DE1567706A1 - Process for the preparation of crystalline aluminosilicates - Google Patents

Description

Process for the production of crystalline aluminosilicates

The invention is directed to a method
for the production of crystalline aluminosilicates that have a low alkali metal content.

It is desirable to have such a low sodium content in crystalline aluminosilicates to be used as catalysts by base exchange
bring about as possible; this is known, for example, from US Pat. No. 3,14024-9. It is also known, for example from the USA patent ^v j 210 267j, that - if the catalysis in question is the cracking of hydrocarbon oils for the production of hydrocarbons of lower boiling range - that which occurs

BAD ÖÖ98 38 / 16SÖ.

Ion, by the sodium in such a base exchange is replaced, advantageously consists of rare earths.

The invention is generally applicable to such processes for the preparation of ultimately as catalysts Crystalline aluminosilicates to be used in which the aluminosilicate used is originally present mono- or divalent cations are eliminated and trivalent cations are introduced into the aluminosilicate. In the Implementation of such working methods have resulted in difficulties with regard to the manufacture of an end product, which has as low a content of monovalent or divalent cations as that due to the extent of the base exchange, to which the starting material has been subjected to remove these ions would have been expected. Farther it has been observed that the end product in some cases has a lower content of the introduced trivalent Cations than expected based on appropriate considerations and that the degree of crystallinity of the end product in some cases is greatly reduced, especially in those cases where a relaxation or

S 'Flash drying as a stage in the manufacturing process is used.

It has been found that the first of these difficulties appears to be due to the fact that a lesser proportion of the original cations - usually

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Sodium - of the crystalline aluminosilicate with the silicon-oxygen-aluminum-G-round lattice is bound in a somewhat different way than the majority of these cations, the difference being of such a nature that it is the smaller proportion of the amount resistant to removal through base exchange, in relation to the main proportion, power. This lower proportion can therefore be present in the aluminosilicate remain after a base exchange treatment to such an extent that one can expect that the total amount of sodium cations would have to be removed, provided that the total amount of these cations in would be connected to the grid in the same way.

The second difficulty can also relate to the nature of the union between the trivalent cation, often rare earth metal cations, and returned to the lattice v / earth. It has been found that rare earth metal ions, their presence in a crystalline aluminosilicate tends to impart resistance to the aluminosilicate to conditions which would otherwise cause degradation of the crystalline Material to an amorphous state, to a relatively strong or a relatively weak union with the grid. It can therefore be assumed that the decreased content of Rare earth metal cations in the final product on a training only with the comparatively weak association

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the lattice when these ions are introduced by base exchange, with the result that subsequent work stages of the overall production a separation this bond or union can bring about what once leads to a reduction in the content of rare earths itself and further to a reduction in the resistance of the aluminosilicate to loss of crystallinity leads.

It has now been found that at least a portion of this proportion of mono- or divalent cations which is resistant to removal by base exchange can easily be made removable by base exchange when the crystalline aluminosilicate containing such ions is heat treated. According to the invention it is then provided that the aluminosilicate is heated to a temperature in the range of 65-927 ° G (15c - 170O ⁰ I?) Before carrying out a base exchange to remove this portion; the length of time over which the material must be kept at the heating temperature corresponds to the time required at that temperature to reduce the moisture content of the aluminosilicate to less than 90 ^c / ° of the saturation value. Furthermore, it has been found that if the heating takes place above a certain minimum temperature, the further effect achieved is an increase in the bond strength of the trivalent cations present to the lattice. A pre-

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BATHROOM QRiGINAL-

I OD / / UD

.zugte embodiment of the invention is accordingly characterized in that the heating of a crystalline aluminosilicate, which has previously been subjected to a base exchange to introduce trivalent cations, in particular rare earth metal cations, in the range of 121-927 ° C (25c - 1700 ⁰ F ) is carried out. The product obtained in the preferred embodiment has increased resistance to loss of crystallinity or of rare earth metal cations and also has the particular advantage that it can be processed by the flash or flash drying method without losing its crystallinity.

Dra-valent metal cations which, according to the invention, are present in that can be fixed to the zeolite include the ions of rare earth metals, yttrium, scandium, manganese, iron, Chromium, ruthenium, rhodium, gold, indium, gallium, and aluminum, with rare earths and yttrium being preferred.

Suitable cations that are present in the zeolite by ion exchange (after the zeolite has undergone a thermal treatment to bring about a redistribution of those present therein subjected to monovalent and / or divalent cations has been introduced) at the expense of one or more of the aforementioned monovalent and / or divalent cations include ammonium ^ rare earth, Beryllium, calcium, magnesium ions and other metal

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cations from groups IA, IB, HA, HB, IHA, HIB, IVB, VIB, VIIB and VIII of the periodic table.

Other technical advantages and features of the process according to the invention go from the following explanation in connection with the attached drawing emerged.

Pig. 1 is a graph showing relative crystallinities of rare earth aluminosilicates heat-treated according to the invention shows.

FIG. 2 uses a diagram to show relative amounts of residual sodium in a heat-treated according to the invention and ion-exchanged rare earth aluminosilicate are present.

Pig. 3 is a graph showing relative retention on rare earths after ion exchange for rare earth aluminosilicates shows which, according to the present invention, have been heat-treated prior to such ion exchange.

4 shows relative crystallinities in a diagram after treatment with various acidic solutions for rare earth Al! aminosilicate that according to the invention have been heat-treated prior to such acid treatment.

The aluminosilicates containing trivalent metal cations, e.g., rare earth aluminosilicates, are produced by structural replacement of an alkali aluminosilicate, which has a uniform pore structure with openings that

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OBlGlNAL INSPECTED

by an effective pore diameter of more than 3> preferably more than 5 and "particularly preferably between 6 and 15 angstrom units are marked. The alkali aluminosilicate can be a material of the A-type, X-type, Ϊ-type, L-type, D-type, T-type, K-G-type, mordenite-type or any other known form of molecular sieve; the material can be according to one of the general Working methods have been prepared as described in U.S. Patent 2,882,243 (Α-type), U.S. Patent 2,882,244 (X-Type), U.S. Patent 3,130,000? (ϊ-type), the German patent specification 1 100 009 (L-type), the German patent specification 1 099 511 (D-type), the USA patent specification 2 950 952 (T-type) or U.S. Patent 3,056,654 (K-G type) are described. In the case of the aluminosilicates it is also about naturally occurring materials, e.g. mordenite, ghabasite, gmelinite, offretite (erionite), Heulandite, Clinoptilolite and Stilbii.

Crystalline zeolites in which silicon has been replaced by gerraaniuu and / or aluminum has been replaced by gallium, can also be crystallized. A. Procedure for The synthetic preparation of such zeolites is described by Barrar and co-workers in J. Ohem. Society (London), Page 195 (1959).

The base exchange of the alkali aluminosilicate is generally brought about by treatment with a solution,

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which are characterized by a pH value above about 4.5, preferably by a pH value in the range of 5-10 » isij and those to be introduced into the aluminosilicate by exchange Contains cations «

The extent of the exchange that is brought about differs with the various zeolites., For example, with zeolite X, a conventional ion exchange takes place relatively rapidly, until about 0.1 equivalents of alkali metal per equivalent of Al remain in the lattice. With zeolite Y with a silica / alumina molar ratio from 6, the conventional exchange proceeds rapidly until there is about 0.25 equivalents of alkali metal per equivalent of Al. In the case of alkali metal cordenite, the exchange proceeds until about C, 5 equivalents of the alkali metal per equivalent of Al have remained.

The lowest pH that the base exchange solution has Can be used by the molar ratio of oil to aluminum oxide in the crystal lattice of the aluminosilicate determined. Pure silica / alumina-col ratios below about 4 the lowest pH is generally limited to about 4.5. For silicon dioxide / Aluminum oxide molar ratios of about 4-8, the lowest pH value is about 2. In the case of silicon dioxide / aluminum oxide molar ratios Above S, the pH can be 1 or even less.

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ORIGINAL INSPECTED

The alkali metal content of the finished base-exchanged The aluminosilicate screen is desirably less than about 0.3 equivalents per equivalent of Al in the zeolite lattice, preferably less than 0.6 equivalents per equivalent Al in the lattice and more preferably less than 0.3 equivalent per equivalent of Al in the lattice. The base exchange is generally carried out over a sufficient period of time and under suitable temperature conditions, by at least about A-C> a of the exchangeable ions, e.g. Alkali metal rations originally found in the aluminosilicate are included to replace.

S ¹ Any soluble compound of a trivalent metal, ZoB. a rare earth metal. In general, an aqueous solution of a trivalent metal salt, in particular a rare earth metal salt or a mixture of rare earth metal salts, is used. The rare earth metal salt (or the salt of another trivalent metal) can be a chloride, sulfate, kitrate, formate or acetate. The metal cation can be ger, lanthanum, praseodymium, lieodymium, samarium or other rare earths, as well as scandium, yttrium or the like. Act. It is also possible to use solutions which contain basic elements of these ions and mixtures of the same with other ions, for example ammonium ions. In the latter case, the aluminosilicate then contains not only trivalent

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BATH ORIGINAL

iletal cations, soiidom aucii Aniaoniuvakatioiiaa. 'Tonu sia iar-like aluminosilicate Liit ö.reiueriv'. ^ Eu Mol .11, e.g. a rare earth.i-.lva'a'-olilicate, is heated. Anuonial: released so that hydrogen remains υ.- .. ". C> ^.: F.-I ci · - _w '". ■ ;: ... c aluminosilicate contains both hydrogen ions and also re ·: .- valent metal cations. In such zeolites, which have sufficiently large openings to accommodate large ions, ".. ^ / lu .on alkyl ammonium ions, ζ.B ₀ methyl ammo nium ions, Dimethylammonium ions, Trimethyiamnoniuiiionen, tetramethylammonium ions and the like. Used instead of ammonium cations will"

According to the invention, such aluminosilicates with trivalent metal cations and hydrogen ions, e.g. Rare earth hydrogen Y-aluminosilicates are used and includes the term "trivalent metal aluminosilicate" or "trivalent metal aluminosilicate" thus also aluminosilicates, which in addition to trivalent metal cations, other cations, such as hydrogen, ammonium etc., included.

While water will normally be the solvent in the base exchange solutions used, so can other solvents are used, e.g. alcoholic solutions, etc.

The concentration of the in the base exchange solution The compound used, the cation of which is to be exchanged, and the amount of solution used can vary depending on the situation the type of connection used in detail,

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BATH ORIGINAL

- "11 -

the type of alkali metal aluainosilicate to be treated and the conditions under which the treatment is carried out, change »The total amount and concentration of the exchanging cation, however, is usually greater than is theoretically necessary in order to obtain the total I sodium content of the to remove original alkali aluminosilicate. However, it has been found that conventional ion exchange does not removes all of the sodium cations, even if a two or three-fold excess of the replacing cation is applied. In general, the concentration of the compound whose cation is originally in the aluminosilicate Replaced cations present, in the range from 0.1% by weight to saturation.

The temperature at which the base exchange is effected can be varied within wide limits; it is generally in the range from the edge temperature to an elevated temperature below that temperature at which the crystallinity of the aluminosilicate is destroyed by the treatment solution. Preferably, the exchange at temperatures between about 10 ° and 371 ° C (50 to 700 ⁰ F) is performed. The volume of the base exchange solution is generally chosen so that an excess is used; this excess is removed after a suitable period of contact. The contact time between the base exchange solution and the crystalline aluminosilicate is appropriate

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ORIGINAL INSPECTED

so that the cations originally present in the aluminosilicate, ζ. B ₀ alkali metal cations, can be replaced to such an extent that the content of such original cations in the zeolite after the base exchange is less than 0.6 equivalents per equivalent of Al in the zeolite. This contact time can be varied within wide limits, depending on the Temperature of the solution, the type of aluminosilicate used and the "special compound" used for the base exchange. Thus, the contact time can vary from a short period in the region of a few minutes for small particles of some zeolites to longer periods in the region of months for large crystals extend. After the base exchange treatment, the product is removed from the treatment solution. It is desirable to remove soluble ions introduced by the treatment with the base exchange solution, and this can be easily done by washing with Y / water. Furthermore, multiple contacts between zeolite and base exchange solutions can be carried out according to known countercurrent and cocurrent methods. The conditions are set so that the above-mentioned degree of exchange is achieved.

According to one aspect of the invention, a trivalent metal aluminosilicate zeolite is subjected to heat treatment to make the trivalent metal ions resistant to a further exchange, the crystals Resistance to treatment with acids and acidic

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ORiGiNAL INSPECTED

I \ J KJ I /

To give salt solutions and to give the crystals stability during spray drying. The heat treatment should expediently be carried out under such temperature and time conditions that a product is produced which has a moisture content not greater than 6% by weight (Hull to 6% by weight), advantageously from about 0.3 - 6% , preferably from about 1.5-6% and particularly preferably from about 1 »5-3% by weight«. The temperature at which such heating is carried out should be in the range from about 121 ° to about 92? ° C (250-1700 ⁰ F) and preferably from about 315 - 927 ⁰ C are ⁽⁰ 600-1700 P). Naturally, the higher the temperature, the shorter the time required at such a temperature to bring about the desired degree of dehydration. While heating for many days in completely dry air at 121 ⁰ C (250 ⁰ F) may be necessary, a few minutes of heating at temperatures in the region of 315 ⁰ C (600 ⁰ F) can be sufficient, and only a few milliseconds are required at temperatures in the Geg-end of 927 ° C (1700 ⁰ F) required Seih. Of course, if such elevated temperatures are used, the level of the temperature and / or the time must not be so great that the crystallinity of the zeolite is destroyed.

As a result of the aforementioned heat treatment, the trivalent metallics are newly "fixed" in the zeolite crystal or "fixed" so that such ions are much more resistant to

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ORiGlMAL INSPECTED

removal by ion exchange methods than that would be the case with a similar zeolite which has not been subjected to the aforementioned heat treatment. About that In addition, the heat-treated zeolite can be subjected to later processing operations with acidic solutions without this either the characteristic zeolite structure or the catalytic one Activity of the zeolite is adversely affected.

When such heat-treated aluminosilicates are subjected to hate processing steps using an acidic solution, the pH of the solution that is allowable will depend on both the silica / alumina molar ratio of the zeolite and its alkali metal content. I ^{1 For} rare earth faujasite with a molar silicon dioxide / aluminum oxide ratio of 2.5 and a sodium content of 1.3% by weight, solutions with a pH value of 2 can be tolerated. Crystalline material of the same type with 4% Na can only tolerate an exchange solution with a pH of 2.8. The pure sodium form of this zeolite is made amorphous by solutions at this pH. Selteaer earth mordenite, which has a silica / alumina molar ratio of 10, can tolerate exchange solutions with a pH of at least 1. In these cases, there are no adverse effects on the rare earth zeolite. Typical acidic solutions that can be used in such wet processing are, for example, aqueous mineral acids such as sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, acetic acid,

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as well as: solutions of acidic salts, e.g. aluminum sulfate, aluminum chloride, Iron (III) sulfate, iron (III) chloride, chromium nitrate, Zirconium sulfate, litane sulfate, etc.

Another advantage due to the above heat treatment is that the resulting zeolite can be spray dried. While such a zeolite which has not been heat treated, wherein spray drying is a drastic reduction of its crystallinity and can in fact be completely amorphous, it was found that in spray-drying of an inventive heat-treated zeolite, no significant reduction in the crystallinity of the zeolite occurs _B Spray drying is generally by spraying of the aluminosilicate or a G-emischs of aluminosilicate and a hydrogel in a current of hot air, for example at ⁰ (10OO ⁰ F.) or high carried out. The cooling entering through the water reduces the temperature of the Sjste'ms "The temperature of the dried product is usually about 95-260 ⁰ O (200 - 5QO ⁰ P).

According to a further aspect of the invention it has been found that a crystalline zeolite, e.g. Al-uminosilicate zeolite, dej? typically 1 - 5% by weight contains residual alkali metal, a heat treatment with subsequent ion exchange with a solution which Holds cations which are in ae. 2eolite are introduced

should, can be subjected; this causes such cations to enter the zeolite at the expense of the remaining alkali metal ions introduced. It can be assumed that the heat treatment redistributes those present in the zeolite Causes alkali metal ions. As a result of this redistribution, the alkali metal ions undergo an ion exchange accessible with the cation contained in the exchange solution made.

It is often advantageous to add the crystalline zeolite to water prior to calcination and ion exchange to wash. Such water washes serve to remove water-soluble ions and are desirable but not necessary.

In the embodiment explained above, the temperature and the duration of the heat treatment can be changed within wide limits. For example, temperatures as low as 65 ° 0 (15Ο ⁰ ]?) Can be used. However, a period of up to several months at such relatively low temperatures may be required. On the other hand, temperatures as high as about 327 ° 0 (17 ⁰ O ⁰ ^) can also be used, the time in such cases being very short, in the region of a few milliseconds. As in the previous embodiment, the upper temperature limit is determined by the temperature at which the zeolite tends to lose its crystallinity.

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Galcination conditions should be sufficient to reduce the moisture content to less than 90% of the saturation value. The saturation point is to the pores of the zeolite to fill the amount of water that is necessary complete, it includes but not any water between crystallites "a" It is preferred that the! Moisture content about 70% of the saturation value, and more preferably about 20 % of the saturation value does not exceed.

The aforementioned heat treatment is expedient by thermal treatment carried out in air, water vapor, air-water vapor or any other medium containing the zeolite is not adversely affected, for example, in an inert gas such as nitrogen, exhaust gas, oxygen, hydrogen, etc. The thermal Treatment is most convenient at atmospheric pressure carried out, but higher or lower pressures can also be used come into use.

In order to further reduce the remaining alkali metal content of the zeolite, the thermiscl] (treated ''; e zeolite subjected to ion exchange. It is desirable that about 0.05 to 0.2 equivalents of alkali metal per equivalent of Al be exchanged in the zeolite structure.

The ion exchange can take place with the "pure" zeolite be performed. Then the zeolite, which now contains no or only very little alkali metal, can be used as a catalyst

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OBiGlNALINSPECTED

lysätor, e.g. in a fluidized bed, pressed in IOrBi Pellets or bonded extruded materials in fixed or moving beds, or as active catalytic Component in a composition formed from such a zeolite dispersed in a porous matrix is to be used. The matrix can consist of an inorganic oxide, e.g. silica-alumina, clay, etc., or of Metal salts, e.g. barytes, etc. exist. The clay can be untreated or acid-leached.

The order of the work stages can be changed. For example, a catalyst composition be prepared by first transferring the thermally treated zeolite (before the ion exchange) through a porous inorganic oxide matrix is dispersed and such a composition is then subjected to an ion exchange treatment so that those present in the ion exchange solution Cations enter the composition at the expense of residual alkali metal (1) present in the matrix and (2) in the dispersed zeolite

The thermal treatment of the crystalline aluminosilicate zeolite makes the residual alkali metal contained therein much more accessible to ion exchange and, accordingly, much easier to remove. As a result, in a subsequent ion exchange, an aluminosilicate zeolite is obtained which contains less than 80 % of the amount of alkali metal

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ORIGINAL INSPECTED

holds, which is contained after the galling but before the ion exchange, preferably less than 75% of this amount and in many cases less than 5 ° / ° of this amount. In fact, to put a residual alkali content in the range of about 0.03 to 0.2 wt -.% Of zeolites obtained. In the case of a porous matrix composition containing previously heated aluminosilicate zeolite dispersed therein, ion exchange of such a composition results in a residual alkali metal content of less than about 0.2 Gev /.% Of the composition and typically of about 0.05%. 0.15 %.

Y / eiin the crystalline zeolite in a porous matrix If it is to be dispersed, other finely divided materials can be used also be dispersed in this same matrix, e.g. fines containing silicon dioxide, Λ-aluminum oxide fines high density, lower density materials, e.g. catalyst return fines, uncalcined clay and the like, other materials include those in U.S. Patent 2,900,34-9 named substances. The optimal fine particle size and concentration changes depending on the one used in the individual case special material. In general, however, the Particle size of the fines in the range of about 0.1-4-0 microns, by weighing certain mean. Tellehdiameter, lie.

Suitable matrix materials include. z ^ B '. Slllclumdioxydgel., _; MlschgeXe ^ from silicon dioxide ^ and: a metal oxide,

Clay, activated carbon, metal salts, metals, etc. When a mixed gel of silica and a metal oxide is used as a matrix, the metal can be act one or more metals from groups II, HIA, IYB and VIB of the periodic table. Suitable mixing gels are e.g. silicon dioxide-aluminum oxide, silicon dioxide-magnesium oxide, Silica-Zirconia, Silica-Thorium Oxide, Silica-Beryllium Oxide, Silica-Titanium Oxide, as well as ternary combinations, e.g. silicon dioxide-aluminum oxide-thorium oxide, Silica-Alumina-Chromium Oxide, Silica-Alumina-Zirconia, Silica-Alumina-Titanium Oxide, Silica-Alumina-Beryllium Oxide, Silica-alumina-magnesia and silica-magnesia-zirconia. The silica content of the silica-metal oxide gel matrix is generally in the range of about 75-99% by weight, having a metal oxide content ranging from about 1 to about 25 weight percent.

An alkali silicate is generally used as a reactant to prepare the silica-metal oxide matrix. Sodium silicate is commonly used, but other alkali silicates such as potassium silicate can also be used. The concentration of the alkali silicate solutions used in the process according to the invention is generally such that their silicon dioxide content is between about 5 % and about 30% by weight.

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In general, a slurry of finely divided dehydrated rare earth aluminosilicate formed and added to the alkali metal solution, together with an acidic Solution containing one or more metal salts of the "above The type described may contain oxides of this type Metals are mixed-gel with silicon dioxide. The at Acidic solutions used in gelation may include sulfuric acid, hydrochloric acid, nitric acid, acetic acid, and the like. in which one or more metal salts, such as aluminum sulfate, aluminum chloride, aluminum nitrate, zirconium sulfate, titanium tetrachloride, Magnesium sulfate, chromium sulfate and the like are mixed in. The result is a hydrosol that quickly turns into a hydrogel stiffens. This hydrogel then consists of a silicon dioxide-metal oxide matrix, in which finely divided aluminosilicate zeolite is dispersed.

As already mentioned, other fines can also dispersed in the silica-metal oxide gel matrix, e.g. silica-containing gel fines made from silica gel or the above-described silicon dioxide-metal oxide mixed gels, Metal oxide fine parts made of aluminum oxide, kyanite, etc. Of course, such elements should essentially be free of substances that could act as poisons in the hydrocarbon conversion process. For example is it is known that the presence of various metals such as nickel, vanadium, iron, sodium and the like, in specific

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Quantities detrimental to the conversion of hydrocarbon oils influenced. Fines containing such toxins should be avoided.

The product of crystalline aluminosilicate zeolite and inorganic oxide can be made into any desired physical shape. The sol, which contains added finely divided crystalline aluminosilicate, can be allowed to solidify in bulk to form a gel, which is then dried and broken into pieces of the desired size. The pieces obtained in this ^T .Yiese of dried gel are generally of irregular shape. Uniformly shaped pieces of dried gel can be obtained by extrusion or pelletizing of gel containing powdered aluminosilicate with a suitable binder such as bentonite clay or the like. In addition, the hydro sol can be inserted into the holes of a jbc plate and held therein until the sol has solidified into a gel, after which the shaped pieces of gel are removed from the plate. It is often desirable that the catalyst be in the form of something . 1 spherical particle is present. The sol containing powdered aluminosilicate can be made into spherical particles by any suitable method, for example by working methods such as those described in US Pat. No. 2,384,916. In general, such methods include the introduction of a sol into a column of a water-immiscible liquid,

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BATH ORIGINAL

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where the sol breaks up into droplets, e.g. in "an oil medium, in which droplets are formed from the sol »these form a gel solidify and the spheres formed subsequently flow into an underlying layer of water from which they for further processing measures, such as base exchange, Water washing, drying and galvanizing, discharged will. Larger globules are usually in the range from about 0.4 to about 6.35 e ™ diameter (1/64 to about 1/4 inch), while smaller spheres, commonly referred to as microspheres, range from fall about 10 to about 100 microns in diameter. The application of the roughly spherical particles is of particular importance Benefit in hydrocarbon conversion processes, including moving catalyst bed processes, the vortex layer method, etc., in which the spherical gel particles are subject to constant movement will. Ensure that the beds are resting when used spherical catalyst particles provide effective contact between the reactants and the catalyst Avoidance of channel formation.

When making the composition from crystalline Zeolite and metal oxide is a substantial amount of sodium or other alkali metals that are derived from the alkali silicate In order to remove the alkali metals and in particular, present in the resulting composition

the composition of the sodium is usually base-exchanged, generally with a solution containing ammonium ions. This base exchange takes place through treatment with a suitable ammonium solution such as ammonium chloride, ammonium sulfate, ammonium acetate and the like a pH value greater than about 4.5, preferably a pH value in the range of 5-10. The base exchange treatment continues until the finished catalyst has a sodium content below about 0.4% by weight, suitably below about 0.2 wt%, preferably less than about 0.12 wt% and more preferably less than about 0.10 weight percent. The duration of the base exchange contact can vary from one short period in the area a few hours for small particles to longer periods in the area of Extend days for large pellets.

Instead of the aforementioned base exchange with ammonium ions, the aluminosilicate zeolite (or the Composition containing such a zeolite dispersed therein) are exchanged with a solution containing Metal cations, e.g. rare earth ions, aluminum ions, Calcium ions, etc., to thereby remove residual alkali metal and to add such metal cations substitute. The ion exchange can also be carried out using a solution containing different cations contains, e.g. ammonium ions and rare earth metal ions.

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BATH

It may be desirable to use a variety of exchange treatments, such as _o with solutions of rare earth ions and / or solutions of ammonium ions. In any event, it can be assumed "that the comparative ease with which the residual alkali metal of the aluminosilicate zeolite is replaced by cations from the ion exchange solution used in the individual case is due to the initial heat treatment of the zeolite.

Pa the thermal treatment of a trivalent: Crystalline aluminosilicate containing cations make the material resistant to salt solutions of low pH can make alkali metal present using low pH solutions instead of applying such Solutions with a higher pH value, e.g. solutions of rare earth metal salts and / or solutions of ammonium salts. For example, aluminum salt solutions can be used with a low pH of about 3 »8 or acidic solutions, E.g. acetic acid with a pH value of about 2.8 or sulfuric acid with a pH range of about Ί, Ο ,, can be used.

In general, water is used as the solvent for the lonenaust from crilö sung used. However, it can also other solvents may be used, but this is customary less preferred. For example, in addition to acidic solutions, alcoholic solutions, etc., can also be of suitable. Connections never described above,

009838/1658 _BAE > _Qmm i

can be used for base exchange treatment.

The concentration of the solute in the ion exchange Compounds used will vary depending on the eggs Type of particular compound or compounds used, on the particular conditions under which the treatment occurs, and similar factors change.

In general, the concentration of the dissolved substance in the ion exchange solution is in the range of 1 - 1 ^ weight-vu, with a more preferred range about 1-10 Ge?; .- ', ^ and a particularly useful range of about 1-5 wt .- ^ is.

The temperature at which the ion exchange takes place can be varied within wide limits; she is generally in the range from room temperature to an elevated temperature below the boiling point of the treatment solution. The volume of the applied ionic

Exchange solution can be varied over a wide range, but generally an excess is used and that excess is removed after a suitable period of contact. The contact time can also be within wide limits oändert _O, depending on the temperature of the solution, the particular for the uasenaustausch used compound or compounds, etc. Demg-y. j'ß the duration of contact can be a v, 5rliältnii>; u ^; oig short period of time in the giving of some obstacles or it can be over a longer period of time in the Gegerul of several days orsbi'eckeii.

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Thereafter, the treatment solution is removed from the product. Anions resulting from the treatment with the ions Exchange solution have been introduced by washing removed with water.

The washed product is then dried in superheated steam to remove essentially all of the water therefrom. Drying may take place at ambient temperature in air, it is · However, preferably at a temperature of about 126-171 ° G (260-340 ⁰ I?) About 2 to 24 hours or even longer to dry in superheated water vapor.

When the aforesaid zeolite is incorporated into an inorganic oxide matrix to form a composition suitable for cracking treatments, such a composition is generally subjected to a treatment to impart higher attrition resistance and better catalytic selectivity. Such treatment involves heating the composition in an atmosphere which will not adversely affect the catalyst, such as water vapor, air, nitrogen, hydrogen, exhaust gas, helium or other inert gas. In general, the dried composition is heated in steam or a fiber vapor / air mixture to a temperature in the range of about 260-815 ° C (500-15Op ⁰ I ¹ ) for a period of at least about 1 hour and usually between about 1 and 48 hours

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heated. The finished catalyst product has a surface area within the range of about 50 - 4-00 m / g

If desired, the zeolite, which is heat-treated according to the invention (and optionally also ion-exchanged) into a fluidized bed or fluidized bed catalyst system be introduced. Such a fluidized bed or fluidized bed catalyst can, for example prepared by mixing sodium silicate with an equal Volume of water diluted, the pH value adjusted to about 10 with aqueous sulfuric acid, induces aging, adding enough aluminum sulfate solution to make a pulp which contains the equivalent of about 1 part by weight of aluminum oxide per 9 parts of silicon dioxide, and concentrated Add ammonium hydroxide to raise the pH to about 8. Then the calcined treated aluminosilicate is added. (Alternatively, the calcined aluminosilicate can also be added earlier, i.e. to the mixture of sodium silicate, Water and sulfuric acid). The material is then spray dried, followed by a base exchange with a dilute ammonium sulfate solution to increase the sodium content less than about 0.2 weight percent.

A cracking using the catalysts described herein may be in catalytic cracking conditions using a temperature within the range of about 371-648 ⁰ C (700 to 1200 ⁰ F) and under a pressure ranging from subatmospheric to up to several hundred

009838/1 658

ORlGlMAL INSPECTED

^;; .. ■■■ ^: ■■■■. '■■ - 29 -:: ^; '" ^:

Atmospheres are carried out. The contact time of the oil with the catalyst is in each case, depending on the conditions, the excess charge used in the individual case and tailored to the particular results desired so as to cause substantial cracking to lower boiling points Products. The cracking can in the presence of the invention prepared catalyst are carried out using "known working methods, for example those working processes in which the catalyst is in a still bed, as a compact particulate moving bed or as a fluidized bed of the particles is applied.

The cracking activity of the catalyst is a measure of its ability to catalyze the conversion of hydrocarbons, and it is expressed here as the percentage conversion of a mid-continent gas oil with a boiling range of 232 - yiO ° C (450 - 95O ⁰ F) to gasoline with an end point of 210 ⁰ C (410 ⁰ F). In bead or pelleted catalyst, the vapors of this gas oil at 4-68 ⁰ C (875 ⁰ F), at substantially atmospheric pressure and at a feed rate of J volumes of liquid oil per volume of catalyst per hour for operating runs of 10 minutes between! Regenerations by passed the catalyst.

The invention is illustrated by the following examples v / pus illustrates. All parts refer to that Weight, unless otherwise stated.

009838/1658

example 1

A crystalline Sodium aluminosilicate of the X-type with uniform pore openings between 6 and 15 Angstrom units, which was used as starting material for the production of rare earth aluninosilicate, was produced according to the procedure described in US Pat. No. 2,882,244 " was base-exchanged by adding an aqueous solution that contained 4- Qqv: --- j rare earth metal chlorides and contained gerchloride as the main component together with the chlorides of praseodymium, lanthanum, neodymium and samarium.The amount of 4 percent rare earth chloride solution used was 1 , 67 kg for each kg of sodium aluminosilicate per base exchange. 12 one-hour base exchange treatments were carried out at solution temperatures of 82 - 93 ⁰ O (180 - 200 ⁰ IT). The resulting rare earth aluminosilicate was washed free of soluble salts and ground in a ball mill, to reduce its size to about 4 microns, the selto Non-earth aluminosilicate product, ie, a rare earth seolite X (SEX), contained 26.5% by weight rare earth oxides (SE ₀ O-,) and 1.5% by weight sodium on a dry basis. The silica / alumina molar ratio was 2.5

Examples 2-6

Samples of the material produced according to Example 1 were ^{dried at 121 0} O (250 ⁰ P) for 48 hours. The dried one

009838/1658 _{ÖAD 0R} , G.NAL

- - 31 -

Powder was placed in the form of a 3.2 mm (1/8 ") thick layer on a floor. The sample was then placed in a preheated oven in a steam atmosphere and heated 1 stand at the desired temperature. The chamber pressure was one atmosphere The temperature was measured by means of a thermocouple 1.6 mm (1/16 ") in diameter, which ran parallel to the bottom plate of the floor through the cement of the powder layer. Separate samples were in this way for 1 hour at 204 ⁰ C (400 ⁰ IP), 343 ° C 427 ⁰ G (800 ° F), 593 ° C (1100 ⁰ F), 760 ⁰ C (140o ⁰ S ¹⁾ and 815 ° heated (calcined). It took the sample about an hour to reach the desired temperature. Upon removal from the oven chamber, the sample quickly cooled to room temperature.

The crystallinity, the exchangeability of residual sodium, the fixation of rare earth metal ions and the Stability of heated (calcined) faujasite in acid solutions were all determined with these samples.

X-ray crystallinities were determined. The samples were analyzed as they were removed from the oven without any additional heating. Hach contact with. Solutions, the samples were dried at 34-3 ° C (650 F) before x-ray analysis. Were the Cyclohexanadsorptionsprufungen vmrden with samples carried out at 2 hours at 343 ⁰ C (650 ⁰ F) is heated (calcined).

/ 009 8 3 8/16 58

In the ion exchange and acid resistance tests, 10 g of the heated (calcined). Sample stirred for 24 hours with 100 ml of solution at ambient temperature. The samples were washed and then ^{dried at 343 0} G (650 ⁰ P) for 2 hours before analysis. 1 η solutions of KH ^ Gl, AIp (SO ^) - ,, HGl, GeCl-, and a 0.26 η AIp (SO ^.) ^ Solution were used.

The X-ray crystallinities, the cyclohexane adsorptions and the contents of rare earth oxide were plotted as dependent variables in FIGS. 1 to 4 as reduced values. The calcined at 4-27 ⁰ C (800 ⁰ F) sample was taken as the basis for calculating the reduced values of the crystallinity. The data from which these reduced values were calculated are given in Table I.
Discussion of the results

Crystallinity

Samples that were calcined at temperatures up to 760 ^° C. (1400 ^° F.) largely retained their crystallinity. However, there was some loss of crystallinity above 538 ^° C (1000 ^° F). At 815 ° C (1500 ⁰ F), the crystalline material was amorphous. These results are shown in FIG. This figure shows the crystallinities of the materials used in all of the other studies described below.

009838/1658

¹ ■ 2 2o, 5. jjaüelle T
X ■ ■. 5. ■. ■ ο '■ ^; ·,; Treat. 14.6 Analysis of the Products l \; acl:, oeiicirial · « jLvach treatment., Example Sr “. ■ ■: ^{CALCINATION CONDITIONS} ^ * ai>
jj ο sung. 120 D ■ ■ 4th with 1 η / - ■> with ü, .2ö ψ j κ ■ .. '■■ Before 204 ° G (400 °?), Lh, in water 0 i \ acli Behaildl. x \ iach volume. steam, atmospheric pressure 1.3 with l / n «,
iNiF .01
~ H '■ with / 1 yia ο SEpO-, wt .-> ö 12.9 21.4 c »Gyqlahexanadsorpt. ,, g / iO0g 7.0 11.2 <° Crystalline act, % {2) 26.5 21.2 14.4 10 120 ^^^ change (shift), fo 14.5 15.7 9.8 0 25 ν ^ Ha, wt .- ^ (3) 175 I do 20th - ■ ο, 45, ^ν . ^, 343 ⁰ G (650 ⁰ F), lh, in iiasser- 15th 15th 50 co steam \ _f atmospheric pressure: 0.61 0.24 2 ^SE 2 ° 3 »wt .- ^>. 23.8 - 25.4 Gy clüh.exanad s or pt., G / 100g 13.2 12.7 Crystallinity, j »(2) 26.5
15.4 28.5 21.2 Ι6ϋ 160 change (shift), jo 180 15.0 12.6 15th 10 Sa, weight-) »(3) 15th 170 140 5 427 ° 0 (800 ° J?) _T 1h, in water 0 10 W steam, atmospheric pressure : Ü, 29 § SEgO · ^, wt .- ^
© GyülOliexanadsorpt., G / 100g 24.0
14th 25.8
13.9 % Crystalline tat, 70 (2) 145 ¹⁷⁵ <£ ' ψ. A ^ vein (shift), j « 27.3
■ 15.5 21.3
13.1 15th 0 ^<Jn Ha, ¹ wt. -Jo (3) 170 125 10 15th CD 0.20

Table_I continued

Example Sr.

593 ⁰ O

(110O ⁰ P), 1h, in water vapor, atmospheric pressure

, g / 100g
(2)

m ^ / g

Cyclohexane adsorpt,
Kristallini did, yo
change (shift),
iä'a, wt .-; * (3)
Surface area,

7β0 ° 0 (14OO ° FJ, 1h, in
steam. Atmospheric pressure

CyülDhexanadsorpt., G / 100ß
Crystalline! Tat, fr (2)
Change (shift), ρ
Sa, G-ew.- yo (3)

26.5 15.4 170 10

565

26.5 14.1 155

55

815 ⁰ C (1500 ⁰ F), lh, in water vapor, atmospheric pressure

3EpOtt wt. -Fr

OyclOhexane adsorpt., G / 1 ΰθ £ ·
Crystallinity, # (2)
Change (shift), ye
La, wt .- / 0 (3)

(O

(2)

(3)

Rehearsal before

according to '^ »^

26.5

0.4 1.4

26.6 15.3 170

10

25.1

14.3 I60 4o 0.22

26.7 C, 2

21.6 24.3 26.0 13.2 14.1 13.4 120 155 170 40 10 O

16.9 22.8 25.0 1 1 1 14.1 12.7 V » 95 125 163 -F ^ 50 4ü 1Ü I. O, 14th

VL) 1 24, 4th 2, 1, ü 1, Ό. 1, C.

Analysis oei -, based on game 1 to 1.0

vo ^ u £) dried.
Reference substance (Lie reference substance

26.3
0.4

the

The product was gewascnen, dried and 'd iiatriumanalyse on Glühbasis. Annealing at Gew. -Jo i'.a has been exchanged

otunden at:
(110O ⁰ C).

vrar,

Of the

consisted of juatriua zeolite i., amount 26.5 wt .- / o ₉

Crystallinity was measured in two ways: firstly by the height of the tip in the X-ray powder slide for Gu-K ^ radiation at 23.1 ° Bragg's angle 2Θ; second, through the adsorption capacity for cyclohexane a Cj ^ clohexane partial pressure of 20 mm.

-If the samples are calibrated above 343 ° G (G ^ C ⁰ F), the crystallinities et?, Ra measured by X-ray analysis and by cyclohexane adsorption are the same. Below about 34-3 ° C (650 ⁰ F) gives the X-ray crystallinities e.nanalyse lower than the Gyclohexanadsorption, because of a change in the structure when the material is dehydrated SEZ. This is not due to a change in the amount of crystalline material in the sample, as indicated by the high cyclohexane adsorption capacity of the dried samples.

The increase in Oyclohixaria adsorption between 543 ⁰ G (650 ⁰ F) and 4-27 ⁰ C (80 ⁰ F) is probably due to greater dehydration and, accordingly, a greater adsorptive capacity for samples that were originally above 34-3 ⁰ G (650 ⁰ F) ) were calcined.

Removal of residual sodium by ion exchange; one-step exchange . _; - - '

After calcining, the sodium is more easily exchangeable. This can be seen from FIG. 2 and Table I, Example -3 j. emerged. However Hach calcination at 815 ° G (1500 ⁰ F) of the crystal to amorphous material collapsed and

00983B / 1658

no sodium could be exchanged from the amorphous solid.

Fixing of rare earth metal cations Galcination at 34J ⁰ C (650 ⁰ F) and higher temperatures also fixes the rare earth metal cations in the structure and makes an exchange of these ions difficult. This is shown in Figure 3 and Examples 3-6.

Ammonium chloride solution exchanged no rare-earth metal cations in SEX-samples were calcined above 343 ° C (650 ⁰ F). Aluminum sulfate solutions and hydrochloric acid solutions extracted some rare earth metal ions, even from calcined samples.

The amorphous sample (calcined at 815 ° C (1500 ⁰ F)) spoke in the same manner as the crystalline samples for extraction of rare earth by each of the solutions. The more dilute 0.26 η aluminum sulfate solution pulled out less rare earths than the 1 η aluminum sulfate solution. Accordingly, calcined rare earth faujasite can be brought into contact with dilute salt and acid solutions without exchanging rare earth ions. Crystal resistance to acid solutions Calcined rare earth faujasite retains its crystallinity after contact with dilute acid solutions. In contrast, Sodium X is made completely amorphous by the same treatments. Non-calcined rare earth faujasite falls between Sodium X and calcined

0 0 9 8 3 R / 1 6 5 8 _{ßÄD 0Rie} , _NÄL

I UO / / UU

• Rare earth X.

The retention of crystallinity after contact with various acid solutions and an ammonite post chloride solution is shown in Sig. 4 and in Examples 3-6. The Λ η hydrochloric acid and AIo (SO ^) - solutions destroy rare-earth X-crystals that have been unterhalb'343 ⁰ O (65O ⁰ IF) calcined. More dilute aluminum sulphate solutions cause less damage or destruction.

The resistance of a crystalline aluminosilicate, which has a molar silica / alumina ratio of 2.5, compared to acid solutions is completely unexpected and surprising. Acid resistance is usually associated with a silica / alumina molar ratio of over 5 »0. The above results show that fixed cations also give a zeolite acid stability can lend.

When more than 50 % of the rare earth ions were extracted by aluminum or hydrogen ion exchange, no significant amount of crystallinity was retained.

Examples 7-8

These examples show that sodium levels are very low can be achieved through multiple calcinations, when every galining is followed by an ionic exchange stage. The sodium removal from two samples is compared below.

009838/1658

Both samples (which were produced by the method according to Example 1) were ^{calcined in steam at 593 ° C. (11CC 0} I?) For one hour and then exchanged twice. One sample (Example 8) was calcined a second time in air between the two exchange treatments.

Example 7 Example 5

Sodium content, wt .- / £, after

first exchange with 1 η 0.26 0.26

Ge Cl-7 solution

Sodium content, wt .-%, after

second exchange with 1 η C, 09 0.03

Ce Cl -, - solution

In example 8, in which the sample was calcined between the two ion exchange stages, the sodium content was significantly lower i Apparently the sodium and rare earth metal ions are redistributed in the crystal positions after each calcination, whereby some of the remaining sodium ions are redistributed after each calcination becomes easier to replace.

Examples 9-10

These examples show that a rare earth faujs ^ it, which has been heated (calcined) is subjected to rapid drying without any significant impairment of the crystallinity can be flash dried.

A difficulty in the production of tlie bed or fluidized bed catalysts was a loss of crystallinity

009838/1658

BATH

of the uncalcined SEX component during spray drying, Two samples of SEX zeolite, both prepared according to the method described in Example 1, were dropped onto a hot plate that was heated to 760 ⁰ G (1400 ⁰ I ) had been preheated. The contact time of the SEX material with the plate was 30 seconds. One sample had not been calcined '. The other sample had been calcined in the manner described above at 593 ⁰ G (1100 ⁰ I ^1). Both samples were slurried in water and then equilibrated in ambient air for 4 days. The flash drying results of these materials at 76O ⁰ G (140O ⁰ P) are shown below:. ■

the Example 9
non-calci-
nated SEX Example 10
calcined
SEX Crystallinity Quick drying the 100 % 100 % Crystallinity after Quick drying 75 % 95 %

The above results show that the crystal structure is much more stable with rapid drying, when the rare earth paujasite is first calcined.

Examples 11-12 ■

These examples show that a Seitener-Erden paujasite (SEX), which has not been subjected to any heat treatment, a considerable amount when exchanged with an aluminum sulfate solution "Shows loss of crystallinity while a similar one

0 09838/16 5> ö

ORIGiNALINSPECTED

However, the product that has been heat exchanged is only one loses a small proportion of its crystallinity in such an aluminum sulfate treatment.

Samples of the material prepared according to Example 1 were exchanged with (1) aqueous rare earth chloride solution and (2) aqueous aluminum sulfate solution under the conditions described in the table below. Other samples were first heated (calcined) for 12 hours at 593 ° 0 (110O ⁰ I ¹ ) and then subjected to the same exchange treatments. The crystallinity was determined by the cyclohexane adsorptive capacity and in some cases also by measurements of the X-ray crystallinity. The following results were obtained:

00 98 38/1658

Treatment treatment βίο sung *

Kr. O 1 ep co OO 2 38 / σ> erv

Tabel

Example 11 SEX from Example 1

X-ray cyclohexane crystallinity, adsorption, based on the yo weight product from the

Treatment; number 1

Example 12

SEX from Example 1, heated (calcined) at 593 ⁰ C (110O ⁰ F)

over 12 hours ; _i

■, eb * nt genstrahlen- ■

Cyclohexane crystallinity,

adsorption, based on the product

% By weight from treatment no.

2% by weight rare earth chloride

2% by weight

15.8 8.1

100 %

20% 14.5

100 % . 90 ..%

«* ♦ 1000 ml of solution were brought into contact with 40 g of SEX, dry basis, for 16 hours.

cn

CD

The above figures show that the aluminum sulfate treatment the crystallinity (measured by cyclohexane adsorption) of the uncalcined sample (Example 11) was significant while there is no appreciable reduction in the crystallinity of the calcined sample (Example 12) brings about.

Example 15

This example illustrates the preparation of an active and selective cracking catalyst; the catalyst consists of a silica-alumina gel matrix, the rare earth aluminosilicate dispersed therein contains, which had been subjected to calcination prior to its incorporation into the matrix, to form the rare earth metal cations to "fix" in the aluminosilicate.

There were 0,4-54- kg (one pound) Rare earth Faugasit, which had been prepared according to Example 1, 12 hours at 593 ⁰ C (HOO ⁰ F) is heated (calcined). The calcined powder was then added to 2.84 kg (6.25 pounds) of water to form a slurry. To this, 0.1 kg (13.9 pounds) of sodium silicate and 3.18 kg (7.02 pounds) of water were added with constant stirring. An acid solution was then prepared by adding 12.95 kg (28.55 pounds) of water, 962 g (2.12 pounds) of Al ₂ (SO ₄ ) WI 2 O, and 440 g (0.9 pounds) of 96.7 pounds by weight '.entige H ₂ SO ^ were mixed. The silicate and acid solutions were continuously fed through a nozzle with

_B AD 009838/1658

. ■ - 43 -.

4-92 cm ⁵ / min of the ^{silicate solution at 19.4 0} C (67 ⁰ F) and 390 cm ⁵ / min of the acid solution at 5.5 ° G (4-2 ⁰ F) -mixed to form a hydrosol with a pH value of 8.5 to form the gelled in 1.9 seconds at 17.2 ⁰ C (GJ ⁰ I ¹⁾ to form a solid hydrogel. The hydrogel was then beaded in a conventional manner and treated every 2 hours with an equal volume of fresh 2% by weight aluminum sulfate solution for a total of 12 hours. Any sodium esters was flushed from the hydrogel by a single two hour treatment with a 1 percent ammonium sulfate solution. The Eyurogel was then washed free of sulfate ions, dried, ■ 5. Hours in air at 7O4 ° C (13OQ ⁰ E ¹⁾ calcined and steamed 24 hours at 643 ⁰ C (120C ⁰ I ¹⁾ with steam of 1.05 atm (15'psig). .

A second catalyst (ICo nt ro lip robe) was used in produced in a corresponding manner, but with the rare earth iPauiasite was not calcined prior to its incorporation into the matrix «,

The catalyst made using the calcined SEX material gave a conversion of 67 % while the catalyst made from uncalcined SEX material gave a conversion of only 39 % .

Example 14-

This example shows the effect of different base exchange solutions on rare earth aluminosilicate

009838 / IRS »BAD0W8.NAL

_ 44 -

fines that were initially calcined.

Wet cake rare earth aluminosilicate fines (55 wt% solids) were prepared as described in Example 1. These fines contained 1.3% by weight of Na, based on bone-dry material. The fines were divided into two parts; a portion was not subjected to any calcination, while the other durcii heating for 12 hours at 593 ° C (1100 ⁰ F) was calcined, was up to a residual moisture content of 2 Gevj .-% was reached. The moisture content was calculated as follows:

/ Weight loss with 1 hour of calci-

FpurhtiP-keit-- \ ^nierun S ^with a ge üeucircigKei-cs- y ^ _0710n φ _ρ ™ _ρ ™ <: πτ.

temperature

Weight loss with 1 hour calcination at 982 C (1800 F)

salary -: ■ -

Weight loss with 1 hour galcination at 982 C (1800 ° F)

Thereafter, each of the foregoing portions was divided into separate samples and each such sample underwent a base exchange with the various solutions given in Table III. In each case, 40 g of SEX in 1000 ml of solution are introduced and the mixture is stirred for 24 hours with interruptions.

009838/16580 ™ g ^j Nael inspected

Table III

ζ-yii ater

co2 percent rare eco Brd chloride solution

> 2 percent calcium * chloride solution

percent aluminum sulfate solution

2 percent aluminum nitrate solution

Cheese one-part cake

Fines 12 Ii at 593 ° C (11QO ⁰ E). ' .. calcined

Relative Relative

Crystalline-crystallinity,

Well in the cyclohexane, be st. by. Ha in the cyclohexane determined by.

Product, adsorption, cyclohexan-product, adsorption, öyclohexan-

Wt .-% wt .-% adsorption wt .-% G-exv, -% adsorption

15.8

15.8

8.1 13.6

0.7

0.07 0.07

0.04

14.4

14.5 14.3

100 %

100

100 100

CD

CD

From Table III it can be seen that the rare earth aluminosilicate fines that are initially calcined in all cases after the base exchange showed a residual sodium content of less than 0.1% by weight, while the fines that had not been calcined in this way have a residual sodium content after the base exchange from 0.5 to 0.6 wt%.

. Example 15

Y-type crystalline sodium aluminosilicate was prepared from the following two solutions:

A. Silica solution

1551 cm ^ (1870 g) colloidal silicon dioxide with a content of 0.361 g SiO ₀ per cm

B. Sodium aluminate solution

75 S NaAlO ₂ (41.7 wt .- #
30% by weight Na ₂ O)
330 g NaOH (77.5 wt -.%
1345 cm ³ H ₂ O

The aforementioned solutions were mixed at a temperature of about 27 G (80 F) by pouring Solution B into Solution A. The resulting mixture was stirred vigorously for about 1/2 hour to form a slurry. This slurry was then heat treated for 42 hours at a temperature of 93 ° O (200 ⁰ F). The solid material present was then separated from the supernatant liquid by filtration. The filter cake obtained was with a volume

009838/1658 bad ORIGINAL

V / ater washed per volume of initial slurry to free liquor to remove "At this time, the cake j 3 73 ° / ° solids and the solids contained contained 10.0 wt .-% Na.

The X zeolite prepared in the above procedure was base-exchanged with an aqueous solution which contained 4% by weight of mixed rare earth metal chlorides of the following composition: 1.57% gerchloride, 0.83 % lanthanum chloride, 0.17 % Praseodymium chloride, 0.58 % heodymium chloride and traces of samarium chloride, gadolinium chloride and other rare earth metal chlorides (1.5 Q SEGlVg fine particles). The Base exchange was carried out continuously for 2 hours at 82 ° G (180 ⁰ F). The base exchanged material was then washed chloride free and dried at 121 ° C (25Q ° F).

The composition thus obtained had a sodium content of 2.8% by weight and a content of Rare earth metal oxides of 14.6% by weight.

Example 16

In this example, rare earth aluminosilicate fines became of the X-type (SEX), as they were prepared according to Example 15, used. In the present example it is illustrates that in such rare earth aluminosilicate fines residual sodium present is removed much more easily by exchange with rare earth metal ions, when these fines are first calcined and partially becoming dehydrated.

- <00 98 38/1658

The rare earth aluminosilicate fines of the example 15 were made by heating in steam for 2 hours at different temperatures according to the information in of table XV "calcined.

Afterwards the parts were exchanged once over two hours at 32 ° C (18C ⁰ I ¹ ) with a 4 percent SECl-, -SE ^ O solution (g rare earth metal chlorides per g penalty parts), followed by filtration and washing the filter cake free of chloride ions «,

Table IV shows the following: if no initial Oalcinierung was applied exchange with rare earth resulted in a Eestnatriumgehalt of 2. 5 wt * -Depending _fl during one rush in the Oalcinierung ^ and subsequent exchange with rare earth on the values Eestnatriumgehalt from about 0.4 to 0.7 wt%.

IVaeh the aforementioned exchange with rare earths the fines were again subjected to steaming for two hours at the temperatures given in Table IY and then a second exchange with Rare Er & en., subjected to filtration, washing and drying. The results are given in Table IV. It can be seen that a second calcination with a subsequent Bia. Second exchange with rare earths resulted in a further »reduction of the est sodium, content, s * So shows © "Control sample" has an Eestoatiriufflon content of 2.1

BATH ORIGINAL

Table IV ' ^! ·

Production of rare earth aluminosilicate fines (SEY) with low sodium content (less than 0.1% by weight) from liatric aluminosilicate fines (NaY) 5 (dry sodium aluminosilicate fines 73 »3 % solids; 7C / 10 £: crystal reduction (shift); 10, 0% Na; 19.1 cyclohexane adsorption)

· '■ · O
co ■ Exchange of powdered components with 4% fcJJi; ui, "6ilpü solution, 2 h at 82 U, Jj'iltr. And Eq free -»
washing, drying at 121 C (250 ⁰ F) (1.5 g, SEGX, 6H ₀ OZg sodium aluminosilicate fines) Na = 2., 8% Treatment for 2 hours at 343 C treatment 2 h at 704 ⁰ O treatment for 2 hours at 51O ⁰ C
(650F), 100 % water- 100% water vapor, 0 atm 100% water vapor, 0 atm
. steam, 0 atm ^':, resulting in 0.8 wt .-% H ₂ O ■ · ■ .. ■■,, ■ ι ■ '■' ■:. .

Exchange 1x 2 h 82 ⁰ G Exchange 1x 2 h 82 ⁰ C co with 4% SEGl ₃ · οΗ _ο 0 with 4% SECl ^ · 6H _n O

^ (1.5s SEGl.i6H ₂ 6 / gSEY). (I, 5e SEGl,

- »Filtration, washing Filtration, ¥ / as" chung

o> Na = 2.5 % 'Na = 0.69 %

Air temperature sample treatment 2 h at 543 G

100 % water vapor, 0 atm

with 4fo SECl- · 6Ε ^r

h 82 ⁰ C

5 p

Filrraxion, Wench
Drying at 121 ° C
u ^ a - 2.1 Io ;

Exchange 1x 2 h 82 G with 4% SECl-. 6E ₀ O (1.5S SECl- ^ DHpd / filtration-; washing drying at 121 G ITa = 0.21%.

Exchange Ix 2 h 82 C,
with Mr% SECl
(1.5g SE01 ^ ₂
Filtration ^ washing
ITa = 0.55 %

Treatment for 2 hours at 704 ^u C
% Water vapor, O atü

Exchange 1x 2 h 82 O
with 4% SECl ^ .6H ₀ O
(1.5g SEGl ^? 6H _? 6 / gSEY)
Filtration, washing
Drying at 121 o
Na = 0.15 %

Exchange, 1x 2 h 82 ^U C with Ψ / ο SEOl, 6H ₉ O • (1.5g SEC1 ₇ ^ 6H e / gSEY filtration - ^ 'washing SEO ₇ = I9.4% Ha = O, 59

Treat. 2 h at 51O ^U C % water vapor, 0 atmospheres' leads to 0.8% by weight H ₃ O

Exchange 1x 2 h 82 C with 4% SECl _x "6H ₀ O (1.5S SECl? 6H _p e / g Filtration? Washing Drying at 121 C ITa = 0.06 %

90 /. Z, 9Sl

while the samples that are steamed and then with rare earths were exchanged, had residual sodium contents of about 0.06 to 0.2 wt .- #.

Example 16a

This example illustrates the influence of calcining rare earth aluminosilicate components ('SEX) for a subsequent base exchange treatment with an ammonium salt.

A wet Eucheii of ancient earth aluxainosilicate parts made according to Example 1 and the wet cake containing 46.2% by weight was divided into three parts. The first part was ^{dried in air at 116 0} O (240 ⁰ F) and then slugged into a sample 12.7 w & (1/2 ") diameter. The second part was 16 hours with a 1.4 weight percent Ammonium sulphate solution (3 S ammonium sulphate per g of fine particles) exchanged with bases, then washed free of sulphate ions with water, ^{dried in air at 116 0} G (240 ⁰ I?) And combined to form a sample of 12.7 now (1/2 ") diameter ( slugged). The third part was first in air at 11ö ° C (24C ° F) to a ßestfeuchtigkeitsgehalt of 8.7 wt .- # dried and then by one-hour treatment at 593 ° C (110o F ⁰⁾ with 100 percent water vapor at 0, 7 atmospheres (10 psig) partially dehydrated to give a product with oineni excess moisture content; of 1.4 Gevj .-% au obtained. Then the partially dehydrated fines were treated with ammonium sulfate

009838/1658 _{BAD 0RielNAL}

solution "alkali-exchanged, washed, dried and in the same way, as that in connection with the second part described was slugged on a sample.

Table V shows the treatment conditions and the properties obtained. It can be seen that sample 1, both of which had only been dried, had a sodium content of 1.27% by weight and a rare earth content of 26.5% by weight. Sample 2 _5, which was subject to the base exchange with ammonium sulfate, showed a residual sodium content of 0-5 % by weight. earth rG-ehalt only 20.4 wt -.%, respectively .. In contrast the sample showed liierzu Jj which was first steamed to a Eestfenchtigkeiiisgfehalt of 1,4 wt .-%, and base-exchanged danack, a Eestnatriumgehalt of only O ₃ 12% by weight. In addition, the sample showed a "particularly advantageous and desirable result: although the ammonium sulfate exchange with ammonium sulfate was very effective in reducing the sodium content, it did not result in any appreciable reduction in the rare earth content, which remained much more so at 25 * 9 wt., ^.%, compared to 26.5 wt.% for the "control sample" which had not been subjected to any base exchange.:

In äei üabelie Vl are further test values listed for each of the specified samples, it is shown *

009 838/16

ORIGINAL. INSPECTED

licii that | a.ie sample 3 regarding superior results Conversion and hexane cracking resulted compared to the Samples 1 and 2.

009838/1 es 8

Table V Water vapor and heat resistance of rare earth aluminosilicate fines (SEX)

O ^ C ⁰ T) / air ο Ι CD OO CD c ?? cn 03

= 1.27

Rare earth aluminosilicate fines, wet cake

sample

^ Base exchange χ 16 h with 1.4 percent (HH) S0

₄₂₄
(3.0 s (DH ^) ₂ SO ₄ Zg SEX)

washed free So/,- Drying
C (240 ⁰ F) / air 116 °

ITa,
SE ₀

; .-% = 20.4 Sample 3
~ 3

Drying 116 ° O (240 ⁰ E ¹ ) / air

Steam treatment 1 h / 593 C (1100 ° F) / 100% V / water vapor of 0.7 atg (10 psig)

3? Euchtigk. = 1,

SO, .- washed free]

Drying
116 ⁰ O (24O ⁰ F) / air

ITa, wt%

= 0.12 = 25.9

CD

Base exchanges

1 χ 16 h with 1.4 percent ()

CD CD

Table VI

'.Tasserdazipfcestänaislceit, rare earth aluainosilicate fines

sample

Sample 2

sample

1.2? Wt% K

0.45 wt%

% H

0.12 wt% Ha

before c.er naen the Jo test urine test ua _t q loss (D (2)

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(D (2) (1) (2)

? 0, S 15.2

54 ·, δ

SJ , *

. ". aseerdarrpfbeheld, 24 h / 643 ° 0 (12C0 ⁰ 5 ¹ ) / 1GO °, b water vapor / 1.05 atü (15 psig) ^ ■ ua ~ ä £ ru-was £ earth vapor resistance test, 5 li / 548 ^o 0 (1200 ^o I ') / i00 ^ water vapor / 7.03 atü (iOO

'-422 "C ^{(0 -CC?)?} Hourly PuaunGtrömuncs ^ eschv / indiEkeit the lüssiGl l-eit (LIISV) = 16;

cn

CO

O CD

Example 17 '■'.

It Yrardeii rare earth aluainosilicate parts produced, as described in example Λ is. This I ^? one had a rush Kestnatriumgehalt of 0.4 wt "~% The fines were dried * then divided at 116 ° C (24O ⁰ F) mirdeii the fines into five parts. The first part (sample 1), which served as a control sample, was incorporated by mixing in an aqueous slurry of a silicon dioxide-aluminum oxide matrix. The remaining four portions were each subjected to galcination by heating for 2 hours at 34-3 ° 0 (650 ° F) in air. The first of these portions (Sample 2) was then incorporated into a silica-alumina mixed gel matrix as described above, the remaining three shares. (samples 3-5) were formed into specimens of 12.7 in®- (1/2 inch) diameter, (650 ⁰ F) for 2 hours at 34-3 ° G in air and then steamed over different periods of time at 648 ⁰ C (120C ⁰ F) with 100% steam at unterschiedlichen'Drücken and then incorporated into a Siliciumdio ^ IYD-Aluminiumoxydmischgelmatrix.

Each of the above five samples were then annealed for 2 hours at 34-3 ⁰ C (650 ° F> in air, processed into 12.7 mm (1/2 inch) and Durehmesser dann'wurden linität the relative, crystallization and the Rare Earth content (expressed as rare earth) determined. From Table 11 it can be seen that sample 1, the fines of which had not been subjected to an initial partial dehydration, a

showed relative crystallinity of 0.7 and a rare earth content of 1.16 %. In contrast to this, each of the samples 2-5j in which the fines were subjected to partial dehydration showed relative crystallinities of over 10 and rare earth contents of approximately 2% by weight.

The five samples were then tested for water vapor resistance, by steam treatment over 24 hours at 648 ⁰ G (1200 ⁰ E) (15 psig) with 100% steam at 1.05 atm, and then the relative crystallinity was measured. The control sample showed a relative crystallinity of 0.7. The crystallinity of the sample was 5) 5 and that of the samples 3-5 was 10 or more.

Each of the above catalysts were on their own lcatalytisclie A'ctiviü-Ml: checked. Samples 2-5 aeigtea ULVa-IUlanzen- ^ -.-, iscie .. 45 and 53 »2%, compared with one U.av; aiiliarLj; vv. °; ', ·: ι ^ for sample 1. Beyond that were the gasoline yields for each of Samples 2-5 were significantly better than for the catalyst of Sample 1.

009838/1668 _BAD ORISINAL

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to Table VII:

Crack test ^w '- SAMPLE 1

conversion , io 29.6 Gasoline, ok 24.9 Z ^- X of
O ₄ , / ο 5.4 Drying gas , i> 4, o Coke, ok o, 7 Crack test ^ ' - SAMPLE 2 conversion , io 46.6 Petrol, ° / o 38.6 c ₄ , io 9.6 Drying gas , io 5.6 Coke, ° / o o, 9 Crack test ^ ' - SAMPLE 3 conversion , ⁰ Jo 53,2 Petrol, ° / ₀ 44.6 C ₄ , ° / o 11.1 Drying gas ti ⁰ 6, o Coke, ok o, 9
\ Crack test ^ ⁵ ' I.
- SAMPLE 4

Conversion, i> 49.9

Gasoline,? B ■ 41.9

C ₄ , io 1o, o

Dry gas, ° / o 5.4

Coke, io 1, o

0 0 9 8 3 3/16 5

Crack test ^ ³ '- SAMPLE 5

Conversion, $ 45, o Gasoline, i ° 37.4 9, o Tr'ockengas, ^c / o 5.3 Coke, ok 1.1

(T) "XXX / XX" Indicates relative crystallinity or Change (shift)

(2) 7.5% by weight of rare broth aluminosilicate fines and 92.5% by weight of silicon dioxide / aluminum oxide quantity! Matrix (9o ^ SiO ₂ , 10 $ Al ₂ O ₅ )

(3) 482 ⁰ G, IHSV = 4.5, catalyst / oil ratio = 1.3

O O 9 8 3 8/1 6 5 8 ^ ORIGINAL

Example 18

This example shows the influence of the heating time on the content of residual alkali metal after the ion exchange,

10 g of zeolite SEX, which had been prepared according to the procedure according to Example 1 and contained 1.3% by weight of residual sodium, were stirred for 24 hours with 100 ml of a 1 η NEI ^ Cl solution. Prior to this treatment, each 10 g sample of a heating · at 121 ° C was unterworfen.worden (250 ⁰ I?) For the specified time in Table VIII.

Table VIII

Since in the oven
121 ⁰ C (25O ⁰ F),
Air atmo sphere
hours ITodium content according to
IIELCI exchange,
Weight% Ka based
dust-dry
Materials Moisture content *,
g H ₂ O. Each 100 g
dry zeolite 0 1.30 51 1 0.83 22nd 4th 0.62 17th 24 0.43 15th 72 0.43 15th

* 3 determined by loss on ignition at 1100 ⁰ G over 1 hour.

A stay of more than 24 hours followed from the ion exchange did not result in a further decrease the residual sodium content below 0.43% by weight. It should be noted, however, that by using higher temperatures with subsequent ion exchange, the residual sodium content is

009838/1 658

BATH ORIGINAL

borrowed below 0.43 wt .-% can be reduced (cf. e.g. Table I, example 3) «

Examples 19 - 28 "

. These examples explain the production of zeolite -aU3 _o on _a -ssiaterialien. (Examples 29-45 describe the results of exchange treatments of the zeolites according to Examples 19-23, both calcined and uncalcined, with various solutions).

Example 19

üalciumoffretit * Synthetic offretit. (SeolitL T) • would be produced as described in Example 1 of US Pat. No. 2 S ^ O ψ '/ cL . The ewascliene product was aged as a wet filter cake. The LIo! Composition of this s; / ntnc-table Offretite-;, based on dust-dry materials, was 0.3 ^ iTa _? 0 «0.91 K ₂ O.Al ^ O ₇ ..7.2? SiÜ _? or ^ ittelt. The wet cake contained 34 % ■■ test substances. and'6G 50 V / water.

9 ^f ^ \ L this nasaon Offretit — i ^! The filter cake was subjected to three set exchange treatments with BOG £, ^ pi'ozeii'ti ^ er GaGl ₀ solution for each exchange. The exchange rate was 'jL> , ^ ⁰ G (ij »i / ^ü l0 and the time to change for each exchange was _o hours. The cake was made between exchanges, schbehaiialun {j, en mil; aachen. liacli the last "Ausausca v / urde cakes stored in the washed state as a wet cake.

-sentence

Example 20

Lanthanum fretite. The same working method was used as in Example 19, with the exception that a 3> 5% by weight LaCl solution was used instead of the 5% CaCl ₂ solution.

Example 21

Katriumoffretit. The same procedure was used as in Example 19, with the exception that a 10 percent by weight ITaCl solution was used _{instead of the 5 percent by weight GaGl 0 solution.}

Example 22

Ii ¹ err ο ammo niuiiiz eolite T. llatriunzeolitli ΐ was prepared as described in US Pat. No. 3,130,007. Contained the washed wet cake, 40, <> solids and 60% water, had the molar composition nächstohende, based on bone-dry material: 1.02 Ea ₂ O. Al ₂ O ₅ . 5.0 3iO ₂ *

75% wet cakes were subjected to 10 batches of exchange treatments with 300 g of 10 percent ferrous unionium sulfide solution (formula weight 392.16) per exchange. _t: '• or batchwise contact took place over 12 Sbundeii at 90.5 ° ^ (l ^^ ⁰⁾ Each last from Bausch the cake was gewaechen and 16 hours at 121 ° 0 (250 ⁰ F) dried. The nitrogen of the ferroammonium zeolite Y was 1.8% by weight of Na.

BAD ORiQINAL 009838/1658

Example 2g

Chroiazeolite X was prepared according to the procedure according to

Example 22 was prepared, with the exception that a 10 percent solution of chromium chloride hydrate (GrOl _7. 6HpO) with a pH of 1.9 was used instead of the ferroammonium sulfate solution. The dried chromium zeolite X had a sodium content (as Ha) of 1.5% by weight.

Example 24-

Iron mordenite. It became synthetic sodium mordenite (Zeolon Ea from Norton Company) was used. The molar composition, based on the dust-dry material, was 0.8 ITa-O

AlJD-, · 3.5 OiO ₀ · The moisture content was 15 % · 2 $ έ

75% of this zeolite were ion-exchanged according to the procedure described in the example, with the exception that a 5 percent ferric chloride solution (FeCl ^) with a pH of 1.3 was used instead of the ferrous ammonium sulfate solution. The dried product contained 1, 9 G.ew. - ° / o sodium (as ITa), based on dust-dry material.

Example 25

ChroHUüordenit. The chromium mordenite was prepared according to the working method according to Example 24, with the exception that a 10 percent chromium (III) chloride solution (CrOl ₇ ) with a pH of 1.9 was used instead of the ferric chloride solution. based on dust-dry material, amounts to 2.9% by weight as Ia.

BAi ORIGINAL Q09838 / 1658

Example 26

Lanthanum zeolite X. Eodium zeolite X was prepared according to U.S. Patent 2,882,244. The washed filter cake had the following molar composition: Na ₂ O. Al ₂ O-, 2.5 SiO ₂ . The cake contained 55% solids and 45 % water.

400 g of this wet cooking were subjected to six batches of ion exchange contact at 95 ° C. (195 ° C.) with 1500 g of 1C percent CaCl ₂ solution per contact. The final water-washed product was dried for 16 hours at 121 ⁰ C (25O ⁰ F). The product consisted of calcium zeolite X which contained 0.2% by weight of Wa, based on the dust-dry material.

50 g of the calcium zeolite X became three batches Exchange touches at 90.5 ° (195 ° F) using 74-0 g of 3.5 percent LaCl ^ solution per contact subjected. The cake was washed with water between exchanges. The final product was in a washed state stored as a wet filter cake.

Example 27

Lanthanum mordenite. A sample of natural mordenite was analyzed and the following composition, expressed as percentages by weight, was found: K »1.6; Ha = 3.55; SiO ₂ = 72, IjAl ₂ O ₃ = 15.7; Oa «2,4-5. There were 10.8 g of this material and powder coated with a 0.3 η LaCl, solution 1 otunde at 204- ° C (400 ⁰ F) under the autogenous pressure

009838/1658

BATH

brought into contact with the solution. The sample was washed and dried. This product, ie Lanthanmordn | 3it, had the following composition, based on the dust-dry material and stated as percent by weight: K = 1 ₉ 06; Fa = 1.29; SiO ₂ = 72.6; Al ₂ O ₃ = 14.5; La ₂ Q ₅ - 6.93; Ga = 1 The moisture content of the product was 10 %.

Example -28 '

There were 20 g of Oalciumoffretit in the form of the wet cake, which had been prepared as in Example 19, mixed with 100 g of a 5 "5 percent strength by weight aqueous IILCl solution" Temperature of 24 ⁰ O (75 ⁰ S ¹ ) stirred. The solids were then filtered off, washed, dried and analyzed for potassium. The potassium content (K) of the product, based on the dust-dry material, was 3.3% by weight (cf. Table 12). .

■ Example 29

There were 20 g of Galciumoffretit in the form of the wet cake, exactly the same material as was used in Example 28, placed in a crucible. The covered crucible was calcined for 3 hours at 538 ⁰ O (1OOO ° F). By Galcinierung 10.6 g V / ater out were - .. triebeu * The Geuarntmenge of calcined solids, ie 9 "^ L" -was 10.6 ^ water and 100 grams of 5j3 ü'ewichtsprozentisen IIII _Z j.Gl -Ijösun _b -: mixed »; The sample was in a

00 98 3 8 /.16 ^; S-fl *,: · ... ■

ORISINAL

1 1 bottle for 2 hours at a temperature of 24 ° C (75 ° F) touched. Then the solids were filtered off, washed, dried and analyzed for potassium. The Ealium Content (K) of the product, based on the dust-dry material, was 2.1% by weight. A comparison of Examples 28 and 29 shows that the remaining potassium in the calcined sample is more easily exchangeable than the remaining potassium in the uncalcined Sample (see Table IX). .

Examples gO - 45

Ion exchange treatment was carried out using the starting materials shown in Table IX either without a previous calcination step (Examples 30, 32, 34, 36, 38, 40, 42 and 44) or after calcination (Examples 31, 33, 35, 37, 39, 4-1, 43 and 45). In all cases, the ion exchange was carried out using a two hour contact with the exchange solution. The exchange solutions used in detail and the results obtained are summarized in Table IX. In either case, the calcination made the residual cation content more easily exchangeable.

009838/1658 bathroom

co 09 to

Table IX
Ion exchange of calcified and non-calendered zeolites

Bsi el Discarded -ats rl al hau ό ΐ siic hi Ge i G h ■ · spi anvre s e nd e s 5.3St- Kr. ' Kati G- , Art.

Wl rse oehandluris

20th

29

30th

32

33

GaleiuEoifretit '(.Example 19)

Lanthanofiretite K (3example, 20)

iiatriuaoffretit S " (Example 21) · '

34
35 Ferroaatnoniua Y
(Example 22). 23) Ka 35
37 Ohr.om Y
(Example ^a 24) Ka 38
39 (Example %) ■ Ka 40
41 (Example 26) 'Ka 42
43 · Lanthanum X
(Example Lanth'.ir.r.ordenit
(Example 2?) Approx 44
45 K ₅ C

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hen never tracked «20.0

(calcined 3h b.538 ^a 0,

538 ^a

, ISaiokuchen never drunk «(calGiniert 3h ΐ> ^ο

/ Kaß cake never dried. (calcined for 3 h ⁰ C b.538

/ dried. i6h at 1'21 ⁰ O (calcined 3h b.53S ° C

, dried. 1oh at 121 ° 0 (calcined 3h at 538 ° C

/ dried. 16 h at 121 ⁰ C (calcined 3h b.538 ° C

, dried. ySh at 121 ⁰ C (calcined 3, h at 538 ° 0

/ KaSi throat never dried out. (c? lined 3h at 538 ° C

₍ dried ion at_121 ⁰ C (calcined 3h at 538 ° C

'9, 4 ■ 20, 0, 7 * 8th; 15 » O" 6) 1 10, 0 7 * 10 » o _: 7, 7 ' 10, S, .81 10, 0 s _s , 9 20, Ö 9, 3 6, 0 5, 4th

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it

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to (M OJ OJ ro CVj * - ο «- ο

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ο oj cvT * - d

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OO

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BATH

43

to Table IXi.

+ Wet and calcined samples each contain zeolites the same weight of dust-dry pesticides

(1) based on dust-dry material

009838/1658

Claims (7)

Patent claims 1. Yerfahren for the production of crystalline Aluiüinosilicaten low alkali metal content, in which the aluminosilicate containing mono- and / or divalent cations is brought to bring about a base exchange with a solution of other cations in contact, characterized in that the aluminosilicate before the base exchange heated to a temperature in the range of about 65 - 927 O (15Ο - 170O ⁰ P) until the moisture content is reduced to below 90% of the saturation value. 2. The method according to claim 1, characterized in, that one uses an aluminosilicate which contains trivalent cations, in particular rare earth metal cations, which by a base exchange has been introduced prior to heating, and heating at a minimum temperature of 121 G (2 ^ 0 F) performs. 3. "The method according to claim 1 or 2, characterized in that the heating is carried out in a temperature range of 648-760 ⁰ C (1200-1400 ⁰ F). 4. The method according to any one of claims 1 - 3i, characterized in that the final base exchange is continued until the aluminosilicate has a sodium content 009838/1658 BATH ORIGINAL in the range of (3.03 "to 0 _r 2 wt.%. 5. Process according to one of Claims 1-4, characterized in that heating is continued "until the moisture content of the aluminosilicate is less than 20 fo of the saturation value". - 6. The method according to any one of claims 1-5 » characterized in that the aluminosilicate the Base exchange or heating in the form of a composition feeds with a matrix. 7. Method.nach one of claims 1-6, characterized in that the aluminosilicate according to the Subjecting base exchange to flash drying.