BE550461A - - Google Patents

Description

       

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   The present invention relates to novel compositions of catalyst and / or adsorbent products having a high degree of hardness and resistance to abrasion; it also relates to the processes for the preparation of these products and the processes in which they are used. These catalysts are particularly useful in hydrocarbon conversion processes such as cracking, hydrogen cracking, reforming, hydroforming, desulfurization, denitrification, hydrogenation, dehydro-

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 generation, isomerization, alkylation, dealkylation, eto ...



   The present invention relates to a process for uniting small catalyst particles into larger granule forms having high abrasion resistance, and this process comprises: distributing these small catalyst particles intimately bonded to each other in a compound of clay, which has been prepared by thoroughly mixing with water, a powdered benzonitic clay washed with an acid and a powdered kaolinic clay, to form a wet plastic mass in which the kaolin / bentonite weight ratio is between about 55/65 and 5/95 on an anhydrous basis; in bringing this plastic mass to the shape desired for these catalyst granules; finally, to dry and calcine the shaped granules.



   The present invention also relates to abrasion resistant catalyst granules and essentially comprising a compound formed by an intimate mixture of kaolin and acid washed bentonite, this compound having been obtained by a process which consists of intimately mixing with water, a pulverulent bentonic clay washed with an acid and a pulverulent kaolin clay, which makes it possible to form a wet plastic mass in which the kaolin / bentonite weight ratio is between approximately 35/65 and 5/95, on an anhydrous basis; shaping part of this plastic mass to bring it to the desired shape for these catalyst granules; finally, to dry and calcine the shaped granules.



   Generally, the adsorbent and / or catalyst products described herein comprise, as an essential element, a compound of a non-swelling bentonite type clay washed with an acid with certain proportions of kaolin type clays.



  This clay compound is then preferably further mixed with an alumina compound and even more desirably,

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 with in addition one or more of the oxides of heavy metals, that is to say of metals whose atomic number is equal to or greater than 22. It is found that the particulate clay compounds mentioned herein impart to the finished composition a degree of hardness that cannot be achieved with either of these types of clays when used alone. It is found that the clay compound itself has good cracking properties and is useful primarily, though not exclusively, in this field. It is also useful per se as an adsorbent.

   The addition of alumina increases the adsorption capacity of the catalyst as well as its activity to promote reforming reactions such as isomerization and cyclization. The further addition of a heavy metal oxide promotes reforming reactions and also promotes reactions of the hydrogenation-dehydrogenation type, which may result in aromatization, desulfurization or denitrification.



   Modern catalytic processes require the use of catalysts which are not only especially active in the chemical reactions which are to be catalyzed, but which further possess physical characteristics necessary for satisfactory industrial operation. Bulk density and hardness, that is, resistance to attrition, are outstanding characteristics. The ability of a particle to retain its shape, regardless of the mechanical actions to which it is subjected during storage, transport and use, is a primary necessity for a satisfactory catalyst. in modern catalytic processes.



   Catalytic processes can be classified into three categories. In fixed bed type processes, the catalyst is disposed as a bed through which the feed material flows. The bed is fixed. It is better to use

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 catalyst particles having a particle size. predetermined and the particle sizes of which are distributed in a predetermined manner in order to obtain the required free space between the particles. To this end, the sieve analysis of the catalyst, if it is not transformed into granules or grains, or the size of the grains, if it has been put in this form, are carefully controlled during the manufacture of the catalyst.



  It is desirable that the particles or granules retain their size during transportation, handling and loading of the catalyst bed and that they resist crushing caused by the weight of the catalyst forming the bed.



   In moving bed type processes, the catalyst bed is continuously moving. Spent catalyst is continuously discharged from the lower part of the catalysis reactor and fresh catalyst is continuously admitted into the upper part of the reactor. The spent catalyst is regenerated in a regeneration zone and is returned to the catalysis reactor. In a process of this type, the mechanical strength of the catalyst is of great importance because it is subjected to considerable crushing and abrasion forces during its movement.



  It is also subjected to these forces during its movement to the regeneration zone and when it passes through it to gain the catalysis reactor. In this type of process, it has been found that it is more advantageous to use the catalyst in the form of granules or pellets. The strength of the catalyst granules as well as the characteristics of the individual particles which constitute the granules are of the utmost importance.



   In catalytic processes of the fluidized bed type, the catalyst is usually subdivided into small fragments or it is in powder form. It is sent into a moving stream of vapors subjected to catalysis and passes through a

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      reactor while in suspension in the vapor stream. It is then discharged into a separation zone which can be either of the mechanical separation type, or of the Cottrell precipitator type, or a combination of the two. The separated catalyst is then sent to a regeneration zone and the regenerated particles are introduced again into the stream of fluid circulating in the catalysis reactor.

   In this type of process, the individual particles are subjected to abrasion forces of some degree. importance, and particle breaking introduces undesirable variables into the process settings and further makes it difficult to separate catalyst fines.



   In all three forms of catalytic processes, the hardness of the catalyst as manufactured and its hardness under the conditions of the process in which it is used are very important in maintaining the desired particle size and in preventing catalyst losses. .



   The use of granular adsorbents such as silica, alumina, natural clays and the like raises problems analogous to those mentioned above for the fluidized bed catalysts. Fixed-bed and moving-bed type techniques are also used for adsorption processes the object of which is to selectively adsorb and remove one or more of the constituents from a gas or liquid mixture. The adsorption processes are usually carried out at lower temperatures, for example 0-300 ° C., than the catalytic processes, but the general contacting techniques are otherwise similar and problems are often encountered. similar abrasion.



   Besides a suitable hardness; a catalyst must also possess a desirable degree of activity in the particular conversion process in which it is used. Obtaining these

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 two @ @es qualities pose two related problems and, in practice, one cannot combine one of them to the exclusion of the other.



  Occasionally, catalytic materials are combined in such a way that very hard but very low activity catalyst granules are formed. Conversely, one can mix the same materials by other methods and obtain a catalyst having high activity, but unsatisfactory hardness. These two factors must therefore be taken into account when determining the value of any given catalyst.



   Catalysts or adsorbents in the form of aggregates or relatively large pieces are generally prepared by one of two processes, namely pelletizing or extrusion. The term "pelletizing" (as used herein) denotes a process in which powdery raw materials, to which a lubricant such as graphite has or has not been added or not, are first mixed, usually. but not necessarily in a substantially dry state, and in which purties of this mixture are placed in individual small compression molding molds and are compressed by means of a reciprocating piston.



  The pellets are then calcined to activate the calcium materials and to drive off the lubricant by combustion. This process produces hard, adsorbent, smooth surface pellets of any size desired, depending on the size of the mold. This process is itself more expensive than the extrusion process.



   By the term "extrusion" is meant in the present description a process in which the pulverulent raw materials are mixed with sufficient water or other liquid to form a paste which is then extruded through a die of given size. and of a given shape in cross-section, then the extrudate is cut or broken at regular intervals to form granules of any desired length.

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  These granules are then dried and calcined, if desired.



  Extrusion seldom requires the addition of a solid lubricant and therefore it is no longer necessary to burn the lubricant to remove it from the finished granules. Whether for pelletizing, or for extruding, any desired pressure can be used and the hardness of the resulting pellets or granules will generally vary as a direct function of the pressure used. However, for any given mixture of raw materials, it has generally been found that pelletizing results in a harder end product than extrusion.

   However, by changing the composition of the mixture, it has now been found that extruded granules can be produced which compare favorably in activity and hardness with a mixture pelletized and containing the same. essential active ingredients.



   Some catalytic and adsorbent materials, for example alumina, do not have sufficient plasticity as a wet mix to be efficiently extruded, and it was previously considered necessary to form these materials into pellets. It has now been found that such non-plastic materials can be incorporated into the clay mixtures described herein to produce an easy to extrude mass, and that the end product compares favorably with respect to catalytic activity, potency. adsorption and hardness, with the alumina-based compositions put in the form of pellets.



   From the above, it can be seen that the object of the present invention is: - to form catalyst or adsorbent particles having a high degree of resistance to abrasion, regardless of the process used to form the particles; - to obtain compositions which are particularly suitable

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 to form abrasion resistant granules by extrusion; - methods and devices for plasticizing certain non-plastic catalytic or adsorbent compositions with a view to making them suitable for undergoing extrusion to be formed into granules having a high degree of adsorption, hardness and catalytic activity ;

   - To form catalysts having a high degree of activity for cracking, reforming, hydrdforming, desulfurization and denitrification of the hydrocarbon fractions, as well as for other similar materials and processes.



   Other objects will become apparent to technicians during the description which follows.



     OPPOSITE CLAY
The present invention is primarily based on the discovery of a particulate clay compound which gives a maximum degree of hardness to the catalyst or adsorbent compositions in which it is incorporated. This compound contains a major proportion, preferably between about 70 and 95%, of a non-swelling clay of the bentohite type washed with an acid, and a smaller amount, preferably between about 5 and 50 of a clay. of the kaolin type.

   It has been found that mixtures of these clays, taken in the quantities mentioned, and transformed into extruded granules, then dried and calcined, exhibit a degree of hardness which is greater than that of either of these. clays taken singly or in other proportions. This mutual relationship is illustrated in the accompanying drawing, in which Fig. 1 is a graph showing the mutual relationship between the hardness of the particles and their composition. In this drawing, we can clearly see that a maximum hardness is reached when the composition contains between 85 and 90% of "Filtrol", which is a clay of the bentonite type.

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      washed with acid.

   It is found that this optimum relationship between proportions is also valid when materials other than alumina or molytene are incorporated into the mixture. Figure 1 will be explained in more detail later.



   The quality of hardness or abrasion resistance is measured in the present invention using a Humble apparatus for measuring loss through attrition. This apparatus consists of a metal box of cylindrical shape in which are mounted two deflector plates which extend longitudinally along the opposite sides of the cylinder. During operation, the box is assembled with a view to its horizontal and axial rotation, then 100 g of particles and catalyst are introduced into it and then it is made to rotate at 60 revolutions / minute for one hour. At the end of this time, the solid material is removed and passed through a sieve to separate the fines which pass through a 20 mesh sieve.

   The fines collected are then weighed and the loss is expressed by attrition by the following equation:
Weight of fines
A = x 100
Initial weight of / particles The loss through attrition is inversely proportional to the hardness of the particles and the hardness can be expressed as follows:
H = 100 - A
This hardness value thus represents the percentage by weight of initial material which was not detached by abrasion from the particles during the test.



   The hardness values mentioned here all represent the hardness of the finished and calcined particles, not the hardness of the particles which are simply dried for example at 120-205 C. The calcined hardness is the hardness of the particles. which have been heated to a temperature between approximately 315 and 815 0. between 1 and 16 hours, which

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 has the effect of removing combined water and ordinarily activating the composition by altering its crystal structure.



   The activated bentonite type clays and the kaolin type clays used in the present invention can be distinguished from each other and other clays by any of their many different properties.



  Clays of the bentonite type naturally contain. a high proportion of the montmorillonite-type minerals, including montmorillonite, beidellite, nontronite, hesorite, saponite and sauconite. Montmorillonite is often referred to by the formula Al2O3. 4SiOg. H2O + xH2O. Kaolin clays are rich in kaolinic minerals including kaolinite (, il 203 2SiO2. 2H20), dichite, nacrite, anauxite, hallyosite and endellite. It is found that kaolinic clays generally contain between about 30 and 40% of Al2O3 while bentonite clays usually contain less than 20% of this compound.

   Another important characteristic of bentonite clays is their great capacity to act as cation exchange bases, which capacity is usually between 80 and 90 milli-equivalents per 100 g of air-dried clay; the crystal lattice obtained obviously has weak bonds. On the other hand, kaolin clays have a low capacity to act as cation exchange bases, a capacity which is of the order of 10 milli-equivalents per 100 g of dry clay.



  The study of x-ray crystals shows that minerals of the montmorillonite type have three-layered crystal lattices while kaolinic minerals have two-layered crystal lattices. Differential thermal analysis curves established for montmorillonite show that there are three endothermic peaks at

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 150-320 C., 695-730 C and 870-920 C. and a single exothermic peak at 925-1050 C. Similar curves laid out for kaolinite show a strongly endothermic peak at 620 C. and a strongly exothermic peak at 980. C, which clearly differentiates it from other groups of mineral clays.



  Other important characteristics of these clays are mentioned in "Encyclopedia of Chemical Technology, Vol. 4, pp. 24-85; R. E. Kirk, Ed. Interscience Encyclopedia Inc., N.Y. 1949."
The non-swelling or sub-bentonite type clays used in the present invention are mined in regions very distant from each other, for example in the states of Arizona, California, Texas, United States of America. Arksnsas, Permissippi, Kentucky, Tennessee and many other places outside the United States of America. Swelling types of bentonites can also be found in the state of Wyoming, south of the state of Dakota, in the states of Montana, Utah,

          from Nevada and California. It is preferred to use in the present invention non-swelling or sub-bentonite-type clays, since they are much easier to activate, for example by washing with acid, than swelling clays. For this purpose, it is preferred to use a high-quality sub-bentonite containing the major part of the mineral montmorillonite. These clays are usually activated by treatment with a mineral acid such as sulfuric acid.



    45 kg of clay (on a volatile free basis) can be treated with, for example, about 9 to 68 kg of H2SO4. The concentration of the acid can be between about 5 and 60%, calculated on the basis of the total water content of the mixture, including the water content of the clay. The processing time can vary between about 1 and 12 hours and the temperature between about -17 and 1000 C. A desired degree of extraction is such as to give a final desirable content of Al2O3 at which

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 A low FO3 content is added which is between 10 and 20%, preferably between approximately 15 and 20%.

   For example, 45 kg of a typical Arizona sub-bentonite can be treated with 13.6 kg of H2SO4 as a 12% solution, for 6 hours at 93-1000 C. Analyzes of natural clay and acid-treated product show that the following characteristics are obtained (on an anhydrous basis).



   Percentage of weight
 EMI12.1
 
<tb> Before <SEP> After
<tb>
<tb> treatment <SEP> treatment
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> SiO2 <SEP> 67.5 <SEP> 71.5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Al2O3 <SEP> 19.5 <SEP> 16.3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Fe203 <SEP> 1.8 <SEP> 2.4
<tb>
<tb>
<tb>
<tb>
<tb> CaO <SEP> 3.2 <SEP> 2.3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> MgO <SEP> 6.9 <SEP> 4.5
<tb>
 If the catalyst is to be used for the treatment of crude hydrocarbons having a high content of sulfur compounds, it is desirable to reduce the Fe2O3 content of the bentonite clay to as low as is practicable. preferably below about 1%.

   In this way the catalyst is made much more resistant to sulfur poisoning and retains its activity for longer periods of time.



     However, the content of Al2O3 plus Fe2O3 should not be reduced by the acid treatment below 10%, preferably if the catalyst mixture is to be extruded, since more acid-treated clays pushed lose their plasticity and hence their extrudability.



  A very suitable clay prepared in accordance with the general guidelines mentioned above is known as "Filtrol", and is sold by the "Filtrol Corporation" of Los

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 Angeles in California. This material has the following composition in the calcined state:
 EMI13.1
 sio 2 70 H 103 17 FeZ03 .ig0 5
 EMI13.2
 
<tb> CaO <SEP> 5
<tb>
 
 EMI13.3
 H 2 3
The kaolin clays used in the present invention are mined, for example, in North Carolina,
 EMI13.4
 in South Carolina, Georgia, Florida and Vermont (United States of America).

   A type of highly plastic kaolin known as figulin clay, and which is mined in western Tennessee, Kentucky and New Jersey (United States of America) is particularly suitable for processing of the present invention. Usually, these clays do not require any special pretreatment other than grinding for the purpose of reducing coarse aggregates to powder. In some cases washing with dilute acid may be desirable.

   For example, a suitable figulin clay can be obtained from the "Western Talc Company" in Los Angeles, California, and this clay presents the following analysis:
 EMI13.5
 
<tb> SiO2 <SEP> 51.6
<tb>
 
 EMI13.6
 A 12 3 33.7
 EMI13.7
 
<tb> Fe203 <SEP> 0.8
<tb>
<tb> CaO <SEP> 0.14
<tb>
<tb>
<tb> MgO <SEP> 0.27
<tb>
<tb>
<tb> H2O <SEP> 11.9
<tb>
 
 EMI13.8
 EXELiTLE 1
The above types of figulin clay and "Filtrol" clay were used to form the mixture (in their uncalcined state).

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 used to obtain the; data shown in Figure 1 and Table 1.

   In FIG. 1, we plotted on the abscissa, at the upper part the percentage by weight of figuline clay, at the lower part the percentage by weight of "Filtrol" and on the ordinate the hardness calculated using l Humble appliance, and the hardness of 93.4 corresponds to the use of 100% figulin clay (c). In all cases, the compositions are prepared by first mixing the two clays in powder form taken in the proportions indicated on an anhydrous basis, thick with the addition of sufficient water to obtain a plastic mass which can be obtained. extrusion, after which extrusion is carried out at a pressure of approximately 14 kg / cm 2 (relative pressure) through circular orifices of 4.76 mm.

   The extrudate was cut into sections 4.76 mm long, dried at about 1050 0 and calcined at about 395 C for 2-6 hours. This product is designated "B" in Figure 1.



  The hardness is determined as described above. The results are as follows:
TABLE 1
 EMI14.1
 
<tb> Composition <SEP> Hardness
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>% <SEP> in <SEP> weight <SEP> Attrition <SEP> test <SEP> with
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> (anhydrous) <SEP> the device <SEP> Humble
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Catalyst <SEP> Filtrol <SEP> clay
<tb>
<tb>
<tb>
<tb> ¯¯¯¯¯¯¯ <SEP> ¯¯¯¯¯ <SEP> figuline <SEP> ¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 0 <SEP> 100 <SEP> 9.4
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> 50 <SEP> 50 <SEP> 98.0
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 75 <SEP> 25 <SEP> 98.9
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> 85 <SEP> 15 <SEP> 99.3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 5 <SEP> 100 <SEP> 0 <SEP> 98,

  7
<tb>
 
To use these known clay cracking catalyst compounds, the granular material containing 85% of "Filtrol" and 15% figulin clay, a mixture represented by "A"

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 in Figure 1, is brought into contact for example with gas oil vapors from a crude Somma Maria (United States of America), whose boiling range is between 230 and 4800 C. and whose API density (American Petroleum Institute) is 33.



  The reaction conditions are as follows: bed temperature, 495 C .; relative pressure: 2.1 kg / cm2; flow rate, 1 volume of oil (liquid) pure volume of catalyst and per day. The total liquid recovery is about 92% by volume based on the feed, with losses of about 10% as gas and coke.



  The gasoline yield is about 40% by volume. One can use other cracking conditions, for example temperatures from 425 to 650 C., pressures from 0 to 35 kg / cm (relative pressures), hourly volumetric speeds from 0.5 to 10. can use the same catalyst in fluidized bed cracking processes by grinding the granules to form powders with a size of about 200 to 400 mesh (standard sieve) or less.



  In any cracking process, it happens that the catalyst particles become relatively inactive as a result of the deposition of coke thereon. Therefore, they are ordinarily regenerated when they have accumulated 1 to 4% by weight of coke.



    Regeneration is accomplished by combustion with air or oxygen at a temperature between 480 and 815 C.



   To use these clay compounds as adsorbents, the material is pelletized containing 85% "Filtrol" and 15; of figuline clay in contact with the same Santa aria gas oil at a temperature of about 370 ° C. and at atmospheric pressure, using a catalyst / oil ratio of 5.0.



  Under these conditions, 70 to 85% of the organic nitrogen compounds are retained by the adsorbent. When a crude gasoline containing nitrogen is treated at 205 ° C., at atmospheric pressure and with a catalyst / oil ratio of 1.0, between 60 and 80% of the nitrogen compounds are removed as well as most of the nitrogen compounds. diolefins

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 forming gums.



   CLAY AND ALUMINA COMPOSITIONS
Refractory oxides such as precipitated gel-forming alumina, silica, silica-alumina, titanium oxide, thoria, zirconium oxide or magnesia which does not are not extrudable by themselves can be made into easily extrudable mixtures when incorporated therein from about 1 to 70% by weight (anhydrous) of the clay mixture described above. Here again, the relative proportions of the two clays in the final granule obtained is an important factor, with mixtures in which the ratio, by weight, of bentonite to kaolin is between about 2.5 and 30, being. harsher than those which contain other reports.

   Another important factor is the particle size of the aluminum used. It has been found that the hardness of the granules increases when more finely divided alumina is used.



  Thus, a mixture composed of 50% 230 mesh alumina, 42.5% "Filtrol" clay and 7.5% figulin clay can be wetted until plasticity is obtained, extruded under form 4.76mm granules as described above, dried and calcined at 595 ° C. for 10 hours, after which it was subjected to the hardness test as described above using the Humble apparatus to measure the attrition. It is found that the hardness of these granules is between 97.25 and 97.8, while the hardness of similar granules prepared from alumina with a size of 330 mesh is between 98.25 and 99. Therefore, it is preferred to use aluminas or other refractory oxides which have an average particle size of less than about 300 vials.



   The hardness of clay and alumina compositions

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 increases slightly as the total clay mixture content is increased above 50%. Mixtures containing 50% alumina and 50% clay (85% "Filtrol" and 15% figulin clay), when prepared and tested as described above have a hardness of 97 , About 5 while similar mixtures containing only 30% alumina and 70% of the clay mixture have a hardness of about 97.8. This slight increase in hardness is usually overcome by a loss of activity of the aluminum component and therefore it is preferred to use clay-alumina catalysts containing between about 40 and 65% alumina.



   Clay-alumina catalysts are primarily useful for conversion processes which do not primarily involve hydrogenation or dehydrogenation reactions. For example, they can be used for cracking, isomerizing or reforming various hydrocarbon fractions at temperatures between about 4 ° U and 650 ° C., at pressures of between about G and 70 kg /. cm (relative) and with an hourly volumetric speed between approximately, 5 and 10.0. They are also useful in adsorption processes.



   CLAY-ALUMINA AND HEAVY METAL COMPOSITIONS
In their preferred form, the catalysts in accordance with the present invention contain, in addition to the mixture of clay and alumina, one or more of the heavy metal oxides having an atomic number equal to or greater than 22. These include metals of groups VI-B and VIII of the periodic table, especially chromium, molybdenum, tungsten, uranium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel-palladium and platinum.

   A particularly useful group of catalysts useful in conversion processes in which it is desirable to promote hydrogenation and / or dehydrogenation are those which contain an oxide of a metal.

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 from group VI-B, especially molybdenum or chromium. It is also desirable to use the oxides of cobalt and nickel in addition to the metals of Group VI-B, especially if the feed material has a high content of organic sulfur compounds.



   Catalysts from this group can be mixed by either of the following two general methods:
PROCEDURE 1 - In this process, the clay composition, preferably further comprising about 70 to 95% bentonite type clay and 3 to 30% kaolin type clay, is mixed with alumina and with a finely divided dry oxide consisting of at least one of the heavy metal oxides to be used, for example molybdenum oxide.

   The mixture is then wetted to bring it to a plastic state without any suitable liquid, then it is extruded as described above to form granules of suitable size, dried and calcined. After drying or calcining, it may be desirable to further impregnate the catalyst with an aqueous solution of another salt of a metal, for example cobalt nitrate or nickel nitrate. Then, the impregnated catalyst is drained, dried and finally calcined to reduce the metal salt which impregnates it to its oxide form.



   PROCESS 2 - In accordance with this process, the constituents intended to enter into the finished catalyst are firstly incorporated into one another, then the mixture is transformed into granules, for example by extrusion, the granules are dried and then sealed. calcines. In a variant of this process, the clay compound, alumina and dry molybdic anhydride (MoO3) can be ground together and then wet with an aqueous solution of cobalt nitrate or nickel nitrate of sufficient concentration. to give the desired ratio of cobalt or nickel oxide in the calcined catalyst when the solution is used in an amount just sufficient to give the desired plasticity to the mixture in

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 view of the extrusion.

   In another variant, all the heavy metals to be used can be added in the form of an aqueous solution of a salt or salts of these metals. For this purpose, ammoniacal ammonium molybdate or ammonium chromate can be used. , or in general any other heavy metal salts which decompose in the form of oxides when heated for example to 250 to 650 C.



   A catalyst containing molybdenum and cobalt, prepared by one uu. the other of the above processes may have a final composition, after calcination, which is substantially the following:
 EMI19.1
 
<tb> Alumina <SEP> 35 <SEP> - <SEP> 65%
<tb>
<tb> Bentonite <SEP> clay <SEP> 20 <SEP> - <SEP> 45%
<tb>
<tb> Kaolin clay <SEP> <SEP> 2.5 <SEP> - <SEP> 12%
<tb>
<tb> Molybdenum <SEP> <SEP> <SEP> 5- <SEP> 15%
<tb>
<tb> Oxide <SEP> of <SEP> cubdlt <SEP> 1 <SEP> - <SEP> 6%
<tb>
 
The extruded catalysts falling within the range of dom- positions mentioned above have, as has been observed, a hardness substantially equal to that of the clay-alumina catalysts; the heavy metal oxides, when taken in the above range of proportions, do not appreciably modify the hardness.

   Their activity for hydrocarbon conversions such as hydrogen reforming, hydrogenation, dehydrogenation, aromatization, desulfurization and denitrification compares favorably with cobalt-molybdenum-alumina catalysts prepared by the processes of the prior art.



   FIG. 2 is a graphical representation on which the hardness (on the y-axis) as a function of the dimension in miles of the alumina (on the x-axis) has been plotted, this graph also showing the relative hardness of the catalysts containing

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 various alumina / clay and "Filtrol" clay / figuline clay ratios.



  The meaning of the details of this figure will appear during the following example, which is given for illustrative purposes only.



   EXAMPLE II
Calcined catalysts having the composition mentioned in Table 2 are prepared by intimately mixing alumina (activated gel type) with the indicated proportions of clays and molybdenum trioxide powder, adding enough water to give a plastic consistency. rigid at. mixture and then extruding it through circular orifices 4.76 mm in diameter, a cut the extruded product into sections approximately 4.76 mm long, dried, calcined at 595 ° C. for approximately 7 hours and then subjected to the - hardness test in the Humble attrition apparatus.



  The results are as follows:
TABLE 2 Composition, percentage in dry nodes
 EMI20.1
 
<tb> Cata- <SEP> Al2O3 <SEP> Filtrol <SEP> clay <SEP> MoO3, <SEP> Hardness
<tb>
<tb> lyseur <SEP> 230 <SEP> 330 <SEP> figuli-
<tb>
<tb>
<tb> meshes <SEP> meshes <SEP> ne
<tb>
<tb>
<tb>
<tb> 1 <SEP> 30 <SEP> - <SEP> 31 <SEP> 9 <SEP> 10 <SEP> 97.8
<tb>
<tb> 50 <SEP> - <SEP> 34 <SEP> 6 <SEP> 10 <SEP> 97.5
<tb>
<tb> 3 <SEP> - <SEP> 50 <SEP> 34 <SEP> 6 <SEP> 10 <SEP> 98.5
<tb>
<tb> 4- <SEP> 50 <SEP> 34 <SEP> 6 <SEP> 10 <SEP> 98.4
<tb>
<tb> 5- <SEP> 30 <SEP> 40 <SEP> - <SEP> lu <SEP> 96.1
<tb>
 
In Figure 2, a correlation between catalysts 2, 3 and 4 is established to show the effect on hardness of a difference in the size of the alumina (in mesh).

   Catalyst 1 has a slightly increased hardness compared to catalyst 2 due to its higher clay content. Catalyst 5 strikingly shows the result of omitting kaolin from the composition, more than two points of hardness bushing occurring, as seen when comparing with catalysts: and 4.

   This

 <Desc / Clms Page number 21>

 The difference is very important when we move from the commercial scale to the industrial scale.
 EMI21.1
 E .. - JALE III The process used to prepare the cata-
 EMI21.2
 Lysers 0 and 4 in Example II, with the exception that the final catalyst is impregnated with cubite by immersing it in a 20% aqueous solution. of cotalto-nitrate hexahydrate, after which it is drained, dried and again calcined at 595 0. for 6 hours to decompose the salt into cobalt oxide.

   The
 EMI21.3
 final catalyst contains about 3 µ of CaC. When measuring the above hardness co: wu <3, it was found to be about 98.6, the slight improvement probably being due to the second calcination.
 EMI21.4
 EA3.l.i} 'LE IV A nicl # l-all1illin-clay catalyst is prepared by first mixing 210 g of "Filtrol" with 24 g of figuline clay until a homogeneous powder is obtained. The mixture of clays is then intimately incorporated into 200 g of precipitated and activated alumina (320 meshes) and 40 g of powdered dry molybdenum trioxide. The dry mixture is then wetted with 150 g of a 40% aqueous solution of nickelous nitrate hexahydrate.

   A stiff dough forms which is then extruded through dies
 EMI21.5
 of, '7G mm under a pressure of 14 kg / cm2 (relative), and the extruded product is cut into sections / d, 17 mi in length. .after drying and calcination, for 8 hours at 650 C, the granules are subjected to the attrition test in the Humble apparatus and it is found that the hardness is about 97, and that their composition is as follows, on an anhydrous nozzle:

   
 EMI21.6
 
<tb> Weight, <SEP>, <SEP>
<tb> Filtrol <SEP> 39.0
<tb>
<tb> Clay <SEP> figuline <SEP> 4.2
<tb>
 
 EMI21.7
 toi 205 4.0
 EMI21.8
 
<tb> MoO3 <SEP> 8.9
<tb>
<tb>
<tb>
<tb>
<tb> NiO <SEP> 3.5
<tb>
 

 <Desc / Clms Page number 22>

 
The catalysts of Examples II, III and IV and other similar compositions containing one or more heavy metal oxides are all highly suitable for various hydrocarbon conversion reactions, such as desulfurization, denitrification, hydrogenation, hydroforming. , reforming, cracking, destructive hydrogenation (eg hydrogenated hydrocracking) and the like.

   These reactions are generally carried out by contacting the catalyst with a hydrocarbon feedstock at a temperature between about 260 and 815 ° C. and preferably in the presence of hydrogen, such as recycled hydrogen gas. During its use, various amounts of deposits, including mainly carbon, nitrogen and sulfur compounds, accumulate on the catalyst and are periodically removed by regeneration. This is done by passing air diluted with a flue gas, water vapor, nitrogen or other inert gas, over the catalyst, in order to burn the deposits while maintaining the catalyst temperature between approximately 425 and 565 C.

   One completes the combustion in the presence of undiluted air while maintaining the temperature of the catalyst between about 425 and 565 C. The regenerated catalyst, after reduction with hydrogen, has substantially the same catalytic activity as the fresh catalyst. prepared even after a large number of regenerations.



   For the purpose of desulfurizing crude petroleum, shale oil distillates and the like, the catalysts according to the present invention are used under the following conditions: reaction temperatures of between about 315 and 595 C; relative pressures between a pressure substantially equal to that of the atmosphere and 350 kg / cm or more; volumetric speeds of between approximately 0.2 and 10.0 volumes of feed constituted by the crude liquid / volume of catalyst / hour and between 8950 and 178.800 dm3 of hydrogen

 <Desc / Clms Page number 23>

 added per 100 liters of load. The particular set of conditions is determined by the feed to be desulfurized and the nature of the desired product.



   The catalysts described herein can also be used for the denitrification of raw materials such as coal tar distillates, shale oils and heavy fractions from the distillation of petroleums, so that up to and including the removal can be done simultaneously. 99% nitrogen and substantially all sulfur.

   For the derifaction of these materials, the following conditions are used: reactor temperatures between about 370 and 540 Ce; pressures between about 35 and 700 kg / cm2 (relative); flow rates between about 0.2 and 10.0 volumes of liquid raw material introduced / volume of catalyst / hour and about 17,880 to 178,800 dm3 of hydrogen added / 100 liters of feed.

   To remove nitrogen, it is generally desirable to use a two-phase denitrification process in which ammonia synthesized in the first phase is removed from the product of the first phase before entering the second. denitrification stage, and 'in which ammonia and hydrogen sulfide are removed from the streams, of recycled hydrogen gas, in each stage. Under these conditions, the maximum efficiency in removing nitrogen from the feedstocks is achieved.



   The catalysts according to the present invention can also be used for hydrogen reforming, a process which serves to reform a hydrocarbon material whose boiling point is within the boiling range of gasoline and to increase its content of gasoline. aromatic. To treat raw materials with the aim of subjecting them to reforming and increasing their aromatic content, the following conditions are used: reaction temperatures of between approximately

 <Desc / Clms Page number 24>

 425 and 650 C, pressures between approximately 3.5 and 70 kg / cm2 (relative), volumetric velocities between approximately 0.2 and 4.0 volumes of liquid feed / vulume of catalyst / hour and approximately 17,880 to 178,800 dm3 of hydrogen added / 100 liters of charge.

   The particular conditions are determined by the nature of the particulate raw material used and the quality of the desired product.



   The following example is mentioned to show the treatment results obtainable by using the catalysts of the invention for the hydrogenated reforming of a raw feed material.



  EXAMPLE V
An extruded catalyst is prepared by the process described in Example III, using activated alumina with a size of 325 mesh, the final catalyst giving, on analysis, dry:
Percent by weight
 EMI24.1
 
<tb> Al2O3 <SEP> 48.5
<tb> "Filtrol" <SEP> 33.0
<tb>
<tb> Clay <SEP> figuline <SEP> 6.0
<tb>
<tb>
<tb> MoO3 <SEP> 9.5
<tb> CoO <SEP> 3.0
<tb>
 One uses this catalyst in a hydrogen reforming operation on a gasoline coming from a direct distillation and having a high content of naphthene, boiling between 99 and 126 C and containing 0.01% sulfur.

   The operating conditions are as follows:
 EMI24.2
 
<tb> Pressure <SEP> 14 <SEP> kg / cm2 <SEP> (relative)
<tb>
<tb>
<tb>
<tb> Volumetric <SEP> speed
<tb>
<tb>
<tb> hourly <SEP> to <SEP> state <SEP> liquid <SEP> 1
<tb>
<tb>
<tb>
<tb> Hydrogen <SEP> 35.760 <SEP> dm3 / l00 <SEP> liters <SEP> of
<tb>
<tb>
<tb> load
<tb>
<tb>
<tb>
<tb> Temperature <SEP> 480 <SEP> C
<tb>
 

 <Desc / Clms Page number 25>

 The results are the solvents:

   
TABLE 5
 EMI25.1
 
<tb> Load <SEP> Product
<tb>
<tb> Yield <SEP> in <SEP> volume <SEP> @ <SEP> (C4 +) <SEP> - <SEP> 85.0
<tb>
 
 EMI25.2
 Density <>.! #. ï. at 16 C 55.6 "46.3 Olefin content, volume) i 0, E -1.0
 EMI25.3
 
<tb> <SEP> content in aromatic <SEP>, <SEP> vol. <SEP> 13.2 <SEP> 4, <SEP>
<tb>
<tb> aromatics <SEP> synthetic, <SEP> vol. <SEP> - <SEP> 32.3
<tb>
<tb>
<tb> Number <SEP> of octane
<tb>
 
 EMI25.4
 Claire 1-1 5L. , 5 9.3.5 F-l + 3 cm3 lead 77, C iso + L, C4:

   , t et ra ethyl 1 Analysis of the gases H2 produced in diab / lûu liters of chm: '!: 8 7¯4. ; ± r! C -.- C, produced in draS / 100 liters of feed 5.27- Carbon, weight in 1 "of the chmy¯. 1.0
This example illustrates the high synthesis of aromatics:.: And the improvement of the octane number, as well as the low production of C1-C3 gas and the high production of hydrogen.
 EMI25.5
 which can be achieved with the catalysts of this invention.



  Similar results are obtained by replacing cobalt with nickel and molybdenum with chromium.



   EXAMPLE VI
The same catalyst as in Example V is used to subject to hydrogen desulphurization a gas oil of
 EMI25.6
 straight-run distillation from Santa l..aria Valley (: state of California) having a boiling range of SUS-343 C and a specific gravity of 1. * I, .I.



  . de as well as a sulfur content of 2,2; -. The working conditions are as follows:

 <Desc / Clms Page number 26>

 
 EMI26.1
 
<tb> Temperature <SEP> 399 C
<tb>
 
 EMI26.2
 Pressure 35 kg / em (connected)
 EMI26.3
 
<tb> Hydrogen <SEP> 53640 <SEP> dm3 / 100 <SEP> 1.
<tb>
<tb>
<tb> Volumetric <SEP> speed <SEP> hourly <SEP> 2.0
<tb>
<tb>
<tb> to <SEP> the liquid <SEP> state
<tb>
 
The product collected during a 6 hour run contained on average between about 0.04% and 0., Sulfur, representing a sulfur removal of between approximately 96.5 and 98.



   From the foregoing description, it is evident that with the catalysts and adsorbents described herein, a very economical manufacturing process is combined with high catalytic activity, good adsorption capacity and high degree of wear resistance. . However, it is obvious that the foregoing description has been given only as an indication and in no way limiting and that various modifications can be made to it without thereby departing from the scope of the invention.


    

Claims (1)

CLAIMS 1. A method of agglomerating small catalyst particles in the form of larger granules having high abrasion resistance, characterized in that it consists in distributing these small catalyst particles in such a way as to bind them intimately together. -1 to each other in a clay compound, co-compound of clay obtained by intimately mixing in water, powdery bentonite clay washed with acid and powdery kaolin clay to form a wet plastic mass in which the kaolin / bentonite weight ratio is between about 35/65 and 5/95 on an anhydrous basis; in bringing this plastic mass to the shape desired for these catalyst granules; finally, in drying and calcining the shaped granules. 2. Method according to claim 1, characterized in that, to distribute the small catalyst particles in the clay compound, said particles are intimately incorporated into the wet plastic mass before the shaping, drying and calcination phases. . 3. Process according to Claim 1, characterized in that, in order to distribute the small particles of catalyst in the clay compound, an aqueous solution of a compound of a catalytically active component is intimately incorporated into the wet plastic mass. before forming, drying and calcining, and then decomposing this compound during calcination to form these small catalyst particles. 4. A process according to claim 1, characterized in that, for distributing the small catalyst particles in clay, the calcined and previously formed clay compound is impregnated with an aqueous solution of a compound of a constituent having catalytic activity, after which we dry and calcine the <Desc / Clms Page number 28> compound impregnated to decompose it and form the small catalyst particles. 5. Abrasion resistant catalyst granules characterized in that they consist essentially of a compound of a kaolin clay and an acid washed bentonite clay which are intimately mixed, which compound having was fortified by a process which consists of intimately mixing with water, a washed powdery bentonite clay - \ the acid and a powdery kaolin clay, which constitutes a wet plastic trap in which the weight ratio kaolin / bentonite is comprised between about 35/65 and 5/95 on an anhydrous basis, shaping some of this plastic to give it the desired shape for the catalyst granules, and drying and calcining the shaped granules. u. Abrasion resistant catalyst granules, characterized in that they contain at least 10% by weight of a clay compound distributed homogeneously according to the volumes of the catalyst granules, the remaining catalyst granules being composed of finely divided catalytic material intimately bound in a compound of a kaolin clay and an acid washed bantonite clay which are intimately mixed, which compound having been formed by a process of intimately mixing with water, powdery bentonite clay washed with acid and powdery kaolin clay, which constitutes a wet plastic trap in which the kaolin / bentonite weight ratio is between approximately 35/65 and 5/95 on an anhydrous basis, to form part of this plastic mass to give it the desired shape for the catalyst granules, and drying and calcining the shaped granules. 7. Catalyst granules according to claim 6, characterized in that they comprise between about 10 and 70% by weight of the clay compound distributed in such a way. homogeneous, depending on the volume of the catalyst granules and between about 90 and 30% of an adsorbent consisting of a gel-type oxide taken from the <Desc / Clms Page number 29> group consisting of silica, alumina, silica-alumina, titanium oxide, thorium oxide, zirconium oxide, and magnesia, the catalyst granules having been obtained by a process which consists of intimately mixing with water, a powdery bentonite clay washed with acid, a powdery kaolinic clay and this gel-type oxide serving as an adsorbent in powdery form, ca which gives a wet plastic mass in which the kaolin / bentonite weight ratio is between 35/65 and 5/95 on an anhydrous basis, in shaping part of this plastic mass to obtain catalyst granules, then to, subsequently dry and calcine the shaped granules. Catalyst granules according to claim 6, characterized in that they contain between about 22.5 and 57% by weight of the clay compound distributed homogeneously according to the volume of the catalyst granules, between about 35 and 65% by weight of a gel-type oxide serving as an adsorbent taken from the group consisting of silica., alumina, silica-alumina, titanium oxide, thorium oxide, titanium oxide. zirconium and magnesia and between about 6 and 21% by weight of a catalytic oxide taken from the class consisting of the oxides of the metals of group VI B and of group VIII of the periodic system, this gel-type oxide and this oxide catalyst being finely divided and bound in said clay compound obtained by a process which comprises mixing in with water an acid-washed powdery bentonite clay, a pulverulent kaolin clay and this gel-like oxide serving as an adsorbent in pulverulent form, which gives a wet plastic mass in which the kaolin / bentonite weight ratio is between 35/65 and 5/95 on an anhydrous basis, at shaping part of this plastic mass to obtain catalyst granules, then subsequently drying and calcining the shaped granules. 9. Catalyst granules according to claim b, characterized in that they contain between approximately 22.5 "and 27% in <Desc / Clms Page number 30> EMI30.1 weight of the clay compound distributed as hù:! 10i:;. H1G depending on the volume of the catalyst granules, between about .55 and 65 c / a by weight of a gel-like oxide serving as an adsorbent taken up in the a group consisting of silica, alumina, silica-alumina, titanium oxide, thorium oxide, zirconium oxide and magnesia and between about 5 and 15% by weight of an oxide of molybdenum , the above gel type oxide and molybdenum oxide being finely divided and incorporated into said clay compound EMI30.2 obtained by a process which consists in mixing ini, -L11! '3t'10n't with water, a powdery bentonite clay lrTr'. ; "# .7 ':. Eide, a pulverulent kaolin clay and this oxide of the type fel without adsorbent in a pulverulent form, c." t ;; c'.f: r: i. a wet plastic bundle in which the weight ratio b.101injbûl! toll¯: - te is between 35 / v5 and 5 / S5 on an anhydrous basis, to shape part of this plastic mass to obtain 'gra- EMI30.3 nules of catalyst, then to subsequently dry and calcine the shaped granules. 10. Abrasion resistant catalyst granules, ca- EMI30.4 characterized in that they contain between about .5 and 57 "by weight of the clay compound distributed in an honest manner.; depending on the volume of the catalyst granules, between about 35 and 65,. by weight of an oxide of the catalyst. gel type serving as an adsorbent caught in the EMI30.5 group that constituting silica, alu,: ÍJ18, 3a .¯: 1.-c.: - lu:.:. ne, titanium oxide, thorium oxide, nircod oxide u ... ut Magnesia and between about 5 and 15; by weight of a cyde do r '; JJ.y1j- dene and between about 1 and 1J by weight of cot1 t oxide, gel-type oxide, molybdenum oxide and this o-¯: cl .: of cobalt .binding finely divided and incorporated into said compound cl ', r: zI¯L obtained r a process which consists in mixing intz.t ::: .. rit with] t 1- <, t;! 1 .,;: powdered bentonite clay washed with:! 1acldo, a pulverulent knolinic island and this gel-like oxide as an adsorbent <Desc / Clms Page number 31> in powder form, which gives a wet plastic mass in which the kaolin / bentonite weight ratio is between 35/65 and 5/95 on an anhydrous basis, to shape part of this plastic mass to obtain granules catalyst, then subsequently drying and calcining the shaped granules. 11. Catalyst granules according to claim 10, characterized in that the gel-type adsorbent oxide is an alumina gel. 12. Catalyst granules according to claim 10, characterized in that said adsorbent is a powdered alumina gel having an average particle size of less than about 300 mesh. 13. A method of contacting, characterized in that a fluid is brought into contact with adsorbent granules obtained by the method according to any one of [claims 5 to 12 and, in this contacting method, the Granules are normally subjected to mechanical forces of abrasion which remove the adsorbent material by attrition. 14. The method of claim 13, characterized in that said catalytic contacting process is a desulphurization of a mineral hydrocarbon oil at a temperature between about 315 and 595 C and the catalyst granules used comprise between about 22.5 to 57% by weight of the aforementioned clay compound, between about 35 and 65% by weight of alumina gel, between about 5 and 15% by weight of molybdenum oxide, and between about 1 and 6% by weight of cobalt oxide.