CH136364A - Process for preparing catalytically active masses containing base exchange bodies. - Google Patents

Description

  

  Process for preparing catalytique.ment active masses containing base exchange bodies. We have. already proposed to produce non-siliceous base exchange bodies by reaction between at least one compound containing a non-siliceous anion capable of forming the acidic portion of the nucleus of a non-siliceous base exchange body and at least one compound containing a metal element which is amphoteric in at least one of its oxidation stages, the reaction taking place under conditions such that the resulting product is alkaline to. with regard to the sunflower. The precipitate is usually removed from the mother liquor and processed in the usual manner.

   The products obtained by this process have a greater or lesser base exchange power and can therefore be used, for example, for softening or purifying water.



  The authors of the invention have found that (preferably, when at least one of the constituents employed is analytically active, it is possible to operate so as to form mixtures of said exchange bodies of bases with .diluents, very advantageously to obtain masses which are active catalysts for a certain number of catalytic reactions.

   Excellent catalytic masses can be produced by causing at least one metallate component with several different metal salts to act in order to obtain the base exchange body, rather than a single metal salt, or vice versa.



  All base exchange bodies of the kind indicated which are prepared by the reaction of a single metallate with a single metal salt, or bodies produced by the reaction of at least one metallate with several metal salts , or vice versa, possess a remarkable honeycomb structure- killer porous and, in some cases, opal cente.

   They form, when they contain catalytically active constituents, catalysts of remarkable toughness - probably due to the extraordinarily high surface energy of the microscopically porous structure and probably also to the presence of unsaturated valences. , in many cases, and asymmetry of molecules. The molecular groups which are present are apparently large and very complex and the exact chemical makeup has not been determined.

   Such products are, chemically, quite distinct from base exchange bodies containing silicon such as, for example, zeolites and base exchange bodies relating thereto. These compounds do not contain silicon in their structure and, although they share many of the physical properties of zeolites, see: the very porous honeycomb structure and the power to exchange their alkali cations for, other cations, by exchange of bases, are chemically distinct products.



  A number of elements are capable of forming alkali metallates at least in their higher oxidation states, and can be used individually or in mixtures, as metal-containing constituents, for the production of said exchange bodies. bases, it being understood, of course, that the choice will depend on the metallic salts to be used and on the catalytic effects which one wishes to produce.

   Among the elements which form metallates, the following may be mentioned: aluminum, chromium, zinc, vanadium, beryllium, tin, palladium, ruthenium, rhodium, osmium, platinum, titanium, zir conium, lead, uranium, tantalum.

   The elements which form the metallates can be present in the form of their oxides or hydroxides united with an alkali to form simple metallates; or they can be present, in part or in whole, in the form of complex compounds such as, for example, ammoniacal groups, cyanogenic groups, and the like.



  The metal salt constituents include in particular the neutral or acidic salts, soluble in water, of the following elements: copper, silver, -bismuth, gold, beryllium, zinc, cadmium, boron, aluminum, rare earths, titanium, zirconium , tin, lead, thorium, chromium, uranium, vanadium, manganese, iron, nickel, cobalt, platinum, palladium, which can be used alone or in any desired mixture. One does not have to make use of defined proportions of the individual compounds either because mixtures of different compounds are formed or, more probably :, because the enormous size and the very great complexity of the molecule obscures all requirements for definite proportions.



  All products prepared as it has. been said to possess basic exchange powers, to. to a greater or lesser degree, when first prepared in solutions which are substantially neutral to phenolphthalein. However, for catalytic purposes, the base exchange power of the products is not required in the catalytic reactions themselves and it is, therefore, possible to deviate considerably from optimum product conditions as long as possible. as the basics swap powers go.

   In other words, the limits of alkalinity, neutrality or acidity are much wider than in the case (the products which are to be used to soften water and which, therefore, depend mainly on their exchange power of bases.

   Although usually the highest base exchange powers are obtained when the compounds are produced in a mixture which is substantially neutral to phenolphthalein, products having a similar physical structure can be prepared. and desirable for many catalytic reactions, with somewhat different proportions of the constituents such that at the end of the reaction the mixture may possess an alkalinity relative to sunflower while giving an acidic reaction to phenolphthalein.



  Heretofore, even base exchange bodies which contain a single meta.l.late and a single metal salt have only been prepared in solutions which are substantially neutral, or at most slightly alkaline to. , with regard to, phenolphthalein. The authors of the invention have found that, when the solution becomes acidic with respect to phenolphthalein, one can obtain products which still possess much of the physical structure of base exchange bodies and which, for some goals, are valuable catalysts.



  Yet another series of products can be prepared by exchanging some or all of the alkali metal cations for other atoms or radicals by means of base exchange. The number of cations that can be introduced is very large and some of them are included in the following elements and radiations: ammonium, copper, silver, gold, beryllium, magnesium, cesium, zinc, stron tium, cadmium , barium, mercury, aluminum, thallium, titanium, zirconium, tin, .an timoine, thorium, vanadium, bismuth, chromium, molyb, dene, uranium, manganese, iron, cobalt, nickel, palladium ,, platinum. These cations can be introduced either individually or in mixtures, simultaneously or successively.

   The wide possibilities of combination which can be effected by the introduction of various cations by means of base exchange, give the chemist catalyst an almost infinite field of choice in the preparation of catalytic masses with diluents, having just the desired level of activity for the particular uses for which they are intended, and it is an advantage of the invention that it allows the production of catalytic masses of activity regulated in an excessively precise and efficient manner in substantially all of the major catalytic reactions in use today.

   The cations introduced by base exchange can themselves be catalytically active; or, they can activate catalytic constituents existing in the base exchange bodies in non-exchangeable form. The cations can also be introduced as single ions or as complex ions. In all cases, the catalytic activity of the products obtained is increased by their favorable structure.

           A further series of products can be obtained by treating said base exchange bodies, in the presence or absence of reactions introduced by base exchange, with products containing anions which are capable of reacting with the base exchange. base exchange body to form salt-like products.

   These products can be partially or totally insoluble in water: but, for the. For most purposes, relatively insoluble materials are preferable and this somewhat limits the number of acidic compounds which can be treated with a given base exchange body, since not all acids form insoluble compounds. with all the base exchanger bodies.

   Acids of the following elements, whether simple acids, polyacids or complex anions, can be used to produce salt-like bodies with said base exchange bodies -vanadium, tungsten, uranium, chromium, molyb , dene, manganese, tantalum, niobium, anti-monk, selenium, tellurium, arsenic, phosphorus, titanium, bismuth, aluminum, lead, tin, zinc, sulfur, chlorine, platinum, boron, zirconium, thorium.

   Complex ions, such as, for example, ferro- and ferricyanogen, sulfocyanogen, metallic cyanides, ammoniacal groups, etc., can also be used whenever they form bodies similar to salts. with said base exchange bodies. A single acid radical can be introduced, or alternatively a mixture can be used, by simultaneous or successive treatment.

   The amount of the acid radical, which is used, can also be varied so that products may have the character of acidic, neutral or basic salts.



  The large number of active products which can thus be prepared allows the catalyst chemist to choose a catalyst having the desired characteristics for any particular catalytic reaction and these products can be used in practically all catalytic reactions such as, for example. , the synthesis of methanol or fuel for engines, the purification of yaz, the absorption of gas, the separation of 0az, the removal of harmful substances, such as, for example, volatile metal compounds, sulfur, arsenic, etc., for absorption or adsorption in gaseous or suspended liquid phase,

   and for catalytic oxidations, reduc tions, dehydrations, hydrogenations, dehydrogenations, condensations, polymerizations, de.polymerizations, halogenations, etc..



  Examples of reactions belonging to the above classes are: materials containing anthracene to anthraquinone; toluol or derivatives of toluol to benzylic aldehydes and corresponding benzoic acids;

   benzol in maleic acid; acenaphthene to acenaphthaquinone, bisacena.phthylidenedione, naphtha.dehyde acid, naphthalic anhydride and hemimellitic acid; fluorene to fluorenone; eugenol and isoeugenol to vanillin and vanillic acid; methyl alcohol and methane to formaldehyde;

   ethyl alcohol to acetic acid; ethylene chlorohydrin to chloroacetic acid, etc. Organic oxidations in which the impurities are differentially: burnt or transformed into easily removable substances also require precise control.

   Examples of such reaction are: the purification of crude anthracene or crude phenanthrene by differential catalytic combustion of earbazol; the purification of crude mothballs, crude mononu al aromatic hydrocarbons and crude aliphatic compounds such as higher sulphate oils and motor fuels. Ammonia from coal tar can be purified by differential oxidation of organic impurities and requires good temperature control.



  Reduction reactions are an important class for which use can be made of catalytic masses of the present invention. Thus, for example, nitro compounds can be catalytically reduced to the corresponding amines or other intermediate reduction products. Nitrobenzine, nitrotoluol, nitrophenol, nitronaphthalene, etc., are compounds which can be effectively reduced by the catalytic masses of the present invention.

   Hydrogenation reactions are also easily carried out; it's the case. for example, for the hydrogenation of benzol to cyclohexane, of phenol to c -, # Tclohexanol, of naphthalene to tetralin and decalin, crotonic aldehyde to butyl alcohol nor mal, acetic aldehyde to ethyl alcohol, etc. .

      Various synthetic reactions such as, for example, the reduction of carbon oxides to methanol, higher alcohols and helicopters or synthetic fuel mixtures for engines are well suited for the catalysts of the invention. The methods can be practiced with or without pressure.

   Other synthetic reactions like the syntesis of ammonia, hydrocyanic acid, etc., can also be carried out, as well as inorganic oxidations such as the oxidation of ammonia to nitrogen oxides. The diluents which are employed may be more or less inert, or have catalytic activity or catalytic activating power. These diluents can constitute finely divided carriers which are mixed with said finely divided base exchange bodies. Preferably, however, they are incorporated into these bodies during their training, so as to form a homogeneous carcass with them.

   Incorporation can take place in the constituent solutions or in the reaction mixture during formation; or the base exchange bodies can be formed in the pores of finely divided porous diluents. It is also possible to coat, cover or coat with base exchange bodies, with or without dilution of finely divided diluents, fragments of carriers, or else to impregnate the pores with base exchange body. relatively massive carrier. For some purposes, catalytic masks produced in this way have marked advantages.

   Use may be made of any suitable mode of introducing diluents either with the constituents forming the base exchange body, or into this body itself after formation, while it is still in the gelatinous state, or of 'impregnation of the base exchange body, or its constituents, in porous diluents. The invention is not limited to any partial method of introducing diluents; however, key advantageous methods are described in detail in the examples given below. Diluents can be catalytically active or be inert; or they can have activating or regulating effects.



  Some very important catalysts can be prepared in which one or more components possessing little or no catalytic activity by themselves can be activators for catalytically active components. Very finely dosed catalysts of this type can be produced. Of course, the constituents introduced by base exchange or in the form of anions, when preparing salt-like bodies, can even be catalytically, active, or activators.



  In certain cases where the diluents are catalytically active, the base exchange body may be only weakly active and act mainly as an agglomerating agent or mechanical carcass for the catalytic diluents, while nevertheless activating the catalytic diluents or by increasing their activity. The microporous structure of the base exchange bodies, with its desirable physical characteristics, is of great importance in such products and in many cases greatly enhances the efficiency of the catalytic diluents present.



  Preferably, the base exchange bodies are produced by the reactions of component solutions and, although concentrated solutions can be used, and are of importance in the preparation of certain catalysts, it is important to do so. There is an advantage for most products in using relatively dilute solutions, although it is understood that precise concentrations are usually not essential and that solutions can vary within certain limits without affecting the quality of the products, and an advantage of the invention is that many products can be prepared without extreme care.

    



  The products, as soon as they are prepared, usually rush in the form of jellies. Sometimes the precipitation is fast enough without outside help; but it frequently happens, especially in relatively alkaline solutions, that the precipitation of the jellies is greatly delayed and, in some cases, incomplete. It is advantageous, in most cases, to use stirring and in many cases to use a moderately high temperature or the addition of acidifying agents, or depositing salts, such as for example ammonia salts, salts of alkalis, alcohols and other organic compounds. In some cases, it is also advantageous to operate under pressure, in autoclaves.



  The porosity of the products which are prepared can even be further increased by incorporating into the carcass of the base exchanger body products which can be removed by washing, volatilization or combustion and which, once removed, leave. additional porous spaces and produce an even more advantageous physical structure. The substances added may be organic or inorganic in nature and may be added individually - or be in chemical combination with certain - permanent constituents; Thus, for example, some of the constituents can be introduced in the form of complex compounds which, later, are broken down and then leave additional pore spaces.

   Examples of such complex compounds are certain ammoniacal groups which can be broken down by heating the finished product.



  Generally speaking, the reaction of the constituent solutions results in the production of soluble salts which are not dewaxed and it is, therefore, usually good to wash the base exchange body after precipitation and then, to dry it, or to dry it first and then to wash it. Although it is possible in some cases to dry at high temperatures, in most cases it is best to obtain the best results by using temperatures of <B> 100 or less. / B> C.



  In the general methods described above, a metallate component and separately prepared metal salt components were reacted. Although for many purposes these are the preferred methods, it is possible to prepare base exchange bodies by a somewhat different method. Thus, for example, if a solution of an amphoteric metal meta.l- late is carefully neutralized with acid until the strongly alkaline reaction becomes weakly alkaline with respect to the.

         plienolplitalein, or even slightly acidic with low alkalinity to sunflower as a limit, base scavengers are produced which in many cases are of particular importance for catalytic purposes. Instead of metallates, amphoteric metals can also be present as complex metal compounds.



  Likewise, acidic or neutral solutions of hydroxides or amphoteric metal salts can be treated with alkali until: the mixture becomes neutral or alkaline with respect to phenolphthalein, or even acid to which case base exchange bodies are produced in a similar way that described in the previous paragraph.

    Base exchange bodies produced either by neutralizing solutions of metallates or solutions of metal salts in general, do not show quite as great a base exchange power as do those prepared by reacting one of them. with the other, ready-made solutions of metalates and metal salts. However, the physical structure appears to be the same and in many cases, particularly for catalytic uses, extremely high base exchange power is not essential. Many very useful catalysts can be produced in this way.



  Another method of preparing the base exchange body by the wet route consists of reacting alkali metal salts of acids, containing oxygen, of metal elements of the fifth and sixth groups of the periodic system, such as for example vanadium, molybdenum, tantalum, tungsten, etc., with neutral or acid salts of metals, especially metals which are strongly amphoteric.

   Preferably, there should not be an excess of alkali. The salts of the acids of the fifth and sixth groups can be used alone or in combination with metallates.



  In addition to the wet-laid methods which, for most purposes, the authors of the invention find preferable, base exchange bodies can be prepared by due melting processes, for example: by melting oxides or hydroxides -metalate constituents and metal salts with -al cali: sodium carbonate or potassium carbonate for example. Base exchange bodies produced by fusion, although sometimes do not have quite as high base exchange powers, nevertheless have the same microporous honeycomb structure and many of these products are of very high quality. good catalysts.

   Oxides of the metals of the fifth and sixth groups can also be employed to form products somewhat similar to those described in the previous paragraph by smelting processes.



  Well, base exchange bodies prepared as described have sufficient mechanical strength; but, in some cases, for example, in some cases of high dilution, the mechanical strength may be insufficient and in such cases the products may be washed with a diluted solution of water glass, which produces a surface silicification which increases the. mechanical strength of the product and which is not inconvenient in cases where the presence of silica does not adversely affect the particular catalytic reaction for which the product is to be used.

   In some cases also the treatment with diluted water glass may be advantageous, changing the proportion of base and acid in the product, which sometimes has an advantage when the product has to be used in demanding catalysts. non-alkaline catalysts. It is therefore possible to make use of subsequent treatments with water glass solutions to increase the mechanical strength of the product, or to improve its catalytic activity, or to obtain both of these results.



  The most important field of utility of the catalyst masses of the present invention resides, of course, in catalysts of various kinds and it is desirable for many catalytic reactions to subject the catalyst to. a preliminary treatment either with oxidizing or acid vapors, in particular for oxidation reactions, or with hZ-drogen or other reducing gases in the case where the catalyst is to be used as a catalyst reduction.

    These preliminary treatments and, indeed, the catalytic reactions themselves, in many cases, produce a secondary chemical change in the catalyst, especially at the surface, and can markedly affect the exchange powers of the The present invention also encompasses such bodies which have undergone secondary chemical transformations either by virtue of preliminary treatments or by reactions which have occurred during use in various catalytic reactions.



  Good organic oxidations. require a slowing down or a selective adjustment of the action of the catalysts of which it is made usacle, in order to prevent excessive losses by total combustion. We found that the. presence of salts and other compounds of forming metals, alkalis act as regulators. Other compounds, which are lytically active, but which are not specific catalysts for the particular reaction in which the base exchange contact masses are to be employed, appear to increase the efficiency of the catalyst and increase the efficiency of the catalyst. more finely the regulatory action of the regulatory bodies.

   For this reason, such catalytic constituents which are not specific catalysts for a particular reaction in question will be referred to as adjuvants of the regulators without. however, limit the invention to any theory of the action of these bodies. As far as can be judged from the facts, it seems probable that an important factor in the effectiveness of these bodies lies in their modification of the action of the regulatory bodies:

    but it is possible that other factors may also be present and constitute, perhaps, the main reason for the activity of said bodies. It is clear that. it goes without saying that a particular constituent can be a catalyst when the. contact mass in which it is contained is employed in one reaction, and an adjuvant when employed in another reaction.

   Many base exchangers produced as indicated can however be incorporated with regulators; or regulating bodies can be produced by reacting the base exchange bodies with acids or acid vapors, the alkali radicals present in the base exchange body partially or totally reacting with the acid radicals to for mer regulating bodies in intimate mixture with the base exchanger body.



  Many of the examples given below derive from the treatment of base exchange bodies to produce therein: regulatory bodies. In addition to these there is. some products which appear to increase their activity although by themselves hardly possessing any regulating effect. Thus, for example, many silicon-rich materials appear to enhance or promote the regulatory action of alkali-forming metal salts, or other regulators, and it is these products that are referred to. here under the name of adjuvants of the regulatory bodies, for lack of a better term.

   Various adjuvants can be incorporated into the base exchange bodies either in the form of diluents, for example diluents rich in silica such as diesel; guhr, etc., or by treating the base exchange body after formation, such as for example, by washing it:

  with a dilute water-glass solution which, in addition to increasing the mechanical resistance and regulating the alkalinity, as described in the previous paragraph, also introduces, in many cases, sufficient silica to act as an adjunct to regulatory bodies which may be present in the base exchange body. Such mixed catalysts can, of course, be contained in the catalytic masses according to the present invention.

      Hereinafter are described some examples (execution .du process according to the invention, thus due some, of the many fields of utility of the masses thus obtained.



  <I> Example 1: </I> 40 parts of V'Oj are suspended in 500 parts of water and acidified with a little concentrated sulfuric acid. The suspension is heated to almost the boiling point of water and gases containing iO 2 are passed through it until the suspension of varadic acid is completely dissolved in blue va.nadyl sulphate.

   The blue solution is then divided into two parts, one of which is left as is and the other is treated with a solution of potassium hydroxide of a strength five times the normal, at 50-60 C, until that we obtain a coffee brown solution,, clear. This solution is then mixed with 70 parts of cellite. or 40 parts of cellite and 40 parts of fine quartz fragments, stirring the mixture until it becomes homogeneous.

   Other diluents can be used, such as ground glass, neutral silicates, sand, silica gel, crushed rocks, tuffs, lava: of volcanic or eruptive origin, pumice powder or asbestos fibers, or similar materials. which are rich in silica.



  To the suspension containing the potassium vanadite the second = half of the vanadyl sulfate solution is added taking care that even after all the vanadyl sulfate has been added the solution remains alkaline or neutral with respect to , phenolphthalein. The reaction product, after separation from the mother liquor by filtration and drying at 60-70 C, is broken into fragments and constitutes a base exchange body containing potassium and tetra-valent vanadium,

          part of the vanadium playing the role of an acid radical and part, the role of a base in the non-exchangeable portion of the molecule.



  The product obtained is excellently suited for the catalytic oxidation of toluol to benzyl al eldehyde as well as of chlorotoluols, d.ichlorotoluols, chlorobromotoluols, nitrotoluols, chloronitrotoluols, bromonitrotoluols, etc., to the corresponding substituted benzyl aldehydes. vapors of the compounds, with air, in the proportion of 1:15 to 1:30, over the catalyst at temperatures of 320-420 C.



  Thanks to the diluents rich in silica, the bodies, base exchangers are excellently suited for the oxidation of sulphurous anhydride to sulfuric anhydride by passing 6-8% burner gases on the catalytic converter at 440-500 C.



  <I> Example </I> ?: A mass containing the potassium-va-nadyl base-exchanger-body is prepared, as in Example 1, and then inorganic acids are sprayed on. 3-5% such as, for example, sulfuric acid, phosphoric acid, nitrogen acid, etc., until the potassium content of the base exchange body has been neutralized and a body similar to a salt.

    This salt-like body tends to oxidize toluol, and substituted toluols, preferentially, to the corresponding benzoic acids under the reaction conditions described in Example 1. The salt-like body described above is suitable. excellently for the oxidation of fluorene to fluorenone, naphthalene to α-naphthaquinone and phthalic anhydride, depending on the reaction conditions.



  <I> Example 3: </I>. 20 parts of V20 'are suspended in 500 parts of water, as described in Example 1, acidified with a little concentrated sulfuric acid and reduced to sulfate of va.nadyl using gas containing SO2. The resulting blue solution is treated with sufficient potassium hydroxide solution of twice the normal strength to give a voluminous brown precipitate of V20 'which is then filtered off by suction and which 'is suspended in 300 parts of water.

   It is then heated gradually to 60-70 C and an additional solution of potassium hydroxide of twice the strength of the normal is added thereto, until all of the V204 dissolves to form a coffee brown solution. This requires an excess of potassium hydroxide.

   The potassium va.nadite thus produced is then stirred with 60 parts of diatomaceous earth and gradually poured into the solution sulfuric acid of a strength -double normal, with vigorous stirring, until this solution remains just alkaline with respect to, phenolplitalein. Instead of sulfuric acid, phosphoric acid can be used. Sulfuric acid produces a brown precipitate, while phosphoric acid produces a brownish blue precipitate. The precipitates are pressed and then dried at temperatures below 100 C.

   The products thus obtained are separated from a dilute water glass solution, formed from 110 parts of a 33 Baumé water glass solution diluted with 100 parts of water. After impregnation, the product is dried again and broken into fragments, then treated at 450-500 ° C. with 7% burner gases.

    In no time, an excellent contact sulfuric acid production process begins. Example <I> 4: </I> 20 parts of V'O5 are reduced to a sulphate & vanadyl solution, as described in the previous examples and diluted with 60 parts of diatomaceous earth.

   A solution of potassium hydroxide of twice the normal strength is added in portions, while cold, with vigorous stirring, until the mixture remains just alkaline with respect to the phenolphthalein. The precipitated body is treated in the usual manner, as described in the preceding examples;

   it is an excellent catalyst for the oxidation of naphthalene to phthalic anhydride when passing over the catalyst, at 380--420 C, a mixture of vapors of naphthalene and air in the proportion of 1.: 20.

      <I> Example 5: </I> Diluted base exchanger bodies are prepared, as described in the previous examples, with diluents which have been impregnated with ferric oxide, ar oxide. gent or copper oxide, the diluents being incorporated into the base exchange body during its -forma = tion. Sufficient normal sulfuric acid is then sprayed onto these products to form the salt-like bodies and to completely neutralize the alkali content of the base exchange body.

   Such a contact mass, containing: a, nt 6 -, 8% ferric oxide, is particularly effective for the oxidation of anfhracene to anthraquinone at a temperature of 350-400 C when passes a mixture of, authracene and air in a proportion of 1:40 through the catalyst.



  A contact mass as described above, which contains about 4% silver oxide and 6% copper oxide instead of ferric oxide, is excellently suited for the oxidation of. methyl alcohol to .aldehyde form at 370-390 C, by passing the vapors of methyl alcohol and air over the catalyst in the proportion of 1:25 by weight.



  Similar catalysts can be obtained by impregnating the diluents with ferric sulfate, silver nitrate or copper nitrate.



  <I> Example 6: </I> 12 parts of vanadic acid, <B> a </B>, are treated with sufficient double strength potassium hydroxide solution (le.

    normal so that not only all the V \ 0 'is dissolved in the form of potassium vanadate, but there is still an excess of 14 parts of <B> 100 </B>% KOA, the solution is soaked in above described a mixture of 120 parts of quartz, reduced to small particles, and 20 parts of kieselguhr. A secolide solution is prepared by reducing 111 parts of vanadic acid to vanadyl sulfate,

   in the usual manner, and neutralizing the excess sulfuric acid with a solution of potassium hydroxide of twice the normal strength.



       Solution 2 and suspension 1 are thoroughly kneaded together, then dried at a temperature of 1.00 C. The product is a base exchange body containing i20, V20 'and V20'. The product is broken into fragments and, after preliminary treatment with 7% burner gases at 450-500 ° C., it constitutes an excellent catalyst for the oxidation of sulfur dioxide to sulfur trioxide.



       Example <I> 7: </I> Base exchange bodies are prepared as in Example 6 by using potassium tungstate, potassium chromate, potassium molybdate or potassium tantalate in molecular amounts. - the equivalent la.irement instead of potassium vanadate.

   These catalysts are excellently suited for the oxidation of toluol to benzyl aldehyde and benzoic acid and of toluols substituted to the corresponding aldehydes and acids by passing the vapors of these products, mixed with air into the chamber. proportion of 1 <B> .35, </B> by weight, on the contact masses at 840-890 C.



       Example <I> 8: </I> 22 parts -of carbonate: of copper are dissolved under the. form of the compound cuproammonium. 10.2 parts of freshly precipitated aluminum hydroxide are dissolved in enough sodium hydroxide solution of double the strength of <B> normal hydroxide </B> to form a clear solution of sodium aluminate and, finally, dissolved in 100 parts of water 24 parts (copper nitrate containing three molecules of water.

   The solutions of euproammonium carbonate and sodium aluminate are then mixed together and introduced with stirring. vigorously, 100 parts of kie-selbuhr or 150 parts of quartz or pumice powder.

   The solution of copper nitrate is then poured into the mixture, with vigorous stirring, and a blue, gelatinous product is formed which is neutral or slightly alkaline with respect to the. phenolphtalein. The product is. a base exchange body containing sodium, copper and aluminum and is diluted with materials rich in silica.

   The <B>, </B> jelly is squeezed and dried at temperatures below 100 C, then it is left on. it is broken into fragments and reduced to 29-0-300 C with hydrogen trapping gases. This results in an excellent catalyst for the reduction of nitrated aromatic compounds to amines; thus, for example, nitrobenzol vapors mixed with hydrogen are almost quantitatively reduced to aniline at 180-260 C. Nitronaplitalin is reduced to naphthylamine in a similar manner.

    The same contact mass can also be used to dehydrogenate ci-hexanol at 220-820 C. Similarly, boronol is converted to camphor at 280-300 C and the aldehyde can be reduced. acetic and crotonic aldehyde in the corresponding alcohols, at 80-180 C.



  The catalyst can also be used as a chlorine carrier, for example in the production of chlorinated derivatives of methane, or for the chlorination of impurities in aromatic hydrocarbons such as, for example, the chlorination of thiophenes and aliphatic hydrocarbons which exist. as impurities in benzol and which can easily be separated from benzol. after chlorination because of their greatly high boiling point.



  Instead of using the catalysts as described, fragments of pumice or quartz can be coated or coated with them with water glass solution, and can then be effectively used as catalysts after reduction with the catalysts. gas containing hydrogen. In this way, a considerable amount of the catalyst can be saved.

           Exenz <I> pie 9: </I> The following solutions are prepared: here 30 parts of nickel nitrate are dissolved in 200 parts of water containing 6 molecules of water of crystallization and a sufficient amount of water is added. 25% ammonia until a clear solution of nitrate (# of nickel-ammonium.



  A slurry is made of 4 parts of aluminum hydroxide. freshly precipitated with 50 parts of water. then one treats with sufficient a solution of sodium hydroxide of a tenfold strength: of the. normal to form just a clear solution of sodium aluminate.



       : 30 One dissolves in 150 parts. Of water 10 parts of nitrate (chromium with. 9 molecules of water of crystallization, then it is also imitated with a solution of sodium hydroxide of tenfold strength. normal, up to c (@ that sodium chlorite is formed.



       1-o One dissolves in <B> 50 </B> parts of water S parts of zinc nitrate containing 6 mol- (#ules of water of crystallization and is treated with a quantity of hydroxide solution of sodium, of a tenfold strength of the normal <B>, </B> just sufficient to form sodium zincate.



  <B> 50 </B> 40 parts of nickel nitrate are dissolved in 200 parts of water with 6 molecules of water of crystallization.



  60 11 parts of zirconium nitrate are dissolved in 150 parts of water with 5 molecules of water of crystallization. <B> 70 </B> 16 parts of titanium nitrate are dissolved in 160 parts of water.



  Solutions 1, 3, 3 and: 4 are mixed together and 300 parts of kieselgulir, pumice powder or activated charcoal are stirred therein. or a mixture thereof. Instead of these diluents, pulverized sulfur-free nickel ore can be used. A mixture of solutions 5, 6 and 7 is added to the suspension thus obtained, while stirring v: - g @ odorously.

   A 1-elatinous reaction product is formed and, if it is strongly alkaline with respect to phenolphthalein, the excess alkali can be neutralized with 5% nitric acid to that it is just neutral with regard to phenolphthalein, whereby the yield of the base exchange body can be increased. For some bats a very low alkalinity is sufficient, but one should not go to the neutral point at. with regard to sunflower because, then the physical structure of the product would be changed and the exchange powers of bases would be greatly reduced, if not entirely destroyed.



  The product is dried at temperatures below 100 ° C. and it then comprises as a base exchanger body containing sodium, ammonium, nickel, aluminum,: chromium, -zinc, zirconium and titanium. Once broken into fragments, it can be used for various uses. Thus, for example, when it is reduced by hydrogen at 300 ° C., an excellent hydrogenation catalyst is obtained for liquid or gaseous reactions.

   For example, vapors of acetone and other ketones, mixed with hydrogen, can be reduced by making the corresponding alcohols at -100-120 C. The phenol is hydrogenated to form cy-clohexanol at 220-. 260 C. The naphthalene is reduced to tetralin at 180-220 C and finally, acetic aldehyde can be reduced to ethyl alcohol. 200 C.



  The masses can be pulverized .and obtained and reduced by hydrogen to, 300 C; they then constitute excellent catalysts for the hardening of fatty substances and for the reduction of nitro substances, ketones, phenols, aldehydes and hydro: carbons in the liquid state, especially when the reducing agent consists of gases containing hydrogen used at high pressure.

   It is also possible to form catalytic mas its for hydrogenations and reconstructions in the liquid phase by means of hydrogen by coating or coating with exchanger bodies: of powdered bases - of granular carriers such as pumice, diatomatous schists, fragments of pottery, metallic bodies such as aluminum granules, etc., by means of water glass or organic adhesives free of sulfur. The catalysts are then used by causing the substances to be reduced to run off, in the liquid or molten state, on the catalysts, in the opposite direction to a stream of hydrogen.



       Example <I> 10: </I> 66 parts of crystallized aluminum sulphate containing 15 molecules of water of crystallization are dissolved in 200 parts of water and a solution of sodium hydroxide of a force increases tenfold from normal, until all the aluminum is transformed into sodium aluminate. Another 66 parts of aluminum sulphate are dissolved in 100 parts of water. In the first solution diluents, such as rocks, tuffs or trass of volcanic origin, green sand, coke, charcoal, activated charcoal, kieselguhr or manganese dioxide, are stirred in the first solution, until the suspension is just easy to stir.

   The mixture is heated to about <B> 80 '</B> C and the aluminum sulphate solution is added gradually, with vigorous stirring, taking care that even after all of the mixture has been added. in this solution the alkalinity of the mixture remains between the endpoints of phenolphthalein and methyl orange. This usually requires a small excess of alkali in the aluminate solution and the amount of this excess can easily be determined by a small test experiment.



  If the reaction product is strongly alkaline with respect to plienolphthalein, the alkalinity can be reduced by adding sulfuric acid - or hydrochloric acid at a strength of 3--5%. A mass is obtained comprising a: base exchange body containing aluminum, which is freed from its mother liquor by pressaning it and which is dried at temperatures below 100 ° C.

   After hydration with water, the product is an excellent body teenager for water. The metallate component can be replaced, in part or in whole, by inetallates of one or more amphoteric metals such as zinc, lead, chromium, tin, etc. You can also replace. in part or in whole, the aluminum sulphate with one or more heavy metal salts such as, for example, zinc, lead, zirconium, tin or iron salts.

    nickel, cobalt, copper, titanium, clt, manganese and chromium.



  These products are suitable as catalysts in reactions which involve the decomposition of water. Example <I> 11: </I> 60 parts of zinc nitrate containing 6 moles of water of crystallization are dissolved in 200 parts of water and sufficient sodium hydroxide solution is added. The force increases tenfold from the normal until the zinc hydroxide which precipitates first is dissolved as the zincate.

   12 parts of basic copper carbonate are then stirred with 150 parts of water to form a slurry, and enough ammonia is added to dissolve the copper in the form of cupronium carbonate. A little ammonia is then added to the solution of: zincate, then the solution of cuproammonium carbonate is poured into it. To this mixture are added, as diluents, 100 to 150 parts of: quartz, asbestos, manganese dioxide, or a mixture of these.

   30 parts of chromium nitrate containing 6 molecules of water are dissolved in 300 parts of water and 48 parts of cadmium nitrate containing 4 molecules of water are dissolved in 500 parts of water. These -two solutions are then mixed and this mixture is poured into the suspension described above, taking care that the mixture remains alkaline or neutral. with respect to phenolphthalein.



  A gelatinous mass is obtained which is pressed and carefully dried at temperatures below <B> <I> 100 '</I> </B> C, after which it is treated for a time considerable with gases containing hydrogen, at 300 C.

   The base exchange body contains zinc, copper, - chromium and cadmium - diluted with quartz, binder and manganese dioxide, or mixtures, and it is an excellent contact mass. for the reduction of carbon oxides by hydrogen at 250--400 C, at high pressure and, if necessary, in a circulatory process, to produce higher aliphatic alcohols and ketones, eri more -methyl alcohol.



  If ammonium is introduced by base exchange, replacing a maximum of exchangeable bases in the exchanger & bases, the resulting product promotes the production of methyl alcohol under the reaction conditions described above. . Example <I> 12: </I> A mixture of the following three solutions is formed:

    30 parts of zinc nitrate containing 6 molecules of water, dissolved in 100 parts (.water and transformed into potassium zincate by means of a solution of sodium hydroxide of a strength, tenfold normal: 15 parts of cadmium nitrate with 4 molecules of water, dissolved in 200 parts of water, which is also converted into potassium cadmium by means of a solution of sodium hydroxide of a strength. force five times normal;

   10 parts of aluminum oxide freshly precipitated from a solution of aluminum nitrate by means of ammonia and converted into sodium aluminate: with a solution of sodium hydroxide of a strength twice the. normal. We add to. ,: e mixture of asbestos powder or. pumice powder until the residue is just easy to stir. To this suspension is added in a thin stream a solution of 45 parts of ferric nitrate containing 9 molecules of water and dissolved in 450 parts of water.



  The mass formed contains a base exchanger containing potassium, sodium, zinc, aluminum, cadmium and iron. When pressed and dried below 100 C and reduced to 300 C in a stream of hydrogen, the product is an excellent reduction catalyst for obtaining liquid reduction products from gas to purified water, with or without elevated pressure, the reaction taking place at about 300-450 C. The reduction products resemble mineral oils and are well suited as synthetic fuels for engines.



  When the synthesis is carried out without pressure. the catalysts described in Example 11 can advantageously be available in thin layers, at the top of the catalyst described in the present example. The alcohols and ketones produced by the first catalyst are thus condensed, by the catalyst of the present example, into hydrocarbons of a petroleum-like type. Intimate mixing of the three types of catalyst is also beneficial in many cases.



       Example <I> 13: </I> The following four mixtures are prepared: 5 parts of aluminum oxide are dissolved in a minimum of sodium hydroxide solution of a strength five times the normal, to form sodium aluminate.



  14 parts of zinc nitrate containing 6 molecules of water are dissolved in 100 parts of water, and enough sodium hydroxide solution of ten times normal strength is added to dissolve the zinc at l. state of sodium zincate.



  1.8 parts of chromium nitrate containing 9 water molecules are dissolved in 200 parts of hot water.



  40 18 parts of thorium nitrate containing 12 molecules of water are dissolved in 100 parts of water. Solutions 1 and 2 are poured together and 250 parts of carbonated oxidized iron are vigorously kneaded. after which solutions 3 and 4 are added and the whole is also kneaded vigorously. The reaction mixture formed is filtered off with suction, pressed and dried at. a temperature of 150 C.

   We then break into pieces the cake formed which constitutes a screening body - '(#c: core base, containing sodium, aluminum, zinc, chromium and thorium which acts as an adhesive and a porous skeleton for pulverized iron ore.



  The product thus obtained is an excellent contact mass, since the base exchange body which forms its backbone has a very desirable sorbent and adsorbent capacity. We had to make asa; 7th chi product, with excellent effect, as a catalyst for the process: ie manufacture of gas. water in which steam and carbon monoxide are transformed into carbon dioxide and hydrogen. We pass from gas to water, purified or not, together with a slight excess of fear on the contact mass at 400-600 <B><I>C</I> </B>.

           E.reiér7.ple <I> 1.4: </I> The following mixtures are prepared: l o Freshly precipitated iron oxide is prepared by: adding ammonia at 5-6% to. 10-15% ferrous nitrate solution, 1.40--50 C, until the reaction is ammoniacal. The finely divided iron oxide is then washed carefully in distilled water to remove ammonium nitrate and dried at temperatures below 100 o C.



       24 parts of dioxide (lead, in the form of sodium plumbite) are dissolved in water to form a 10% solution.



  5 parts of fresh aluminum oxide are dissolved. precipitated in potassium hydroxide of double strength <1a. normal to form potassium aluminate. 18 parts of thorium nitrate containing 12 molecules of water are dissolved in 100 parts of water.



  50 25 parts of copper nitrate containing 3 molecules of water are dissolved in 100 parts of water.



  We put: the freshly precipitated iron oxide in suspension in the solutions of plumbite and aluminate, then or add the solutions of thorium nitrate and copper nitrate. The resulting reaction product is pressed completely and dried at 80-90 ° C., after which it is broken into fragments.



  The product is: a catalyst containing potassium,. Sodium,. Thorium, and copper greatly diluted with precipitated iron oxide and is excellently suited for the oxidation of ammonia. as nitrogen oxides at (temperatures of 500 --- 600 C using gases containing o:

  zygene. The base exchange body by turning iron oxide can, due to its chemical and physical characteristics, be considered both an adhesive and an agent which increases the catalytic activity of iron oxide. Example <I> 15: </I> 1000 parts of freshly precipitated iron oxide are suspended in 300 parts of water to form a slurry.

    15 parts of freshly precipitated aluminum oxide are dissolved in potassium hydroxide at twice the normal strength to form potassium aluminate, and left therein for 10. '/ o alkali.

   The iron oxide is then stirred therein and, fi nally, is added to the. suspension of alumina and iron oxide 40 parts of zirconium nitrate containing 5 molecules of water, dissolved to form a solution. 5%. taking care that the final mixture remains alkaline at. with regard to phenolphthalein. The product pa is filtered;

  r suction and dry the cake at temperatures below 1. (10. C, after which it is broken into -fragments, - - The resulting mass, containing iron oxide impregnated with a base exchanger body containing potassium, aluminum and zirconium is an excellent catalyst - for the synthesis of ammonia,

   the uniformly distributed base exchange body acting as an exciter in the activity of iron oxide due to the presence of aluminum and zirconium oxides and also acting as a regulator, because of. presence of potassium. In addition to these two desirable characteristics, the physical structure of the base exchange body is highly desirable for catalytic uses and maintains its absorbing and adsorbing powers for nitrogen and hydrogen, even at. high temperatures.

   The duration said catalyst is. very considerable, even at temperatures at which the. synthesis of ammonia takes place and it is, therefore, very effective for long periods of time.



  An excellent ammonia yield is obtained when the catalyst is treated for a short time. time interval, at 1.00-600 C, with a mixture of hydrogen el; nitrogen and then passed a mixture of hydrogen and nitrogen, in the proportion of 3 to 1, over it at a temperature of 100-600 C. <I> Example 16: </I> Efficient catalysts, similar in composition to those of Example 15, can be prepared for the synthesis of ammonia by a fusion process.

   15 parts of aluminum oxide, 11.5 parts of zirconium oxide and 18 parts of anhydrous potassium carbonate are ground together and mixed thoroughly with 1.00 parts of iron oxide, in particular (1 Magnetic iron oxide, or with a corresponding amount of pulverized iron rim.

   The mixture is then melted and this produces a catalyst in which the iron oxide is impregnated with a base exchange body containing potassium, aluminum and zirconium which can be used for the synthesis of ammonia. .oniac under the conditions described in Example 15.



  Instead of performing the. fusion as has just been described, it is possible to introduce an intimate mixture of iron oxide and the constituents of the base exchange body in a tower and to pass over this mixture a gaseous mixture, hot, air and : organic substances preferably having a temperature of .10.0-500 <B> C </B>. A catalytic oxidation process occurs in which organic substances are completely burnt off by the air and impurities are removed. while the heat which is given off in the exothermic reaction causes the constituents of the catalyst to agglutinate or sinter, or melt completely.

   The sintered or molten material contains the base exchange body in its nascent state and constitutes an excellent catalyst for the synthesis of ammonia. The iron oxide can be substituted with iron and the constituents of the base exchange bodies can be ignited in the appliance. spraying of Schopp-11Ieuter. The resulting fried material, in which the.

    Base exchange body is uniformly formed, is very efficient for the synthesis of ammonia. <I> Example 17: </I> 10 parts of aluminum hydroxide are dissolved in a potassium hydroxide solution of double the normal strength, to form potassium aluminate, as this has. been described in the previous examples. 40 parts of chromium nitrate containing 9 molecules of water are dissolved in 300 parts of water and transformed into a solution of potassium chromite with a solution of potassium hydroxide of tenfold strength. from normal. 70 parts of thorium nitrate containing 12 molecules of water are dissolved in 200 parts of water.

   The chromite and aluminate solutions are mixed together and coke, activated charcoal or silica gel is stirred in them until the mixture remains just easy to stir. The thorium nitrate solution is then poured into it, taking care that the whole mixture remains neutral or alkaline with respect to the phenolphthalein. The product is filtered off by suction, dried below 1.00 ° C, hydrated for a short time, then the alkali is exchanged for calcium by digestion with a solution of calcium nitrate at 5%.

   Once the base exchange is complete, the product is washed thoroughly and is subjected to a subsequent treatment with a 2% vanadate solution, whereby it forms, with the vanadate, a salt-like body.



  The product thus obtained is an excellent catalyst for the synthesis of hydrogen cyanide. starting from ammonia and carbon monoxide. The water formed in this synthesis can be easily removed by adding to the catalyst a water gas catalyst, such as that described in Example 13.



       Example <I> 18: </I> Is dissolved in 100 parts of water 80 parts of chrome nitrate, containing 9 water molecules, which is converted into a solution of potassium chromite with a solution of hydroxide with a strength tenfold than normal.

   The alkalinity is then reduced with a 5% solution of nitrogen acid which is added, with vigorous stirring, until the mixture remains slightly alkaline or α neutral, the eq.rd of the phenolphthalene. A gelatinous suspension forms which is mixed with 500 volumes of lignite, coke or silica gel with, if desired, addition of manganese dioxide and dried while stirring to prevent the mass from settling. glutinate,

   the temperature being maintained below <B> 100 '</B> C. After drying, the mass is hydrated with 500 parts of lukewarm water allowing the water to drip slowly through the mass. After hydration, the product is dried again.



  The resulting body, in which the li genite, coke or hydrated silicic acid act as a carrier, and in which the potassium-chromium base exchange body is impregnated, is excellently suited as a gas scrubbing mass to remove sulfur from gas. gas by passing these over the contact mass at 400-450 ° C. The efficiency of the catalyst for gas cleaning can frequently be increased by digestion with ammonium salts to effect a base exchange.



       Example <I> 19: </I> A concentrated solution of sodium aluminumate is prepared by dissolving 10 parts of aluminum oxide in a solution of sodium hydroxide having a strength of 5 times. normal and dissolved in 200 parts of water, 40 parts of ferric nitrate containing 9 molecules of water. 500 parts of ferric oxide are kneaded in the aluminate solution after incorporation of 50 parts of monazite sand-waste.

   The nitrate and iron solution is then added; in small portions, shaking vigorously; the product is pressed, dried below 100 ° C., broken into fragments and calcined. The mass thus obtained contains a sodium, aluminum and iron base exchanger, intimately diluted with ferric oxide and monazite sand, and is an excellent catalyst for flameless combustion, which 'we call surface combustion. Combustible gases are passed through, mixed with gases containing oxygen. on the. contact mass to 350 to. 450 C.



       Example <I> 20: </I> 18 parts of vanadium pentoxide are suspended in 300 parts of water made weakly acidic with -sulphuric acid -concentrated and reduced, with an - sulphurous bydride, in blue vanadyl sulphate, in the usual manner. The solution is boiled and concentrated to 150 parts of water. 10 parts of aluminum oxide are converted to potassium aluminate with a hydroxide solution of a strength fifteen times the. normal.

   One-third of the vanadyl sulfate solution is treated with a potassium hydroxide solution of ten times normal strength. to transform it into the coffee brown potassium vanadite which is then mixed with the potassium aluminate solution and 100 parts of diatomaceous earth are added. After that, the remaining two-thirds of the vanadyl sulfate solution is added with vigorous stirring. The end product <B> of </B> the. reaction: must -demeu rer strongly. alkaline with regard to sunflower.



  The product is pressed, dried as usual below 100 ° C, broken into fragments, then sprayed: above @ 10% sulfuric aid until the body similar to a salt is formed with the potassium, vanadyl and aluminum base exchange body which is diluted with diatomaceous earth. During spraying, the fragments should preferably be heated to stir.



  The product obtained after treatment with air at 400 C is an excellent catalyst for the vapor phase oxidation of naphtha line to phthalic anhydride by not using the catalyst at. 380-410 C, a mixture of mothball vapors and air in 1: i. proportion of 1 to 1.8 by weight. Kremple .'21: We prepare <B> the </B> base exchange body like this. is described in Example 20: but, instead of reacting it with sulfuric acid to form a salt-like body, it is digested for a considerable time with a solution of copper nitrate. 5%, so that part of the alkali is replaced by copper.

   The product thus obtained is an excellent oataly- Spur for the oxidation of methyl alcohol in formaldehyde in the vapor phase at 360--400 C. A mixture of methyl alcohol gas is passed through the catalyst. and air in the proportion of 1 to. 10. Example <I> 22: </I> A catalytic mass is prepared containing a base exchange body as described in Example 21; but, instead of digesting it with copper nitrate, a 5% solution of ferric nitrate is used in order to replace as large a quantity as possible of the alkali by ferric oxide. .

   The product thus obtained is an excellent: catalyst for the catalytic purification of ammonia - tar from boiling by passing over the catalyst ammonia vapors mixed with air at 860-450 C, which causes organic im purities to be oxidized to carbon dioxide and; water, with production of a little elemental nitrogen.

           Example 23: A mass containing a base exchanger is prepared as described in Example 21, but instead of using 10 parts aluminum oxide, or using 20 parts of aluminum oxide. aluminum oxide and a corresponding quantity of potassium hydroxide, the solution of potassium aluminate being diluted with 60-70 parts of kieselguhr, fragments, pumice or quartz fragments, the alkalin base exchanger body being neutralized with,

       .sulfuric acid to form a salt-like body. The product thus obtained is an excellent catalyst for the catalytic oxidation of benzol, toluol, phenol and tar acids to maleic acid. We pass on the catalyzer, to. 360 450 C, the gas mixture of these hydrocarbons or aromatic compounds and air in the proportion of 1 to 20.



       Example .'- 34: The following four mixtures are prepared: <B> 10 </B> 19 parts of beryllium nitrate containing 3 molecules of water are dissolved in 100 parts of hot water and sufficient quantity of water is added. sodium hydroxide solution of five times the strength of normal to form sodium beryllate.



  30 parts of zinc nitrate, containing 6 molecules of water, are dissolved in 100 parts of water, which is also converted into the zincate by means of sodium hydroxide of a strength five times the normal .



  <B> 30 </B> Is dissolved in 200 parts of water 5.5 parts of thorium nitrate containing 12 molecules of water. P 25 parts of zirconium nitrate containing 5 molecules of water are dissolved in 250 parts of water.



  We pour solutions 1 and 2 together and add unglazed porcelain pulverized until the suspension remains just easy to. stir. After that a mixture of solutions 3 and 4 is added, taking care that the resulting mixture remains alkaline. with regard to phenolphthaleine.



  The body obtained contains a sodium base exchanger body. beryllium, zinc, an thorium and zirconium, and. unglazed porcelain as a thinner, and it is an excellent catalyst for so-called aldolizations and crotonizations. When acetic aldehyde vapors are passed through a thick layer of this catalyst at elevated temperatures, they convert to aldol or crotonic aldehyde, depending on the reaction conditions. The latter can be used as a raw material for the. reduction to normal butyl alcohol by means of hydrogen and copper reduction catalysts such as those described in Example 8.

           Example <I> 25: </I> 60-80 parts of kieselguhr are impregnated with a solution of ammoniacal silver vanad.ate prepared by reacting 18 parts of VZO \, under the. form of sodium metavanadate dissolved in 250 parts of water, with 34 parts of silver nitrate also dissolved in 250 parts of water.

   The precipitated yellow silver vanish is then separated from the mother liquor in the usual manner and suspended in 100-150 parts of water to form a slurry. 20% aqueous ammonia solution is added until all of the silver has dissolved. After impregnation, the impregnated li: ieselgnhr is heated to completely remove the ammonia.



  10.2 parts of freshly precipitated aluminum oxide are dissolved with. in about 40 parts of 100% KOH in 300 parts of water to form the 2-potassium aluminate and one. dissolves in 52-parts water 57 parts of ferric sulphate with 9 molecules of water of crystallization.

   The aluminate solution is mixed with the impregnated kieselguhr after which the ferric sulphate solution is poured in with vigorous stirring, thereby forming a base exchange body containing kieselguhr impregnated with the diluent. . The precipitate is pressed, washed with 200 parts of water in small portions, dried in the usual manner at temperatures below 100 ° C. and broken into fragments.

   These fragments are calcined and they form an excellent contact mass for the catalytic oxidation of sulfur dioxide, giving up to 98% of theoretical yield starting with burner gas <<6-9%, the The reaction being carried out between 120 and 450 <B> 0 </B> C. The aluminum-iron base exchanger body forms with silver va.nadate in the form of diluent an excellent catalyst.



  The a.lumina.te can be replaced by other meta.llates such as, for example, potassium benTllate and one can, in the same way, replace the iron sulphate by other metallic salts such as copper sulphate, copper sulphate, carbon sulphate, nickel sulphate, etc.



  The silver vanadate can be replaced, in part or in whole, by other salts of tetrava.lent and penta.valent vanadium such as, for example, copper vanadate, iron vanadate, manganese vanadate or van.ad ate of calcium.

           Example 26: 14 parts of V205 are suspended in 250 parts of water to form a broth; it is acidified with 5 parts of concentrated sulfuric acid and then reduced to blue vanadyl sulphate, in the usual manner, by means of gas containing SO 2 which is passed through the solution. the. boiling temperature.

   125 parts of 33 Baumé water glass are then diluted with 200 parts of water and about 40 parts of cellite are stirred therein. Pour in after that. the. Soluble glass solution in the vanadyl sulfate solution, with vigorous stirring, precipitates vanadyl silicate. Care must be taken that after all the solutions have reacted the resulting mixture is neutral to sunflower.



  10 parts of freshly precipitated aluminum oxide are treated with enough of a half-normal strength KOTH solution to dissolve the aluminum oxide as potassium aluminate and to have an excess of 10. % KOH. Dissolve in 250 --- 00 parts cd'e.au 37 parts of ferric sulfate containing 9 molecules of water of crystallization. Then pour into the aluminate solution, stirring.

    v anadyl silicate diluted with cellite and after that the ferric sulfate solution is added, which produces a base exchange body in which va.nadyl silicate is incorporated homogeneously as a diluent . The reaction product is processed in the usual manner, pressing and drying below 100 ° C., and breaking it into fragments.

   These fragments are calcined with air at 400 C, then with 6-8% burner gases at 420-500 C, which: in a short time gives an excellent catalyst for the manufacture of sulfuric acid by contact.

   Use can also be made of the catalyst for the oxidation of-anthracene to anthraquinone and acenaphthene to naphthalic anhydride by passing these aromatic hydrocarbons over the catalyst, in the vapor phase, mixed with air; in the. proportion: from 1 <B>: 30 </B> to 1: 40, the temperature being maintained around 360--420 C.

           F.reïrtple <I> 27: </I> A vana.dyle base exchange body is prepared by suspending 20 parts of V20 '' in 500 parts of water, adding a little concentrated sulfuric acid , then reducing the V206 with gases containing sulfur dioxide, to the point of boiling, until it is completely transformed into blue vanadyl sulfate.

      The va- nadyl sulfate solution is then divided into two halves, one of which is treated at 50-60 ° C. with sufficient KOH of a strength five times normal to form a coffee-brown, clear solution of potassium vanilla to which are added 50 parts of cellite earth as a diluent, after which the second half of the original solution is added, with vigorous stirring,

   taking care that the alkalinity remains between phenolphthalein red and sunflower blue. The gelatinous product is filtered off by suction, but it is not dried; it constitutes a base exchange body with va.nadyl.



       O.n. Dissolved 10.2 parts of freshly precipitated aluminum oxide with 40 parts of 100% KOH in 200 parts of water. The vanadyl base exchange body described above is then stirred into the solution and to the aluminumate mixture is added, with vigorous stirring, an aqueous solution to. 10% containing 37 parts of ferric sulphate with 9 molecules of water or 44.4 parts of aluminum sulphate with 18 molecules of water, or a mixture of the two.

   The reaction product. : obtained, which is an exchanger body & bases with aluminum and iron and which possesses no catalytic properties only for the catalytic oxidation of sulfur dioxide or for the catalytic oxidation of organic compounds, is diluted with the catalytically active vanadyl base exchanger body and is thereby transformed into a very active contact mass for the processes in question. The reaction product is filtered off by suction, dried and breaks into fragments.

   The fragments can be treated with 5% solutions of copper sulfate, silver nitrate, cobalt nitrate or iron nitrate to partially replace the alkali with these metals. The product can also be treated with salts of the oxygen acids of the metals of the fifth and sixth groups, preferably with a 1% ammonium vanadate solution, resulting in a salt-like body after soluble constituents were washed away.

        The products are calcined with air. Or -gas containing carbon dioxide -de, at 400 C, leaving the. heat-up temperature to rise gradually in order to prevent undesirable changes in the structure of the base exchange body. .after this preliminary calcination, the product is treated with 3-7% burner ga.z, at 400 C, which transforms it into a contact mass for the contact sulfuric acid manufacturing process which can occur at temperatures of 420 to 500 C.

      The same catalyst is well suited for the catalytic oxidation of organic compounds, such as naphthalene to phthalic anhydride and maleic acid, anthracene to ant: hraquinone, acenaphthene to, naphthalic anhydride, toluol and its substitutes. the corresponding benzylic aldehydes or ben zoic acids, .or methyl alcohol in formaldehyde.

   Passed over the catalyst at. 350-420 C, the vapors of organic compounds mixed with air or other gases containing oxygen such as, for example, CO 2 and oxygen, in the. proportion of 1 part -of organic compound to 100 to. 30 parts of air.

      In this example, the aluminum iron base exchange body can be viewed as a complex regulator, for the catalyst, in these reactions. To promote the regulating action of the catalyst in the metering, various adjuvants can be added in the form of silicates or heavy metal oxides such as ferric oxide, copper oxide, titanium dioxide, carbon dioxide. manganese, zirconium dioxide, cerium dioxide, oxide, beryllium, calcium oxide, coâ.a oxide: lt or thorium dioxide.

   They can be added individually or in mixtures and can advantageously be formed in the nascent state. The amount of adjuvant added depends on the desired effect; usually from 2 to. 5% of these adjuvants give good results. Of course, they can be added in the same way as any other -di luent, as has been described, in a: eneralc way, in the introduction to this memory.



  A different way to introduce adjuvants is to substitute for. all. or part of the constituents metal salts of the body exchanging bases of the corresponding amounts beryllium sulphate. -silver nitrate, nickel sulphate, cadmium sulphate or inorganic acid salts similar to these bases.



  In many cases. it is desirable to neutralize the excess alkali in the <B> </B> reaction products with a 5 <B>% </B> mineral acid, te ', than hydrochloric acid, sulfuric acid>.



  <B>, </B> ac, 4de nitrogen, etc.,. Until the alkalinity has been brought to the desired point. Other cata.lytically active base exchange bodies can, of course, be introduced as diluents, instead of that described.

           Example <I> 28: </I> It is also possible to make catalytic masses according to the present invention with zeolites as diluents, the zeolites being catalytically active.

   For example, for the preparation of the zeolite, 18 parts of V = 0 'are acidified with a little concentrated sulphuric acid; it is suspended in 50 parts of water and reduced with gases containing sulfur dioxide. :of the. Usually at elevated temperature to form a solution of vanadyl sulfate which is then treated with KOH of a strength> quintuple of normal to form a clear, coffee brown solution of potassium vanadite.

   24 parts of SiO 2, in the form of 33% potassium-based soluble glass, are dissolved in 4-5 volumes of water and 50 parts of broken bricks, diatomaceous earth, or water are stirred therein. commercial activated silicic acid. The solutions are then poured together, heated to 65-75 C, and carefully added with 5% hydrochloric acid, or sulfuric acid, until all is dissolved. mass solidifies into a gel which is then pressed and washed with 200 --- 300 parts of water.

        Instead of transforming all the vauadyl sulphate into potassium vanadite, we can thus transform a third of it, which is then added to the water-glass solution, and to this add the remaining two-thirds of the sulphate of potassium. vanadyl by forming what may be called a three-component vanadyl zeolite which is separated from the mother liquor in the usual manner.



  A vanadyl zeolite can also be prepared by dissolving 18 parts of V'0 'in normal KOII, to form potassium metavaaiadate, and then reacting it with 1α. dilute water-glass solution that contains brick, debris. diatomite. The reaction can be carried out by mixing the two components at 60--80 C and gradually adding ù.5% hydrochloric acid until the whole solidifies into a jelly. The zeolite thus obtained is then purified in the usual manner.



  Aluminum and iron bases can then be incorporated into an exchange body. As described in Example 27, any of the catalytically effective zeolites so prepared, incorporating it with either of the reaction components, in the usual manner. If desired, -5% of an activator described in the previous example can be formed in situ in order to obtain an even finer assay of catalytic activity.



  The contact masses obtained after scrubbing and calcination are excellently suited for a process for the manufacture of sulfuric acid by contact by operating with 6-9% burner gases at 40l1--80 C. By appropriate proportioning. regulator and activators, we can adapt the. contact mass with the oxidation of organic compounds; gum, for example the oxidation of anthracene to anthraquinone, by passing the vapors of the first, mixed with air in the proportion of 1: -10 by weight, on the. mass (the contact at 3.60-420 C.



       Example 29: 15 parts of V'O 'are dissolved in a KOH solution of half standard strength in the form of potassium metavanadate. One parts of freshly precipitated aluminum oxide are dissolved in 35 to 40 parts of 100% KOH dissolved in 50 parts of water to form a solution. potassium aluminate.

   The two solutions are poured together and a mixture of 20 parts of TiO 2 and 50 parts of kieselguhr is stirred. After that, about 300 parts of water are dissolved in 17 parts of aluminum sulphate with 18 molecules of water, mixed with 20 parts of ferric sulphate having 9 molecules of water and the mixture is gradually poured. solution in the va- nadate suspension, at temperatures of about 50 to G0 C.

   5% sulfuric acid is then added gradually until the desired alkalinity, or neutrality, with respect to phenolphthalein is achieved. The resulting reaction product is a vanadium, aluminum and iron base exchange body diluted with titanium oxide and kie .. selguhr. This product is freed from the mother tea in the usual way, washed with three or four times its weight of water,

    then it is dried at a temperature below 100 ° C. The product is then broken into fragments and it is an excellent catalyst for the process of manufacturing sulfuric acid by contact as well as for the catalytic oxidation of organic compounds. Under the usual reaction conditions, like this. has been described in the foregoing examples, part of the constituents of the base exchange body can be regarded as regulators for the catalytically effective constituents and titanium dioxide appears to act as an adjuvant for these regulators. We can also treat the. mass of conta-and with water, after drying, so -de hydra ter, and the. then calcine before use.

 

Claims (1)

CLAIM I: Process for the preparation of catalytically active masses containing non-siliceous base exchange bodies, which is formed by reaction between at least one compound containing a non-siliceous anion capable of forming the acidic portion of the nucleus of 'a non-silicate base exchanger body and at least one compound -containing a metal element which is amphoteric in at least one -of its oxidation-stages, the reaction being carried out under conditions such that the product exhibits alkalinity with respect to sunflower once the reaction is complete, a process characterized in that the procedure is carried out so as to form .des catal lytic masses .containing such base exchange bodies mixed with diluents. SUB-CLAIMS 1 A method according to claim I, characterized in that diluents are introduced before the base exchange body has fully set. Process according to. sub-claim 1. wherein at least a portion of the diluauts is mixed before reaction with at least one of the reactants. 3. A process according to claim I wherein at least one diluent is catalytically active. 4 The method of claim I, in which one uses, as diluents, solids in small particles which find themselves coated by the base exchange body. 5. A process according to sub-claim 4, wherein at least one of the constituents consists of a soluble compound of an acid, containing oxygen, of a metallic element of the fifth and sixth groups of the periodic system. 6. Process according to sub-claim 4, in which at least one of the reactants is a complex compound. A process according to sub-claim 6, wherein at least one of the components is an easily decomposable complex compound which is decomposed after the base exchange body is formed. A method according to sub-claim 5, -wherein at least one of the components is a salt of an oxygen-containing vanadium acid. 9 The method of claim I, wherein the. reaction is neutral or alkaline with respect to phenolphthalein after 1 ;: base exchange body is formed. 10. A process as claimed in claim 1, characterized in that the relatively acidic constituents are added to the relatively alkaline compounds so as to maintain a continuous alkalinity throughout the course of the reaction. 11 The method of sub-claim 4, further characterized in that the exchanger body, base is reacted with compounds containing anions capable of reacting with it to form bodies similar to. -salts. 12. A method according to claim I, further characterized in that the product is subjected to a treatment with a soluble silicate in order to produce a surface silicification. 13 A method according to sub-claim 4, further characterized in that the base exchange body is subjected to a treatment -in which at least part of the exchangeable bases of said body are exchanged for-bases other than alkali metals. 14 A method according to sub-claim 4, further characterized in that the product is subjected to calcination. CLAIM II: Contact mass obtained by the process according to claim I and la. sub-claim 4 comprising at least one non-siliceous, catalytically active base exchanger body in combination with at least one diluent formed from small particles. SUB-CLAIMS 1.5 A contact mass according to claim II, wherein at least one diluent is itself catalytically active, 16 A mass according to claim II, wherein the base exchange body has been treated to introduce exchange bases. - gibles other than alkali metals. A mass according to claim II, wherein the base exchange body has been reacted with an anion-containing compound capable of reacting with a base exchange body to form a salt-like body therewith. 18 A mass according to sub-claim 17, wherein said. anion is catalytically active. 19. A mass according to sub-claim 18, wherein the subject anion contains vanadium. The mass of claim II, wherein the base exchange body contains vanadium in nan-exchangeable form. 1. A mass according to claim II, characterized in that the base exchange body with the diluent has been subjected to. the reaction of a soluble silicate to produce a surface silicification. 22 Mass according to claim II, charac terized in that the base exchange body with the diluent has been subjected to calcination. 23 A mass according to claim II, in which said small particles are formed from a porous body. 24 Mass according to sub-claim 23, in which the particles of the porous body are impregnated with a catalyst.