MXPA99011269A - Method for oxidizing an organic compound containing at least on c-c double bond - Google Patents

Abstract

The invention relates to a method for oxidizing an organic compound containing at least one C-C double bond or a mixture of two or more thereof, comprising the following steps:(I) production of a hydroperoxide;(II) reaction of an organic compound containing at least one C-C double bond or a mixture of two or more thereof with the hydroperoxide produced in step (I) in the presence of a zeolitic catalyst;(III) regeneration of the at least partially deactivated zeolitic catalyst used in step (II) and (IV) reaction according to step (II) using a zeolitic catalyst which contains the regenerated catalyst from step (III).

Description

OXIDATION OF AN ORGANIC COMPOUND WHICH HAS AT LEAST A DOUBLE LINK CC The present invention relates to a process for oxidizing an organic compound having at least one CC double bond or a mixture of two or more of them by the reaction of the organic compound. having at least one CC double bond or the mixture of two or more of them with a hydroperoxide in the presence of a zeolite catalyst, then by regenerating this catalyst, and by reusing the catalyst for the aforesaid reaction after its regeneration. Methods for oxidizing an organic compound having at least one C-C double bond, especially olefins, preferably propylene, by employing a hydroperoxide are known methods. US-A-5,374,747 presents said epoxidation process employing a titanium-containing molecular sieve having a structure which is isomorphic to the beta zeolite, and the preparation of said molecular sieve. US-A-5, 384, 418 presents an integrated process for the preparation of epoxides by the reaction of a hydroperoxide with an ethylenically unsaturated compound in the presence of a titanium silicalite. Other processes for the preparation of epoxides in the presence of zeolite catalysts are presented, for example, in US-A-5, 63, 090 and EP-A-0 230 949, the first of which produces hydrogen peroxide used for oxidation from an anthraquinone process, while the second one presents the epoxidation of propylene with hydrogen peroxide in the presence of titanium silicalites defined here. According to US-A-5, 599, 955, propylene, which is the most frequently used for these oxidations, can be obtained starting from synthesis gas. US-A-5, 599, 956 presents a process for the preparation of propylene oxide, where propylene is obtained by thermal decomposition in steam, catalytic decomposition, or catalytic dehydrogenation. It is known that in these catalytic reactions, organic deposits are formed after some time, which results in a partial or complete deactivation of the catalysts, especially when catalysts having micropores are used, for example, zeolite catalysts such as titanium silicalite. or else beta zeolite containing titanium. These organic deposits can be removed mostly by calcining the catalyst or by washing with solvent (MG Clerici, G. Bellussi, U. Romano, J. Catal., 129 (1991), 159-167; JP-A -03 114 536).

EP-A-0 743 094 presents a process for the regeneration of a molecular sieve containing Ti by heating the molecular sieve to a temperature higher than 150 ° C and lower than 400 ° C. This reference also shows the fact that it is possible to use the regenerated catalyst in this form for the reaction of organic compounds, for example, for the hydroxylation of aromatic compounds, the ammoxidation of ketones, the oxidation of saturated hydrocarbons to obtain alcohols and ketones, and for the epoxidation of olefin. DE-A-44 25 672 presents. an oxidation catalyst based on titanium silicate or vanadium silicate having a zeolite structure as well as a process for the preparation of epoxides from olefins, hydrogen and oxygen using the catalyst described therein. It is also established that the catalyst described there can be regenerated. The document US-A-5, 599, 955 mentioned above also mentions the possible regeneration of the catalyst used in relation to the process described therein, but details of the regeneration process are not given. As can be seen from the above, there is a broad prior art in terms of integrated processes for the preparation of epoxides, but the problem of the practical regeneration of the deactivated catalyst and the useful integration of said step in the overall procedure remains unresolved . This step and its integration into the overall procedure are nevertheless essential for the economic viability of such a process. In principle it is to carry out regenerations in accordance with that indicated in EP-A-0 743 094; however, these regenerations are not economically viable due to the low temperatures used there and the resulting long regeneration period. It is an object of the present invention to provide a process for oxidizing an organic compound having 1 minus a C-C double bond, regenerating the catalyst employed in this process and reusing the regenerated catalyst for further reaction in the process. We have found that this object is achieved through the method of the invention. The present invention therefore offers a process for oxidizing an organic compound having at least one CC double bond or a mixture of two or more of them, comprising the following steps: (I) preparing a hydroperoxide, (II) making reacting an organic compound having at least one CC double bond or a mixture of two or more of them with a hydroperoxide prepared in step (I) in the presence of a zeolite catalyst, (III) regenerating the zeolite catalyst at least partially deactivated employed in step (II); and (IV) carrying out the reaction of step (II) employing a zeolite catalyst comprising the catalyst regenerated in step (III). Step (I) This step refers to the preparation of a hydroperoxide. For the purposes of the present invention, a hydroperoxide refers to a hydrogen peroxide as well as to organic compounds of the formula R-O-OH, where R is alkyl, cycloalkyl, aralkyl or aryl. In the process of the present invention, preference is given to the use of hydrogen peroxide. Processes for the preparation of hydroperoxides are known and will be mentioned here only briefly for the synthesis of hydrogen peroxide. The hydrogen peroxide is preferably synthesized through an anthraquinone process or directly from hydrogen and oxygen in noble metal catalysts. In the anthraquinone process, a mixture is prepared which is known as a working solution, below. This mixture comprises a solution of 2-alkylanthraquinone, preferably 2-ethyl-, 2-butyl-. 2-hexyl-, 2-hexenyl-, particularly 2-ethylanthraquinone, in a solvent mixture comprising a quinone solvent and a hydroquinone solvent. The quinone solvent is generally selected from the group consisting of aromatic and alkylaromatic solvents, of preference benzene, toluene, xylenes or higher alkylaromatics having from 6 to 20, preferably from 9 to 11 carbon atoms 5 or mixtures of two or more of them, such mixtures being preferred. The hydroquinone solvent is generally selected from the group consisting of alkyl phosphates, alkyl phosphonates, nonyl alcohols, alkylcyclohexanol esters, N, N-dialkylcarbonylamides, tetraalkylurethanes, or N-alkyl-2-pyrrolidone and mixtures of "two or more of these, Tetrabutylurea is preferred The working solution is hydrogenated with hydrogen at a temperature of about 20 to 100 ° C, preferably at a temperature of about 40 to 70 ° C, in a A commercially available catalyst containing at least one transition metal, preferably from 0.5 to 20% by weight of Pt in carbon, more preferably from 2 to 15% of Pd in carbon. The catalyst can be arranged in the form of a suspension or a fixed bed. The resulting hydroquinone-containing solution is oxidized with oxygen, preferably with air, more preferably with a mixture containing oxygen and nitrogen wherein the oxygen is present in deficiency, on the basis of the total mixture, in a suitable apparatus, for example, a column of bubbles. The oxidation is carried out at a reaction temperature of about 20 to about 100 ° C, preferably about 35 to about 60 ° C, until the content of hydrogen peroxide in the solution becomes constant and until the conversion is complete. of hydroquinone in quinone. The resultant hydrogen peroxide mixture is subsequently extracted with a solvent which is not miscible with the solvent mixture, preferably with water, methanol, a monohydric alcohol having from 2 to 6 carbon atoms or a mixture of two or more. of them, more preferably with water. The resulting hydrogen peroxide mixture can be used directly in the step reaction (II) of the process of the invention. Said preparation process is disclosed, for example, in EP-B-0 549 013, which suggests the use of a mixture of water and an alcohol preferably methanol. In addition, the hydrogen peroxide preferably used for the oxidation in the present invention can also be prepared directly from the elements. Processes for the preparation of hydrogen peroxide from the oxygen and hydrogen elements are well known, as can be seen in DE-A-196 42 770, and the aforementioned prior art. In the process of the present invention, hydrogen peroxide is preferably prepared from the elements in accordance with the process described in that described in DE-A-196 42 770, which is incorporated herein by reference in its entirety . The essential aspects of the procedure described here will now be briefly presented below. According to the process described, hydrogen peroxide is prepared continuously by the reaction of hydrogen and oxygen in water and / or C1-C3 alkanols as reaction medium in a formed catalyst body containing palladium as the active component. This process provides a hydrogen peroxide solution having a hydrogen peroxide content of at least 2.5% by weight, based on the weight of the total solution. Catalyst bodies formed are catalysts in which the catalytically active component is on the surface of vehicles in a specific manner. Such vehicles may be conventional packaging elements, for example Rashig rings, saddle bodies, spiral wire Pall® rings or wire mesh rings, composed of various materials suitable for coating with the active component. Details of the aforementioned vehicles can be found in Rompp Chemie-Lexikon, ninth edition, page 1453 et seq. The packing elements provided with the catalytically active component are introduced into the reactor in the form of a loose bed.

The preferred formed bodies have channels with hydraulic radii (in accordance with the definition in VDI-Warmeatras, chapter LEÍ) within a range of 1 to 10 mm. It is preferred to use formed catalyst bodies installed in the reactor in the form of arranged packages and having a large surface area in relation to their volume, due to a multiplicity of through channels. Such formed bodies are known as catalytic monoliths. Suitable reactors for the preparation of hydrogen peroxide according to this procedure are described, for example, in EP-A-0 068 862m EP-A-0 201 614 and EP-A-0 448 884. An additional process for the preparation of hydrogen peroxide, which can also be integrated in the process of the present invention as step (I), is presented in WO 96/05138. This application is hereby incorporated by reference in its entirety for the process for the preparation of hydrogen peroxide described herein and for the apparatus used for this purpose. The process described herein includes the introduction of small bubbles of hydrogen and oxygen into a liquid stream of water and an inorganic acid in the presence of a catalyst comprising a metal of transition group VIII of the Periodic Table. The liquid stream has a velocity of at least 3 m / s (10 ft / s) to create a continuous region of finely dispersed gas bubbles in a continuous liquid phase. For further details of this process for the preparation of hydrogen peroxide, reference is made to the aforementioned document. The hydrogen peroxide used in the process of the present invention can be prepared by contacting a secondary alcohol, for example, alpha-methylbenzyl alcohol, isopropanol, 2-butanol or cyclohexanol with molecular oxygen under suitable conditions to obtain a mixture. comprising a secondary alcohol and hydrogen peroxide and / or a hydrogen peroxide precursor. Said mixture typically comprises a ketone corresponding to the secondary alcohol employed in each case, ie, a ketone having the same carbon structure as the secondary alcohol employed, for example, acetogenone, acetone or cyclohexanone, a small amount of water and various amounts of other active oxygen compounds, for example, organic hydroperoxides. The hydrogen peroxide used can also be generated in situ immediately before or during the epoxidation, according to what is described, for example, in EP-B-0 526 945, JP-A-4 352 771, EP-B -0 469 662 and Ferrini et al., In "Catalytic Oxidation of Alkanes Using Titanium Silicate in the Presence of in situ Generated Hydrogen Ferroxide" (Catalytic Oxidation of Alkanes Using Titanium Silicate in the Presence of Hydrogen Oxide Generated in Situ), DGMK , Conference on Selective Oxidations in Petrochemicals, September 16-18, 1992, page 205-213. Step (II) This step of the process of the present invention relates to the reaction of a compound having at least one CC double bond or a mixture of two or more of them with a hydroperoxide prepared in step (I) in the presence of a zeolite as a catalyst. For the purposes of the present invention, the term "Organic Compound containing a C-C double bond" encompasses all organic compounds having at least one C-C double bond. The compound in question may be a low molecular weight organic compound, ie, a compound having a molecular weight of up to about 500, or a polymer, that is, a compound having a molecular weight greater than 500. However, The process of the present invention is preferably used for organic compounds of low molecular weight of the type described above. They may be linear, branched, or cyclic compounds which may contain aromatic, aliphatic, cycloaliphatic groups or a combination of two or more of them. Preferably, an organic compound is used having from two to 30 carbon atoms, more preferably from 2 to 10 carbon atoms.

The organic compound used is more preferably an aliphatic monoolefin. However, it is also possible that the organic compound used has more than one ethylenically unsaturated double bond, as is the case, for example, in dienes or threes. The compound may contain additional functional groups such as for example halogen, carvi oxide, an ester group, hydroxide, an ether bond, a sulfide bond, carbonyl, cyano, nitro, amino or a combination of two or more of them. It can also be part of a cyclic structure, as is the case with cyclohexene It is also possible to use a mixture of two or more of these compounds Additional examples of suitable organic compounds include unsaturated fatty acids or derivatives thereof, such as for example esters and glycerides of such unsaturated fatty acids, and oligomers or polymers of unsaturated organic compounds, such as for example polybutadiene Examples of organic compounds of this type include: ethylene, propylene, 1-butene, cis- and trans-2-butene, isobutylene, butadiene, pentenes, isoprene, 1-hexene, 3-hexene, 1-heptene, 1-octene, diisobutylene, 1-nonene, 1-decene, camhene, 1-undece or, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, di-, tri- and tetramer of propylene, styrene and further vinylaromatic organic compounds having at least one double bond, diphenylethylene, polybutadiene, polyisoprene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, cyclododecatriene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, vinylcyclohexene, metalyl ketone, allyl chloride, allyl bromide, acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, crotyl chloride, metal chloride, dichlorobutenes, allyl alcohol, allyl carbonate, allyl acetate, allyl acrylate, and ethacrylates, diallyl maleate, diallyl phthalate, unsaturated triglycerides, for example, soybean oil, unsaturated fatty acids, for example, oleic acid, linoleic acid, linolenic acid, acid or ricinoleic, and esters thereof, including esters of mono-, di-, and triglycerides. Mixtures of two or more such compounds, especially mixtures of the compounds exemplified above, may also be employed. Thus, the present invention particularly offers a method of the present type wherein the organic compound having at least one CC double bond is selected from the group consisting of a linear or branched aliphatic olefin, a linear or branched cycloaliphatic olefin, each having up to 30 carbon atoms, and a mixture of two or more of them. The process of the present invention is especially useful for reacting low molecular weight olefins, for example, ethylene, propylene, and butenes, especially propylene. Catalysts used in step (II) of the process of the present invention are microporous, and / or mesoporous and / or macroporous solid containing transition metals. Oxidation of low molecular weight compounds is particularly preferably carried out by the use of microporous solids containing transition metals, with transition metal-containing zeolites being preferred, more preferably a zeolite containing titanium, zirconium, chromium, niobium, iron, or vanadium, and especially a titanium silicalite. Zeolites are crystalline aluminosilicates that have cage structures and channels arranged with micropores. For the purposes of the present invention, the "micropores" correspond to the definition provided in "Puré Appl. Chem." 45, page 71 and following, particularly page 79 (1976), and refers to pores with a pore diameter of less than 2 nm. The network of such zeolites consists of tetrahedra of SiO and AlO., united by common oxygen bonds. A review of the known structures can be found, for example, in "Atlas of Zeolite Structure Types", of W.M. Meier and D.H. Olson, Elsevier, fourth edition, London, 1996. In addition, there are zeolites that do not contain aluminum and that have Ti (IV) partially replacing Si (IV) in the silicate lattice. Titanium zeolites, especially those having a crystal structure of the MFI type, and possible ways of preparing them are described, for example, in EP-A-0 311 983, or EP-A-0 405 978. A part of silicon and titanium, materials of this type may also contain additional elements such as aluminum, zirconium, tin, iron, cobalt, nickel, gallium, boron or even small amounts of fluorine. The titanium in the described zeolites may be partially or totally replaced by vanadium, zirconium, chromium, niobium or iron. The molar ratio between titanium and / or vanadium, zirconium, chromium, niobium or iron, and the sum of silicon plus titanium and / or vanadium, zirconium, chromium, niobium, or iron is usually within the range of 0.01: 1 to 0.1: 1. Titanium zeolites having an MFI structure are known and can be identified a. from a particular pattern in its X-ray diffraction diagrams and, in addition, from a skeletal infrared (IR) vibration band approximately 960 cm "1, and therefore differ from alkali metal titanates or amorphous Ti02 phases Said titanium, zirconium, chromium, niobium, iron and vanadium zeolites are usually employed by the reaction of an aqueous mixture of a Si02 source, a source of titanium, zirconium, chromo niobium, iron or vanadium, for example , titanium dioxide or an appropriate vanadium oxide, zirconium alkoxide, chromium oxide of niobium oxide or iron oxide, and a tempering of a nitrogenous organic base, for example tetrapropylammonium hydroxide, with or without the basic compounds added , in a pressure vessel at an elevated temperature for several hours or a few days, which resulted in a crystalline product.The crystalline product is removed by filtration, washing, High temperature cooking and baking to remove the organic nitrogen base. In the resulting powder, the titanium or zirconium, chromium, niobium, iron and / or vanadium is present at least partially within the structure of the zeolite in varying proportions in 4.5 or 5 times coordination. To improve the catalytic characteristics, it is also possible to carry out a subsequent treatment by repeatedly washing with a solution of hydrogen peroxide containing sulfuric acid, after which the zeolite powder with titanium or zirconium, chromium, niobium, iron or Vanadium must be dried and baked again; this can be followed by a treatment of alkali metal compounds in order to convert the zeolite from the H form into the cation form. The resulting zeolite powder with titanium or zirconium, chromium, niobium, iron, vanadium is then processed into a body formed in accordance with what is described below. Preferred zeolites are zeolites of titanium, zirconium, chromo niobium, or vanadium, the most preferred zeolites are those having a pentasyl structure, especially the types with X-ray assignment to a BEA, MOR, TON, MTW, FER structure, MFI, MEL, CHA, ERI, RHO, GIS, BOG, NON, EMT, HEU, KFI, FAU, DDR, METT, RUT, LTL, MAZ, GME, NES, OFF, SGT, EUO, MFS, MCM-22 or well a mixed structure MFI / MEL. Zeolites of this type are described, for example, in the above reference by Meier and Olson. It is also possible for the present invention to contain titanium containing zeolites having the structure of UTD-1, CIT-1, CIT-5, ZSM-48, MCM-48, ZSM-12, ferrierite or beta zeolite, or modenite. Such zeolites are described, for example, in US-A-5 430 000 and WO 94/29408, whose relevant content is hereby incorporated by reference in its entirety. There are also no special restrictions on the pore structure of the catalysts used according to the invention, ie the catalyst can have micropores, mesopores, macropores, micropores and mesopores, micropores and macropores, or micropores, mesopores and macropores. , the definition of "mesoporous" and "macropores" also corresponds to the definition offered in Puré Appl. Chem, said reference was offered above and is defined as having a diameter of >2 nm to about 50 nm or > approximately 50 nm, respectively. The catalyst used according to the present invention can also be a material based on a mesoporous oxide containing at least one transition metal and silicon or of a xerogel containing a transition metal and silicon. Especially preferred are mesoporous silicon-containing oxides which also contain Ti, V, Zr, Sn, Cr, Nb or Fe, especially Ti, V, Zr, Cr, Nb or a mixture of two or more of them. If low molecular weight olefins, such as propylene, react in the present invention, particular preference is given to the use of titanium-containing zeolite catalysts having exclusively or almost exclusively micropores such as, for example, titanium silicalite 1, titanium silicalite 2 or zeolite Beta containing titanium, more preferably titanium silicalite 1 or titanium silicalite 2, especially titanium silicalite 1. The use of a catalyst having particular mechanical stability is preferred, if the reaction of step (II) is carried out as a procedure in fixed bed. A catalyst having a zeolite structure in accordance with that described in DE-A-196 23 611, which is incorporated herein by reference in its entirety as to the catalysts described herein is particularly suitable for this purpose. These catalysts are based on titanium or vanadium silicates having a zeolite structure. As for the structure of zeolite, reference is made to the preferred structures mentioned above. The catalysts are characterized to the extent that they have been formed by processes of formation and reinforcement. Suitable reinforcement formation methods that can be employed include in principle all the reinforcement formation methods commonly employed for catalysts. Preference is given to processes in which the formation is carried out by extrusion in conventional extruders, for example to obtain extruded products having a diameter usually from 1 to 10 nm, especially from 2 to 5 mm. If binders and / or adjuvants are required, the extrusion is advantageously preceded by a mixing or kneading process.

The extrusion can be followed by a calcination step. The resulting extruded products are comminuted, if desired, preferably to obtain particles or granules having a particle diameter of 0.5 to 5 mm, especially 0.5 to 2 mm. Particles, granules are also shaped shaped catalyst bodies in a different manner that do not contain virtually finer fractions than fractions having a minimum particle diameter of 0.5 mm. In a preferred embodiment, the oxidation catalyst formed employed contains up to 10% by weight of binder, based on the total mass of the catalyst. The particularly preferred content of binder is from 0.1 to 7% by weight, especially from 1 to 15% by weight. Suitable binders are, in principle, all the compounds used for this purpose; compounds, especially oxides, of silicon, aluminum, boron phosphorus, zirconium and / or titanium are preferred. A binder of particular interest is silicon dioxide, which can be introduced into the forming step in the form of a silica sol or tetraalkoxysilanes. Oxides of magnesium and beryllium and also clays, such as, for example, montmorillonites, kaolins, bentonites, haloisites, diquitas, nacrites and anauxites, can also be used as binders. Adjuvants for the reinforcement formation processes include, for example, extrusion aids, a customary extrusion aid is methylcellulose. Said adjuvants are usually completely burned in a subsequent calcination step. The aforementioned titanium and vanadium zeolites are typically prepared in accordance with that described above in the general description of the zeolite catalysts used according to the invention. The resultant titanium or vanadium zeolite powder is then shaped in accordance with that described above. It is also possible to regenerate oxidation catalysts based on titanium or vanadium silicates having a zeolite structure and containing 0.01 to 30% by weight of one or more noble metals selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium, platinum, rhenium, gold and silver, and which are also characterized to the extent that they have been formed by reinforcement training procedures. Such catalysts are presented in DE-A-196 23 609, which are incorporated herein by reference in their entirety for the catalysts described herein. What was said above in relation to DE-A-196 23 611 is applied as regards the reinforcement formation processes, the binders and the adjuvants and the structure of the oxidation catalysts. The catalyst presented in DE-A-196 23 609 contains from 0.01 to 30% by weight, especially from 0.05 to 15% by weight, and particularly from 0.01 to 8% by weight, of the noble metals mentioned above, in each case. case, based on the amount of titanium or vanadium zeolites. Palladium is particularly preferred. The noble metals can be applied to the catalyst in suitable noble metal component forms, for example, in the form of water-soluble salts, during or after the reinforcing formation step. In many cases it is more profitable, however, to apply the noble metal components on the catalyst bodies formed only after the forming step, especially if a high temperature treatment of the noble metal catalyst is undesirable. The noble metal components can be applied to the catalyst formed particularly by ion exchange, impregnation, or spray. The application can be carried out using organic solvents, aqueous ammonia solutions, or supercritical phases such as, for example, carbon dioxide. It is possible to produce noble metal catalysts of various types through the methods mentioned above. Thus, a type of coated catalyst can be produced by spraying the catalyst bodies formed with the noble metal solution. The thickness of these noble metal surface layer can be increased considerably by impregnation, while the catalyst particles are coated substantially uniformly with a noble metal through the cross section of the bodies formed in the case of ion exchange. In the process of the present invention, preference is given to the use of a zeolite catalyst that can be obtained through a process comprising the following steps: (i) mixing a mixture comprising a zeolite or a mixture of two or more of them with a mixture comprising at least one alcohol and water, and (ii) kneading, shaping, drying and calcining the mixture in step (i) • In step (i) of this catalyst preparation process, a zeolitic material is processed, preferably the zeolites described in greater detail below, particularly the titanium or vanadium zeolites described in greater detail below, with a mixture comprising at least one alcohol and water, a binder, optionally one or more organic viscosity enhancers and other additives of the prior art in order to obtain a plastically deformable material. This plastically deformable material obtained by the intimate mixture, especially the kneading, of the aforementioned components is then formed, preferably by extrusion, and the resulting formed body is dried and finally calcined. The catalyst which is preferably used according to the present invention and its preparation can be described more precisely in the following way: The zeolite used according to the present invention is preferably a zeolite containing titanium, zirconium, chromo niobium, iron, or vanadium, and especially a titanium silicalite, which in turn is preferably a picroporous titanium silicalite, more preferably a microporous titanium silicalite having a restructuring of pentasyl zeolite. What we said in the general description of the zeolite used according to the present invention in terms of composition, structure, pore distribution and preparation of the zeolite is also applied here. Suitable binders include, in principle, all the compounds used to date for this purpose. Compounds are preferred, especially silicon oxide, aluminum, boron, phosphorus, zirconium and / or titanium. A binder of particular interest is silicon dioxide which can be introduced into the forming step in the form of silica sol or tetraalkoxysilanes. Oxides of magnesium and beryllium and also clays, for example, montmorillonites, kaolins, bentonils, haloisites, diquitas, nacrites and ananxites, can also be used as binder. The preferred binders added in step (I) of the process of the present invention are, however, a metal acid ester or a mixture of two or more of them. Particular examples of these are orthosilicates, tetraalkoholxysilanes, tetraalkoxytitanates, trialkoxyaluminates, tetraalcoxyzirconates, or a mixture of two or more of them. Particularly preferred binders are tetraalkoxysilanes. Specific examples are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane, the corresponding tetraalkoxytitanium and tetraalkoxyzirconium compounds as well as trimethoxy, triethoxy, tripropoxy, tributoxyaluminium, with tetramethoxysilane and tetraethoxysilane being particularly preferred. The "especially preferred catalyst used in accordance with the present invention, in the form of a shaped body, contains up to about 80% by weight, more preferably from about 1 to about 50% by weight, especially from about to about 30% by weight, of binder, in each case based on the total mass of the formed body, the binder content is calculated based on the amount of metal oxide formed.The metal acid ester employed is preferably employed in an amount such that the content of The metal oxide resulting in the solid is from about 1 to about 80% by weight, preferably from about 2 to about 50% by weight, especially from about 3 to about 30% by weight, in each case based on the total mass of the formed body As can already be seen from the foregoing, mixtures of two or more of the aforementioned binders can also be used It is essential to employ a mixture containing at least one alcohol and water as a paste-forming aid when preparing this formed body. The alcohol content of this mixture is generally from about 1 to about 80% by weight, preferably from about 5 to about 70% by weight, particularly from about 10 to about 60% by weight, in each case based on the total weight of the mixture. The alcohol employed is preferably the same as the alcohol component of the metal acid ester preferably used as the binder but the use of another alcohol is not a critical factor. Any alcohol can be used provided it can be mixed in water. Accordingly, monoalcohols having from 1 to 4 carbon atoms and polyhydric alcohols miscible in water can be used. Particularly used are methanol, ethanol, propanol, iso-hyperbutanol, as well as mixtures of two or more of them.

Customary organic viscosity builders also include all substances of the prior art suitable for this purpose. Organic polymers, especially hydrophilic, are preferred, for example cellulose, starch, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene and polytetrahydrofuran. These substances primarily promote the formation of a plastically deformable material during kneading, with formation and drying creating bridges between the primary particles and also ensuring the mechanical stability of the body formed during the formation and drying stage. These substances are removed from the body formed during calcination. Additional additives which can be used are amines or amine-type compounds such as tetraalkylammonium compounds or aminoalcohols and substances which. they contain carbonate such as calcium carbonate. Additional additives of this type are presented in EP-A-0 389 041, EP-A-0 200 260, and W095 / 19222, the contents of which are hereby incorporated by reference in their entirety. It is also possible to use acidic additives instead of basic additives. Among other things, these acidic compounds can cause a faster reaction of the metal acid ester with the porous oxide material. Organic acid compounds are preferred which can be removed by calcination after the forming step. Especially preferred are carboxylic acids. It is also possible to include mixtures of two or more of the aforementioned additives. The sequence in which the components of the material containing the porous oxide material are added is not a critical factor. It is possible to add the binder first, followed by the organic viscosity enhancer and the additive, if used, and finally the one containing at least one alcohol and water, but you can also change the binder sequence, organic viscosity enhancer and additives . After the addition of the binder to the porous oxide powder to which the organic viscosity enhancer may have been added, the material still usually powdered is homogenized in a kneader or extruder for 10 to 180 minutes. This is usually carried out at a temperature within a range of 10 ° C up to the boiling point of the pulping aid and at atmospheric pressure or at slightly superatmospheric pressure. Subsequently, the remaining components are added, and the resulting mixture is kneaded until the formation of a plastically extrudable material. The kneading and forming can, in principle, be carried out by using any of numerous kneading and forming apparatuses and processes customary in the prior art which are commonly employed for the preparation, for example, of formed catalyst bodies. As indicated above, processes are preferred where forming is carried out with extrusion from customary extruders such as, for example, to form extrudates having a diameter typically from about 1 to about 10 mm, especially from about 2 to about 5. mm. Such extruders are described, for example, in "Ullmanns Enzyklopadie der Technischen Chemie", fourth edition, volume 2, page 295 et seq., 1972. After extrusion, the resulting formed bodies are dried at a temperature generally comprised between 30 ° C. and about 140 ° C (for 1 to 20 hours, atmospheric pressure) and calcined at a temperature of about 400 ° C to about 800 ° C (atmospheric pressure). It is possible to crush the resulting extruded products. They are preferably ground to obtain pellets or granules having a particle diameter of 0.1 to 5 mm, especially 0.5 to 2 mm. These pellets or granules and also particles formed differently contain virtually no finer fractions than fractions having a minimum particle diameter of about 0.1 mm. Even when there are no special limitations regarding the apparatus used for the reaction, step (II) of the process of the present invention is preferably carried out in a reactor bank packed with one of the catalysts which can be used in accordance with the present invention, which consists of 2 to 7, preferably from 2 to 5 reactors, the catalyst is in the form of a tablet or an extruded product that forms a fixed bed or has the appearance of a powder forming a suspension. Examples of reactor types that may be used that may be mentioned are stirred tank reactors and tubular reactors, with or without external circulation In the reaction, a hydroperoxide-containing stream, preferably hydrogen peroxide comprising an organic compound having the less a CC double bond, preferably a C2-C olefin, more preferably propylene, comes into contact with an organic solvent, preferably a Ci-Ce alcohol, preferably methanol, and is converted into the desired oxidized compound, preferably in the epoxide, at a temperature in the range of about 20 ° C to about 120 ° C, preferably about 30 ° C to about 80 ° C. The preferred solvent, methanol, used may be fresh methanol or recycled methanol from the epoxidation.

The ratio between the compound to be reacted and the hydroperoxide is not a critical factor and is found in a molar ratio of from about 100: 1 to about 1:10, preferably from about 1: 1 to about 6: 1. The hydroperoxide content in the reactor (without the compound to be reacted) is generally from about 0.1 to about 10%, the methanol content is from about 10 to 90%, and the water content is from about 5 to about 50. %. The amount of catalyst present in the reactor can also vary within wide limits. The amount of catalyst present must be sufficient to terminate the desired reaction within a short period of time. The optimum amount depends on many factors, for example temperature, ratio between the compound to be reacted and the hydroperoxide, the reactivity of the compound to be reacted, the reaction pressure, the residence time, and the flow rates of the compounds introduced in the reactor. The temperature of the reaction is generally within a range of about 20 ° C to about 120 ° C, preferably about 30 ° C to about 100 ° C, more preferably about 30 ° C to about 80 ° C. The temperature is generally chosen such that the desired reaction can be carried out within an economically viable time period. The residence time is within a range of about 10 minutes to about 24 hours, preferably 10 minutes to about 1 hour per reactor. The reaction pressure is usually chosen within a range from about 1 to about 100 bars, preferably from about 15 to about 40 bars. The reaction mixture is preferably in liquid form. The temperature of the reaction, the residence time and the reaction pressure should be selected such that the conversion of the hydroperoxide is at least 50%, preferably at least 90%, particularly 99% or more. After the end of the reaction, the oxidation product formed can be separated from water, solvent and any by-products. The separation can be carried out by the separation methods of the prior art, with distillation separation methods being preferred. The unconverted organic compound having at least one C-C double bond and the obtained solvent can in the same way be separated and recycled to the reaction of step (II) if desired. The reaction of step (II) can be carried out continuously, in batches, or partially continuously depending on the reactor used, for example, a fixed bed, a mobile bed, a liquid bed, or else a suspension method in an agitated or not agitated way. It is also possible to carry out the reaction in a single-phase system or in a multi-phase system, for example a two-phase system. This reaction is preferably carried out in a fixed bed process. Once the epoxidation has advanced to a certain degree, the desired oxidation product can be. separated from the reaction mixture by any separation method of the prior art capable of separating the oxidation product from the reaction mixture. Distillation separation methods are preferred. The resulting oxidation product is obtained essentially free of the catalyst employed, especially when the reaction is carried out as a fixed bed process, and can therefore be further prepared without additional steps of catalyst separation. The unconverted initial material, ie, the organic compound having at least one CC double bond or the mixture of two or more of them and the unconverted hydroperoxide, can be removed and recycled in the same manner or fractionated to form products such as water or alcohol and oxygen, for example. In some embodiments of the present invention, especially when the hydroperoxide is prepared from a secondary alcohol, in that case the hydroperoxide-containing mixture used for oxidation also contains a secondary alcohol or the corresponding ketone, the latter can in turn be converted to the secondary alcohol 5 through a hydrogenation step and recycled in the epoxidation step (I). Hydrogenation reactions of this type are well known in the art, and hydrogenation is preferably carried out in a transition metal catalyst containing, for example, Raney nickel, ruthenium or palladium. • It is also possible to dehydrogenate the secondary alcohol, if present, by known methods in order to obtain additional valuable products, such as, for example, styrene. This step refers to the regeneration of the catalyst At least partially deactivated zeolite used in step (ID) The activity of the catalyst decreases with an increasing reaction time due to the increasing deposits which are mainly of organic origin.

Particularly organic may be, among other things, oligomers or polymers of the oxidation product formed, for example, propylene oxide. In the process of the present invention, the catalyst is regenerated if its activity falls below a certain limit value. East The limit value generally corresponds to an activity of 60% or less, preferably 40% or less, and especially 20% or less, in each case based on the initial activity of the catalyst to be regenerated. If the process of the present invention of the present invention is carried out in suspension, that is, using a zeolite catalyst in the form of a powder, the catalyst can be separated from the reaction mixture by means of customary separation methods. solid / liquid such as for example simple filtration, cross-flow filtration, centrifugation, etc., and regeneration. The regeneration is preferably carried out by the continuous separation and regeneration of the catalyst present in the reactor and its recycling in the reactor in regenerated form. If the zeolite catalyst in the reactor is packed as a fixed bed, the regeneration is advantageously carried out in the reactor itself, ie the catalyst is not removed but remains in the fixed bed in the reactor in a been packed. To recover the product of value present in the catalyst, the catalyst can be further washed with a solvent for the product of value obtained after the reaction of step (II) and before the regeneration of step (III). Solvents that can be used for washing include all the solvents capable of dissolving the product of value desired in each case. Particular examples of solvents are water, alcohols, aldehydes, acids, ethers, acids, esters, nitriles, hydrocarbons and mixtures of two or more of them, as commented in the comments on the preferred variation of regeneration in the present invention. Generally speaking, the catalyst is then heated in. a stream of inert gas, either in the reactor or separately to effect regeneration. Oxygen is added to the inert gas stream once a certain temperature has been reached. This temperature is generally from about 200 to about 800 ° C, preferably from about 250 to 600 ° C and more preferably from about more than 400 ° C to about 600 ° C. The amount of oxygen that is added to the inert gas is regulated in such a way that the temperature during the regeneration, said temperature rises due to the heat generated by the composition of the mainly organic deposits, does not exceed approximately 800 ° C, preferably approximately 600 ° C, more preferably about 550 ° C, and does not fall below about 400 ° C, preferably about 450 ° C, in such a way that regeneration is carried out sufficiently quickly on the one hand and that it is avoided on the other hand an irreversible damage to the structure of the catalyst. After the complete removal of the mainly deactivating organic deposits, which is indicated by a medium of a downward catalyst temperature despite an increasing oxygen content at the regenerator outlet, the catalyst is cooled slowly, again in an atmosphere of inert gas. As indicated above, the regeneration of step (III) is carried out in an atmosphere of an inert gas containing oxygen or substances that supply oxygen. The term substance that supplies oxygen includes all the substances that can liberate -oxygen or remove carbonaceous residues under the indicated regeneration conditions. The atmosphere is preferably a nitrogen-containing atmosphere, which comprises oxygen or a substance that supplies oxygen. The oxygen supplying substance is preferably a nitrogen oxide of the formula NxOy, where x and y are selected in such a way that the nitrogen oxide is neutral, N20, a waste gas stream containing N20 produced by an adipic acid plant, NO, N02, ozone or a mixture of 2 or more of them. If C02 is used, the temperature is within a range of 500 to 800 ° C. The oxygen content in the gas mixture used for the regeneration is preferably less than about 50% by volume, more preferably less than about 30% by volume, especially less than about 10% by volume, and more preferably less than approximately 5% by volume. In a further embodiment of the process of the present invention, the gas stream can be wetted with steam or solvent vapor when the regenerated catalyst has cooled below about 200 ° C, preferably about 150 ° C, and with greater preference approximately 100 ° C. Solvents that may be employed for this purpose include the same solvents as those used to wash the catalyst at least partially deactivated before the regeneration itself. Preferred solvents are described below in greater detail "in the remarks of the preferred regeneration of step (III) of the process of the invention, after reaching the temperature of the reaction in which step (II) is carried out and then if sufficient solvent moistening is carried out, if the regenerated catalyst is introduced into the reactor and the reactor is charged with the solvent for oxidation and re-employed? c for the reaction step (II). the reactor as a fixed bed during regeneration, the reactor is filled with the solvent for oxidation and the reaction of step (II) is carried out A preferred embodiment of the regeneration of a zeolite catalyst at least partially deactivated in accordance with the Step (III) is described in detail below.

In this embodiment, the regeneration comprises the following steps: (a) heating a at least partially deactivated catalyst at a temperature of 250 ° C-600 ° C in an atmosphere containing less than 2% by volume of oxygen, and (b) subjecting the catalyst to a gas stream containing an oxygen or oxygen generating substance or a mixture of two or more thereof in an amount within a range of 0.1 to 4% by volume at a temperature comprised between 250 ° C and 800 ° C, preferably 350 ° C to 600 ° C. This preferred regeneration preferably comprises an additional step (c): (c) subjecting the catalyst to a gas stream containing a substance that generates oxygen or oxygen or a mixture of two or more of them in an amount within a range from 4 to 100% by volume at a temperature of 250 ° C to 800 ° C, preferably 350 ° C to 600 ° C. The regeneration is carried out essentially in the same way as the regeneration of catalysts in the form of powder that were used as a suspension, when catalysts are regenerated packed in a fixed bed in the form of a formed particle, and when crystallized catalysts are regenerated. networks, for example, stainless steel, Kanthal or gaskets, and surface-coated catalysts consisting of an inert core Si02, alpha-Al203, highly calcined Ti02, steatite and a surface layer of active catalyst comprising a zeolite, preferably a zeolite in accordance with what is defined above. If the catalyst has been used in suspension, it must first be separated from the reaction solution through a separation step, for example by filtration or centrifugation. If the catalyst has been used in suspension, it must first be separated from the reaction solution through a separation step, for example, filtration or centrifugation. The resulting powder catalyst, at least partially deactivated, can then be regenerated. By using powder catalysts of this type, the steps carried out at elevated temperatures during the regeneration process are preferably carried out in rotary tube furnaces. When a catalyst used in suspension is regenerated, it is especially preferred to combine the suspension reaction and the regeneration process of the invention by continuously removing a part of the catalyst at least partially deactivated from the reaction, regenerating it externally by using the process of the invention and recycling the regenerated catalyst in the suspension reaction. As well as the regeneration of catalysts in powder form, it is also possible to regenerate catalysts in the form of formed bodies, for example, shaped bodies packed in a fixed bed. The regeneration of a catalyst packed in a fixed bed is preferably carried out in the reactor itself without the need to discharge or introduce the catalyst in such a way that it is not subject to any additional mechanical stress. The regeneration of the catalyst in the reactor itself includes the suspension of the reaction, the removal of the reaction mixture present, the regeneration and then the continuation of the reaction. According to step (a), the catalyst is heated to a temperature from about 250 ° C to about 600 ° C, preferably from about 400 ° C to 55 ° C, especially from about 450 ° C to 500 ° C, in an atmosphere containing less than 2% by volume, preferably less than 0.5% by volume, especially less than 0.2% by volume of oxygen, either in the reactor or in an external oven. The heating of step (a) is preferably carried out at a heating rate of about 0.1 ° C / min to about 20 ° C / min, preferably from about 0.3 ° C / min to about 15 ° C / min, especially 0.5 ° C / min-10 ° C / min. In this heating phase, the catalyst is heated to a temperature at which the fully organic deposits present begin to decompose while at the same time the temperature is controlled through the oxygen content and does not increase to a level such that it damages the catalyst structure. Once a temperature range of about 250 ° C to about 800 ° C has been reached, preferably from about 350 ° C to about 600 ° C, especially from about 400 ° C to about 600 ° C, which is desirable for the decomposition of the deposits, the catalyst can remain at these temperatures in the atmosphere "defined above , if desired, or if necessary, due to the presence of a large amount of organic deposits In step (a) of the regeneration, if desired in combination with leaving the catalyst at the indicated temperature, Coke most of the deposit This step includes the removal of the catalyst of the substances formed in this process, for example, hydrogen, water, carbonaceous substances The removal of the deposits by coking in this step significantly reduces the amount of energy generated during the burning of the catalyst in steps (b) and possibly (c) of the process of the invention by subjecting the catalyst to a gas stream containing s oxygen, so that the slow heating step (a) of the process of the invention is, itself, an essential step in prevention of local heating of the catalyst. In step (b) of this regeneration, the catalyst is then subjected to a gas stream containing a substance that generates oxygen or oxygen or a mixture of two or more of them in an amount within a range of about 0.1. to about 4% by volume, preferably from about 0.1 to about 3% by volume, more preferably from about 0.1 to about 2% by volume, at a temperature of from about 250 ° to about 800 ° C, preferably about 350 ° C at approximately 600 ° C. The amount of molecular oxygen or substances that supply oxygen that is added is a critical factor to the extent that the amount of energy generated in this step through the burning of coked organic deposits is accompanied by an increase in the temperature of the catalyst , such that the temperature in the regenerator should not leave the desired temperature range from about 250 ° C to about 800 ° C, preferably from about 350 ° C to about 600 ° C. The amount of molecular oxygen or substances that supply oxygen is chosen such that the temperature in the apparatus is within a range of about 400 ° C to about 500 ° C. With an increasing burnt of the deposits, the content of molecular oxygen or substances that supply oxygen in the inert gas stream must increase up to 100% by volume to maintain the temperature required for the regeneration in such a way that after the completion of the step (b), the catalyst is subjected in step (c), to a gas stream containing a substance supplying oxygen or either a mixture of two or more of them in an amount within a range of more than about 4 to about 100% by volume, preferably from more than about 3 to about 20% by volume, more preferably from about 2 to about 20% by volume, within the temperature range defined for step (b). A process is usually followed here in which the amount of oxygen or substance supplying oxygen in the feed gas stream increases continuously as the temperature in step (b) decreases. The temperature of the catalyst itself is maintained within a temperature range from about 250 ° C to about 800 ° C, preferably from about 350 ° C to about 600 ° C, especially from about 400 ° C to about 600 ° C, by appropriately controlling the oxygen content or the content of substances that supply oxygen in the gas stream.

The chelating of the organic deposits is complete when the temperature of the gas stream is flowing at the outlet of the reactor decreases in spite of increasing amounts of molecular oxygen or substances that supply oxygen in the gas stream. The duration of the treatment in accordance with step (b) and step (c), if necessary or desired, is generally from about 1 to about 30 hours, preferably from about 2 to about 20 hours, especially from about 3 to about 10 hours in each case. The term "substances that supply oxygen" is defined in accordance with the aforementioned. In another embodiment of the process of the present invention, the at least partially deactivated catalyst is washed with a solvent in order to remove valuable product still adhering to the catalyst before heating step (a). The washing is carried out in such a way that the valuable products that adhere to the catalyst can be removed therefrom, but the temperature and pressure are not high enough to remove the essentially organic deposits as well. The catalyst is preferably simply rinsed with a suitable solvent. Suitable solvents for this washing process include all the solvents in which the product of the reaction is readily soluble. Such solvents are preferably selected from the group consisting of water, alcohol, for example, methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, allyl alcohol or either ethylene glycol, an aldehyde, for example acetaldehyde or propionaldehyde, a ketone, for example, acetone, 2-butanone, 2-methyl-3-butanone, 3-pentanone, 3-pentanone, 2-ethyl-4-pentanone, or either cyclohexanone, an ether such as for example diethyl ether or THS, an acid, for example formic acid, acetic acid, or propionic acid, an ester, for example methyl formate, methyl acetate, ethyl acetate, butyl acetate or ethyl propionate, a nitrile, for example acetonitrile, a hydrocarbon, for example, propane, 1-butene, 2-butene, benzene, toluene, xylene, trimethylbenzene, diclomethane, chloroform, carbon tetrachloride, 1, 1- dichloroethane, 1,2-dichloroethane, 1,1-trichloroethane, 1,1-trichloroethane, 1,1,1,2-tetrachloroethane, dibromoethane no, allyl chloride or chlorobenzene and mixtures of two or more of them, if they are miscible. Solvents which act as solvents in the reaction are preferred, for example olefin epoxidation using the catalyst to be regenerated. Examples of such solvents for the epoxidation of olefins are: water, alcohol, for example methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-proponal, 1-butanol, 2-butanol, allyl alcohol or ethylene glycol or ketones, for example acetone, 2-butanone, 2-methyl-3-butanone, 2-pentanone, 3-pentanone, 2-methyl-4-pentanone or cyclohexanone. The amount of solvents used and the duration of the washing procedure are not critical factors, but the amount of solvent and the duration of the washing process must be sufficient to remove most of the valuable product adhered to the catalyst. The washing process can be carried out at the reaction temperature or at higher temperatures, but the temperature should not be so high that the solvent used for the washing itself reacts with the product of value to be removed. If temperatures higher than the reaction temperature are used, a range of 105 ° C to 150 ° C above the reaction temperature, in particular also according to the boiling point of the solvents used, is generally sufficient. The washing procedure can be repeated more than once if necessary. The washing process can be carried out under atmospheric pressure, under high pressure, or under supercritical pressure. The atmospheric pressure or elevated pressure is preferred. If C02 is used as a solvent, a super critical pressure is preferred. If a powdered catalyst that has been used in suspension is subjected to regeneration, the removed catalyst is washed in an external reactor. If the catalyst is packed in a reactor as a fixed bed, the washing can be carried out in the reactor used for the reaction. In this case, the reactor containing the catalyst to be regenerated is rinsed once or several times with a solvent in order to recover the valuable residual product. Subsequently, the solvent is removed from the reactor. The catalyst is generally dried at the end of the washing process. The drying process is not critical per se, but the drying temperature must not exceed in a very important way the boiling temperature of the solvent used for the washing in order to avoid an abrupt evaporation of the solvent in the pores, especially micropores of the - zeolite catalyst, since this can also damage the catalyst. In the regeneration of powder catalysts, the drying is carried out again externally in a heating apparatus under an inert gas atmosphere. In the case of catalysts in a fixed bed, the catalyst in the reactor is subjected to a stream of inert gas at moderate temperatures. It is possible, but not necessary, to dry the catalyst completely. Powdered catalysts are usually dried until the powder can flow. It is also not necessary to completely dry the fixed bed catalysts. In another embodiment of this regeneration, the regenerated catalyst obtained in step (c) is cooled in an inert gas stream in an additional step (d). This inert gas stream may contain up to about 20% by volume, preferably from 0.5 to about 20% by volume, preferably from about 0.5 to about 20% by volume of a vapor of a selectable liquid within the group consisting of water, an alcohol, an aldehyde, a ketone, an ether, an acid, an ester, a nitrile, a hydrocarbon in accordance with that described above in the context of washing the catalyst, and a mixture of two or more of them. It is preferred to use water, alcohol, or a mixture of two or more of them as liquid vapor. As regards the preferred alcohols, aldehydes, ketones, ethers, acids, esters, nitriles or hydrocarbons, reference is made to the corresponding comments on the solvents that can be used in the washing process of the process of the present invention. It is also important to cool slowly when the cooling operation of step (d) is carried out, since too rapid cooling (rapid cooling) can negatively accept the mechanical strength of the catalyst. The mechanical properties of the catalyst can also be adversely affected by rapid rinsing of the formed, dry, regenerated catalyst bodies during the restart of the reactor for further reaction. For this reason, it is advisable to add a vapor of a liquid according to what is defined above during the cooling phase. It is even more preferable however • Do not add steam until the temperature is below a limit temperature defined by the boiling point of the liquid used for the steam. The limit temperature is usually below about 250 ° C, preferably below about 200 ° C, especially below about 250 ° C, preferably below ~ about 200 ° C, especially below about 150 ° C. After regeneration, the catalyst can be treated by basic compounds and / or silylation in order to remove acidic centers. Particularly suitable compounds are dilute aqueous solutions of ferrous alkali or alkali hydroxides, ferrous alkali or alkali carbonates, ferrous alkali metal hydroxycarbonates, acetates and phosphates of Ni, K, Na; as well as silylation esters such Tetraalkoxysilane, tetraalkoxymonoalkylsilane and hexamethylenedicilane. Step (IV) This step relates to the reuse of the regenerated catalyst in accordance with step (III). For this one For the purpose, the regenerated catalyst is recycled into the reactor (if the at least partially deactivated catalyst has been externally regenerated) and the reaction is carried out or proceeded in accordance with that described in step (II). If the regeneration was carried out in the reactor, the reaction proceeds in accordance with that described in step (II) upon completion of the regeneration. If, in the process of the present invention, the organic compound having at least one CC double bond is selected from the group consisting of a linear or branched aliphatic olefin, a linear or branched aromatic olefin and a linear or branched cycloaliphatic olefin, each one having up to 20 carbon atoms, that is, if an olefin reacts with the hydroperoxide, this olefin can be obtained by dehydrogenation of the corresponding saturated organic compound to form the olefin and the hydrogen. Processes of this type for converting an alkane to the corresponding olefin are known per se, particularly in relation to the dehydrogenation of propane. These processes are known in the literature as STAR processes, CATOFINE © or OLEFLEX ® and are described in detail, for example, in Chem. Systems Report 91-5, 1992, page 50 et seq., And are also mentioned in numerous patents, example in US-A 4,665,267 or EP-A 0 328 507 and US-A 4,886,928. These processes are characterized by an endothermic reaction that dissociates the alkane to form the olefin, that is, propane in propene, for example, and hydrogen. Widely used catalysts are zinc and aluminum spinels doped with noble metals, chromium oxide / aluminum oxide, and also supported platinum catalysts. In addition, iron oxide catalysts promoted for dehydrogenations of alkane are known from DE-A 39 23 026. The olefin which is preferably used as starting material, particularly propylene, can also be obtained starting from the corresponding saturated hydrocarbon by decomposition by steam, catalytic decomposition. Such processes are described in greater detail, for example, in US-A 5,599,955 and US-A 5,599,956 mentioned at the beginning, and in the prior art mentioned herein, both references including the prior art mentioned herein are incorporated herein. by reference in its entirety. In the process of the present invention, especially when carried out as an integrated process, that is, a process in which all the volumetric currents are closed loops, it is advantageous to obtain the olefin, especially propylene to be used in the step of epoxidation by dehydrogenation of the corresponding "saturated organic compound", since the epoxidation step tolerates the unreacted alkane which is present in addition to the olefin and which comes from the dehydrogenation step and therefore renders costly alkane / olefin separation unnecessary, especially propane / propene separation. The hydrogen coming from the dehydrogenation of alkane can also be used directly in the formation of hydrogen peroxide, for example, in accordance with the anthraquinone process described at the beginning of the process starting with the elements described at the beginning of the comments in step (I) of the process of the present invention. The endothermic dehydrogenation step of alkane can also be combined with the esothermic reaction of step (II) in an integrated heat and energy system. As indicated above, the process of the present invention is particularly suitable as an integrated process, that is, a multi-step process where the currents of the various components used in the process are partially or totally closed loops, more preferably in combination with a Appropriate integrated system of heat and energy where the amounts of energy generated in the exothermic steps of process (II) and (III) can be used directly to perform the endothermic passage (I). The following examples illustrate the invention.

EXAMPLES Example 1 Synthesis of hydrogen peroxide by the anthraquinone process. 10 kg of a Pd hydrogenation catalyst in carbon (10 wt% of palladium) was added to 600 kg of a working solution consisting of about 10 wt% of 2-ethylanthraquinone dissolved in a mixture of 70% by volume of Shellsol NF and 30% by volume of tetrabutylurea and the mixture was placed in contact with hydrogen at a pressure of 1.5-2 bar at a temperature of 45 ° C in a stirred tank until the theoretical hydrogen consumption was reached. Now a black color was cooled to room temperature and the catalyst was filtered off.The solution containing hydroquinone was oxidized with dilute air (10% _ by volume of oxygen, 90% by volume of nitrogen) in 3 batches of 200 kg each. one in a jet tube reactor until the hydrogen peroxide content was constant.After oxidation, approximately 15 kg of DI water was added to 200 kg of the mixture which now contained about 1% by weight of hydrogen peroxide, and this mixture was vigorously stirred for 15 minutes. The aqueous phase was then separated. This aqueous solution now contained approximately 9% by weight of hydrogen peroxide and was vigorously stirred with eL. next batch of 200 kg for 15 minutes. The separation provided a mixture having "a hydrogen peroxide content of about 15% by weight in which it was used to extract the last batch of -200 kg in the same manner." This procedure provided approximately 15 kg of an aqueous solution containing about 20% by weight of hydrogen peroxide Higher yields of hydrogen peroxide can be obtained by employing a continuous backflow extraction, for example, in a sieve plate column, a pulsed sieve plate column or a packed column. Example 2 Synthesis of hydrogen peroxide according to DE-A 196 42 770 In the preparation of hydrogen peroxide according to the aforementioned application, the reaction vessel used was a 270 ml autoclave equipped with an agitator, with temperature control and pressure regulation at 50 bar This reactor was equipped with a catalyst monolith centered on the of the agitator shaft in such a way that the agitator supplied the monolith uniformly with liquid and gas, prepared in the following manner. Feed lines for oxygen, hydrogen and the reaction medium were placed at the base of the reactor. A discharge line from which the product and gas mixture could be continuously discharged was placed on the top of the reactor. After subtracting the volumes from all inmates, an effective reaction volume of 208 ml was obtained. The catalyst monolith used was prepared as follows: A corrugated network and a smooth steel net V4A (1.4571, maya size: 180μm, wire diameter: 146μm) were placed on top of each other and rolled up in order to offer a cylindrical monolith 5 cm in height and 5 cm in diameter. The ends of the nets were fixed by welding points. The distance between the ends of the smooth nets was at least 1 mm. The monolithic support was treated in succession with acetone and distilled water and then dried. The monolith was then treated with a solution of 25% by weight of concentrated hydrochloric acid and 75% by weight "of distilled water at a temperature of 60 ° C for 10 minutes and rinsed with distilled water. ml of distilled water 10 drops of concentrated HN03 and 36 ml of a 1% by weight aqueous solution of hypophosphoric acid and then 20 ml of a palladium nitrate solution (1% by weight) were added. at a temperature of 60 ° C for 17 minutes and then at a temperature of 80 ° C for 1 hour, the mixture was then cooled and the catalyst monolith was washed with distilled water and dried at a temperature of 120 ° C for 16 hours The medium of the reaction employed for the preparation of hydrogen peroxide consisted of methanol with 0.4% by weight of sulfuric acid, 0.1% by weight of phosphoric acid and 6 ppm of bromide (in the form of sodium bromide). The reactor was flooded with the reaction medium. A current of 72.8 g / h of the reaction medium, 48.6 1 / h of oxygen and 5.5 1 / h of hydrogen (the gases refer to standard temperature and pressure) was then passed through the reactor. The product / gas mixture was continuously discharged at the top of the reactor. The hydrogen-based conversion was 76% (in accordance with a determination of the hydrogen content in the effluent gas) and the selectivity was 82%. The concentration of the resulting methanolic hydrogen peroxide solution was 7% by weight (titration with K Mn04 0.1 N). Example 3 Epoxidation of propene with hydrogen peroxide a fixed bed catalyst Flows of 27.5 g / h of hydrogen peroxide (20% by weight, obtained as in example 1), 65 g / h of methanol and 13.7 g / h of propylene were passed through a battery of reactors consisting of two reactors that had a reaction volume of 190 ml each and packed with 10 g of titanium-1 silicalite (TS-1) formed in extruded from all the catalysts with a diameter of 2 mm at a reaction temperature of 40 ° C and under a reaction pressure of 20 bar. The reaction mixture exited the second reactor and was depressurized at atmospheric pressure in a Sambay evaporator. The low boiling point elements were analyzed online by gas chromatography. The liquid reaction effluent was collected, weighed, and also analyzed by gas chromatography. The conversion of hydrogen peroxide decreased during the entire time of the experiment of 96% initially to reach 63% after 400 hours. The selectivity, based on the hydrogen peroxide was 95%. Example 4 Regeneration of Deactivated Catalyst The deactivated fixed bed catalyst of Example 3, which was coated with organic products, was rinsed with ethanol, and then dried at a temperature of 120 ° C for 5 hours. 56 g of catalyst formed was placed in a rotating tube. First, the rotating tube was rotated very slowly (2rph) and heated to a temperature of 500 ° C at 4 ° C / min in a nitrogen atmosphere (20 1 / h). A gas mixture containing 9% by volume of oxygen and 91% by volume of nitrogen was then fed into the rotary tube at a temperature of 500 ° C for two hours. The volume percentage of the oxygen in the gas stream was then increased to 18% by volume at a temperature of 500 ° C for 14 hours while keeping the gas quantity constant (20 1 / h). The regenerated catalyst was then cooled under a constant stream of gas. The weight loss was approximately 7%. Example 5 Reuse of regenerated catalyst Flows of 27.5 g / h of hydrogen peroxide (20% by weight, obtained as in example 1), 65 g / h of methanol and 13.7 g / h of propylene were passed through a battery of reactors consisting of 2 reactors having a reaction volume of 190 ml each and packed with 10 g of the regenerated catalyst according to that described in example 4 at a reaction temperature of 40 ° C and under a reaction pressure of 20 bars. The reaction mixture exited the second reactor and was depressurized at atmospheric pressure in a Sambay evaporator. The low low boiling elements were analyzed online by gas chromatography. The liquid reaction effluent was collected, weighed, and also analyzed by gas chromatography. The conversion of hydrogen peroxide decreased during the entire time- of the experiment from 96% initially to 63% after 400 hours. The selectivity, based on hydrogen peroxide, was 95%. Example 6 Dehydrogenation of propane to obtain propene 210 ml of dehydrogenation catalyst based on chromium oxide / Al203 in the form of 2 mm extruded products were placed in a double jacket tube reactor (length 50 cm, inner diameter 35 mm). The reactor was heated to a wall temperature of 550 ° C through a heat transfer medium in a salt bath. Propane was passed in the reactor to which nitrogen (20:80 volumetric ratio) was added from a front cylinder at a controlled pressure of 1.5 bar (LHSV = 0.15 / h). The effluent reaction mixture consisting of propane, propene and hydrogen was cooled to a temperature of 30-40 ° C and liquefied by compression at about 35 bar to separate the C3 products from the hydrogen. This mixture of gas and liquid was used in the epoxidation without further purification, since only the propylene reacted there and the propane was sufficiently inert. After the epoxidation, the mixture of propane C3 without conversion / propene was depressurized after carrying out the test to determine the absence of peroxide and said mixture was recycled in the reactor for the dehydrogenation of propane. At 3 hours, the conversion of propane per passage was typically about 35%, the propene selectivity being 83% molar (analysis of gas chromatography upstream of the compressor) The deactivated catalyst could be regenerated again by addition to the Nitrogen vehicle gas (maximum 2% by volume of oxygen) after closing the propane feed line Example 7 Direct synthesis of hydrogen peroxide in water The same catalyst as in example 4 was used. The reaction medium consisted of of water to which were added 0.4% by weight of sulfuric acid, 0.1% by weight of phosphoric acid and 6 ppm of bromide (in the form of sodium bromide) The parameters of the reaction were the following: 268.0 g / h of reaction medium, 291.6 1 / h of oxygen, 32.4 1 / h of hydrogen, T = 42 ° C. The hydrogen-based conversion was obtained by determining the hydrogen content of the spent gas and was 43% with a selectivity of 70%. The concentration of the hydrogen peroxide solution obtained was 5.6% by weight.

Claims (1)

1. CLAIMS A method for oxidizing an organic compound having at least one CC double bond or a mixture of two or more of them, comprising the following steps: (IJ ... preparing a hydroperoxide; (II) reacting a compound organic having at least one CC double bond or a mixture of two or more of them with the hydroperoxide prepared in step (I) in the presence of a zeolite catalyst, (III) regenerating the at least partially deactivated zeolite catalyst employed in step (II), wherein the regeneration comprises at least the following steps: (a) heating the catalyst in an inert gas stream, (b) adding oxygen at a temperature within a range of 200 ° C to 800 ° C; (c) regulating the amount of oxygen such that the temperature is within the range of 400 ° C to 800 ° C, (IV) carrying the reaction of step (II) through using a zeolite catalyst containing the catalyst regenerated in step (III). to ae according to claim 1, wherein the organic compound having at least one CC double bond is selected from the group consisting of a branched linear or branched aliphatic olefin, a linear or branched aromatic olefin, a linear cycloaliphatic olefin or each one having up to 30 carbon atoms, and a mixture of two or more of them. A process according to claim 2, wherein the olefin is obtained by dehydrogenation of the corresponding saturated organic compound to obtain the olefin and hydrogen. A process according to claim 3, wherein the dehydrogenation is carried out in the presence of a heterogeneous catalyst containing at least one of the following elements: Se, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Faith, Ru, Os, Co, Rh, Go, Ni, Pd, Pt, Cu, Ag, Au, B, Al, Ga, C, Si, Ge and Sn. A method in accordance with claimed in any of claims 1 to 4 wherein the zeolite catalyst has micropores, mesopores, macropores, micropores and mesopores and macropores micropores or micropores, mesopores, and macropores. A process according to any of claims 1 to 5, wherein the zeolite catalyst is selected from the group consisting of a silicate containing titanium, zirconium, vanadium, chromium or niobium and having MFI, BEA, MOR structures, TON, MTW, FER, CHA, ERI, RHO, GIS, BOG, NON, EMT, HEU, KFI, FAU, DDR, MTT, RUT, LTL, MAZ, GME, NES, OFF, SGT, EUO, MFS, MCM 22, MEL mixed structure MFI / MLE and a mixture of two or more of them. A process according to any of claims 1 to 6, wherein the zeolite catalyst employed is a catalyst obtainable through a process comprising the following steps: (i) adding to a mixture comprising a zeolite or a mixture of two or more of them a mixture comprising at least one alcohol and water and (ii) kneading, shaping, drying and calcining the mixture of the step (i) • A method according to any of claims 1 to 7, wherein the at least partially deactivated zeolite catalyst of step (ii) is regenerated through the following steps: (a) heating a at least partially deactivated catalyst at a temperature of 250 ° C-600 ° C in an atmosphere containing less than 2% by volume of oxygen, and (b) subjecting the catalyst to a gas stream containing a substance that generates oxygen or "oxygen or a mixture of two or more of them in an amount that is within a range of 0.1 to 4% by volume at a temperature of 250 to 800 ° C, preferably at a temperature of 350 to 600 ° C. according to claim 1 in any of claims 1 to 8, wherein the regeneration of step (III) of the at least partially deactivated catalyst is carried out in an apparatus for carrying out the reaction of step (II) without removing the catalyst from z Eolite of this device.