DE1442888A1 - Fluidized bed catalyst and process for its preparation - Google Patents

Description

Socony Mobil Oil Company, Inc., New York, N.Y. (V.St.A.)

Fluidized bed catalyst and process for its

Manufacturing.

The invention relates to catalysts and Catalyst compositions or their production and use. In particular, the invention relates on fluidized bed catalysts (fluid catalysts) or processes for the production of fluidized bed catalysts with improved properties and processes using fluidized bed catalysts.

A variety of fluidized bed catalysts are currently available and these generally include fine

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Particles of catalytically active material that lead to a Suspension in a stream of a fluidized fluid are capable. It has been found that a wide variety of chemical Reactions promoted by contact with a fluidized bed of such particles or in their effectiveness can be improved.

A number of properties contribute to the successful use of finely divided catalysts in the form a fluidized bed or a fluidized bed. More important properties include abrasion resistance, Uniform porosity, easily controlled particle size, a satisfactory level of catalytic activity and persistent catalytic properties.

Fluidized bed catalysis is based on a variety of chemical reactions including both inorganic ones as well as organic reactants and have been shown to be particularly useful in the petroleum industry is useful where such working methods have found application to reforming, isomerization, hydroprocessing and induce cracking or conversion. The catalysts according to the invention show general Applicability in catalytic fluidized bed processes and excellent suitability for the conversion of petroleum feedstocks.

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Catalytic fluidized bed processes are for Conversion of hydrocarbons and for performing other reactions with petroleum-derived materials, e.g. reforming, isomerization and hydroprocessing. Albeit conventional Working methods were generally satisfactory, development work continued with the purpose been, the fluidized bed catalysts, the methods for the production of fluidized bed catalysts and the processes " to improve using such catalysts.

It has been found that there are catalysts which have extremely high activities, especially for Conversion of hydrocarbons. The magnitude of the activities of the novel catalysts is actually so high that ^ m conventional cracking processes and apparatus fail to take full advantage of their high activity. It was however, it has been found that the activity of such catalysts can be lowered to a level by certain methods which can be satisfactorily and practically used in conventional cracking plants leads to a considerable increase in the effectiveness of standard procedures. Furthermore, there are new working methods has been developed to take full advantage of the higher activities present in such catalysts.

Accordingly, a main feature of the invention is the creation of novel fluidized bed catalysts which

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excellent activity and improved physical Have properties.

Another feature of the invention is the creation of novel highly active fluidized bed catalysts, which include crystalline aluminosilicates.

Another feature of the invention is its creation of processes for the production of overactive fluidized bed catalysts, that have good abrasion resistance and controlled particle size and density.

Yet another feature of the invention is that
Creation of highly active fluidized bed catalysts, particularly useful in hydrocarbon cracking processes and plants
are useful and have excellent selectivity, reduced
Have a tendency to form coke and good reactor and regenerator stability.

Another important feature of the invention is to provide methods of making and using the novel fluidized bed catalysts according to the invention.

The above features and purposes as well as the technical advantages achieved by the invention are evident from the The following detailed description of the invention emerges.

As already mentioned, the catalysts according to the invention have such an unusually high activity that their full utilization in conventional hydrocarbon conversion processes cannot be achieved. If that-

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term catalysts are subjected to conventional test methods to determine their effectiveness for hydrocarbon conversion they initially appeared to be relatively worthless. However, it was later found that this was due to the Overactivity of the catalysts was due. Newly developed test methods then showed that the novel catalysts In fact they can be extremely useful for hydrocarbon conversion if given additional treatments which would normally reduce the activity of a conventional catalyst.

The standard catalyst inspection test used for the hydrocarbon cracking catalyst test specimen is widely used, both for the preliminary examination and for the control during the technical Use by testing activity is known as the "CAT-A test". This test is a specific Borrowed O&T Texas gas oil by passing over the catalyst in a plague bed at an hourly space velocity the liquid (LHSV) of 1.5 using a catalyst / oil ratio of 4/1 with an average Real temperature of 427 ° C (800 ° P) and below atmospheric Cracked pressure. The percentage of gasoline produced is that Activity index (A.I.). When the fresh crystalline aluminosilicates If checked in this way, they produce little gasoline and relatively large quantities of liquefied gases and

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Coke. According to this, as already mentioned, these materials appeared to be catalysts for the cracking of hydrocarbons to be unsuitable.

A new test method was therefore developed which with small amounts of feed and catalyst and with a much higher accuracy of control than the CAT-A test can be operated and is able to follow the course of the reaction in successive periods of time and at determine exact temperature levels.

This test can be viewed as a micro-method. The su tested catalyst is in a refractory Rohr {^ © «n, -e-i-ft technical glass with a high silicon dioxide content is suitable) with an outer diameter of about 8 mm and inserted therein through suitable porous plugs, e.g. from Glass wool, held as a compact body. This reaction tube is placed in an electrically heated oven. A suitable furnace is, for example, one of about 2.5 inches (1 inch) inside diameter. At about 5 cm of catalytic material are an oven about 15 cm (6 inches) long and. a reaction tube about 30.5 cm (12 inches) long suitable. A thermocouple is inserted into the annulus surrounding the reactor and the ends of the furnace are opened Glass wool clogged.

Ss is ersiohtlioh that the physical dimensions this device are such that a very precise regulation

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the reaction temperature can be achieved. At both A three-way valve is arranged at the ends of the reaction tube. To introduce the reactant, an inert gas such as helium is passed through a layer of the liquid reactant bubbled so that it carries the reaction material into the reactor. The three-way valve on the inlet side allows pre- and post-reaction flushing, if desired, and still allows introduction of the regeneration gases after the investigation of a reaction, if this is desired. The three-way valve on the outlet side allows all draining material to be directed to a product collection device or the draining material during a certain time interval or at a certain temperature for sampling and analysis.

The chromatographic analysis of such samples allows the results to be determined very quickly and precisely the transformation in relation to numerous variables. The quantities of reactants carried in with the inert gas are determined by the partial pressure of the reactant at the temperature of the feedstock vessel and controlled by the flow rate of the gaseous carrier! precautions can be taken to control the temperature of the reactant feed.

When examining the highly active crystalline Alueinoeillcatmaterials according to the above-described

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Method were hexane as the reactant and helium gas introduced in an amount of 20 cnr / min as that inert carrier gas selected. The helium and hexane were kept at room temperature and atmospheric pressure.

When tested in accordance with the above method, it was found that the crystalline aluminosilicates have quite surprising levels of activity, which are far higher than previously thought possible.

For example, if a certain rare earth exchanged synthetic crystalline aluminosilicate, which has the crystalline structure of faujasite, is treated in this manner with hexane at an LHSV of 0.5 and a partial pressure close to about 150 mm at a temperature of 240 ° C (4-65 ⁰ F) was tested over a period of 10 minutes, a conversion gave about 20% of the hexane. In contrast to this, on an amorphous silica-Aluminiumoxydkatalysator conventional type, having an activity index of about 46 in accordance with the CAT-A-Test, are substantially not detected Conversion of hexane until temperatures of the order of 500 ⁰ C (930 ⁰ P ) are reached. An examination of the reaction rate and the temperature relationships involved leads to the conclusion that the reaction rate constant over the crystalline aluminosilicate is up to 10,000 to 15,000 times that over conventional ones

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amorphous silica-alumina gel catalysts.

The investigation of a fairly wide range of crystalline aluminosilicate materials led to the finding that that the stated activity is actually present and is not simulated. There were many crystalline ones Aluminosilicate materials were examined and they were found to have comparatively high activities. Continue to have the test results proved to be reproducible. Similar Tests performed with decane confirmed the results, and these results are in agreement with other, catalytic abilities of the substances and they can be related and correlated with general knowledge of catalytic processing.

The materials exhibiting the overactivity described above all belong to the general type of crystalline aluminosilicate materials of both natural and synthetic origin.

In general, the crystalline aluminosilicate materials contemplated by the present invention have in the Salt form the following general formula:

M ₂ O. Al ₂ O,. YSiO ₂ . ZH ₂ O;

where η is the valence of the metal cation M, Y is the number of moles of silicon dioxide and ZHgO is the water of hydration.

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Crystalline aluminosilicates of the above structure, sometimes referred to as crystalline zeolites or molecular sieves, can be activated by removing the water of hydration; when activated in this way are, they have posts that promote catalytic Conversions are capable. After dehydration, the aluminosilicates are found to be highly porous and they possess numerous surface cavities and internal pores, which connect the cavities. These pores are essentially constant in diameter, generally in the range of 3 to 1.5 Angstrom units; the exact size will depend on the composition and structure of the particular aluminosilicate.

To modify the properties of such substances, can be the original cations of the aluminosilicates, usually Sodium, potassium and / or calcium, can be changed by ion exchange processes. It has been shown that the Ion exchange of the original ions is a particularly favorable one Effect on the catalytic cracking properties of the crystalline aluminosilicates.

Suitable crystalline aluminosilicates for use in the preparation of the fluidized bed catalysts according to of the invention include both natural and synthetic crystalline aluminosilicates or zeolites. ■

There are a considerable number of natural crystalline zeolites and among these, faujasite has proven to be

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proved to be a particularly useful material for the preparation of the catalysts according to the invention. Others satisfactory natural crystalline zeolites are for example analcite, paulingite, Clinoptll © llt, ferrierite, chabazite, Gmelinite, Levynite, Erionite and Mordenite.

The most suitable synthetic crystalline aluminosilicates include the synthetic faujasites both X and Y types, which have a crystal structure correspond to those of natural faujasite. The preparation of such X-aluminosilicates is in the United States patent 2,882,244. The manufacture of the Y-type is described in Belgian patent 577,642.

Another important synthetic crystalline zeolite that does not have a corresponding natural form is zeolite A. The preparation of this crystalline aluminosilicate is described in U.S. Patents 2,882,24 and 2,982,612 .

Other suitable synthetic crystalline zeolites which can be used in the context of the invention include, for example, zeolite Y, zeolite B, zeolite D, zeolite E, zeolite F, zeolite G, zeolite H, zeolite KQ, zeolite J, zeolite L, zeolite M, zeolite KM , Zeolite Q, Zeolite R, Zeolite S, Zeolite T, Zeolite U, Zeolite W, Zeolite Z and others.

Since the natural crystalline aluminosilicates are not * all «available in sufficient quantities , the

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synthetic zeolites more often as starting materials for the preparation of catalysts according to the invention used.

Very suitable crystalline aluminosilicate catalysts can be prepared, for example, indemman sodium-X molecular sieve is subjected to ion exchange with a solution of rare earth chlorides, until the sodium content to about 1.0 to 1.5 wt -.% Of sodium is reduced to about 25 wt. -% of rare earth ions, calculated as SE ₂ (K, are introduced.

The various forms of synthetic crystalline aluminosilicates are sometimes also indicated by suffixes, e.g. Kk, 5A and lj5X zeolite. The 4A and 5A materials are zeolites with a crystalline Α structure, which have a pore size of about K A and 5Ä3, respectively. A 1.3-X material has an X crystal structure and a pore size of approximately 10 Angstroms in diameter.

The aluminosilicate materials can also be converted to the H or acid form in which hydrogen ions occupy the cation sites. Such a conversion can be followed, for example, by ion exchange with ammonium ions from heating to drive off NH- ,, or by Controlled acid leaching can be achieved with a hydrochloric acid solution or a similar reagent. In general, the Η-shape more stable in materials that have SiOg / AlgO ^ ratios

SAD ORlQ) NAU

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of 3.5 or higher. Useful catalysts are also created through a combination of ion exchange treatments. For example, the crystalline aluminosilicates can be converted by acid leaching into the H- or acid form and then with a solution of rare-earth metal can be ion exchanged salt to catalysts, such as with the rare earth and hydrogen exchanged mordenite, with rare earth and hydrogen exchanged synthetic faujasite to generate, from the X or Y type, and many other useful ion-exchanged catalysts. It will also be seen that more than one type of metal cation can be used to ion exchange the crystalline aluminosilicates and that the order of the ion exchange treatments can be varied . For example, acid leaching to introduce hydrogen ions can precede or follow an ion exchange treatment to introduce metal cations.

For the purpose of comparing the overactive catalysts according to the invention with conventional catalysts , a scale has been developed which is based on the conversion activity of a conventional amorphous silicon dioxide-aluminum oxide gel cracking catalyst (10 % aluminum oxide) with an activity index of about 46, measured according to the CAi A-Te st, is based. This conventional cracking catalyst is assigned a relative conversion activity d equal to one. E3 was found to be a lot of the overactive

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Aluminosilicates according to the invention have a ^ - value on the order of about 2000 and above.

After once the availability of a whole class of catalysts with exceptionally high activity has been found, the development of methods for controlling the activity of such materials is special Attention has been paid to these substances in currently available catalytic devices, which have required very large economic expenditures on the part of the petroleum industry and other chemical industries, to be able to use.

Although it can be foreseen ^ that novel "process and devices which take advantage of the high activities of crystalline aluminosilicate catalysts are able to be developed and applied soon, the initial efforts at adaptation have become of the catalysts aimed at conventional process engineering.

This direction of investigation has led to the finding that the extremely high activities of the crystalline Aluminosilicates by combining the crystalline aluminosilicate component with a less active or inert material, by steam treatment, by exchange the original metallizations * usually sodium, Potassium and calcium, against other metal cations or water

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material ions and can be modified by calcination.

A preferred method of reducing the activity of the aluminosilicate catalysts is to combine the aluminosilicate with a relatively inactive matrix material. The term "relatively inactive" is used herein to denote materials which have catalytic properties in the conventional range of d. = 1, or materials that are less active. For example, a rare earth aluminosilicate with an activity on the order of cA ^ 2000 or higher can be reduced to an activity level useful for current cracking technology by incorporating about J> - 15% of such an aluminosilicate in a matrix of amorphous silica-alumina gel an activity on the

iA- -scale incorporated one and then a steam treatment performs.

It can be seen that diluting matrix materials of various levels of activity can be used in this manufacturing process and, furthermore, any amount of the highly active material can be used to bring about the desired level of activity in the final catalyst. Suitable matrix materials that can be incorporated into such catalyst compositions are, for example, inorganic oxide gels, e.g. those of silicon dioxide, zirconium oxide, aluminum oxide, magnesium oxide and combinations thereof with one another, clays, aluminum oxide,

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Metals and refractories.

As a modification of the above method of combining substances to reduce the activity of crystalline Aluminosilicate catalysts can have the active crystalline aluminosilicate component in finely divided form mechanically with fine Particles of lower activity are mixed, e.g. with sand and other silicas and silicas other than sand, metal oxides, clays, and others relatively inactive components. As the frequency of contact between reactants and catalyst in a fluidized bed from a statistical point of view, contact between the highly active aluminosilicate particles and the reactants may occur on average by adding and mixing in the desired proportion of relatively inactive particles Fluidized bed, together with the crystalline aluminosilicate catalyst particles, be managed.

It was also found that the activity dex crystalline aluminosilicate catalysts in question can be reduced by a steam treatment process and that controlled steaming can be applied to catalysts with any desired level of activity to create. The degree of dampening of a particular catalyst to achieve a desired level of activity is largely dependent on the type of catalytic material.

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For example, the crystalline aluminosilicate catalyst, in an atmosphere containing between about 5% and about 100% steam, at temperatures of about 260 - 87i ⁰ C (500 - l600 ° F) and pressures ranging from subatmospheric to up to several hundred Atmospheres are treated until the desired modification of the properties of the catalyst is achieved.

Cations that are suitable to replace the original cations of a crystalline zeolite by Ion exchange processes for the purpose of modifying their catalytic properties Properties that can be used are, for example: Ba, Ga, Ce, Li, Mg, Ag, Sr, Zn, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Mn, Be, Ti, Zr, Hf, V, Cr, Fe, Co, Ni, Cu, Cd, Al, Sn, Pb. A relatively small one The amount of polyvalent metal cations improves, for example, the structural stability of the crystalline aluminosilicate, into which it has been introduced, to a considerable extent, particularly in terms of thermal and water vapor stability of the material.

As an example of activity control by ion exchange, a crystalline aluminosilicate of the ljJX type can be base-exchanged with a mixture of rare earth chlorides of the type described above to give a rare earth aluminosilicate with a rare earth content of about 20-25 %, calculated as SEpO ,, to manufacture.

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This material has in the freshly prepared state, a very high relative activity, but the relative activity can this material by controlled steaming, for example, be lowered by treatment in a steam atmosphere for 5 hours at 704 ° C (1300 ⁰ F) to more suitable levels.

The natural and synthetic crystalline

Aluminosilicates have a network of SiO ₂ and AlOh tetrahedra, which are cross-linked due to the proportionate membership of oxygen atoms. The electrovalence of the tetrahedra is balanced by the inclusion of a cation in the crystal, usually by the inclusion of a metal ion such as Na, K or Ca.

The original metal ion can partially or completely through various base exchange methods other metal cations are replaced. Alternatively, the original cations can initially be partially or completely converted to the acid form and then exchanged with other metal cations. The relative concentrations the reagents and material treated, the size of the particles and the reaction conditions all can be changed and adjusted to achieve desired levels of replacement or ion exchange.

The nature and extent around a particular exchange the metal cation in the alumino si iioatlcomplex influence

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in this way also the relative conversion activity of the catalyst. Divalent cations, e.g. calium ions, contribute special properties when they are incorporated through ion exchange.

It has also been found that it is possible to improve the properties of crystalline aluminosilicates by calcining to modify, i.e. by heating at high temperatures but below the sintering temperature of the particular Aluminosilicate over different periods of time.

Furthermore, it is possible to carry out crystalline aluminosilicates with a suitably reduced activity to produce a combination of the above procedures. For example, a sodium Y-aluminosilicate material can be base-exchanged with a mixture of calcium and hydrogen ions to form a calcium-hydrogen-Y zeolite with a relatively high _- \ value. Then the activity of this material can be controlled by matrix dilution or the preparation of compositions of matter in the manner described above can be reduced to a finished catalytic material with a relative To generate conversion activity about twice that of the original Na Y material and for use is suitable in existing cracking processes.

After the type of crystalline aluminosilicate catalysts used in the invention and the various Modes of work have been described according to which

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their activities can be modified and brought to levels suitable for use in conventional catalytic converters Conversion plants are suitable, various working methods according to the invention for production are described below of such catalysts specified for use in catalytic fluidized bed processes.

Under catalytic fluidized bed processes are to be understood in which a chemical or physical process through contact with fine catalyst particles, which are suspended in a fluidizing medium, introduced or increased in its effectiveness. Taking the hydrocarbon conversion process as an example, a hydrocarbon feed is used Cracked to hydrocarbon products of lower average molecular weight by removing particles of catalytic Material in a stream of hydrocarbon vapors under conditions of transformation of temperature and pressure suspended.

It is therefore important that this be catalytic Fluidized bed material has a particle size such that the particles are suspended in the fluidizing medium can be. Although the exact size of the particles depends on the conditions of the reactor and the The type of feed to be converted will be particles approximately 20-200 microns in size generally for suspension in fluidized beds

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pi

satisfactory.

Since particles of different sizes' by a and the same flow of pluidizing agent are affected differently, it is highly desirable that the Fluidized bed catalyst particles have a relatively constant Have particle size. Otherwise the finer particles will be fluidized too easily and they will separate rapidly separate from the larger particles, which will tend to accumulate in a dense phase. It is therefore, it is very desirable to manufacture the catalysts by a process which allows precise control of particle size and density allowed.

Persistence is from the same point of view against abrasion, breakage or disintegration an important property of fluidized bed catalyst particles. When the particles have the tendency during pluidization and promotion easily broken or disintegrated by the whole of the particular plant used, a large amount of Form penalty parts, which must be removed from the system and require constant replacement. The need for Maintaining a large supply of catalyst to replace the loss of particles due to abrasion reduces profitability of processes using such catalysts to a large extent.

Without going too far into the theory of the catalytic activity of crystalline aluminosilicates

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underlying it can generally be said that their activity is related to the crystalline structure of the particular material. Accordingly, it is very desirable that in any process used to form such materials comprehensive fluidized bed catalysts are used, the ordered or crystalline structure of the material is preserved so that its activity is not damaged.

It is also desirable to use fluidized bed catalyst particles Controlled size and density to be able to produce, so that the properties of fluidized beds made of such particles are as uniform as possible.

Further valuable properties of airborne coating catalysts, in particular of fluidized bed catalysts for use in hydrocarbon cracking plants, are good thermal and water vapor resistance under regeneration conditions, good circulation activity ^, stability in the reactor and high product selectivity,

The preferred method of making fluidized bed catalysts according to the invention the measure comprises an overactive crystalline aluminosilicate component with to combine a relatively inactive matrix component. There are several satisfactory ways of working Manufacture of composite fluidized bed catalysts have been developed and these procedures generally include

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the incorporation of finely divided aluminosilicate particles into a matrix component, which preferably consists of an inorganic Oxide gel, e.g., a silica-alumina gel.

A preferred procedure for producing highly active fluidized bed catalysts which are crystalline Containing aluminosilicate components include the following general work stages:

(a) Preparation of the aluminosilicate component: "

A suitable crystalline aluminosilicate is selected for incorporation into the matrix component. Although the crystalline aluminosilicate can be used in an unmodified state in the manufacture of some catalysts, it is normally treated to modify its properties, particularly when the finished catalyst is to be used for hydrocarbon conversion.

A preferred starting material for the production of the catalysts of the invention is a synthetic X-type faujasite. This catalyst can be ion exchanged by contact with a solution of rare earth chlorides to remove at least about 75 % of the sodium content of the original screen.

The catalytic properties of the material can be further reduced at this point by means of a «water vapor treatment.

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to be changed.

It has also been found that the maintenance of the crystallinity of catalysts prepared according to the invention can be improved by calcining the crystalline aluminosilicate. For example, if the crystalline aluminosilicate is to be dispersed in a relatively inactive matrix material, such as a silicon dioxide-aluminum oxide gel, it has been found possible to maintain the crystallinity of the aluminosilicate, e.g. Expelling water is calcined, thereby forming a more stable structure and minimizing the loss of crystallinity during subsequent rapid drying, for example through spray drying, wet processing, steaming and aging. The calcination can be by heating the crystalline Aluminosilicatsiebs after ion exchange to a temperature below the sintering temperature of the sieve and generally in the range of 26O - 87i ⁰ C (500 - l600 ° F) take place.

The precalcination of the crystalline aluminosilicate can also be accomplished by high temperature spray drying of the aluminosilicate particles after formation. For example, wet rare earth ion exchanged particles of synthetic Faujasite can be precalcined by spray drying them in a stream of air having an inlet temperature

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of 5 ^ 8 ° C (1000 ⁰ P) and an outlet temperature of 246 ° C

F) has. Other working methods for precalcination

for example, the calcination of the crystalline aluminosilicates over a period of 3 hours at 593 ° C (1100 ⁰ P) in air or in a water vapor atmosphere at 1.05 kg / cm ² (15 psig).

Particles of the resultant rare earth exchanged crystalline aluminosilicate which have a through Weighing certain mean part diameters up to about 40 u can then be used in preparation for the 'formation of the composite catalyst slurried in water will.

(b) Preparation of the solutions forming the gel matrix: In general, the gels can be prepared by neutralizing solutions of salts of gel-forming oxides. In a preferred embodiment of the invention a silica-alumina gel matrix is used. This is usually done by neutralizing a Solution of sodium silicate made with an acid solution. The acid solution can also contain a salt, e.g. aluminum sulfate, which brings about the aluminum oxide content of the gel. Accordingly, gel-forming solutions are first prepared as a preliminary stage of gel formation. The gel-forming solutions for use in preparing a silica-alumina gel will generally comprise an aqueous solution of Natrlumsllicat and an aqueous solution containing an acid and

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Contains aluminum sulphate.

The matrix can also be produced by other working methods, as indicated in the patent literature are, for example, by the methods of U.S. Patents 2,701,793, 2,859,184, 2,941,961, 3,003,951 and 3,023,172.

The matrix material can also be treated to make it more susceptible to deactivation by water vapor close. This can be done by forming a matrix with a high silica / alumina ratio, because such materials are more easily deactivated by water vapor will. This can also increase the susceptibility of the matrix to deactivation by steam treatment be that you have a relatively large amount of sodium left in the silica-alumina gel.

The activity tader matrix can also be pre-merged with the highly active aluminosilicate component by adding catalytically inert particles to the matrix - " incorporated.

Instead of steam tempering the product to reduce the activity of the matrix, as in the above procedure described, it may be preferable to use a matrix of low activity and thereby to make steam treatment unnecessary. Suitable Matrix materials with very low activities are, for example, clays, aluminum oxides, hydrated metal oxides,

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Silica gel, alumina gel, thorium oxide gel, Alkaline earth oxide-silicon dioxide gels, gels or precipitates of cerium or rare earths, zirconium oxide gel, hafnium oxide gel, Tin oxide gel, titanium oxide gel, etc.

(c) Introduction of the crystalline aluminosilicate component in the gel-forming solutions:

In the process of the invention for preparing the catalyst, it is generally preferable to use the crystalline Introduce the aluminosilicate component by adding a slurry of aluminosilicate particles to the gel-forming solutions. Usually the addition to the sodium silicate solution is made with constant stirring or agitation, to keep the particles in a fully dispersed state.

The addition of overactive crystalline aluminosilicate particles can also be added to the acid solution or to the silicate and acid solutions after they have been mixed but before the formation of the gel take place.

In accordance with the preferred procedure, it has proven very desirable to add to the hydrogel-forming solutions To add punishments. Return fines from a spray drying system or from the catalytic reactor itself are suitable for this purpose. These fine parts are preferably reduced to an average particle diameter determined by weighing milled from 2-7 microns and they can be mixed with the crystalline aluminosilicate particles prior to

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Agreement with the gel-forming solutions slurried in water will. It has been found that the addition of the recycle fine particles in this way improves the hardness and the density of the fluidized bed catalyst particles formed by spray drying is increased. In addition, this way of working is very economical in the total production of the catalyst by they waste in the form of fines that can be generated at any stage of the process, be it during the Grinding, spray drying or any other processing steps eliminated.

Those added to the aluminosilicate and gel matrix Fine particles can have a size up to an average particle diameter of, as determined by weighing about 40 microns. Special benefits can also go through Addition of fines below about 7 microns and preferably Sx can be achieved in the size range 0.3-3.0 microns.

For improved abrasion resistance and a higher diffusivity of the product, other finely divided solids can also be incorporated into the matrix, for example dried silicon dioxide-aluminum oxide, other oxide gels, clays, metal salts such as barytes, etc. The added fines and active components together are generally about 5-50 vol .- #, and preferably 15 - J50 vol -.% make the finished product.

Incorporation of fine particles is not important in all cases, although it is useful in many cases

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can be. Catalysts of the type discussed are without addition of recycle fines has been produced with excellent results.

It has also been found that good results can be obtained using a matrix hydrogel, e.g. B. a silica-alumina hydrogel having a pH adjusted to the range of about 6-11 and preferably in the range of about 7.0-10.0. The pH value λ can be adjusted by adding alkalis, for example sodium hydroxide, ammonium hydroxide, calcium oxide or calcium hydroxide, magnesium oxide or magnesium hydroxide, etc., if the matrix is too acidic. If the matrix hydrogel is too alkaline, acids or acidic salts such as ammonium chloride can be used. The hydrated matrix can be washed substantially free of soluble salts and the sodium content should be less than 0.5 % sodium (on a dry pesticide basis) and preferably less than 0.2 % sodium. (

It has been found that using a high pH in the hydrogel matrix prior to spray drying opens the structure of the matrix and improves the physical properties of the catalyst.

(d) Beading:

The pulp of aluminosilicate particles and fines, if fine parts are used, is then added to the MatriXgel-forming solutions are dispersed; the latter will be

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mixed and allowed to solidify into a hydrogel, which the Contains aluminosilicate particles dispersed therein. The hydrogel formation can be carried out by mixing the mixture gel-forming solutions and dispersed aluminosilicate particles are formed into droplets and the droplets are formed by a settling or Lets solidification medium, e.g. an oil column, sink. The acidity of the hydrogel is regulated to the properties of the product gel and to create such a setting time that the solidification during the passage the droplet comes to an end through the solidification column.

After washing or rinsing, the beads obtained in this way can be subjected to further treatments e.g. an additional ion exchange treatment with rare earth chloride or ammonium solutions.

Furthermore, in some cases it has been found desirable to reduce the density of the beads by using a heat treatment step either concurrently with or prior to washing. For example, the heat treatment can be carried out by holding the hydrogel beads in lock or rinse water for a period of 4 hours at a temperature of about 38 ^° C. (100 ^° C.) in order to reduce the density of the product. A heat treatment can also be carried out over different periods of time at elevated temperatures.

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(e) Formation of fluidized bed catalyst particles:

In accordance with the preferred procedure, the beads are then stirred or whipped in water to form a paste or to form a slurry in which particles of the composition are finely divided and fully dispersed. This watery one Slurry is then preferably sprayed to form microspheres of the catalyst which are suitable for use in catalytic applications Fluidized bed processes are suitable.

The spraying of the catalyst forming sludges or solutions can be done by a number of methods, e.g. by spray forming the droplets in air or by directing the sprayed droplets in cocurrent, countercurrent, Semi-countercurrent or circular current in relation to a flow of a drying gas.

Spray molding can be carried out with or without drying. In any case, the spraying is used for formation of small approximately spherical particles of the catalyst. When removing substantial amounts of moisture the spray is normally in a stream of heated drying gas.

Spray drying, using a semi-countercurrent technique, causes the droplets to move upwards in a chamber sprays which contains drying gas and in which the droplets are partially dried, whereupon the Droplet is allowed to descend in countercurrent to one

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to trickle down an ascending stream of a drying gas.

. The drying medium in the spray drying device can consist of superheated steam; this one has the Inclination to the catalytic properties of aluminosilicates to obtain.'

(f) Post-Formation Treatments: After the fluidized bed catalyst particles have been formed by spray molding, spray drying, etc. Having formed, it may be desirable to subject the particles to certain additional treatments. According to a preferred procedure, the composite catalyst particles can be treated with water vapor. For example, when the composite particles about 5 wt -.% Of exchanged rare earth synthetic faujasites, X-type and 95 wt -. Comprise% of a silica-Aluminiumoxydgelmatrix, the composition may, for example, 24 hours at ⁰ (1200 ⁰ P) in water vapor at 1.05 kg / cm (15 psi). Alternatively, the water steam treatment can be carried out via 1.6. Hours at 704 ° C (130O ⁰ F) in steam at atmospheric pressure to achieve the desired modification of the catalytic properties of the product.

In addition to ion exchange and steam treatments after formation, the composite catalyst can also be subjected to other chemical treatments, to deactivate it, to improve the selectivity or the catalytic properties of the material in others

* 0 9811/0 884

Way to modify. For example, the compound Catalyst for modifying its properties with a calcium acetate-acetic acid solution or with a calcium hydroxide solution be treated.

The invention is explained further below with the aid of exemplary embodiments.

example 1

Were% of a particulate rare-earth exchanged synthetic faujasites, X-type, in which 90% of the original sodium ions by rare earth ions replaced manufactured - it was a slurry of 2,6l wt.. The particles were 2-7 microns in diameter. To this slurry, 17 ^ 9 wt -.% Of recirculated Peinteile made of a composite catalyst, which was milled to a particle diameter of 2-7 microns, was added. The fresh crystalline aluminosilicate was added to 80 wt -% added water and completely dispersed therein..

Then, a solution was prepared by adding 54 * 65 wt -% sodium silicate, and 2.47 wt -% water were dissolved -% of a Natriumhydroxyds in 42.88 wt.... A second solution was prepared by dissolving 3.29 wt - (100%) and 5,8o wt .- # Al ₂ (SOW), in 90.91 wt% H ₂ SO ^ -.% Water..

The pulp of active particles, which contains fresh aluminosilicate and recycled particles of the combined

809811/0884

U42888

The catalyst contained was then added to the solutions dispersed in the following relative volumes: 0.229 volumes of slurry, 0.853 volumes of sodium silicate solution and 1,000 volumes of acid-alum solution.

Drip away from the union of slurry · and solutions were then passed through a solidification oil column at a temperature of about 20 ° C (68 ⁰ F). The gel time of the sol was 4.6 seconds.

The temperature at which the above solutions were formed im'Bereich- was 10 to 12.8 C ^0. (50 - 55 °) * ■ and the resulting pH of the hydrogel was adjusted to about 7.9 - 8.0 set. _ ■

The beads were then withdrawn from the oil column and treated with a solution of 1.2 % (NH ^) ₂ SOiJ for about 2 hours at ambient temperature. treated to remove oil from the surface of the pearls. remove.

The beads were then subjected to an ion exchange step by contacting them with a 3.9% aqueous solution (NH ^ I ₂ SO ^, for about 4 hours at ambient temperature. This base exchange treatment was repeated five times, with the beads were subjected to the continuous flow of treatment solution for 75 % of each four hour circle.

Then the beads were circulated over 4 hours Duration washed with water and each cycle was five times

8098 1 T / 0884

repeated.

Subsequently, the beads were washed with water into a paste with a Peststoffgehalt of 6-10 wt -% milled and then processed in a conventional spray drying means.. The inlet temperature of the air in the spray dryer was 427-538 ° C (800-1000 ⁰ P) and the outlet in the air was between 177 ° and 204 ° C (350-400 ° F). The product from the spray drying was in the form of microspheres with a moisture content in the range of 10-15 wt.

The microspheres were then steam annealed using a 100 # steam atmosphere at a temperature of 7O4 ° C (1300 ° F) for a period of time were exposed for 16 hours.

Example 2

There were solutions and slurries in the following Way made:

1) 8.73 kg (19.25 lbs) sodium silicate (N grade; 28.9 wt .- ^ SiO ₂ ) was dissolved in 4.42 kg (9.70 lbs) water and

785.42 g (1.73 lbs) clay (87 % solids) was then dispersed into this solution;

2) 458.54 g (1.01 lbs) of Y-type sodium aluminosilicate (47.5 % solids) was slurried in 3.98 kg (8.95 lbs) of water and this slurry was then thoroughly dispersed in solution 1) to give a solution with a specific gravity of 1.203 at 26.7 ° C (80 ⁰ F) was formed;

80981 1/0884

3) 898.92 g (1.98 lbs) sulfuric acid (97 %) and 1.92 kg (4.23 lbs) aluminum sulfate (Al ₂ ^) ₃ . 18 HgO) were dissolved in 25.94 kg (57.10 lbs) of water.

The solutions prepared in the above manner

and slurries were then continuously passed through a mixing nozzle

mixed together, with 428 ml / min of the dispersed Y-alumino-

o silicate containing silicate solution at 18.3 C (65 F)

436 ml / min of the acid-alum solution was added at 5 ° C (41 ° F). This mixture formed a hydrosol having a pH of 8.5 and a gelation time of 3 * 3 seconds at 18.3 ° C (65 ⁰ F). The hydrosol was then made into hydrogel beads by forming it into droplets which were passed through a column containing a liquid setting agent.

The calculated composition, on a dry basis, at this point was: 74.99 wt.% Silica-alumina matrix (93.8 wt. % SiO ₂ - 6.11 wt. % AlgO-,) and 25 wt. % added fines, of which 6.07 wt .- ^ Natriumaluminosilxcat of Y-type and 18.93 wt -% consisted of clay..

The beads produced in this way were ion-exchanged with a 2 # rare earth chloride solution (SECl. 6H ₂ O) for 16 hours using half a volume of solution per volume of hydrogel and then a continuous ion exchange with a 1.4 # (NH ^ J ₂ SO ^, solution for 24 hours, after which the exchanged hydrogel beads were washed and homogenized in water

809811/0884

spray dried to fluidized bed size microspheres to obtain.

Example 3

A fluidized bed catalyst was prepared as in Example 2, with the exception that the hydrogel beads after the (NHj,) pSOu ion exchange and washing treatments according to Example 2 again with a 0.25 percent by weight SECl,. 6H ₂ O solution were brought into contact for 4 hours. The beads were then washed free of chloride and sulfate ions, homogenized and spray dried to form fluidized bed particles as in Example 2.

Example 4

Solutions and slurries were prepared in the following way:

1) 15.32 lbs. (6.895 kg) sodium silicate (N grade; 28.9 wt. ^ SiO ₂ ) was dissolved in 7.72 lbs. (3.484 kg) of water and then 0.725 lbs. (330.15 g) of McNamee - Clay (87 % pesticides) dispersed in this solution;

2) 562.96 g (1.24 lbs) of 13X sodium aluminosilicate (55.8 # pesticides) and 143.01 g (0.315 lbs) of 4A sodium aluminosilicate (100 % solids) were mixed in 3.214 kg (7.08 lbs ) Slurried water. This slurry was then thoroughly dispersed in the solution 1), being a solution with

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a specific gravity of 1.193 at 28.3 ⁰ C (83 ⁰ F)

was formed; 3) 898.92 g (1.98 lbs) sulfuric acid (97 %) and 1.92 kg (4.23 lbs) aluminum sulfate (Al ₂ (SO ^) _3. 18H ₂ O) were added

dissolved in 25.94 kg (57.1 lbs) of water.

The above solutions were mixed through a mixing nozzle by adding 460 ml / min of the silicate solution containing dispersed clay and X- and A-aluminosilicates at 21.1 ° C (70 ⁰ P) to 436 ml / min of the acid-alum Solution at 4.44 G (40 ⁰ P) was added; in this manner, a hydrosol is formed, which had a pH of 8.5 and a gel time of 3.0 seconds at l8,3 ° C (65 ⁰ P).

Then, droplets of the hydrosol were formed and passed through a column of a solidifying liquid to produce hydrogel beads. The hydrogel beads were then ion-exchanged by contact with a 2 percent by weight solution of rare earth chlorides (SECl ^. 6H ₂ O) for 16 hours using half a volume of solution per volume of hydrogel beads. After the rare earth ion exchange treatment, the beads were continuously ion exchanged with a 1NHnCl solution for 24 hours and then washed to remove chloride ions. The wet hydrogel was then homogenized and spray dried to obtain fluidized bed size particles.

809811/0884

Another method of producing composite overactive fluidized bed catalysts, the one Forming an essential embodiment of the present invention comprises incorporation of the crystalline aluminosilicate into a synthetic gel, e.g., a silica-alumina gel, which is produced by precipitation.

One such method generally involves forming a silica gel by neutralizing one Alkali silicate solution with an acid, while the pH of the Geles is kept on the alkaline side. Solutions of sulfuric acid ,. Acetic acid, hydrochloric acid, carbonic acid and others Acids can be used to neutralize the silicate solution. The silica hydrogel is then washed with an aqueous mixed with an acidic solution of a salt, which is capable of forming aluminum oxide. Then it becomes hydrous Alumina precipitated within the silica gel to form a silica-alumina gel. After Precipitation, the gel is obtained and made fluidizable by spray molding, spray drying or other procedures Particles, e.g., microspheres, are shaped.

In the conventional procedure, the silica-alumina gel produced by this method is used recovered by filtration and it can then prior to spraying or otherwise forming into fluidized bed particles getting washed. In some processes, the washing stage is

809811/0884

- 4ο -.

omitted before spraying.

The particles can also be washed after they have been used to remove residual ions, e.g. sodium or Sulfate ions, have been sprayed, and they can then be subjected to a further drying step.

. In a modification of this procedure, this can Alumina are precipitated in the pores of the silica gel, from solutions of salts in which Aluminum in which the cation is present, e.g. aluminum sulphate, and also from solutions of salts in which aluminum is present in the anion, e.g. sodium or potassium aluminate. the Applying separate solutions of this type leads to a double precipitation of alumina within the silica gel. ,

The crystalline aluminosilicate particles can be added at any stage prior to the formation of the final parts Composition into the silica-alumina gel matrix be incorporated. The preferred mode of incorporation of the overactive component involves the addition of a Slurry of crystalline aluminosilicate particles to the alkali silicate solution. However, good results are also obtained if the crystalline aluminosilicate particles are used in the course from subsequent stages of the process.

The crystalline aluminosilicate particles can be added, for example: (1) with the acid solution,

8098 1 1/0884

(2) to the acidified silicate solution before it has solidified into a gel, (3) to the silica hydrogel after this has been precipitated (4) to the silica gel after adding the aluminum salt solution, (5) to the silicon dioxide gel after precipitation of hydrous aluminum oxide within the pores of the silica gel, (6) to the silica-alumina gel after recovery Filtration and (7) to the silica-alumina gel after filtration and washing in such working methods that use a wash stage before spraying.

The particles produced by this process Fluidized bed size can also have one or more ion exchange treatments after being made. If such downstream exchange treatment When used, the catalyst particles, e.g., sprayed microspheres, are usually used to remove remaining ions from the exchange treatment washed and then dried «

The procedure described above for production of overactive catalysts according to the invention explained in more detail in the following exemplary embodiments.

Example 5

Particles of a synthetic Y-type faujasite exchanged with rare earths, of which about 90 % of the original metal cations are replaced by rare earth metal cations

80 98 11/0884

1A42B88

Slurried in 37.9 liters (10 gallons) of water. The amount of crystalline aluminosilicate in the slurry is calculated to result in a final composite catalyst product containing about 7.0 % of the overactive component

Thereafter, 7.57 1 (2 gallons) sodium silicate solution, which contains 28.6% SaO _2, thoroughly mixed with the slurry of the crystalline aluminosilicate for a period of one hour at 31, I ⁰ C (BS ⁰ P).

2.6.9 liters (0.71 gallons) of a 35% solution of sulfuric acid and 2.433 liters (0.1642 gallons) of an aluminum sulfate solution with a content of 7.8 % Alg ⁰ V are then added to the silicate solution over a period of 35 minutes added. An aqueous solution of 0.165 gallons (0.625 l) sodium

aluminate, which contains 23.6 % AIoO-, is then combined with a

■■■ - '. ■ & *? ■■■ ■ -. "■ - ■

further amount of 2.501 1 (0.66 gallons) of water vermiseht * The sodium aluminate solution, the previously prepared mixture is added to ⁼ to a final pH in the range of 5.5 - 6.0 to provide. ,

The resulting precipitated hydrogel then becomes pumped out of the reaction vessel and filtered on drum filters. The filter cake is spray-dried in hot air ^ to fluidized bed size catalyst microspheres form. .

Example 6

The catalyst is prepared as in Example 5,

8 0 9811/0 88 4

- 43 -

with the exception that after spray drying the microspheres are ion exchanged with a 2% by weight solution of rare earth chlorides (SECl _5. 6H ₂ O) for 16 hours using half a volume of solution per volume of solution per volume of microsphere.

The microspheres are then washed to remove chloride ions, and dried at about l4j5 ° C (300 ⁰ F).

The fluidized bed catalysts according to the invention - can also be produced using a hydrosol instead of a hydrogel. For example, fresh aluminosilicate screen alone or together with recycle fines having an average particle size determined by weighing of 0.1-20.0 microns can be dispersed in a silica sol prepared by adding ammonium hydroxide to a silica hydrogel under atmospheric pressure. The silica hydrosol with dispersed aluminosilicate can then be spray dried to produce fluidized bed catalyst particles in the form of microspheres.

Another main procedure for preparing the catalysts of the invention involves blending active aluminosilicate particles with matrix particles in an aqueous slurry and spraying the slurry to form Fluidized bed size particles.

Table 1 below contains a number of examples of various combinations of active and

80981 1/0884

Matrix components obtained by this method in a more satisfactory manner Way can be processed into very useful fluidized bed catalysts. It is clear that different Aluminosilicate components or mixtures thereof in the Sludge can be used.

A preferred procedure for preparing the catalysts according to the table below includes one physical mixing of the aluminosilicate, e.g. synthetic faujasites exchanged with rare earths, with particles of the matrix, e.g. clay or silica-alumina hydrogel, and spray drying the resulting sludge. This general procedure was used in manufacture the catalysts of all examples listed in Table 1 below were used.

«09811 / 0B84

.- •• .Λ-; ; : ■

Table 1 Examples of catalysts produced by spray drying

Example active component

£ 7.5 of steamed rare earth exchanged synthetic faujsaite

7 * 5 % dried synthetic faujasite exchanged with rare earths

5 % dried synthetic faujasite exchanged with rare earths

7 * 5 % dried synthetic faujasite exchanged with rare earths

7 * 5 % dried synthetic faujasite exchanged with rare earths

7.5 # rare earth exchanged synthetic Faujasite

7.5 # rare earth exchanged synthetic Faujasite

7 * 5 % synthetic faujasite exchanged with rare earths

7.5 % synthetic faujasite exchanged with rare earths

Matrix component

92.5 % EPK Florida cocaolin

92.5 % EPK Florida cocaolin

95 * 0 ^^ Floridakaolin

92.5% EPK Floridakaolin, calcined at 871 C ^(Ü 16oo F)

92.5 % EPK Floridakaolin + 0.8 % tetrapotassium pyrophosphate as a dispersing agent
^ O % clay, 62.5 % silica-alumina gel1

66% clay, 26.5% SiIiciumdioxyd-alumina gel homogenized before spray drying 92.5% silica-alumina gel

92.5 pounds silica-alumina gel containing 16 % silica-alumina gel fines of 4 microns

Table 1 (continued)

Belsp. Active component 7.5 % synthetic faujasite exchanged with rare earths

7.5 % more subdued with

12th

Matrix component
92.5 0 silica-alumina gel and parts-per-million alkylphenol ethylene oxide polymer as surfactant (Renex 690 - Atlas Powder Company)
92.5 % silica

Rare earth exchanged alumina gel, 16

the synthetic faujasite

7.5 % synthetic faujasite exchanged with rare earths

7.5 % synthetic faujasite exchanged with rare earths

7.5 % rare earth exchanged synthetic faujasite (1 micron size)

7.5 % of a synthetic faujasite exchanged with rare earths, which after composition had been subjected to a subsequent exchange with an aqueous solution of rare earth trichloride (SECl ^ .6H0O)

80 98 11/0884 silica-alumina gel fines from
Containing 4 microns
92.5 % silica-alumina gel, 8 %
Containing 4 micron silica-alumina gel fines
92.5 % silica-alumina gel, 16 % silica-alumina gel fines of
Containing 4 microns
92 ^ 5 % silica-alumina hydrogel

92.5 % silica-alumina

BAD ORfQtNAL

Ex.
16

- 47 -

Table 1 (continued)

Active component 7.5 % of a synthetic faujasite exchanged with rare earths 10 % synthetic faujasite exchanged with rare earths

7.5 % synthetic faujasite exchanged with rare earths

20% of rare-earth exchanged syntheteischer faujasite, calcined for 3 hrs. At 593 ⁰ C (1100 ⁰ F) 40% rare earth exchanged synthetic faujasite, 3 hrs. At 593 ° C (HOO ⁰ F) calcined 80% Rare -Earth exchanged synthetic faujasite, calcined for 3 hours at 593 ° C (HOO ⁰ F) 7.5 % synthetic faujasite exchanged with rare earths, 24 hours at 649 ° C (1200 ⁰ F) and 1.05 kg / cm ' (1200 ⁰ F) and 1.05 kg / cm ² (15 psig) steamed (15 psig) with steamed 7.5% rare earth exchanged synthetic faujasite, 24 hr. at 649 ° C

Matrix component

92.5 % silica-alumina hydro gel

90 % silica-alumina gel

92.5% silica-alumina gel, 16% SIII c iumdioxyd-alumina gel of 4 microns comprising

80 % silica aluminum oxide hydro gel

60 % silica-alumina hydrogel

20 % silica-alumina hydro gel

52.5 % silica gel, 40 % kaolin

92.5 % alumina gel

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T442888

- 48 -.

The ability of mixed slurries with clay and aluminosilicate particles for spray processing

Vcwtn

drying by adding a dispersing agent, e.g. Tetrapotassium pyrophosphate, or a surface active agent By means of how it was done in Examples 5 and 10 of the table, can be greatly improved. The application such materials allows a satisfactory Spraying of sludge with a much higher solids content with a corresponding increase in the yield. The usage such dispersants also improve the uniformity of the particle size obtained during spray drying is obtained. It is also with good success possible, dry pulps of aluminosilicate and matrix particles containing dispersants, with the addition of a binder to produce particles with increased hardness.

In the manufacture of catalysts by slurrying and spraying aluminosilicate and matrix components can also be the procedure that is used in the preparation of catalysts by the method according to Example 1 application, can be used to advantage, i.e. fine particles from the spray drying chamber or other sources can be returned to the required size ground and then in the aluminosilicate matrix pulp

^f BAp ÖRKMNÄL

809811/0884 -

to be absorbed.

It. has also proven to be very beneficial, the sludge or pulp with high pesticide content directly from a homogenous! direction, e.g. a Sonic or supersonic homogenizer, to the spray nozzle to pump, so that the least possible delay or Hold up occurs and the material has little or no opportunity to solidify before it is sprayed f and clog the nozzle.

Furthermore, it has generally been found to be advantageous to add crystalline aluminosilicates slowly dry, as this increases the crystallinity and thus the catalytic Properties of such materials preserved. Table 2 below shows a comparison of the relative crystallinity of crystalline aluminosilicates, which were partly dried slowly, e.g. in an atmosphere of water vapor, and partly dried quickly,

eg by spraying it directly on a hot plate. After the two process, dried catalysts further heating for 2 hours at 3 ^ 3 ° C (65O ⁰ F) and then subjected to their relative crystallinity was measured by an X-ray diffraction method.

809811/0884

- 50 Table 2 Comparison of the relative crystallinity

catalyst

Relative

Crystallinity when drying on a hot plate

Relative
Crystallinity when drying in water vapor

synthetic faujasite exchanged with rare earths and $ 93 Georgia kaolin made by slurrying in water and-, drying 14.8

Composite catalyst of 7.3 % rare earths “exchanged synthetic faujasite and 92.5 $ silica-alumina gel 1.6

Composite catalyst from 7 * 5 $ with rare earths exchanged synthetic faujasite and · 92.5 ^ silicon dioxide-aluminum oxide gel, ion-exchanged with rare earth chloride solution after the union 8.6

8 0 9811/0884 BAD ORÜINÄL

UA2888

Further investigations have shown that air or steam tempering of the aluminosilicate component, e.g. synthetic Zh exchanged with rare earths before mixing with the matrix, e.g. a silicon dioxide-aluminum oxide gel, the retention of crystallinity is also improved.

Another way of working to maintain the crystallinity in fluidized bed catalysts, which according to the The method described above, including spray drying or other rapid drying, is produced includes the incorporation of a relaxing agent, e.g. of non-shrinking pesticides into the catalyst composition. The pesticides can be in the form of particles up to 40 microns in size with aluminosilicate particles of up to 7 microns in size, i.e. the non-shrinking particles are larger than the aluminosilicate particles. j It can be assumed that the loss of activity during the rapid drying of aluminosilicate-containing fluidized bed catalysts, especially during spray drying, on damage to the crystalline structure of the Alutninosilicate as a result of strong forces exerted on the material Pressure forces based (stems). About 20 to 30 percent by volume of calcined alumina particles can be used in this procedure with 4 to '5 microns in diameter in the pulp out with

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Rare earth exchanged synthetic faujasite and Silicon dioxide-aluminum oxide gel are incorporated, with the aluminosilicate particles range in size from 1 to 5 microns in diameter. The aluminum oxide particles show on drying practically no shrinkage and considerably reduces the pressure applied to the aluminosilicate particles,.

An increase in the maintenance of crystalline v The fact of the aluminosilicate is generally also achieved when using clay instead of silica-alumina gel used as matrix material before spray drying. Of the Clay tends to be due to its larger pores and its size lower water content to reduce internal pressures during drying. ■

It was also found that the loss of crystallinity of the aluminosilicate in the course of catalyst-forming

:. - ■. ■■■. ■■■■ ■ ... H

fast drying processes, e.g. spray drying, can be reduced by using a special drying process. For example, an aqueous Synthetic sludge exchanged with rare earths Paujasite and silicon dioxide-aluminum oxide gel initially up to to the lowest possible weight content of water (based on on dry solids), and then can replace the partially dried product with another Spray drying or oven drying treatment or by Introduction to the catalytic fluidized bed reactor to be completely dried. ■ · .. '■

8098Ί1 / 088Α

It has also been found that the abrasion resistance of fluidized bed catalysts made from slurries or pulps -made of clay and aluminosilicate, by addition a small amount of sodium hydroxide can be enhanced to the sludge or slurry. Such an addition leads to a modification of the clay surface and improves the abrasion resistance of the product. The same result can also be achieved by taking a small amount of one Chelating agent incorporated into the composition to make alumina from the clay structure so that it can serve as a binder in the composition.

Fluidized bed catalyst particles can also be prepared by adding fines of a crystalline aluminosilicate s combined with organic and inorganic binders. For example, $ 5 to $ 4 can be penalized for one synthetic faujasite exchanged with rare earth elements with a particle diameter of 1 to 5 microns Solvent or emulsification methods are dispersed in a sulfonated polystyrene resin. The organic matrix material can also have a catalytic function, in addition on the catalytic activity of the aluminosilicate. The dispersion of aluminosilicate in an organic matrix can then be made into fluidized bed catalyst particles by spraying them from a solution or emulsion

BATH 80 9811/0 884

will. Particles of the desired size can also pass through Pelleting, granulating and agglomeration methods are formed from the dispersion.

The fluidized bed catalysts according to the invention can also be produced by a process, which physically mixing an aluminosilicate component with a matrix component in the form of a wet cake includes. The cake can be dried, ground and cut to size sifted or it can be processed as a pulp and be spray dried. The matrix can consist of one tone, one Gel or a mixed gel, e.g. silica-alumina gel, or a similar binder material.

The fluidized bed catalysts according to the invention can also be produced by referring to "aluminasillcattella." moistened with a gel-forming solution and then a: - ■■ solidification or shaping of the gel around the overactive · Brings about core particles.

¹ One of the most important processes for producing fluidized bed catalysts according to the invention is the incorporation of finely divided catalytic aluminosilicate material into a matrix of relatively inactive material. This union can take place in a number of ways. A satisfactory way of working involves agglomeration of powdered aluminosilicate with a binder, e.g. clay, silica-alumina, organic materials,

8 0 9 8 1 1/0884 _mmÄL

including natural and synthetic plastics
and resins, inorganic materials including silica solutions, and the like.

Another method of combining the aluminosilicate with a relatively inactive material to produce suitable fluidized bed catalysts involves mechanical compacting of the aluminosilicate
with the matrix material. This can be done by mixing powder of the overactive material and the matrix and then mixing them under the influence of heat and / or pressure
compacted to create self-supporting masses.

The fluidized bed catalysts according to the invention
have proven to be very useful for the conversion of hydrocarbon insets to hydrocarbon products of lower average molecular weight. -

Fluidized bed catalysts of the type discussed here, which comprise crystalline aluminosilicates, can be used for |

Creation of a wide range of activities
will. Accordingly, in connection with such catalysts there is now the possibility of the properties of the
Catalyst to adapt the reactor conditions, the type of hydrocarbon feed and the desired products.

It has also been shown that the fluidized bed catalysts according to the invention are very superior

8098 11/0884

.Selectivity compared to conventional catalysts own. This ability to produce a high amount of valuable products in a feedstock general C, - + gasoline, and a reduced proportion Converting less valuable products, e.g. dry gas and coke, is an extremely important feature of the catalytic cracking.

To the technical advantages of a catalytic vortex show layer cracking with the novel catalysts, A number of pilot plant fluidized bed cracking runs were performed, some with a conventional one Silica-alumina gel catalyst and others with the catalyst prepared according to Example 1.

The results of three runs with the conventional catalytic converter and six runs with the Catalysts according to Example 1 are given in Table 5.

80 98 1 1/0 8 84

809811 / 088A

Table 3

gractamg of Kld-Oontinent-GaBgl (sp. wt. 0.882; 29 ⁰ API) with Wlrbelsohloht catalysts

Catalyst Silletuauiioxyd-llumlnlumoxyd- VilrbelscMchtcatalyst with crystal.

WlrbelgcMchtkatalyaator Alumlnoalligat

Attempt -.r. 12 3 4 5 6

Catalyst adhesive

Eelative activity 0.15 ■ 0.44-

Carbon production factor! »30-- ———------ ■ -....- 0.8I-

Water dissipation factor 4.3

Reactor operating conditions

Pressure 0.70 kg / cm (10 psig)

jjlspersionswasserdampf, Gew.-; » ■■ -10

Oil by weight / h / catalyst bed by weight 1.5 0.69 0.27 3.3 2.8 1.8 3.8 6.3 2.9

S catalyst / Cl, wt. 10 --— ■

Sharpness factor (cat / oil / WE3V) 6.7 14.5 37.7 3.0 3.6 2.6 2.6 1.6 3.5

O carbon on regen.Kat, weight> 0.50 ^ -0.20 - 0, ^ ·

Carbon "consumed.Kat" 0.95 1.08 1.69 0.76 0.99 0.79 0.80 1.02 1.1 *> Product yields

Conversion (22 KO, -43O ⁰ JF) VoI ^ 50.7 55.3 69.8 ■ 68.1 71.2 68.4 68.7 64.3 70.6 Coke (90> carbon) wt. i 4.5 5.8 11.9 5.6 7.9 5.9 6.0 5.2 6.9 dry ice, H _{P to} C _p , wt .-? έ 1.5 2.2 3.7 2 , 0 2.1 2.0 2.2 1.9 2.5 propylene propane, wt .- ^, 4.2 5.3 7.3 7.1 6.8 6 _f 6 6.7 6.4 7.7

3ut-3utane fraction, vol / 10.3 11.8 I6j4 18.2 16.7 16.9 17.1 15.5 18.9

C ₁ - ³ -430 F (221 ⁰ G) VT gasoline "38.7 40.0 40.6 46.3 48.9 48.4 48.4 46.3 46.2

Total circuit oil ·. OO

(221 ⁵ 0; 430 ^Ό ϊ ·) Vol.-jt. 49.3 44.7 30.2 31.9 28.8 31.6 31.3 35.7 2y, 4 oo

Liquid weight (0 ₄ +), \ Tol .-> 98.3 96.5 87.2 96.4 94.4 96.9 96.8 97.5 94.5

+ Composition, 3-5i #> synthetic faujasite exchanged with oils, dispersed molicium dioxide-aluminum oxide gel (10 / o Al ₀ U,)

The values in Table 3 show that the composite crystalline aluminosilicate catalyst is considerably more active than normal technical silica-alumina gel equilibrium catalysts. To the. same level of conversion with the silica-alumina gel catalyst to obtain one must work at a much higher heat factor than with the fluidized aluminosilicate catalysts. The sharpness factor as used herein refers to Kat / Oil / WHSV.

From the results of cracking runs with the same percentage conversion it is also clear that a fluidized bed catalyst which contains about 3 to 5 % of a rare earth exchanged synthetic paujasite dispersed in a silica-aluminum oxide gel matrix and prepared according to the procedure according to Example 1 is considerably more selective than a conventional synthetic silica-alumina gel catalyst. For a given conversion level, less coke and gas are produced, butane production is about the same, and gasoline yields are about 6-8 volume percent higher. In Table 4 below, the results that were obtained with the individual catalysts at 70 vol.-Ji conversion are compiled and compared.

809811/0884

catalyst Table 4

Silica-alumina gel fluidized bed catalyst

Composite fluidized bed catalyst with krista3 & nem Alumino

1 50 silicate 0, 3 44 0.5 Experiment no. 0.15 12.0 2 0, 8th Relative activity 1.3 7Π 3 Carbon factor 11.2 [\ j - 6.8 Conversion, Vol .- # 16.5 f QfIfV ^ T? ^ temperature 482 ° C 40.6 9.8 Cat./Oil ratio s . 1 Λ - 18.2 Carbon on the 46.8 regenerated kata lysator, wt. % Sharpness factor 0.5 0.2 (Cat./Öl/WHS?) Coke, wt -.% 3 Drying gas 6.4 (C, and lighter, weight) Butane, Vo 1. -Ji 9.0 Petrol, vol .- # 17.5 48.6

The regeneration rates for the overactive catalysts have also proven to be the same or better, than those for silica-alumina under the same conditions.

There were also crack runs in the test scale (bench scale) with an overactive catalyst of the same composition as the catalyst according to Example 1, but the size of the fluidized bed ground or crushed and not spray dried into microspheres. This dis-

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comminuted or ground catalyst and the spray-dried composite catalyst in the form of microspheres, which crystalline aluminosilicate dispersed in silica-alumina gel were made using conventional silica-alumina gel catalyst in the fluidized-bed cracking of feed materials from light, wide-cut and heavy Mid-continent gas oil compared. The following are the input materials as light MC gas oil, wide-cut MC gas oil or heavy MC gas oil.

In connection with the light gas oil MC of the novel catalyst is in the form of ground particles about 12 wt -.% More C ^ + gasoline with 50 wt .- ^ conversion. This gasoline advantage is even greater at high conversions. The coke yield for the novel catalyst, both in the form of ground particles and in the form of spray dried microspheres, is much lower than the coke yield with conventional silica-alumina gel fluidized cracking catalysts. The reduction in coke deposition is of the order of 70-75 %.

In conjunction with the broad-cut MC gas oil, the ground particle catalyst gives an increase of about 4.5 wt % C4 gasoline at 40 wt % conversion compared to the same level of conversion over conventional silica-alumina fluidized bed catalyst , and

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Just as with the light MC gas oil, the petrol advantage increases with increasing conversion. The yield for the novel catalyst in the form of powdered or ground particles is also about 50 % less than that obtained with the silica-alumina.

Similar benefits are also seen in cracking a heavy mid-continent gas oil feed with the fluidized bed catalysts achieved according to the invention. ι

The fluidized bed catalysts according to FIG of the invention has broad applicability and suitability for other processes using fluidized bed catalysis, e.g. Isomerization, alkylation, polymerization, hydrogen transfer, Hydration, dehydration, disproportionation, dealkylation, hydrocracking, and the like, as well as other processes and reactions involving the conversion of organic compounds.

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Claims (1)

Patent claims I ₀ fluidized bed catalyst, characterized in that it comprises particles of a crystalline aluminosilicate or composite particles with at least one crystalline aluminosilicate component and a matrix component or a particle mixture. Which contains crystalline aluminosilicate and relatively inactive material, 2 * fluidized bed catalyst according to claim 1, characterized »that the matrix component is proportionate is inactive * 3 fluidized bed catalyst according to claim 1 or 2, characterized in that the crystalline aluminosilioate steam treated, calcined, ion-exchanged or natural or synthetic treated after some combination of dampening, calcination and ion exchange Aluminosilicate particles, preferably of faujasite from X-, Y or Α type. 4 · Wirbelachiohtkatalyeator according to the claims 1-3, characterized in that the original metal cations of the Aluainoailioats at least partially and preferably at least about 75 pounds by ion exchange ORIGINAL INSPECTED other cations, particularly rare earth metal cations and / or caloium ions. 5. fluidized bed catalyst according to any one of claims 1-4, characterized in that the matrix component an inorganic oxide gel, in particular silicon dioxide gel, aluminum oxide gel or silicon dioxide-aluminum oxide gel, Clay or alumina or a mixture of silica-alumina gel and sound includes » 6. fluidized bed catalyst according to any one of claims 1-4, characterized in that the relatively inactive Material made of an inorganic oxide gel, preferably a silicon dioxide-aluminum oxide gel, sand, clay or aluminum oxide consists. 7 · Fluidized bed catalyst according to one of the claims 1-6, characterized in that the catalyst particles are fine particles of a solid, in particular of silicon dioxide-aluminum oxy-nails, Clay or non-shrinking alumina particles, with a mean value determined by weighing Particle diameters of less than 40 microns and preferably in the range of 0.3-7.0 microns. 8. The process of making a fluidized bed catalyst according to any one of claims 1-7, characterized in that particles of a crystalline aluminosilicate a cushioning in at least about $ 5 water 80981 1/0884 serdampX containing atmosphere "at a temperature below the sintering or melting point of the particles or a calcination at temperatures below the, Sintering point of the aluminosilicate or an ion exchange to replace at least some of the original metal cations of the particles with others Cations or any combination of these working steps subject to the particles with proportionately; inactive mixed
Particles or a composition of the particles and a matrix and forms this composition into particles of fluidizable size. 9 «Method according to claim 8, characterized in that that by the ion exchange rare earth metal ions, calcium ions, hydrogen ions or rare earth metal and introduces hydrogen ions, 10. The method according to claim 8 or 9 »characterized in that the aluminosilicate particles in one dispersed gel-forming solution, a hydrogel from the solution forms, in which the aluminosilicate particles are completely distributed, a dispersion of fine particles of the hydrogel in a liquid medium and this dispersion to form catalyst particles in IOrm of microspheres fluidizable size spray-dried " 809811/088 11 _β method according to claim 10, characterized, in that one sprays the dispersion of the hydrogel particles in an opposite direction or the same direction flowing stream of a drying gas or sprayed into a rectified current flowing the drying gas and then cascaded J trickle down the partially dried particles countercurrent to the gas leaves. 12. The method according to claim 11, characterized in that that the dispersion in a steam atmosphere sprayed. 13β Method according to any one of claims 10-12, characterized characterized in that the hydrogel is mixed with a solution which forms an aluminum oxide gel and aluminum oxide deposited in the pores of the hydrogel. 14 · Process according to one of claims 10 or 11, characterized in that the hydro ge ITd ildung is included Use of carbonic acid, sulfuric acid, hydrochloric acid, nitric acid or acetic acid. 15. The method according to claim 8, characterized in that that one crystalline aluminosilicate particles and particles from a relatively inactive matrix material, preferably clay, dispersed in a liquid medium, optionally adding NaOH or a chelating agent and SAD 0RI8INAL 80981 1/0884 the dispersion microsphere holes spray-dried. 16 _d Process according to claim 8, characterized in that fine! Particles of a crystalline aluminosilicate are agglomerated in the presence of a relatively inactive binding matrix component or pressed with this matrix component and the mass obtained is comminuted into particles the size of a fluidized bed » 8098 1 1/0884