Method for producing a solid containing zeolites

Production of a solid material containing zeolite-containing

Full description

Background of the invention

This invention relates to a method for concentrating at least a partially crystalline solid containing at least one zeolite in a mixture that ignites at least one additional material, such as a template compound, and said solid. Specifically, the method includes ultrafiltration of the mixture at stage (II) to divide the mixture into a retentate and a permeate portion, the solids content of the retentate portion being higher than that of the mixture and the solids content of the permeate portion being lower than that of the mixture. This method allows the addition of additional compounds, specifically template compounds, which are present in the permeate section to be recycled in the crystallization stage (I), corresponding to the stage (II).

Methods for producing objects containing formed zeolite zeolite are described, for example, in commonly known documents, specifically international patent 55229 R98. This document focuses on the selection of the binder that allows the solid material containing zeolite to be combined to produce a shaped object. International Patent 55229/98 does not describe any methods for concentrating the solid matter present in the original liquid that are not carried out by traditional filtration and/or centrifugation methods.

US Patent 6,106,803 describes a method for preparing granular titanium silicalite comprising crystallizing a synthetic gel (=a synthesis mixture; a silicon source (Si) and titanium (Ti), a templating agent, a base and water under hydrothermal conditions, allowing By obtaining a zeolitic suspension, this suspension is subjected to spray drying or granular spray drying using a barrier layer after optional concentration and/or adding other materials and determining the percentage of solids in the mixture before the drying stage

Spraying is about 10%. This relatively low percentage of solids ultimately results in unnecessarily low catalytic activity per unit mass in the formed body, especially when additional materials are added to the granular conversion mixture.

European patent 0.638.362, including, refers to a method for preparing a titanium silicalite catalyst, and here in particular the agglomeration of primary particles, that is, the fine particles that are formed during the crystallization stage in the synthesis of titanium silicalite. Agglomeration is performed by imitating the pH of the solution containing the primary molecules (zeolitic suspension) to a value between 5 and 01. This agglomeration forms part of an integrated method in which first (i) the primary molecules are prepared from a synthetic mixture from the previous field, (ii) next, the secondary molecules are agglomerated as previously described by lowering the pH, and (iii) finally the secondary molecules are fragmented by heat . However, with regard to the concentration of primary or secondary particles before the agglomeration process and/or extraction of the components of the original liquid, European patent 638.362.0 does not provide any more information than that described in the previous section.

Likewise, US Patent 4,701,428 refers to the problem of agglomeration in a mixture containing zeolitic microcrystals (in this description: smaller than 5 micrometers). This problem is solved by a special method of agglomerating titanium silicalite. This method involves adding titanium silicalite crystals to a solution containing tetraalkyl orthosilicates at specific temperatures and rapid drying. Likewise, this document does not present any more information than that described in the previous section regarding the concentration of titanium silicalite crystals and/or the extraction of the components of the original liquid. A similar method is described in European Patent 1,106,576.

General description of the invention

The purpose of this invention is to provide a method for concentrating a mixture resulting from at least partial crystallization of a synthetic mixture containing at least one additional substance, for example a molding compound.

template compound in a basic liquid, and at least partially crystalline solid (containing at least one zeolitic substance). In this method, the proportion of solids in the mixture is increased, and at the same time, optionally, at least part of the original liquid containing the template is separated from the solid. A higher percentage of solids ultimately results in a higher catalytic activity per unit of mass.

The method should also allow for the simplification of the integrated method for producing formed bodies containing entirely zeolite, for example by omitting the stages of thermal disintegration of the intermediate compound. The method must also reduce the consumption of costly or environmentally harmful chemicals, such as molding agents.

It has been found that this goal is achieved by ultrafiltration, after stage (I), of a mixture (I) that includes at least one additional substance and a solid containing at least partially crystalline zeolite in stage (II) to divide the mixture into a retentate section and a permeable section. permeate, that is, for a concentration, and the percentage of solids in the retentate section is higher than in the mixture (I) resulting from phase (I) and the percentage of solids in the permeate section is lower than in the aforementioned mixture. This method allows the addition of additional compounds, especially template compounds, present in the permeate section to be recycled in the crystallization stage mentioned before.

Detailed Description:-

The solid material described in this invention can be combined at a further stage to produce a formed body that can be used particularly as a catalyst for the epoxidation of organic compounds.

The method of the invention may also form part of an integrated method, i.e. a method for preparing a corrosion-resistant shaped body containing at least one zeolitic material. This method can be divided in a clear schematic manner into the following stages:

Stage (I): at least partial crystallization of a solid containing at least one zeolite from a synthetic mixture to produce the mixture (I) containing said solid and at least one additional material;

Stage (II): Concentration of the solid in the mixture (1) by ultrafiltration to produce a retained fraction and a permeate fraction. This stage optionally includes solid/liquid separation, for example, the solid from the original liquid;

Stage (III): Agglomerating or granulating the solid particles in the concentrated retentate portion of step (II); This step optionally includes drying the solid particles;

Stage (S): Formation of the output of step (II) or (III); Stage (C): Calcination of the product of step (III) or (S); Stages (S) and (C) are optional stages in each case.

The present text discusses the solid material containing zeolite according to this invention and the formed body resulting from it among its uses in the field of catalysis. However, this should not be understood to mean that a solid and/or shaped object cannot be used in other applications or fields.

This invention provides a method for concentrating at least a partially crystalline solid containing at least one zeolite from a mixture that ignites at least one additional substance, typically said solid, which includes ultrafiltration of the mixture at stage (II) to partition the mixture into a retentate phase. And the permeate phase, where the percentage of solids in the retentate phase is higher than in the mixture, and the percentage of solids in the permeate phase is lower than in the mixture.

The basic terms used in the context of this invention are defined below.

For the purposes of this invention the term "synthesis mixture" means any mixture from which a suspension of a solid in a mixture, preferably a basic liquid, is obtained by crystallization, wherein the solid must (i) be at least partially crystalline and (ii) must It must contain at least one zeolitic substance. The synthetic mixture may be a sol, gel, solution, or suspension.

Zeolites (dzeolites) are crystalline aluminosilicates with arranged channels and cage structures containing micropores. The term “micropores” as used in this invention corresponds to the definition given in “Pure Appl.” Chem, 45, p. 71, especially p. 79 (1976), and refers to micropores with a diameter of less than 2 nanometers. The network of these dzeolite zeolites consists of SiO4 and AlO4 tetrahedra, which are interconnected by bridge bonds of oxygen. A general description of known structures is given, for example, by .w. M Meier and D. H. Oison in 'Atlas of Zeolite zeolite Structure Types'; Elsevier, Fourth Edition, London 1996. In addition to micropores, the solid materials of the invention containing at least one zeolite may also have mesopores and/or macropores.

For the purposes of this invention, a solid, as it exists eg after crystallization of a synthetic mixture, is any immolecular substance that (i) contains at least one zeolitic substance, and (ii) differs as a separate phase from the mixture (i) such that It can be subjected to separation and/or concentration processes. The solid exists in the form of particles suspended in a basic liquid, the molecular size of which allows it to be collected by the membrane filter used in the method of the invention (during ultrafiltration or diafiltration). The particle size is at least 2 nanometers. The solid may exist in the form of “diafiltration” (after crystallization) or secondary particles (after the agglomeration and/or granulation step).

For the purposes of the invention, “mother liquor” is any liquid phase that may contain any substance in dissolved form, but is free of particles larger than 2 nanometers in size. Here the main fluid may contain up to 5% by weight of particles larger than 2 nanometers in size. For the purposes of this invention the main fluid may also contain unreacted components of the synthesis mixture, i.e. additional materials, such as at least one compound used as a molding agent for the synthesis of the zeolitic zeolite-containing solid in phase (I). For the purposes of this invention, the main liquid exists only after stage (I) has been completed, i.e. bound to a suspension containing solid particles of the aforementioned type. In stage (II), the permeate portion consists mainly of the main fluid.

For the purposes of this invention, “templating agent” is any substance that renders the solid formed during the formation of at least one zeolitic material from the synthetic mixture having at least one type of pores (micropores, mesopores, macropores). Nitrogenous organic bases are used, which are understood as an illustrative example and not as a limitation of the scope of the invention.

Stage (II) of this invention relates to “concentrating” the mixture containing the solid from stage (I). For the purposes of this invention, “concentrating” means any stage at the end of which a mixture is obtained in which the solids content is increased compared to the original mixture used. Mixtures may be suspensions of solids, but they do not have to be. The term “separating” the solid from a mixture or from a suspension is used as a special case in defining “concentrating”.

For the purposes of this invention, “shaped body” means any three-dimensional object produced in the shaping step (S) as also described below. The shaped body is obtained by combining solid matter. This solid substance is obtained in turn

Of stage (II) and/or (III) with optional thermal disintegration in step calcination

(C).

“Ultrafiltration” as used in this invention describes a conventional process in which particles (particles, macromolecules, etc.) and solvent (solvents) are initially separated according to their particle size (where the charge of the molecules has little effect). It uses a pressure gradient across a semipermeable membrane, which is anisotropic. The smaller the membrane pore size, the greater the energy output, which is determined by the pressure gradient used, which is necessary to affect concentration. Microfiltration processes, i.e. filtration using membranes with a pore diameter in the micrometer range, are included in the ultrafiltration method of this invention as long as they are distinguished from the usual paste filtration as previously known.

There is no fundamental difference between “diafiltration” and ultrafiltration, in particular the former similarly uses membranes also described before with specific pore sizes. In contrast to ultrafiltration, permeate filtration is characterized by a different method, namely the fact that the permeate portion (definition references described before) is continuously or partially replaced by water or another solution. Thus, a purification stage can optionally be performed after the concentration stage, i.e. ultrafiltration.

For the purposes of this invention, ultrafiltration includes the use of membranes with a pore size from 1 nanometer to 1 micrometer. Therefore, the type of filtration described in this description for the purpose of concentration, i.e. increasing the percentage of solids, differs clearly from what preceded it in the field, in which the paste is filtered and a mixture containing zeolite is filtered and centrifuged. Separation/concentration is possible with these methods only for solid particles with a volume larger than 10 microliters.

Ultrafiltration or membrane filtration separates the original mixture used into two different phases, that is, they can be separated, namely: the permeate phase and the

Retentate - For the purposes of this invention “permeate” is that portion of the mixture remaining after stage (II) which is removed from the film background. That is, the side with the least pressure (in conventional filtration, this phase is called the filtrate). Accordingly, a “retentate” phase is formed on the side of the membrane exposed to the highest pressure, in which solid particles that cannot pass through the pores of the membrane are concentrated.

The terms “granulation” and “agglomeration” are used in this invention with equal meanings and refer to any possible method by which the diameter of particles can be increased. This increase occurs by kneading the particles or increasing them in other layers. Granulation includes, without limitation, methods involving wetting the particles with at least one liquid. Furthermore it is possible, but not at all necessary, to add binding agents that activate or enable agglomeration or granulation.

The individual stages of an integrated method for producing a shaped object containing at least one zeolitic material and the accompanying embeddings are given below. Of particular interest, a new method of this invention essentially corresponds to step (II). As already mentioned, the integrated method can be divided schematically into the following sub-stages:-

Stage (I): at least partial crystallization of a solid containing at least one zeolite from a synthetase to produce the mixture (I) containing said solid and at least one additional substance;

Stage (II): Concentrating the solid in the mixture (I) by ultrafiltration to produce a retentate and a permeate fraction. This step optionally includes solid/liquid separation, for example the solid from the original liquid;

Stage (III): Agglomerating or granulating or agglomerating or granulating solid particles in the concentrated retentate portion of stage (II); This stage optionally includes drying of solid particles;

Stage (S): Formation following stage (II) or (III); Step (C): Calcification following stage (III) or (S); Stage (I): Synthesis Mixture

There are no limitations regarding at least one zeolite present in the solid or shaped body of this invention. It is preferable to use zeolite containing titanium, zirconium, chromium, niobium, iron, boron or vanadium, especially titanium silicalite.

Titanium zeolites, especially those with a MFI-type crystalline structure, and the possibilities for their preparation are described, for example, in International Patent No. 55228/98,

International 03394/98, International 03395/98, European 311.983 or European 405.978 are all included as references in this description. In addition to silicon and titanium, these materials can also contain additional elements, such as aluminum, zirconium, tin, iron, cobalt, nickel, gallium, boron, or small amounts of fluorine. In zeolite catalysts, preferably prepared by the method of the invention, some or all of the zeolite titanium may be replaced by vanadium, zirconium, or chro; Or niobium, or a mixture of two or more of them. The molar ratio of titanium and/or vanadium, zirconium, chromium or niobium to the sum of silicon and titanium and/or vanadium and/or zirconium and/or chromium and/or niobium ranges between 1 0.0:1 to 1.0:1.

Titanium zeolites with MFI structure are known to be distinguished by their

The red color is at about 960 cm-1, and thus differs from alkali metal titanates or the crystalline and amorphous phases of TiO2.

The aforementioned titanium zeolites, zirconium, chromium, niobium, iron, and vanadium are usually prepared by reacting an aqueous mixture from a SiO2 source, from a titanium source, zirconium, chromium, niobium, iron, or vanadium, for example. Titanium dioxide or vanadium oxide, zirconium alkoxide, chromium oxide, niobium oxide or iron oxide, From a nitrogenous organic base template, for example tetrapropylammonium hydroxide, with or without the addition of basic compounds; In a pressure vessel at high temperature for several hours or several days, resulting in a product that is at least partially crystalline. In this invention, the integrated method step for obtaining a formed body containing zeolite is referred to as excursion (I).

In a preferred embodiment, stage (I) includes using at least one template compound. It is preferable to use it, among other uses, to obtain the required pore size. There are basically no limitations regarding the template compound except the fact that it must contribute to the formation of pores. Examples of suitable template compounds include tetrapropylammonium hydroxide, tetrapropylammonium bromide, tetraethylammonium hydroxide, and tetraethylammonium bromide.

Mide, diamines, or other template compounds known in the references.

In a more preferable embodiment, the at least one zeolitic zeolite produced is selected from the group including: titanium zeolites, germanium, tellurium, vanadium, chromium,

Niobium and zirconium, with the composition of pentasil zeolites, especially the types determined by AEN, BEA, AWW, AWO, ATV, ATT, ATS, ATO, ATN, AST, APD, APC, ANA 'CLO, CHI, CHA, CGS' CGF, CFI, CAS, CAN 'BRE', BPH, BOG' BIK 'EPI 'EMT 'EDI 'EAB 'DON 'DOH 'DFT 'DFO 'DDR 'DAC 'CZP 'CON 'JBW, ITE, ISV, IFR, HEU 'GME 'GIS 'FER' FAU, EUO, ESV, ERI ' MEL,MEI,MAZ,LTO' LTL,LTA'LOV,LOS'LIO,LEV 'LAU, KFI, MTW, MTT, MTN, MTF, MSO 'MOR, MON 'MFS, MFI, MER, MEP, RSN, RON, RHO, PHI, PAU 'PAR, OSI, OFF, NON 'NES, NAT, MWW 'STI' STF, SOD, SGT, SFF, SBT, SBS, SBE, SAT 'SAO, RUF, RTH 'RTE, YUG, WEN' WIE, vsv, VNI, VFI, VET, TSC 'TON, THO, TER, STT or ZON. Mixed compositions contain two or more of the previous compositions. Zeolites containing titanium with the composition 4-, TTM-1, SSZ-24, ITQ 1-CIT-1, UTD or 5-CIT can also be used in the method of the invention. Other titanium zeolites that can be mentioned are those with the composition 48-ZSM or 12-ZSM.

It is preferable to use titanium zeolites with MFI, MEL, or mixed MEL/MFI composition in this invention. Specifically, the preferred catalysts are titanium zeolites, commonly referred to as TS-1, TS-2, TS-3, and titanium zeolites with a structural composition morphologically similar to beta zeolite. Stage (II): Ultrafiltration

In the methods of the above field, the mixture obtained by the hydrothermal reaction in stage (I) is a suspension of at least a partially crystalline solid containing zeolite in a base liquid, and is separated by filtration, centrifugation, spray-drying, or granulated by spraying. According to traditional methods.

In the method of the invention, an ultrafiltration step (II) is performed to concentrate and thus increase the percentage of solids after stage (I) and before stage agglomeration or granulation (III). In contrast to the previous field, this concentration takes place without significant granulation/agglomeration.

Ultrafiltration and permeate filtration methods are convection methods in which solid particles are separated or concentrated primarily depending on their molecular size. Gradient pressure is applied across a porous membrane. The smaller the pore size of the membrane, the greater the energy output, which is determined by the pressure gradient used, which is necessary for separation. The choice of membrane is of particular importance, as will be described below

In stage (II), the resulting mixture from stage (I), i.e. usually a suspension, is divided into a retained phase and a permeate phase, where the content of solids in the retentate phase is greater than in the mixture and the percentage of solids in the permeate phase is less. Of it in the mixture. In a preferred embodiment, the percentage of solids content in the retained phase at the end of stage (II), that is, after at least one pass through ultrafiltration or diafiltration, is between 20 and 80%, where the percentage of solids before stage (II) is ) from 1-0 2% by weight. The solid percentage in the retained phase after stage (II) is 50-80% by weight. The weight percentages in each case depend on the total weight of the mixture or the retained phase, respectively.

The percentage of solids in the permeate phase must not exceed 7.0 permeate by weight, and in a preferred embodiment it must not exceed 1% of the weight, in each case depending on the total weight of the permeate phase. In a more preferred embodiment, the percentage of solids in the permeate phase is so low that the permeate phase becomes transparent (i.e., when observed using light with a wavelength between 400 and 800 nm) or when the percentage of solids cannot be determined by drying.

To avoid excessive accumulation of a covering layer (secondary membrane) of solid containing zeolite on the membrane surface, which may lead to an apparent decrease in the permeate flow current, a relative velocity between the membrane and the suspension of 1.0 is generated. - 01 m/s by means of a pumping cycle, mechanical stirring of the membrane or by means of agitators between the membranes.

Concentration may be achieved in batches by passing the suspension several times through the membrane units or continuously by a single pass through one or more feed and perfusion stages connected in series. Furthermore, at least two or two membrane units may be connected in series or in parallel.

The membrane process uses membrane separation layers that have a pore diameter between 1 nm (molecular cut-off limit is about 1 KD & known distance) and 1 µm, preferably from 1 0 nm (molecular cut-off limit about 2 KD) to 5 0 0 nm. Particular preference is given to pore diameters of 0 5-0 0 2 nanometers. The separating layers may consist of at least one material selected from a group of organic polymers, in particular cellulose derivatives, regenerated cellulose, polyolefins, polycarbonates, polysulfones, polymers with NC bonds in the backbone. ; Ceramics, especially silicates, aluminas, glasses, metals, especially ferrous metals, specifically non-steel materials. stainless particular ferrous metals; carbon modifications; Especially materials produced by thermal decomposition of carbon raw material compounds. Combinations or mixtures of at least two of the aforementioned materials.

Moreover, all the materials constituting the film must be practically inert and stable in the feeding environment, i.e., in the current state in the aforementioned industrial mixture. For mechanical reasons, separator layers are generally placed on one or more single or multiple subject layers

Layers made of the same material as the separation layer material or of a different material than the separation layer. Examples of possible combinations of materials are given in the following table:

<img file="SA1647B1_D0001.tif" />

Membranes can be used in any geometric shape known to experts in this field, and priority is given to flat, plate, tubular, coil, multichannel-element, capillary, or wound geometries. It is essential that the geometry chosen is suitable for the corresponding pressure jacket that allows separation between the confinement (zeolite-rich) and the outlet (zeolite-poor or zeolite-free filtration product).

The best transmembrane pressures between retentate and permeate depend mainly on the diameter of the membrane pores, the hydrodynamic conditions affecting the formation of the coating, and the mechanical stability of the membrane at the filtration temperature. These pressures range, depending on the type of membrane, between 0.2 and 0.6 bar, preferably between 0.5 and 2.0 bar. Higher pressures across the membrane usually result in higher permeation fluxes. When several units are connected in series, the pressure across the membrane for each unit can be reduced and thus adjusted by increasing the permeate pressure.

The operating temperature (filter temperature) depends on the stability of the membrane and the temperature stability of the synthetic mixture. It is preferable that the temperature be between room temperature and 150°C, taking care that the solvent in the industrial mixture does not evaporate to an unacceptable range. In particular, temperatures between 30-08°C are preferred.

Higher temperatures usually result in higher permeate flows. The permeate fluxes that can be achieved are strongly dependent on the membrane type and geometry used, process conditions and feed composition (mainly zeolite concentration). Permeate flows typically range between 5 and 500 kg/m3/hour. Examples of membranes that can be used are:

<img file="SA1647B1_D0002.tif" />

<img file="SA1647B1_D0003.tif" />

SolidlLiquid Separation Steel/steel separation

Also at an optional stage, which typically follows the ultrafiltration stage and forms part of the aforementioned stage (II), the solids content of the retentate suspension can be increased further by conventional processes. This can be achieved, for example, by dividing the resulting suspension into a group of fractions and then separating the solids contained in one of the fractions by cake filtration, centrifugation and other appropriate methods.

The filter cake resulting or precipitated in this way can then be dropped into the remainder of the suspension, if necessary after the washing phase. Stage (III): Agglomeration/Granulation:-

After stage (II) of concentrating and/or separating, the solid particles can be enlarged by any known process of agglomeration and/or granulation. It explicitly includes the stages of the drying process that typically lead to at least partial agglomeration and/or are carried out after the agglomeration stage. These operations are referred to in the following, non-exclusive, illustrative list:

(1) Spray drying;

(2) drying with fluidized substrate;

(3) spray drying with a complementary fluidized substrate;

(4) continuous charge-discharge drying;

(5) Drying on a conveyor belt;

(6) drying by granular transfer by spraying with fluid substrate;

(7) Continuous contact drying;

(8) Continuous drying by grinding paste;

(9) Fine granular conversion in a spray tower;

(10) Agglomeration by adding a binding agent;

(11) Agglomeration by changing pH.

With regard to points (i) and (vi), the relevant text from German Patent No. 19731627 or US Patent No. 6106803 is included in its entirety in the context of the present application. Regarding point (xi), the relevant text of European Patent No. 638362 is included in its entirety in the context of the present application.

For all points (i) through (xi), add at least one addition before, during or after,

Or before and after, or before, during, during and after, or before, during and after the drying stage

respective drying/granulating/agglomerating. These additives can be selected, for example, from the following group: binders; Fillers, components of pore formers, and with regard to choosing these additions, we apply the notes mentioned later, with the exception of one section for shaping.

In a preferred embodiment, some or all of the agglomerate/granulation product is returned to step (III).

Aftertreatment:-

To improve the catalytic behavior, stage II, stage III, or both, in each case sometimes in combination with drying and/or calcination, we may perform a subsequent treatment with repeated washing with a solution of hydrogen peroxide and sulfuric acid, after which the The solid is re-dried and then calcined (placed at roasting temperature). This can be followed by treatment with alkali metal compounds to convert the zeolite from the H form to the cation form. Then the resulting solid can be processed into a body with a specific shape, as described below. Stage (S): Shaping

The method of the invention begins with the crown of a formed body containing zeolite from the concentrated material, and sometimes from the solid agglomerated material after stage (II) or (III) or from a dried powder and sometimes (calcined) and/or agglomerated later processed.

In each case, the formation steps include the formation of a material that can be plastically reconstituted containing at least one solid material containing zeolite as well as a binder, and, if necessary, a pore-forming material based on dispersible polymers, capable of being suspended or emulsifiable in aqueous solvents. aqueous solvents, and when needed a mixture containing at least one alcohol and water, and when needed one or more organic viscosity improvers and other additives known from the previous field.

It is preferable to shape the material that can be reshaped by plasticizing the resulting material by thoroughly mixing, especially kneading, the previous components by extrusion, and then the resulting formed body is dried and finally calcined.

Useful binding materials are essentially any elements that impart stronger adhesion and/or bonding between the molecules to be linked, here the solid (atomic) material, than the natural absorption that exists in any case without the binding material. The preferred binding materials are chosen from the group that includes orthosilicates, tetraalkoxysilanes, tetraalkoxytitanates, tetraalkoxyzirconates, or a mixture of two or more of them, preferably tetramethoxysilane and tetraethoxysilane.

tetraethoxysilane; Tetrapropoxysilane, tetrabutoxysilane, and the corresponding compounds of tetraalkoxytitanium and tetrabutoxysilane.

Alkoxy-zirconium, trimethoxy, triethoxy, and tripropoxy-derivatives, with particular preference to colloidal particles in a liquid of tetramethoxysilane, tetraethoxysilane.

tetraethoxysilane, and silica. Other preferred binders are bipolar materials, that is, molecules with a polar and nonpolar component, and graphite.

graphite.

The preferred binders used to produce the formed objects subject of the invention are those containing aluminum. Examples in particular are synthetic clay minerals, and natural aluminas. Such as alpha, beta, gamma, delta, eta, kappa, chi, and theta-alumina, and compounds whose primary materials are inorganic or organometallic, such as gibbsite and bayerite. Boehmite, pseudo boehmite, and trialkoxyaluminates, and a third is preferred.

Aluminum isopropylate. Aluminum triisopropylate

Binding materials can be used either individually, as a mixture of two or more of them, or in addition to other binding materials used for zeolite materials, such as the aforementioned substances and/or oxides of silicon, boron, phosphorus, zirconium and/ Or titanium. Specific examples in this context in particular are silica, and SiO2 may be introduced into the formation stage as a colloidal solution in a liquid (as a sol) of silica or in the form of tetraalkozysilanes, and clays, such as

Montmorillonites, kaolins, bentonites, halloysites, dickites, nacrites, and ananxites.

It is preferable that the shaped body that is the subject of the invention contain about 0.8, preferably between about 0.1 and 75, and especially about 25 - 5.4% by weight of binder, depending in each case on the total mass of the formed body.

As already noted from the above, mixtures of two or more of the aforementioned binders can be used in any case.

In the method of the invention, it is possible to add polymeric polymers to create a specific pore size, or a specific distribution of pore size and pore size, and if required, use dispersible polymeric polymers capable of being suspended or emulsified in aqueous solvents according to the invention for this purpose.

It is preferable to choose a polymer from polymeric vinyl compounds.

Such as polystyrene, polyacrylates, polymethacrylates, polyolefins, and polyamides. Polyesters. These polymers are essentially increased from the formed body again during calcination. If present, the percentage of polymer during the production of the formed body ranges between about 5-0.9, preferably 5-1-75, and especially from about 25-55% by weight, attributed in each case to the amount of solid material containing zeolite in the mixture.

In addition, a kneading agent is used in producing the shaped object that is the subject of the invention.

All materials suitable for this purpose and known from the previous field can be used as kneading agents. Preferably organic, especially hydrophilic polymers, such as cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene and polytetrahydrofuran. These elements essentially activate the formation of a material that can be plastically reshaped during the kneading, shaping and drying stages by creating a bridge for the primary particles as well as ensuring the mechanical stability of the formed body during shaping and drying. These materials are removed from the formed body again during calcination.

Amines or amine-like compounds can be included, such as tetraalkylammonium compounds or amino alcohols, and elements containing carbonate containing substances, such as carbonates.

Calcium carbonate, as other additives. These further additions are described in European Patent No. 41 0 389, European Patent 260 00 34, and International Patent No. 9222 1/95, and their relevant contents are fully incorporated herein by reference in the context of the present application.

Instead of basic additives, acidic additives may be used. This may lead to,

In general, the metal acid ester (=binder) reacts faster with the solid containing zeolite. Preference is given to organic acid compounds that may burn after the calcination step. Carboxylic acids, such as formic acid, are particularly preferred. These acids modify the surfaces of existing formed objects.

It is possible to use other additives and solvents that help plasticize the material to be formed.

These additives and solvents are known to experts in this field.

It is also possible, of course, to use mixtures of two or more of the above-mentioned additives.

The order in which the components of the zeolite-containing substance (mixture) are added is not important.

We may add first either the binder, then the water-dispersible or emulsifiable polymer, the organic viscosity improver and, if needed, the additive and finally the kneading agent, or we may alter the order of the binder, polymer, organic viscosity improver and additives.

After adding the binder to the zeolite-containing solid, to which an organic viscosity improver may be added, the seed material is usually (but not necessarily) homogenized in a kneader or extruder for 0-180 minutes. This is generally done at about 10°C from the boiling point of the kneading agent and at atmospheric pressure or a pressure slightly higher than atmospheric pressure. This is followed by adding the rest of the ingredients, and kneading the resulting mixture until it forms a plastic, extrudable material.

For the purposes of this invention with regard to methods of the forming process, preference is given to methods in which the forming is carried out by extrusion in conventional extrusion devices, for example to make extruded products having a diameter of about 1-10 mm, especially between 2-5 mm. These extruders are described, for example, in Ullman's book Encyclopedia Determination Chemistry, Fourth Edition, Volume 2, Page 295, 1972.

Basically, on the other hand, all traditional kneading and shaping devices and methods, generally known as large old-fashioned preparations for producing, for example, shaped objects, can be used for shaping. The following stages can generally be distinguished:

(i) Molding, i.e. mechanical pressing of a matrix material with or without binder and/or other materials,

(ii) granulation, i.e. incorporating wet atomized material by circular/rotary motions and (iii) sintering, i.e. subjecting the combined material to heat treatment.

Specifically, the molding stage (S) may be selected from the following combination, a combination of at least two of those methods expressly including: die and embossing, cylinder pressing, ring cylinder pressing, bondless molding; Granulation, melting, spinning methods, sedimentation, foaming, spray drying, curing in shaft furnace, convection furnace, moving bar screens, rotary tube furnace, heating.

Fusion can be performed at or above atmospheric pressure, for example, in a pressure range from 1 bar to several hundred bar. Consolidation can also be performed at or above room temperature, for example in the range of 20-300°C. If the forming step includes drying and/or curing, temperatures up to 1500°C are permissible. Finally, mixing may occur, for example, in a room or in a controlled atmosphere. Tight atmospheres are, for example, protective gas envelopes, reducing and/or oxidizing atmospheres.

Subsequent processing and calcination of the formed body

After the end of at least one forming process, the formed bodies are generally dried at about 30-140°C (for 1-2 hours, atm) and calcined at about 400-800°C (for 3-10 hours, atm).

Of course, the resulting strands or extrusions can be collected. It is preferable to connect them to produce granules or slices with a granule diameter between 0.1-5 mm, and especially between 0.5-2 mm.

These granules or chips, as well as the shaped objects produced by these methods, virtually do not contain any finer fractions than those with a minimum grain diameter of about 0.1 mm.

The formed bodies that are the subject of the invention or the formed bodies resulting from this process that are the subject of the invention have good mechanical stability in combination with improved activity and/or selectivity compared to the corresponding old-fashioned formed bodies.

In addition to the aforementioned process for producing a solid substance containing zeolite, this invention also includes the aforementioned solid substance, such as that produced by a process that includes at least the following stages:

Stage (I): - at least partial crystallization of a solid containing at least one zeolite from a synthetic mixture to produce the mixture (I) comprising at least said solid and at least one auxiliary substance;

Stage (II) Concentration of the solid in the mixture (I) by ultrafiltration to produce retention and permeation products; This step optionally includes the separation of the solid/liquid, for example the solid from the original liquid;

Stage (III) agglomeration, granulation, agglomeration and gelatinization of solid particles in the concentrated retention product of stage (II); This step optionally includes drying the solid particles.

In addition, the process optionally includes separation and calcination of the intercalated solid particles

Or the beloved.

This invention also includes a formed body containing at least one zeolite material, which can be obtained from the aforementioned solid materials by performing the following stages: - Stage (S): subsequent formation, stage (II) or (III);

Stage (C): subsequent calcination of stage (III) or (S).

What was previously mentioned applies regarding the sub-steps that may be used for shaping and the conditions under which the agglomerated, non-agglomerated or compacted solid material can be burned.

Finally, this invention presents the use of a solid material containing zeolite resulting from one of the aforementioned processes, or the solid material or the formed body itself, as described before. In particular, the solid materials or formed bodies that are the subject of the invention, or the solid materials or formed bodies resulting in accordance with the invention, can be used for the catalytic transformation of organic molecules. Reactions of this type include, for example, oxidation, especially redundant oxidation of compounds with at least one C-C multiple bond.

In a preferred embodiment, this relates to the over-oxidation of olefins, such as the preparation of propylene oxide from propylene and H2O2, the hydroxylation of aromatics, such as the preparation of aqueous ketones from phenol and H2O2 or the conversion of toluene to cresol, the conversion of alkanes to alcohols, aldehydes and acids. Furthermore, this catalyst can be used for: isomeric conversion reactions, for example the conversion of peroxides to aldehydes, as well as reactions described in the written text and the use of zeolite-containing catalysts such as those described, for example, in WH Oldrich &amp; Zeolites: Catalysts for the manufacture of organic compounds, Alsevier, Study, Serv, Sanis. Catal 49 (1989) pp. 69-93 (Amsterdam). Especially for possible oxidation reactions, in the name of Notari in Study. Surf. Sanis. Cathal. 37 (1987), 413-425.

The previously described solids or shaped bodies containing at least one zeolitic substance are particularly suitable for the overoxidation of olefins with 2-8 carbon atoms, preferably ethylene, propylene or butene, and especially propene to produce the corresponding olefin oxides. Accordingly, this invention relates specifically to the use of a zeolite solid or shaped body described herein to prepare propylene oxide starting from propylene hydrogen peroxide. Other details of the reaction system of ancient methods are well known. In this context, the following documents jointly registered for the same client in full are present in this application: International No. 36094/34298,1/1, 1/72739, 10855/1 and 5 2194/1.

Furthermore, this invention relates to the use of the formed body that is the subject of the invention or the formed body produced in accordance with the invention or a mixture of two or more thereof for the hydroxylation of aromatic organic compounds, for the conversion of alkanes into alcohols, ketones, aldehydes and acids, and for the treatment of ketones, by adding Amoxy and to prepare N oxides - for amine.amine

Example:-

The membrane used for ultrafiltration according to stage (II) was a single-channel tubular membrane

Ceramic from ATK. InnovationsG MBH has an outer diameter of 10mm, an inner diameter of 6mm and a length

750 mm. An actual filtration membrane made of ZrO2 with a pore size of 0.5 mm is placed on the inside of the ceramic tube made of a-AI2O3.

The synthetic solution contained about 6.9% by weight zeolite and about 4. 3% by weight tetrapropylammonium hydroxide (details can be obtained from European Patent No. 0991469B).

The membrane was inserted into a pump circuit consisting of a storage vessel, pump, heat exchanger,

A pressure tube for the membrane and a valve to maintain pressure. Furthermore, place a flow meter, thermometer and manometer before the membrane, and place a manometer after the membrane.

The suspension to be concentrated is pumped through the tubular membrane, and a sub-stream is drawn through the membrane as a permeable material and removed through the ceramic substrate. It is collected on a scale. The flow speed of the suspension in the tubular membrane is set at 5 m/s, the filtration temperature is set at 0 6 C, and the pressure across the membrane is set at 1 bar. The flow during batch concentration was about 0.9 kg/m/h at the beginning and about 4 kg/h, and at the end the percentage of zeolite was 62.5% and the percentage of tetrapropylammonium hydroxide (TPA) was 3.4%. The percentage of solids (zeolite and TPA) is determined by drying, or for TPA, by titration. The inlet stream was free of zeolite, far beyond the experimental limit of detection, and it contained tetra hydroxide.

Propylammonium concentration of about 4. 3%.

Figure 1: The percentage of total solids (zeolite plus TPA as a percentage by weight) produced using that experimental setup was graphed on a horizontal axis as a function of the permeable material current (kg/m/h) plotted on the vertical axis.