CH147440A - A process for the catalytic oxidation of organic compounds. - Google Patents

Description

  

  A process for the catalytic oxidation of organic compounds. The present invention relates to a process for the catalytic oxidation of organic compounds, in which use is made of a particular catalytic mass.



  Processes are known in which organic compounds have been catalytically oxidized, in particular in the vapor phase, by means of contact masses containing, as at least one of their constituents, when they are freshly prepared, base exchangers, siliceous and not so licious, and their reaction products with anions, so-called salt-like bodies.

   It has now been found that the enormous contact mass efficiency of base exchange bodies is shared to a large extent by contact masses which contain substances resulting from leaching of base exchange bodies by acids or acids. acidic compounds, i.e. products obtained by treating base exchange bodies, preferably with dilute acids, for example dilute mineral acids, such as hydrochloric acid, sulfuric acid , nitrogen, etc.

   The base exchange body subjected to extraction can also be a "salt-like body" obtained as set forth in 1a. after. This acid leaching first gradually removes the exchangeable bases, then, when pushed further, gradually removes the more basic portion of the non-exchangeable nucleus from the base exchange body and, if pushed to completion, leaves only the aid portion of the nucleus. In the case of base exchange bodies containing silicon, ie zeolites, the final product is a complex silicic acid.

   In the case of non-siliceous bodies, the product. final of a complete waste contains only the relatively acidic constituent (s) of the non-exchangeable nucleus. Strange as it sounds, this leaching does not appear to destroy to any great degree the very porous physical structure of the heat exchangers. bases and the effectiveness of the contact masses used in the process of the present invention can be attributed, to a considerable extent, to the fact that they have a physical structure similar to that of the base exchange bodies from which they were produced. prepared.



  When the base exchange bodies are themselves catalytically active and the leaching, in the case of zeolites, is not carried out to completion, the leached body may contain chemically combined catalytically active elements. in. However, if in the case of zeolites the scavenging is complete, the resulting complex silicic acid is not itself catalytically active, but acts as an extraordinarily effective carrier for catalytically active constituents.

   The invention includes the use of contact masses in which some or all of the catalytically active constituents may be present, partially or totally, in the form of physically associated diluents, preferably in a form. homogeneous, with the leached base exchange body.



  Care should be taken to distinguish the contact forms used in the process according to the present invention from salt-like bodies in which the reacting anion remains chemically combined with the base exchange body, forming with it a group presenting many <B> cl-, </B> salts properties. Leaching with dilute acids, which produces the contact masses used in the present process, generally does not leave a significant amount of the acid radical united with the base exchange body.



  The base exchange bodies forming the raw materials for the contact masses which are used in the present invention can be diluted or undiluted, preferably diluted. If a diluted base exchange body is leached, the diluents are usually, but not necessarily, unattacked and remain in close physical association with the carcass formed by the product resulting from the leaching of the base exchange body.

      Diluted or undiluted base exchange bodies can be divided into two classes: zeolites, i.e. base exchange bodies containing silicon in their nucleus, and non-siliceous base exchange bodies in which silicon is completely replaced by suitable acidic or amphoteric oxides, usually metal oxides.



  Zeolites belong to two general classes: those with two components and those with multiple components. Two-component zeolites are the reaction products of two types of initial constituents, i.e. metallates and silicates (using the word metallate in a broad sense here, such as that which will be defined later in this memoir) or metallic salts and so licate.

   Frequently, more than one member of one type can react, that is, a silicate can react with more than one metallate or with more than one metal salt. Multi-component zeolites are the reaction products of at least three types of components, i.e. at least one silicate, at least one metallate and at least one metal salt. . By metal salt, we mean salts which are not metallates.



  The catalytically active components can be found in the catalyst mass employed in four main forms, as follows: They can have been physically mixed with leached or non-leached base exchange products, or be impregnated therein; They may have been incorporated physically, in a homogeneous manner, into base exchange products before these have been fully formed, in the form of catalytically active diluents or in the form of diluents which have been impregnated. . catalytically active substances;

   3e 'They can be chemically combined in the products resulting from the leaching of the base exchangers in non-exchangeable form, that is, they can form a non-exchangeable core part of the leaching product of the base. .base exchange body which is present in the final product or which is derivatized, or they may have been chemically combined with the exchange bodies. bases in the form of catalytically active anions which together with the base exchange body, or its leached derivative, form bodies resembling. salts;

    40 They may have been chemically combined in an exchangeable form, ie. during the formation of the base exchange body or, by base exchange, after formation. Of course, the same catalytically active constituents or different catalytically active constituents can be present in more than one of the above-mentioned forms and an advantage of the invention is that catalytically active substances can be introduced in a wide variety of forms which give a large choice for the catalyst chemist.

  



  Although the different base exchange products can vary widely in their chemical characteristics, they all have a similar physical structure which is characterized by greater or less porosity, frequently micro-porosity, and high resistance to high temperatures. temperatures and, in the case of products which have not been leached with acids to the point of removing all catalytically active constituents, these constituents are distributed throughout the carcass -products in atomic or molecular dispersion this chemical homogeneity is one of the important advantages of some of the contact masses used in the process according to the invention.



  Although the catalytically active substances can be contained in undiluted ba al exchanger leach products as well as in dilute products, it has been found that, for most reactions, dilute contact masses of homogeneous form provides an advantage, particularly if the diluents are of such a physical or chemical nature that they exert a desired influence on the catalytic activity of the contact masses as when, for example, the diluents are rich in silica which has been found to have an activating power, or when diluents, due to high porosity,. of high capillarity or high surface energy, can.

   be regarded as physical catalysts, or activators.



  Base exchange bodies behave as if they were extremely high molecular weight products, since catalytically active constituents can be introduced either into the non-exchangeable core or in the form of substantially exchangeable bases. .

   all desirable proportions and the ordinary law of chemical combination proportions, which in low molecular weight compounds restricts the proportions in which constituents can be chemically incorporated, appears to be without force, which makes it reasonable to assume that the molecular weight -is so high that it completely obscures the effect of the law. It is, of course, possible that the base exchange bodies, or some of them, then feel to be solid solutions of several compounds of lower molecular weight. It has not been possible, until now, to settle this question definitively, because base exchange bodies do not allow themselves to be easily analyzed for their chemical structure.

   The invention is of course not limited to any theory; but, whatever chemical reactions it rests upon, the fact that catalytically active constituents can be introduced chemically in any desired proportions is of enormous importance to the etalyst chemist and enables him to produce a almost unlimited number of catalysts with finely and gradually dosed contact masses for the various oxidations of organic compounds.

   In all cases, the contact masses produced are very effective because of the. desirable physical structure of the leached base exchange products contained therein and wide limits of homogeneous dilution of catalytically active molecules or atoms, with resulting uniformity and smoothness of action, which is of great importance, especially in sensitive reactions such as the oxidation of many aromatic compounds in the vapor phase which is a field of oxidation catalysis of organic compounds for which contact masses which are used in the present invention are particularly suitable.



  In addition to the important characteristics with which the bodies obtained by leaching as indicated endow the contact masses, it has been found that, for many reactions falling within the scope of the invention, it is desirable to regularize and regulate the action. contact masses. This may. be done by associating with said leached bodies, or by incorporating or forming therein, compounds of alkali metals, alkaline earth metals and strongly basic earth metals with oxides not reducible by hydrogen. These compounds appear to slow down or soften the catalytic reaction and will be referred to throughout this specification as regulators.

   The regulators can be physically mixed with said leaches or, if the scavenging is not sufficient to remove all the exchangeable bases, the latter can act as regulators and, for some reactions, are particularly effective since they are in chemical combination with the leached body and are thus finely. distributed evenly throughout the contact mass.



  It is difficult to determine exactly the degree of leaching in some cases and, if very close control of alkalinity is desirable, a leached base exchange body can be treated from which, perhaps, too much base exchangeable have been removed. with suitable alkalis which will replace part or all of the bases removed by leaching. This gives an additional possibility of controlling the final catalyst composition.



  In addition to the use of regulators which are important in a large number of organic oxidations, in particular oxidations to intermediates or oxidations which aim to remove by combustion one or more constituents a mixture of organic compounds, such as, for example, crude aromatic hydrocarbons such as anthra:

  However, without significantly attacking the other constituents of the mixture, it has been found that the action of the regulator and the very high efficiency of the contact masses can, in many cases, be greatly increased by association with these masses, or the chemical combination therein of elements or radicals or groups which are catalytically active, but which do not possess specific catalytic activity for the particular reaction to be carried out. So, for example,

   in the case of certain oxidations resulting in the production of water as a by-product, dehydration catalysts may advantageously be present in the contact mass. In other oxidation, where condensation or polymerization is desired, catalysts which promote these reactions may be present.

   Those catalytically active components which are not specific catalysts for the particular organic oxidation in question will be referred to herein as auxiliary catalysts. They seem to increase the dosing effect that can be obtained with regulators. In some reactions, auxiliary catalysts without regulators can be used, although in general this is not desirable.

   It goes without saying that the action of the regulators, while probably being due mainly to a slowing down or stabilization of the action of the catalytically effective constituent, specific to the contact mass, has not in all cases , nor even normally, results in a lower yield. On the contrary, the yields of a particular oxidation product, especially if it constitutes an intermediate oxidation stage, are normally increased by the choice of a suitable regulator and in many cases the yield, particularly in certain circumstances. vapor phase oxidations can be increased, and in some cases greatly increased, by the presence of regulators.

   However, in all cases the choice of suitable regulators, with or without suitable auxiliary catalysts, increases the overall efficiency of the reaction.



  The enormous range of chemical groups which can be combined in or with, or incorporated into permutogenetic products (base exchange bodies or their derivatives) allows a wide choice of auxiliary catalysts as well as special catalysts. .cific and allows their association with the contact masses in an extremely homogeneous and catalytically effective form.

    Thus, many base exchange bodies or their derivatives can constitute at the same time specific catalysts, regulators and complex auxiliary catalysts, because all these elements can be present in the same chemical compound and participate in the advantages deriving from its structure. physical and its desirable chemical properties.

       Of course, both the regulators and the auxiliary catalysts can be mixed in part or in whole with permutogenetics and a single regulator or a single auxiliary catalyst may be present, partly in physical mixture and partly in chemical combination, such as. the experienced base exchange chemist will readily understand.



  The base exchange bodies which form important constituents or the starting material for derivatives, in contact forms used in the process according to the invention, can be prepared by any of the well known processes. Thus, for example, bicomponent zeolites can be prepared by wet processes in which metallate constituents, or metal salt constituents, some or all of which may be catalytically active, are reacted with soluble silicates to form zeolites of the aluminosilicate or aluminum double silicate type, or else the constituents can be melted, preferably in the presence of fluxes.

   It goes without saying that the expression metallate encompasses not only alkaline solutions of amphoteric metal oxides or hydroxides, but also salts of alkali-forming metals of metal acids, such as the oxyacids of metals of the fifth. and sixth groups which, in at least one of the oxidation stages, are not strictly speaking amphoteric, but which are capable of reacting with silicates to form zeolites, or with other constituents to form exchange bodies. non-siliceous bases.

   Throughout this memo, this definition of metallates will be strictly adhered to. In the formation of <B> two-component zeolites </B> by a wet route, the final reaction product must. be alkaline with respect to sunflower and, for products with a high base exchange power, it must be neutral or alkaline with respect to phenolphthalein. In order to produce base exchange bodies for use in the preparation of contact masses for carrying out the process according to the present invention, it is sometimes unnecessary to provide high base exchange power and, for many purposes, it is unnecessary to provide a high base exchange power.

   zeolites formed under conditions resulting in a final reaction product which is acidic with respect to phenolphthalein, but alkaline with respect to sunflower, have an advantage. It is not clear whether the :; products obtained under such conditions are homogeneous chemical compounds although in many ways they behave as such. There is however reason to believe that, in certain cases at least. mixtures of exchanger and non-exchanger polysilicates. basics can occur.

   For the purposes of this specification, a product will be considered as a base exchanger if it has any base exchanging capacity, however low. h1 is desirable for many purposes, and in particular if it is desired to have two-component zeolites with high base exchange power, to add the relatively acidic components, for example the metal salts in the case of silicates of aluminum nail silicate type, with relatively more alkaline constituents, such as, for example, soluble silicates.

   By these means, a continuous alkalinity is ensured and this procedure can be regarded as that which is preferable to adopt in most cases; but the reverse procedure is advantageous for certain contact masses.



  Multiple component zeolites can be prepared by any of the foregoing processes, using at least three types of components, i.e. at least one metallate, at least a metal salt and at least one soluble silicate. In the case of multiple component zeolites, as in the case of two component zeolites, the calinity conditions must be observed and, for many purposes, it is advantageous to add the relatively acidic components to the components. relatively alkaline constituents in order to ensure a continuous alkaline reaction.

    The multi-component zeolites produced vary in nature depending on the proportion of the different reactive components. Thus, when metallates and silicates predominate over metal salts, the resulting products resemble two-component zeolites of the alumino = silicate type. If the metallic salts and silicates predominate over the metallates, the products resemble two-component zeolites - of the double aluminum silicate type and, finally,

   if the metallates and metal salts outweigh the silicates, the resulting product looks more or less like non-siliceous base exchange bodies. It is clear that there is no sharp dividing line between the three types of multi-component zeolites and that one merges into the other as the proportions of the different components change.

   An advantage of multi-component zeolites over bicomponent zeolites is that the choice of catalytically active components is wider, since some catalytically active elements or groups can only be incorporated in the form of metallates and others only. in the form of metal salts. In a multi-component zeolite, each catalytically active group can be incorporated in the form in which it is most beneficial.



  Non-siliceous base exchange bodies are obtained by the general methods described above; but, instead of carrying out reactions between silicates and other metal oxide constituents, two or more oxymetallic compounds are reacted, of which, in general, at least one will be a metallate and at least one a metal salt. or, in certain cases, it is possible to carry out a reaction between two different metallates in which one of the negative radicals is more acidic than the other.

   It is possible to produce non-siliceous base exchange bodies in which several metal oxides are present. It is also possible to produce non-siliceous base exchange bodies in which only one metal is present. Thus, for example, some metals may be of a sufficiently bitter type to form both metallates and metal salts which are capable of reacting with each other to produce base exchange bodies.



  A special way of producing non-siliceous base exchange bodies is. gradually neutralize strongly alkaline salts of oxyacids of metallic elements of the fifth and sixth groups in oxidation stages in which they are sufficiently amphoteric. Neutralization of other strongly alkaline metallates can also determine the formation of non-siliceous base exchange bodies. The reverse method, whereby non-alkaline salts of suitable metals are gradually treated with alkali until the reaction is sufficiently alkaline to allow the formation of base exchange bodies, can also be employed.



  Many metals are only able to enter the base exchange formation in certain stages of oxidation and it is sometimes necessary to introduce these metals in a stage of oxidation different from that which is desired in the body. final base exchanger, the change in oxidation stage preferably being carried out during the formation of the base exchange body. Certain other elements can be incorporated in the form of complex compounds of the most diverse types, such as, for example, ammoniacal groups, etc.



  In addition to the artificial base exchange bodies briefly described above, use may be made of natural base exchange bodies such as nepheline, leucite, feldspar, etc.



  The most important contact masses for many reactions according to the invention contain leached permutogenetic products in which, preferably, the diluents are incorporated in a homogeneous manner in the base exchange bodies. before the formation of these last ones or, at least, before the base exchanger body has taken after formation. Use can be made of many diluents, both inert and regulators, activators, specific catalysts or auxiliary catalysts.

    Here are some of them: all kinds of diatomaceous earth, in particular earth, natural or treated cellite, siliceous powders of various types, pulverized permutogenetic products, natural or artificial powders of rocks, stones, tuff, trass, lava and similar canic products which are frequently very porous, green sand, glauconite or its acid-leached derivative:

   glaucosil, pulverized slag wool, cements, sand, silica gel, pulverized pottery, clay. fuller, talc, glass powder, pumice powder, asbestos, graphite, activated carbon, quartz powder, various pulverized minerals, rich in quartz, metal and metal alloy powders, salts of oxymetallic acids, such as tungs- tates, vanadates, chromates.

   uranates, manganates, -cerates, molybdates, etc., in particular those of copper, silicates, such as copper silicate, iron silicate, nickel silicate, cobalt silicate, aluminum silicate, silicate of titanium, minerals or ores, especially those rich in copper, etc.

   Finely divided diluents have a great advantage, especially if the average particle size is less than 60 microns in which case the diluents have a high surface energy, which increases the adsorptive and absorptive capacity of the contact mass, the speed. diffusion and porosity. These finely divided diluents can be viewed as physical catalysts or activators.

   Dilute permutogenetic bodies can also be finely divided and used as part or all of the diluents of other base exchange bodies.



  The following nine procedures are the most effective for introducing diluents; but use may be made of any other suitable method, the leaching being carried out either before, or after, or still during formation. Examples of methods of incorporating diluents have already been described elsewhere and any one of these methods can be used as a key: 1o The diluents can be mixed with one or more liquid constituents of the base exchange bodies to be formed. when preparing these by wet process.



  The constituents, whether specific catalysts, auxiliary catalysts or the like, can be precipitated in diluents, or impregnated therewith which are then incorporated into the base exchange bodies by any method of preparation. suitable incorpo ration.



  <B> 30 </B> Diluents can be mixed with base exchange bodies, when the latter are still in the form of jellies, by kneading or kneading, in which case the base exchange jelly behaves like an adhesive. The homogeneity and uniformity of the distribution of diluents are not. natural -ent, not all <B> to </B> made as large by this method <B> 1 </B> as by method 10; but, for many catalytic oxidations of organic compounds, extreme uniformity is not essential.

        Diluents can be formed during the formation of base exchange bodies by mixing compounds. suitable for the constituents of the base exchange bodies, so that the particles of diluents are precipitated during formation. Protective colloids can be added to prevent coagulation of the diluent particles before the base exchange bodies have set sufficiently.



  Compounds can be added which react with some of the base exchange bodies to form components to produce diluents; for example, one can add -salts of the acids of metals of the fifth and sixth groups in sufficient excess so that they react with -components of the exchange body -of bases to form -insoluble diluents such as, for example , with heavy metal oxides.



  Preformed base exchange bodies, diluted or undiluted, artificial or natural, can be impregnated with true or colloidal solutions of catalytically effective constituents and then dried.



  <B> 70 </B> A preformed base exchange body, diluted or undiluted, can be impregnated with several solutions, which react therein to precipitate any desired diluents.



  <B> 80 </B> Or can add acidic diluting compounds to constituents forming a base exchange body which, after formation, retains the compounds in solution and which the year dries, without washing it, or which the treated to precipitate the compounds.



  90 Diluted or undiluted base exchange substances, natural or artificial, or their derivatives, can be impregnated with solutions of the desired compounds which are subsequently precipitated by means of reactive gases.



  The nucleus, or non-exchangeable portion, of the molecules of the base exchange bodies is usually considered to consist of two types of oxides, namely: relatively basic metal oxides, usually amphoteric, and relatively acidic oxides, such as SiO2, certain amphoteric metal oxides and certain metal oxides which exhibit a distinctly acidic character.

   The nucleus behaves like a single anion; but it is advantageous to regard the two portions of the nucleus as the basic and acidic portions, bearing in mind, of course, that the nucleus coalesces as a sibling group. The metal compounds which are capable of forming the basic portion of the nucleus are those of ml:

    following rates: copper, silver, gold, bismuth, beryllium, zinc, cadmium, boron, aluminum, certain rare earths, titanium, zirconium, tin, lead, thorium, niobium, antimony, tantalum, chromium, molybdenum, tungsten, ura nium , vanadium, manganese, iron, nickel, co balt, platin, palladium. Compounds of these elements can be introduced, singly or in mixtures, in any desired proportion, and they can be in the form of simple or complex ions. It goes without saying that some of the elements, in certain stages of oxidation, can be introduced either as metallates or as metal salts.

   Others can only be introduced in one of the forms and still others can be introduced in an oxidation stage other than that desired in the final base exchange body, or in the form of complex compounds. Among the complex ionogens, mention may be made of ammonia, hydrocyanic acid, oxalic acid, formic acid, tartaric acid, citric acid, glycerin, etc.



  Many metals are specific catalysts; others are regulators and still others are auxiliary catalysts. Of course, the condition of an element as a specific catalyst or as an auxiliary catalyst will vary with the particular oxidation reaction for which the final contact mass is to be employed and the choice of such catalysts, as well as the proportions, will be determined. by the particular catalytic oxidation of the particular organic compound for which the contact mass is to be employed.



  Examples of constituents forming the relatively acidic portion of the base exchange nucleus are the alkali metal silicates, which are soluble in the alkali, and the alkali metal salts, of acids such as those of boron, phosphorus,, nitrogen, .tin, titanium, - vanadium, tungsten, chromium, niobium, - tantalum, uranium, antimony, manganese, etc.



  The exchangeable bases of the base exchange bodies can be substituted by exchange of bases and the elements which can be introduced individually or in mixture, by exchange of bases, are the following: copper, silver, gold, ammonium, beryllium, calcium, manganese, cesium, potassium, sodium, zinc, strontium, cadmium, barium, lead, aluminum, scandium, titanium, zirconium, tin, antimony, thorium, vanadium, lithium, rubidium, thallium, bismuth, chromium, uranium, manganese, iron, cobalt, nickel, ruthenium, palladium, platinum and cerium.



  Depending on the reactions in which the contact mass is to be used, the exchangeable bases introduced can be specific catalysts, they can be regulators or they can be auxiliary catalysts. They can be introduced as single ions or as complex ions and they can increase the catalytic activity of the final contact mass, improve its physical structure, or act in both ways.



  It is also possible to coat or coat bulk carrier granules with leached, diluted or undiluted base exchange bodies, in the form of films, or to impregnate these granules with them. The massive carriers can be inert, activating or themselves be catalysts. For example, use can be made of certain catalytic alloys containing vanadium, chromium, tungsten, uranium, molybdenum and other metals which are oxidation catalysts.

   Metal carrier fragments, and especially metals of high thermal conductivity, such as aluminum, play an additional advantageous role in that their relatively high thermal conductivity tends to prevent local overheating, which is of great importance, since Most of the organic oxidations within the scope of the present invention are highly exothermic and some of them are excessively sensitive to temperature conditions and tend easily to get out of control with excessive temperatures.



  The leaching can be carried out in any convenient manner and the term "leaching" embraces processes in which the base exchange body is washed with dilute acids. In fact, any treatment with an acid which results in the removal, by chemical action, of any portion of the bases present in the base exchanger, should be considered to be covered by the term "leaching". .



  For good. Organic oxidations. it is desirable to subject the contact masses to preliminary calcination with air or with acid gases. The latter treatment is not as important if the sivage has been carried out to a high degree, since one of its most important roles is in the reduction of a strong alkalinity which is effected by it and, of course, in amply leached contact mas s, the alkali nity is almost completely destroyed.

         However, calcinations and treatment with acid gases can be used and they have an advantage, with a large number of <B> contact </B> masses, in particular contact masses where the Leached bases can itself be employed as a diluent in other catalytically inactive or active base exchange bodies. In such cases the body may not show excessive alkalinity in itself for some reactions, but it may be combined with other constituents which are too strongly alkaline: to give good results and , in such cases, treatment with acid gases is of great importance.

   Calcination and the catalyses themselves, especially vapor phase catalysis, usually result in some chemical transformations in the contact mass, especially on its surface, which are not well defined and the contact masses of the invention are defined here as when they are freshly prepared, in accordance with the mode of definition customary in catalytic chemistry.



  If the leached base exchange bodies contain considerable amounts of basic constituents, and especially if the leaching has been stopped before the complete removal of exchangeable bases, one can prepare salt-like bodies of the base exchange body. bases. Acid radicals which can be reacted may be catalytically active, inert, or may act as auxiliary catalysts.

         Among: Important catalytically active radicals are those of the oxyacids of metals of the fifth and sixth groups of the periodic system, in particular the elements such as vanadium, molybdenum, tungsten, uranium, chromium, etc. Other acidic radicals such as those of manganese, selenium, tellurium, arsenic, phosphorus, sulfur, chlorine, bromine, fluorine, nitrogen and boron can be used.

   Simple acids or their salts can be used, or peracids or complex acids such as those containing ferro- and ferricyanogen, sulfocyanogen or other metal-cyanogen groups can be employed. Ammoniacal groups are also effective.

   The catalytic activity of the contact masses consisting of salt-like bodies may reside in part or in whole in the nucleus of the leached base exchange body, in the acid groups united with it or in the form of diluents. physically associated with the contact mass.

    The contact masses which are used in the invention are effective in all organic oxidations and the following are examples: 1e Reactions in which an intermediate oxidation product is obtained:

   Oxidation of benzol, toluol, phenol, tar phenols or furfurol and other compounds containing the group -CHZ-CH = CH-CH = - to maleic acid and fumaric acid or mesotartaric acid; from cresol to salicylic aldehyde and salicylic acid; of toluol and of the various halogenated substituted toluols and of the corresponding aldehydes and acids;

   - xylenes, pseudocumene, mesitylene, paracymene and other derivatives in the corresponding aldehydes and acids; from naphthalene to naphthaquinone, phthalic anhydride to maleic acid and fumaric acid, from anthracene to anthraquinone; phenanthrene to phenanthraquinone, diphenic acid, phthalic anhydride -and maleic acid;

       acenaphthene to acenaphthylene, acenaphthaquinone, bisacenaphthylidenedione, naphthaldehyde acid, naphthalic anhydride and hemimellithic acid; from fluorene to fluorenone; -eugenol and isoeugenol to vanillin and vanillic acid; methyl alcohol and methane in formic aldehyde;

   ethyl alcohol _ to acetic acid; from ethylene chlorohydrin to -chloroacetic acid, etc.



  Reactions in which unwanted impurity is burned, such as the purification of crude anthracenes - of varying degrees of impurity with complete combustion of carbazol, unused oils and, in some cases, phenanthrene ; the purification of crude mothballs and crude mononuclear hydrocarbons, such as benzols, etc., the purification of ammonia from coal tar with combustion of organic impurities such as the phenolic substances present, and so on.



  Oxidation of mixtures of organic compounds to desired intermediates, with removal of impurities, such as oxidation of crude anthracenes, crude phenanthrenes, etc., to intermediates such as anthraquinone, phenanthraquinone, acid diphenic, phthalic anhydride, etc., with concomitant removal of carbazol and unused oils by total combustion;

        oxidation of crude tar acids to maleic and fumaric acid, with combustion of certain impurities, etc.



  The most important elements in oxidation catalysts for the first and third groups are the metals of the fifth and sixth groups of the periodic system and, in particular, vanadium although, of course, the invention is not at all. limited to the use of contact masses which contain one or more of these elements. For Group 20 reactions, other elements are frequently more effective as catalysts; thus, for example, copper, cobalt and iron appear to be particularly effective, with or without metals from the third and fourth groups of the periodic system.

   Purifications, especially when a heterocyclic impurity, such as carbazol, frequently requires a large amount of regulator, and in some cases the contact mass must contain more regulator than ca. specific analyzer, while, in most of the contact masses to be used according to the invention - and in particular in those which are intended for the reactions enumerated above. in group 1, the elements, cataly- tically effective are normally -excess on regulators.

   Scrub reactions also effectively utilize strongly alkaline regulators. On the other hand, the reactions included in group 1 are normally best carried out with non-alkaline regulators or, at least, with regulators not possessing a strong alkalinity.



  Due to the enormous number of organic oxidation which can be carried out by the process according to the invention, the choice of specific catalyst, regulator and auxiliary constituents will vary greatly and these constituents will be chosen by the chemist. Catalyst experienced according to the particular catalytic reaction in which he is interested.

   In this regard, it will be borne in mind that a component which may be a specific catalyst for one reaction may be an auxiliary catalyst for another reaction and, therefore, the designs of specific and auxiliary catalysts do not. should not be taken as defining chemical classes of compounds in an absolute sense; on the contrary, they are relative terms depending on the particular oxidation reaction in which use is made of the contact mass.



  <B> It </B> is described below, by way of example, the preparation of catalytic masses, and their use in accordance with the invention.



  <I> Example 1: </I> The following three mixtures are prepared: <B> 10 </B> 280 parts of pumice powder or asbestos fibers are impregnated with a solution of manganese nitrate containing 1 manganese and .diluted sufficiently to allow good impregnation of the material. The product is then washed with a <B> 10% ammonia solution, </B> then with water, in order to remove the ammonia. The impregnated pumice is stirred in a solution (about 33 Baumé water glass, containing 24--30 parts of SiO2 diluted with 5-6 parts of water.



  9.1 parts of V205 are dissolved in an amount of normal sodium hydroxide solution sufficient for the product to be approximately neutral to tour nesol. About 19.5 parts of Fe80, plus 7H20, are added as a suitably diluted aqueous solution, and a prepicity of iron vanadate mixed with iron oxide is obtained.



  18.2 parts of V205 are treated with 2% by weight of concentrated sulfuric acid and diluted with 200 parts of water. The mixture is gently boiled and S02 gas is passed through it until a clear blue solution of the vanadyl sulfate is obtained. The blue solution is gradually treated with <B> ION </B> caustic soda until the precipitate of vanadium hydroxide which first forms dissolves in the caustic soda to form a coffee brown sodium vanadite solution.

        The 10 and 20 suspensions are then poured together and the solution 30 is immediately introduced in a thin stream with vigorous stirring. Most of the excess alkali is neutralized with <B> 10% </B> sulfuric acid and the jelly that forms is pressed well, washed two or three times with 300 parts. of water and dried at a temperature of about 100 ° C. The product is a zeolite containing tetravelling vanadium diluted with pumice powder or asbestos fibers impregnated with iron vanadium.

   The product is carefully washed with <B> 2-3% </B> hydrochloric or sulfuric acid to remove the exchangeable alkali, then washed to remove the acid and / or dried, preferably at 100 ° C. The leached base exchange body, thus obtained, which is then an effective catalyst for the catalytic oxidation of anthracene to anthraquinone under the usual reaction conditions, is pressed into suitable granules.

   An even more effective contact mass can be obtained by pulverizing the leached base exchange body and suspending it both in a solution of an agglutinating agent such as potassium sulphate, bisulfate or acid phosphate, so solution which may advantageously contain 10 to 15% of the agglutinating agent with a sufficient quantity of water to form a good suspension. This suspension is then sprayed onto pumice stone fragments or rough quartz fragments to produce a uniform and effective coating.

    The contact mass, whether in the form of granules or whether it is coated or in the dress of fragments, is well suited, after calcination with air at about 450 ° C., for the vapor phase oxidation of anthracene to anthraquinone and acenaphthene, acenaphthylene or their halogenated derivatives to the corresponding naphthalic anhydrides. The vapors of the aromatic compounds in question, preferably having a purity of about <B> 90%, </B>, are mixed with air in the proportion of 1:18 by weight and passed through the contact earth at 3G0-420 C.

   Excellent yields of the desired product are obtained and impurities such as carbazol and phenanthrene, in the case of anthracene, are completely burnt off. The ratio of aromatic hydrocarbons to air can be varied within fairly wide limits without seriously affecting the yield.



  Instead of preparing a two-component zeolite by reacting a vanaditre with water glass, zeolites can be prepared by reacting sodium or potassium vanadate with water glass under the conditions described above and, once leached, these zeolites constitute excellent catalysts.



  Instead of making use of solutions of metallates, such as the vanadites and vanadates discussed above, one can make use of solutions of metal salts in which the metal bases are sufficient. amphoteric;

   it is thus, for example, that the corresponding zeolites can be prepared by the reciprocal action of vanadyl sulphate and soluble glass by choosing the amounts of the constituents, so as to obtain a product of reaction which thirsts alkaline with regard to (sunflower or, preferably, alkaline or neutral with regard to phenolphthalein.



  Corresponding three-component zeolites can also be prepared by reacting water glass with potassium or sodium vanadite and vanadyl sulfate, first mixing the vanadite solution with the water glass solution and then adding . vanadyl sulfate, with vigorous stirring, until the jelly-like reaction product remains alkaline with respect to sunflower or, preferably, alkaline or neutral with respect to phenolphthalein.



  Leaching of dilute zeolites can be carried out. dried, described above, by hydrating in the usual manner, then by running dilute organic or inorganic acids over the zeolite until some or all of the exchangeable alkali has been washed away.

   Instead of using fragments of quartz or pumice stone as carriers, it is possible to coat with suspensions of zeolites leached from large granules, natural or artificial, of diatomaceous earth, of filter stones, silicates, rocks, certain ores, etc., by making use of water glass or an alkali metal compound as binding agents.



  Instead of applying the leached, ground zeolites as a coating or coating to fragments, they can be mixed with water glass solutions, or alkali metal compounds, and then formed into suitable pellets, in the desired shape. for use in converters for the catalytic oxidation of organic compounds, for example: bath tubular converters.



  Instead of leaching the base exchange bodies directly, they can first be hydrated and then treated with saline solutions in order to exchange some or all of the exchangeable alkali for bases of the bases. solutions.

   Thus, for example, one makes ruis seler solutions to <B> 5-10% </B>. Of copper sulphate, of ferric chloride, of carbon nitrate, of nickel nitrate, of manganese nitrate. , etc. .. individually or as a mixture, on the base exchanger body up to. so that there is no more exchange of bases. Such a zeolite, for example a cuprovanadium zeolite, if the solution was a copper salt solution, is treated with dilute acids, such as sulfuric acid or <B> 2-3% hydrochloric acid < / B> or an ac idt. 10-15% organic, such as acetic acid, maleic acid, phthalic acid, etc.,

    in order to remove by leaching some or all of the exchangeable bases. Leaching can be carried out by placing the material on an ordinary filter and trickling the acid solutions off for half an hour to two hours depending on how much more leaching is desired.



  Leached zeolites, containing heavy metals, introduced by base exchange, are well suited for the catalytic oxidation of benzol, toluol, phenol, tar acids, furfurol or phthalic anhydride to maleic acid when passing them. values of any of these substances, mixed with air in the proportion of 1: 16-25 parts, by weight, of air on the contact mass at 350 - d20 (". good yields of maleic and fumaric acids and the quality is excellent.



  Another class of leached zeolites can be obtained by forming. first the bodies resembling salts of zeolites, then leaching them.

   For example: a cuprovanadium zeolite, such as that described above, can be reacted with compounds containing acid radicals: of metals of the fifth and sixth groups of the periodic system, such as solutions with 1% of ammonium or potassium va nadate, tungstate, molybdate or tantalate, or a mixture of these solutions.

   Salt-like bodies are leached in the same manner as ordinary zeolites and, after leaching, the contact masses produced are well suited for the oxidation of toluol to ben zoic aldehyde and benzoic acid. A mixture of toluol and oxygen-containing gas is passed through in the proportion of 2 parts toluol to 25-30 part. in poi.cls. air on the contact mass, at 34a) -380 P. in a converter fitted with powerful key cooling means.

   Air may be used, or a mixture of carbon dioxide and oxygen in the ratio of 10:?, Carbon dioxide acting as an inert, permanent gas, oxygen being. introduced at a suitable place in the ring and the benzoic aldehyde as well as the benzoic acid being separated at another point.

   In order to carry out this very sensitive reaction, it is often advantageous, whether one works in a circulatory process or by catalysis in a single jet, to carry out the reaction in the presence of protective agents in the form of gas or vapors, such as carbon tetrachloride vapors or other vapors which are hardly oxidizable. The yields of benzoic acid and benzoic anhydride are significantly increased by carrying out the reaction in the presence of such protective vapors.



  The contact masks described above can also be used for the catalytic oxidation of methyl alcohol or methane to formaldehyde using air as the oxidizing agent. We get good returns.



       @ .. u instead of using vanadium in various oxidation stages, in the non-exchangeable part of the zeolite, it is possible to substitute partially or entirely other sufficiently amphoteric elements such as, for example, tungsten, aluminum, etc. manganese, chromium, etc., or a mixture of two or more of these.

           Example <I> 2: </I> 100 parts of an ordinary artificial zeolite, containing aluminum and sodium, which can be prepared either by melting or by wet process, are digested several times or similar amount of natural zeolites, with a 5% lead ni trate solution, which introduces lead into the zeolite by base exchange. The excess lead nitrate is then removed by washing the product and treating it with a 109% vanadate solution until a lead zeolite vanadate is obtained.

   This being done, the excess vanadate solution is completely removed by washing, the product is dried at a temperature below 100 ° C., then it is washed on a filter with 500 parts of sulfuric acid at <B> 2 -3%. </B> The excess acid is then removed by washing with the same quantity of water and the leached mass is calculated to about 100 "C: which is placed in a converter. pass over the contact mass, at 300-450 C, a mixture of acenaphthene vapor and air in the proportion of 1:14 by weight.

    Excellent yields of acenaphthylene of a beautiful golden color are obtained. Other effective derivatives can be prepared by substituting copper, nickel, cobalt, silver, manganese, chromium or aluminum for some or all of the lead and then treating with. one or more compounds containing -aci radicals of -metallic elements of the fifth and sixth groups of the periodic system, such as vanadic acid, tantalic acid, tungstic acid, uranic acid, chromic acid,

      or bismuthic acid, or a mixture. The zeolites are then washed with 2--3% hydrochloric acid or 8-10% <B> </B> acid and can then be used. as contact masses for the catalytic oxidation of ortho- and <RTI

   ID = "0014.0041"> parachloro- and bromotoluols, dichlorotoluols, chlorobromotoluols, nitro-toluols, bromonitotoluols, etc., to the corresponding benzoic aldehydes and benzoic acids. For this purpose, the vapors of the compounds, mixed with air, are passed in the proportions of 1: 10 to. 1 <B>: 35, </B> on contact ground, at 320-450 C.

   These contact masses can also be used for the catalytic oxidation of homologs of toluols, such as xylol, mesitylene, pseudocu- lead, paracymene, etc., to the corresponding aldehydes and acids.



  Use can also be made of the leached base exchange bodies as carrier materials to which are applied, as a coating or coating, other catalytically active materials, thus forming mixed contact masses which are valuable for the oxidation of compounds. organic.



  <I> Example 3: </I> The following three solutions are prepared: 42 parts of SiO2 are diluted in 200 volumes of water in the form of a 33 Baumé water-glass solution and 70 parts are stirred therein. of cellite earth.



  18.2 parts of V20 "are dissolved in a concentrated caustic cup solution to form a solution; <I> 10% potassium vanadate. </I>



       P 5 parts of aluminum oxide are dissolved in 5N potassium hydroxide solution to form potassium aluminate.



  We pour the three mixtures together, heat to <B> 60-70 '</B> C and pour in, while stirring vigorously, <B> 10% sulfuric acid, </B> until so that the whole mass solidifies into a jelly which must, however, remain alkaline with respect to the sunflower. The jelly is filtered off with suction, squeezed well, completely, dried at temperatures below 100 ° C., broken into pieces and hydrated by running water over them. 1--3% sulfuric acid is then trickled onto the zeolite in order to wash out some of the exchangeable alkali.

   This done, the contact mass is calcined with air and diluted SOZ gases, at 420-500 C. After calcination, a mixture of naphthalene vapors is passed over the contact mass at 380-420 C. and air in the proportion of 1:10 to 1:15. Excellent yields of high purity phthalic anhydride are obtained.



  If we change the proportion of mothball vapor to air from 1:30 to 1:40 and if we lower the reaction temperature to 360-380 C, we obtain: waxes yields α-naphthaquinone accompanied by small amounts of phthalic anhydride.



  If desired, the base exchange body can be reduced to small particles and coated or coated with massive natural or artificial granules such as fragments of ilmenite, bauxite, silica-rich minerals, such as fragments. rubble quartz, -fragments of quartzose filter stones, fragments of cellulite bricks, metal granules, such as aluminum granules, granules of metal alloys such as ferranadium, ferro-molybdenum , ferrosilicon,

          silicon-ferroman- ganese, silicon-aluminum-ferromanganese, ferrotitanium, ferrotungsten, etc. The coating can be done by heating the massive carrier fragments to 100-150 ° C, with agitation, then spraying on them a suspension of the leached base exchanger body and accompanying this spraying with a second spray of 'a dilute agglutinating agent, such as a solution of water glass based on potassium, potassium sulfate,

    potassium bisulfate or potassium phosphate. In this way, a uniform and strongly adherent film is formed.



  Coated contact masses are well suited for the oxidation of naphthalene to phthalic anhydride. If iron, cobalt or manganese are introduced, by exchange of bases, before leaching, the contact masses are suitable for the catalytic oxidation of anthracene to anthraquinone or aeenaphthene or acenaphthylve to. naphthalic anhy dride.



  <I> Example 4: </I> 2 2 parts of basic copper carbonate are dissolved in the form of a euproammonium compound. <B> 10.2 </B> parts of freshly precipitated aluminum hydroxide are dissolved in a quantity of a 2N sodium hydroxide solution sufficient to form a clear solution of aluminum hydroxide. sodium. 24 parts of copper nitrate, containing 3 molecules of water, are dissolved in 101) parts of water.

   The cuprammonium carbonate and the aluminate solution are then mixed together, and the copper nitrate solution is then poured in with vigorous stirring. A gelatinous product is formed which is neutral or slightly alkaline with respect to phenol phthalelil <B> CI </B> and which constitutes a non-siliceous carbon exchange body containing sodium, copper. and aluminum. The jelly is pressed and dried at temperatures below <100 ° C, then hydrated with water.

   Once this is done, the non-siliceous base exchange body is placed on a suitable filter and it is thoroughly washed with 2-5% sulfuric acid, streaming 250-500 parts of the acid radically over it. dilute acid. If desired, we can replace part of the alkali exchangeable by bases such? as iron, cobalt, manganese, chromium, titanium. zirconium, copper or thorium by causing 5-10% solutions to flow onto the base exchange body: corresponding salts. This done, the product is leached to remove the exchangeable alkali.



  It is also possible to form bodies resembling the salts of the base exchange body, as described above, in the previous examples, and then leach them.



  After leaching, the contact masses are kneaded with 15-20%, by weight, potassium sulphate, potassium nitrate, <B> </B> potassium chloride,. Potassium hydroxide, < B> -of </B> potassium carbonate, the key to potassium or other alkali metal compounds, in the form of aqueous solutions; or else soluble glass solutions can be used as agglutinating agents. The kneaded products are formed into suitable pellets and calcined at temperatures above 400 C.

   These contact masses are well suited for the catalytic purification of crude anthracene into superior quality anthracene with total combustion of the main impurities, such as carbonazol, and more or less complete combustion of phenanthrene, depending on the reaction conditions. .

   Thus, for example, 25-50% crude anthracene, especially 30% anthracene cake, is sprayed uniformly with air in the ratio of about 1: 20 by weight. -.- 35%, then passed over the contact mass at 380-430 C. The purified anthracene obtained contains 70-80% anthracene, practically no carbazol, and the remainder is practically pure phenanthrene.

   After recrystallization of the minimum quantity of naphtha .dissolvent, sufficient to dissolve at. 80 ° C, clean anthracene followed by cooling to 15 ° C, recrystallized anthracene contains <B> 95-97% </B> anthracene, is practically colorless and of excellent quality. In catalytic scrubbing, yields exceeding <B> 90% </B> of the anthracene present in the crude anthracene can be obtained. The phenanthrene which can be obtained from the mother liquor of crystallization is also of excellent purity.

   Instead of using the contact masses as described, the leached base exchange body can be reduced to small particles and coated with fragments of pumice stone, quartz, iron ore, ores. of copper, diaspore, etc., - these contact masses. Coatings are also well suited for the catalytic purification of anthracene under the reaction conditions described above.



  Instead of introducing copper in the form of the compound cuproammonium, it can also be used in the form of copper salt, such as copper sulfate or nitrate. When carrying out a reaction between a solution of copper salt and the aluminate, it is necessary to take care that the reaction product remains neutral or alkaline with respect to the phenolphthalein. Copper can also be partially or completely replaced by one or more saline solutions containing iron, cobalt, nickel, (chromium, aluminum, titanium, cadmium, thorium, zirconium, tin or vanadium in the form of vanadyl compounds These contact masses are very effective,

   especially when iron or cobalt are present. The aluminate solution can also be partially or completely replaced with one or more other solutions of metallates, such as, for example, zincates, cadmiums, plumbites, etc.



  The above-described contact masses are not only suitable for the catalytic scrubbing of crude anthracene, but can also be used for the scrubbing of crude naphthalene, crude benzine or other crude coal tar fractions. Another field of applications for which the contact masses are well suited is the catalytic purification of coal tar or ammonia obtained as a by-product, the organic impurities being burned off - or transformed into acids.

   Ammonia, obtained as a by-product, mixed with air, preferably using a large excess of air, is used on the contact mass, at 380-450 C, in accordance with the organic impurities present. The organic impurities are completely burnt, transformed into water-soluble compounds, and the result is a purification of ammonia by differential oxidation of the impurities.



       Example <I> 5: </I> 18 parts of vanadium pentoxide are suspended in 250 parts of water acidulated with sulfuric acid, concentrated and reduced to the sulphate of vanadium. blue dyle using sulphurous anhydride. The solution is boiled and concentrated to 150 parts of water. 10 parts of aluminum oxide are converted to potassium aluminate by means of a 5N solution of potassium hydroxide.

   One third of the vanadyl sulfate solution is treated with 10 N potassium hydroxide to convert the vanadyl sulfate to coffee brown vanadyl sulfate which is then mixed with potassium aluminate. and there are stirred 100 parts of diatomaceous earth, after which one adds, with vigorous stirring, the remaining two-thirds of the solution of vanadyl sulphate. The final product, which must remain strongly alkaline with respect to the sunflower, is pressed, dried as usual, preferably below <B> 100 'C, </B> it is broken into pieces , it is hydrated with water, in the usual way,

   then it is washed cleanly with 200 parts of 5% sulfuric acid, which can be done by trickling the acid onto the base exchange body. The leaching product is then calcined with air at 400 C; : It is an excellent slow mass contact for the vapor phase oxidation of naphthalene to phthalic anhydride. For this purpose, a mixture of naphthalene vapors and air is passed through the contact mass at 380-420 ° C. proportion -of 1 <B>: 18, </B> by weight.



  <I> Example 6: </I> The following three solutions are prepared: <B> 10 </B> Diluted with 6-8 volumes of water, 210 parts of 33 Baumé soluble glass solution and stirred therein a mixture of fine particulate silicates and kieselguhr until the suspension just remains easily stirred. The mixed diluent should preferably contain more than 25% diatomaceous earth.



  18 parts of V20 'are reduced to a blue solution of vanadyl sulfate in a hot aqueous solution acidified with sulfuric acid, using sulfur dioxide as a reducing agent. The vanadyl sulfate is converted to a brown potassium vanadite solution using a sufficient amount of 10 N caustic potassium solution.



  A <B> 100% aluminum sulfate solution is prepared. </B>



  Slurry <B> 10 </B> and solution 20 are poured together and added in a thin stream, with vigorous stirring, an amount of the aluminum sulfate solution sufficient to bring the reaction mixture to temperature. a neutrality to phenolphthalein, or to a point that is right on the alkaline side. The mass solidifies into a dirty green jelly; it is filtered with suction, washed lightly and dried; it is a three-component zeolite containing tetravalent vanadium, aluminum and SiO2 in the non-exchangeable form. If desired, the diluents can be suspended in solution 20; or they can be brewed in a mixture of soluble glass and aluminum.

   Some or all of the aluminum in solution 20 can be substituted with corresponding amounts of a potassium vanadate solution prepared by dissolving VZO 'in 2N potassium hydroxide. can partially or totally replace the vanadate by other metallates.



  Instead of using aluminum sulphate in solution 30, it can be partially or completely replaced by one or more other metal salts such as, for example, sulphate: copper, nickel sulphate, cobalt sulphate, iron sulphate, trace of manganese, ferric chloride, zinc sulphate, cadmium sulphate, titanium nitrate, thorium nitrate, zirconium nitrate, etc.



  After having dried the products, preferably at 100 ° C., they can be subjected to a base exchange after hydration; or we can form salt-like bodies. Once this is done, they are leached with 2-4% hydrochloric acid and the leaching can be extended as far as necessary, depending on how much alkali you want to keep in the product. After leaching, the material is formed into suitable pellets using a small amount of potassium water glass as a binding agent.

   These contact masses containing vanadium are well suited for the catalytic oxidation of naphthalene to phthalic anhydride, under the reaction conditions described in the preceding examples. Use can be made of contact masses which contain iron or manganese in a non-exchangeable form, in addition to vanadium,

   for the catalytic oxidation of anthracene to anthraquinone. These contact masses can also be used for the direct catalytic oxidation of crude anthra cene to anthraquinone. Thus, 40 to <B> 50% </B> of crude anthracene are vaporized uniformly with air, in the proportion of 1:25 and passed over the contact mass at 380--450 '    VS.



  Use can be made of contact masses which contain copper, silver or iron in exchangeable form for the catalytic oxidation of methanol and methane to formaldehyde.

   Similar contact masses are well suited for the catalytic oxidation of isoeugenol to vanillin and vanillic acid, of fluorene to fluorenone, of ben zol to benzoquinone, of cresol to salicylic aldehyde and salicylic acid, of phenan threne to maleic acid and d. ethyl alcohol and ethylene thlorohydrin in the aci of the corresponding acetics.

   Contact masses which contain iron and aluminum in the. The non-exchangeable portion of the leached base exchange body, or are provided as diluents, are suitable for the catalytic oxidation of acenaphthene and cenaphthylene to naphthalic anhydride and hemimellithic acid.



       Example <I> 7: </I> The following three mixtures are mixed: 6.6 parts of freshly precipitated A12O3 are dissolved in a normal KOH solution in order to form the corresponding potassium aluminate. To this solution, diluents rich in silica are added, such as crushed rocks, tuffs, lava of volcanic or eruptive origin, artificial and natural zeolites, kieselguhr, debris of cellite bricks, etc. When using debris from cellite bricks or kieselguhr, 50 to 80 parts are sufficient.



  80 parts of a 33 Baumé potassium-soluble glass solution are diluted with 100 parts of water.



       24 parts of aluminum sulfate are dissolved in 150 parts of water with 18 molecules of water.



  The 1o luminate suspension is mixed rapidly with the water glass solution, with vigorous stirring, then the aluminum sulfate solution is introduced in a thin stream; it precipitates, in a gelatinous form, a three-component zeolite. diluted. The mother liquor is removed in the usual way, the cake is dried below <B> 100 </B> C and it is broken into heaps.

   To increase the yield, it is possible to use a small quantity of very dilute sulfuric acid (5%); but care must be taken that the reaction product and mother liquor remain substantially neutral or weakly alkaline with respect to phenolphthalein. In this zeolite, the silicate and metallate components predominate over the metal salt component, so that the resulting product resembles an aluminosilicate type zeolite. If desired, the order in which the three classes of components are reacted can be changed in order to produce modified zolites.

   The relative amounts of the constituents can also be changed, for example as follows: <B> 10 </B> 3.4 parts of freshly precipitated A1203 are dissolved in gOH to form an aluminate solution of potas sium.



  120-150 parts of a 33 Baumé potassium water glass solution are dissolved in about 200 parts of water.



  30 We do. dissolve in 200 parts of water 44 parts of aluminum sulphate with 18 water molecules.



  Catalytically active diluents, regulators, auxiliary catalysts which are inert or which have two or more of these characteristics can be added to either of the alkaline reaction constituents and, preferably, the solutions are mixed together. aluminate and water glass, then aluminum sulfate is added, as described; but we can proceed in reverse. The zeolites obtained resemble two-component zeolites of the silicate - aluminum double type.

   Three-component zeolites can be produced using the following solutions in which the metallate and metal salt constituents predominate over the silicate constituents and which resemble non-siliceous base exchange bodies: <B> 10 </B> 5 parts are converted , freshly precipitated A1z03 in a corresponding potassium aluminate solution.



  2o Is dissolved in 200 parts of water 34 parts of aluminum sulphate with 18 molecules of water.



  50 parts of 33 Baumé potassium water glass are dissolved in 100 = 150 parts of water.



  The diluents described in the first part of this example can be added to one of the constituents or to the mixture of the alkaline constituents. Preferably, the aluminate and silicate constituents are mixed together and the aluminum sulphate is added, with vigorous stirring. The reaction product is freed from the mother liquor and dried in the usual manner. It is also possible to reverse the order of reaction of the constituents.



  One or more metalates containing vanadium, tungsten, molybdenum, lead, zinc or cadmium can be partially or completely substituted for the aluminum oxide in the metallate component.



  Aluminum sulphate can be partially or totally replaced by one or more other metal salts such as those containing vanadium, especially vanadyl sulphate, zinc, cadmium, titanium, zirconium, copper, nickel. cobalt, silver, beryllium, cerium,. zinc,. thorium, manganese, chromium or iron.



  The base exchange bodies obtained are washed, as described above, and these bodies may or may not themselves be catalytically active. When non-catalytically active components are present in the base exchange nucleus, the catalytic components can be introduced in the form of acidic groups uniting with the base exchange bodies to form salt-like bodies.

   The patalytic power of the leaches can reside entirely in the zeolite or in constituents in chemical combination with it; or it may reside partly in the original zeo lithe and partly in diluents combined therewith to form a homogeneous structure.



  Leached zeolites can also be used as carriers for. catalytic matter. An example of the introduction of catalytically active constituents is the introduction by base exchange;

  . For example, it is possible to substitute some or all of the exchangeable alkali for heavy metals, such as iron, copper, nickel, cobalt, manganese, silver, titanium, zirconium and aluminum by running solutions 5- 105% of the corresponding salts on the zeolite at moderately high temperatures to accelerate the exchange of bases.

   Thus, just before starting the base exchange, it is advantageous to hydrate the base exchange body by running water over it; after this treatment, the base exchange bodies are reacted with ammonium vanadate or other suitable vanadates to form a salt-like body. The zeolite is preferably impregnated with a solution of vanadate and the alkali washed off after reaction.

   The color of the zeolite changes to that of the corresponding vanadates. 1-10% solutions of vanadates are. which ones are preferable. The mass is dried, then washed with acetic acid at 5-1010 °, then washed thoroughly. and we then fill a converter. Toluols, and -di to substituted nitrated toluols, are vaporized with air in ratios such as 1:40 and passed through the contact mass at 340-420 C, which produces the benzoic aldehydes. and corresponding benzoic acids.

   Xylenes, pseudocumenes, mesitylenes, para-cymene and other organic side-chain compounds can be oxidized in a similar manner to the corresponding aldehydes and acids under the same conditions.



       The introduction of catalytically active diluents such as, for example, 5 to 10% of salts of acids - metals of the fifth and sixth groups - of the periodic system increases the catalytic power of the contact masses.

   Particularly effective compounds are silver vanadate, copper vanadate and iron vanadate or the corresponding tungstates, molybdates, uranates, tantalates, chromites, or mixtures thereof. After leaching, the catalytic power may reside partially or entirely in the diluents.

 

Claims (1)

CLAIM: Process for the catalytic oxidation of organic compounds, characterized by the fact that said compounds are reacted with an oxidizing agent in the presence of a catalytically active contact mass, which contains at least one substance resulting from leaching by a helper body of a base exchange compound or a salt-like derivative of such a compound. SUB-CLAIMS: 1 Method according to claim, in which the substances to be treated are brought to the vapor phase on the catalytic mass. 2 The method of sub-claim 1, wherein said substances are brought into mixture with inert gases or vapors. 3 The method of claim, wherein said substance formed by leaching a base exchange body contains a caatalytically active component specific for the desired oxidation. 4. A method according to claim, wherein the specific catalyst component for the desired oxidation is physically associated with said substance formed by leaching. 5. The method of sub-claim 3, wherein said specific catalyst component is contained in said substance as an exchangeable base. 6 Process according to the sub-claim in which the non-exchangeable core of said substance formed by leaching contains a catalytically active constituent, specific for the desired oxidation. 7. A process according to claim, wherein said substance results from leaching of a salt-like body obtained by reacting a base exchange body with a compound having a combinable anion in that form. 8 The method of sub-claim 7, wherein the anion combined with the base exchange body is a specific catalyst for the desired oxidation. 9 The method of claim, wherein the .catalytically active component is present in the bulk in the form of. diluent of said substance formed by leaching. A method as claimed in claim in which a mass further containing, in addition to the constituent, is used. catalytically active, a reaction regulating component. 11 The method of sub-claim 10, wherein said component is an alkali or alkaline earth metal. 12 The method of sub-claim 10, in -lequel said component is an earth metal, oxide not reducible by hydrogen. 13 The method of sub-claim 10, wherein said regulating component is part of said substance formed by leaching. 14. The method of sub-claim 10, wherein said regulatory component is physically mixed with said substance. A process according to claim 1, in which a mass is used which still contains a constituent which, without being a specific catalyst for the desired oxidation, promotes the reaction. 16. The process according to sub-claim 15, wherein said auxiliary catalyst is a constituent element of said substance formed by leaching. 17 Method according to. Sub-claim 15, wherein said auxiliary catalyst is physically mixed with said substance formed by leaching. 18 The method of claim, in which the constituent. The specific catalytically active agent is vanadium. 19 Method according to claim, characterized in that the contact mass still contains one or more diluents which are themselves base exchange bodies. A method according to sub-claim 19, wherein said base exchange bodies are of the non-siliceous type. 21 A method according to sub-claim 19, wherein said exchanger bodies <B> (the </B> bases are of the zeolite type. 22 A method according to sub-claim 8, wherein said catalytically active radical contains vanadium. 23 The method of claim, wherein one uses a catalytic mass formed of granules carrying on their surface a thin layer containing the ca.talytically active constituent. 24 The method of sub-claim 23, wherein said granules are formed from a metal. <B> 5 </B> A process according to sub-claim 10, 22 in which the substance obtained by the sivage contains a regulating body and a catalytically active component specific for the desired oxidation. 26 The method of sub-claim 15, wherein the substance obtained by the sivage contains a specific catalyst component for the desired oxidation, and an auxiliary catalyst component. 27 A process according to sub-claims 25 and 26, in which the specific catalyst, the auxiliary catalyst and the regulator are chemically associated in said substance formed by leaching.