO ₃ ; Phosphoric acids, in particular H ₃ PO ₃ , H ₃ PO ₄ ; zinc-containing compounds, in particular zinc sulfate; Platinates, especially dihydrogen hexachloroplatinate (IV), silicic acids, and mixtures of these compounds. Method according to one of the preceding claims, the total content of one or more in water under anion and / or cation formation soluble compounds preferably at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably at least 0.007 mol / l to 4.2 mol / l, further preferably 0.007 mol / l to 1.2 mol / l, in particular 0.009 mol / l to 0.8 mol / l. A method according to any one of the preceding claims, wherein the treatment fluid is a solution having a total content of sodium and potassium cations, preferably potassium cations, of at least 0.007 mol / l, more preferably at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably from 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l, or wherein the treatment fluid is a suspension and wherein the solution obtained after separation of the undissolved present in the suspension components, a total content of sodium and potassium cations, preferably of potassium cations, of at least 0.007 mol / l, preferably at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably from 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l , in particular from 0.009 mol / l to 0.8 mol / l. Method according to one of the preceding claims, wherein the treatment fluid is a solution containing a total content anions of at least 0.007 mol / l, preferably at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably from 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l up to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l, or wherein the treatment fluid is a suspension and wherein the after separation of the undissolved present in the suspension Components obtained solution a total content of anions of at least 0.007 mol / l, preferably of at least 0.009 mol / l, more preferably at least 0.01 mol / l, preferably from 0.007 mol / l to 4.2 mol / l, more preferably from 0.007 mol / l to 1.2 mol / l, in particular from 0.009 mol / l to 0.8 mol / l. Method according to one of the preceding claims, wherein the shaped body, with the at least one treatment fluid is brought into contact, is a molding, at least comprises an MFI-type or beta-type zeolite and preferably in the form of an extrudate, and in which the treatment fluid is a potassium chloride solution with a Content of 0.05 to 0.09 mmol of KCl / g of molding, preferably with a content of 0.06 to 0.08 mmol of KCl / g of molding, in particular with a content of about 0.07 mmol of KCl / g of molding is, or a tetrapropylammonium hydroxide (TPAOH) solution with a content of 0.15 to 0.20 mmol of TPAOH / g of molding, in particular with a content of about 0.188 mmol of TPAOH / g Shaped body is. Method according to one of the preceding claims, wherein the treatment fluid is greater than 2, preferably more than 7, preferably more than 9, more preferably more than 10, in particular from 4 to 12. Method according to one of the preceding claims, wherein the treatment fluid and / or the molded body to be treated at least one SiO ₂ source, wherein it is preferably in the SiO ₂ source to water glass, in particular a water glass solution, and / or silica, in particular precipitated silica or colloidal silica. Method according to one of the preceding claims, characterized in that the treatment fluid further comprises: Silanizing or metal salts, preferably salts of catalytic active metals, in particular copper salts, nickel salts, platinum salts and / or palladium salts. Method according to one of the preceding claims, characterized in that the shaped body granules, an extrudate or a compact. Method according to one of the preceding claims, characterized in that the shaped body a finished Catalyst or a catalyst precursor. Method according to one of the preceding claims, characterized in that the shaped body comprises at least one binder, wherein the at least one binder is an aluminum-containing binder, in particular boehmite and / or alumina, alpha-alumina, gamma-alumina, teta-alumina, a cement is a silicate binder and / or SiO ₂ -containing binder, wherein the at least one binder is preferably selected from the group consisting of aluminum silicates, silicas and mixtures of alumina and SiO ₂ -containing binders. Method according to one of the preceding claims, characterized in that the contacting of the shaped body with the treatment fluid by immersing the molding into the treatment fluid and / or by spraying the shaped body with the treatment fluid and / or by mixing with the treatment fluid done with shaking. Method according to one of the preceding claims, wherein calcining the contacted with the treatment fluid Shaped body at temperatures of more than 170 to 1800 ° C above a period of 1 to 16 hours. A method according to any one of the preceding claims, wherein in step c) after drying and / or calcined molded articles has a BET surface area which is smaller by at least 5%, preferably smaller by 12 to 30%, than the BET surface area of the shaped article which was provided in step a). Method according to one of the preceding claims, which further comprises applying one or more at least sectional coatings on the molding, wherein the coating selected at least one component consisting of a group consisting of titanium oxides, vanadium oxides, silicon oxides, aluminum oxides, Phosphorus oxides, metals, metal salts and mixtures thereof, such that preferably a catalyst or a catalyst precursor is obtained. Use of an aqueous fluid, the one or more in water with anion and / or cation formation includes soluble compounds for the treatment of a or more Tectosilicate comprising molding, the is selected from the group consisting of non-calcined Moldings and calcined moldings, wherein the content of the one or more in water under anions and / or cation-forming soluble compounds at least 7 mmol / l. Use of an aqueous fluid after Claim 22, one or more in water under anion and / or Cation formation comprises soluble compounds, to increase the mechanical strength, in particular the lateral compressive strength, a molding comprising one or more tectosilicates. Use of an aqueous fluid after Claim 22 or 23, which comprises one or more in water under anionic and / or cation formation comprises soluble compounds, for changing the surface, in particular for Reduction of BET surface area and / or pore volume, a molding comprising one or more tectosilicates. Shaped body, available through a Method according to one of claims 1 to 20. Catalyst or catalyst precursor available by a method according to claim 21.