WO2012131687A1 - Supports de catalyseur en couches et leur procédé de fabrication - Google Patents

Supports de catalyseur en couches et leur procédé de fabrication Download PDF

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Publication number
WO2012131687A1
WO2012131687A1 PCT/IN2011/000243 IN2011000243W WO2012131687A1 WO 2012131687 A1 WO2012131687 A1 WO 2012131687A1 IN 2011000243 W IN2011000243 W IN 2011000243W WO 2012131687 A1 WO2012131687 A1 WO 2012131687A1
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Prior art keywords
carrier
catalyst
carrier material
mixture
alumina
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PCT/IN2011/000243
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English (en)
Inventor
Rikeshchandra Sharadchandra JOSHI
Dhananjay Prabhakar SABDE
Rustom Minocher Cursetji
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Süd-Chemie India Private Ltd.
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Publication of WO2012131687A1 publication Critical patent/WO2012131687A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B01J37/0223—Coating of particles by rotation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B01J35/51—

Definitions

  • This invention relates to layered catalyst carriers that are used in chemical, petrochemical, petroleum refining, hydrocarbon processing and other processing industries and more particularly to layered-catalyst carriers having catalyst support coating(s) provided on particulate cores of spherical or other configuration.
  • This invention provides a process/method for laying thin and uniform catalyst carrier (layers)coatings on inert core supports.
  • This invention also relates to a synergistic mixture of two catalyst carrier materials, the first being a wide pore carrier material and the second being a said carrier material that inter alia synergistically provides better adherability to the mixture.
  • this invention relates to layered catalysts for dehydrogenation of hydrocarbons and other processes in the industry sectors mentioned hereinabove.
  • the three major members of a layered catalyst architecture are: a. the inert core support;
  • An inert core support is the basic mechanical support (substrate) whereupon the catalyst architecture is built up, an example whereof are said spheres (spherical elements) referred to hereinabove. Said carrier and catalyst element are laid on said spherical elements.
  • a carrier is the element of said catalyst architecture that primarily provides the large internal and external surface area for the dispersal of the catalyst element thereupon.
  • Said carrier is installed on a said core support(s) in the form of a coating(s)(layers).
  • One or more said catalyst elements, as required, are either dispersed onto said carrier or impregnated thereinto.
  • the catalyst element is the component (member) that provides the catalytic action. It may be any of the metals or compounds that provide catalytic action. Examples of such metals are the group of precious metals (PGMs) which includes platinum(Pt), rhodium(Rh), palladium(Pd) and others.
  • a layered catalyst carrier(LCC for short) comprises a said inert core support and a said carrier, with the latter laid on the former, as mentioned, in the form of a layer.
  • said cores are in the form of spherical elements the carriers are formed into coatings(shells) around the spherical surfaces thereof.
  • the term 'inert core support is shortened to either 'core' or 'inert support' in the further specification hereinbelow.
  • said cores may be spherical in shape or may be in other forms and shapes, regular or irregular, for example, pellets and tubular structures, They may be prepared by any of the known processes of agglomeration, such as for example, granulation, pelletisation and others.
  • the cores of the invention may also be in the form of extrudates.
  • RIOs Refractory Inorganic Oxides
  • cores of metallic construction are also within the scope of the invention.
  • hollow and solid spherical cores(spherical elements) are within the scope of the invention.
  • RIOs examples of RIOs that may be used to form said cores, without limitation to the scope of the invention, are alpha alumina, silica, zirconia, titania, cordierite, indialite and others. These may be used singly or as mixtures. Said cores may be also of non-oxide inorganic materials such as, for example, silicon carbide.
  • the preferred materials of construction for the cores of this invention are the RIOs: cordierite and indialite. More preferably, said material of construction is indialite.
  • the material of construction of said carriers are also RIOs or mixtures thereof and any of them can be adopted as the carrier material within the scope of the invention.
  • Examples of said carrier RIOs without limitation to the scope of the invention are: the various aluminas including transitional alumina, rare earth oxides, silica, clay minerals, and other metallic and non-metallic oxides. Non-RIO materials such as zeolites are also used. The preferred materials for this invention are discussed hereinbelow.
  • the RIO material for the formation of said core elements may further comprise one or more suitable additives for control and modification of the physical and chemical properties thereof such as porosity, thermal conductivity, bulk density, impact strength and others.
  • the RIO material for use as the carrier material may further comprise one or more suitable additives that promote catalysis, or are modifiers or structure stabililisers or others.
  • outer and inner RIOs are used to refer to the RIO materials of construction adopted for the said carrier and core respectively.
  • first and second aluminas refer to the two aluminas forming the coating material mixture as elaborated further hereinbelow.
  • RIO as used in reference to said cores or said carriers is intended to include all suitable materials, refractory inorganic oxides, non-oxide inorganic materials, metallic, non-metallic oxides and other compounds.
  • Said catalyst elements may be any of the metallic or non-metallic elements and compounds that possess catalytic activity. Examples are the PGMs. Non-precious(base) metals and also some oxides and other compounds that possess the required catalytic properties for the reaction being considered can also be simply and easily installed on the LCCs of the invention. Any said catalyst element(s) may be easily and simply dispersed/impregnated on the layered carriers of the invention by means of known processes in the art.
  • the LCCs of the invention are easily and simply adapted to produce catalyst assemblies for numerous process applications by simply dispersing/impregnating the appropriate powdered catalytic material thereupon.
  • the layered carriers of the invention may be loaded with one or more of the said catalyst elements or otherwise. Further, within the scope of the invention the loading of the catalyst elements on the carriers of the invention may be carried out before the laying of said carriers on the cores or thereafter. Catalyst elements may be installed individually or as mixtures. As mentioned, different processes are known in the art for said dispersal/ impregnation of the catalyst element onto the carrier.
  • 'layered catalyst compositions', 'coated substrate', 'coated carriers', 'layered catalysts' are used in the art to refer to said layered catalyst carriers which, are the subject of this invention.
  • Cores are also referred to in the art as substrates and said catalyst elements are referred to alternatively as active elements or just as catalysts.
  • Said carriers are also referred to in some parts herein as support coatings or supports. The said terms may therefore be considered to be synonymous.
  • the completed catalyst architecture comprising the support and the catalyst element and including said carrier is referred to as the 'catalyst assembly' herein.
  • Said assembly may additionally contain one or more further components that provide secondary and/or
  • complementary catalyst activity such as promoters and modifiers.
  • additives may also be, for functions such as carrier structure stabilisation, oxygen storage and others as mentioned above,.
  • the layered carrier product according to the different aspects of the invention and the process for making the layered carrier product of the invention are described only in the context of cores that are in the form of a plurality of discrete spherical elements such as are widely used in petroleum refining, petrochemical and hydrocarbon sectors. This is in the interests of conciseness and without limitation to the scope of the invention.
  • the process of the invention is simply and easily adapted to making other types of layered carriers referred to hereinabove, that is, of types other than said particulate spherical entities. Because of that, with reference to terms such as, for example, layers, surfaces, coatings, cores, catalyst elements and others, sometimes the singular may be relevant to the context and sometimes the plural. In some cases, both the singular and plural may be relevant. The interpretation that confers the widest scope to the text may be considered to be applicable and may be adopted.
  • Various slurry-based processes are used in the art for the application of said carriers on said spherical elements. In these processes, the carrier material in appropriate particle size(s) is slurried in a suitable liquid, which is generally water. The spherical elements are contacted with the slurry and thereafter subjected to a process of calcination that bonds the carrier to the core.
  • the calcination process is regulated such as to obtain the right degree of porosity and other properties of the carrier layer(coating).
  • Said contacting is by immersion, by spraying, by the incipient wetness method or other methods.
  • binders are used during said contacting.
  • slurry-based processes as used herein includes processes wherein the carrier material is employed in the form of colloidal solutions (cols), sols and other types of dispersions.
  • DL diffusional limitation
  • the crux of the problem is the variations in the thickness of said carrier layer across the surfaces thereof and the variations in the mean pore diameters and other pore parameters across the carrier surfaces. Diffusion resistance is greater the greater the said thickness and the non-uniformity thereof arises from the said variations in layer thickness and in pore characteristics.
  • Said deep interior sites also arise by migration of catalyst elements from sites located closer to the pore mouths into the pore interiors. Depending on the porosity of the core(sphere) material such migration may extend into the core material also. Said migration occurs over time during the life of the catalyst and also leads to said underutilisation.
  • This invention observes that, in view of the above, it is important that: i. said layers are thin;
  • said layers are uniform, that is, the layer thickness is substantially uniform across the layer surfaces;
  • diameters thereof are such that the said diffusion resistance is minimised and that it is substantially uniform across said surfaces;
  • Rende D et al primarily deals with the problem of insufficient attrition resistance and provides for fibrous reinforcement of the layers. Rende et al, however, report that by using a fluidisation process of layer deposition, layer thicknesses down to 40 microns are possible although the degree of layer thickness uniformity achievable is not disclosed.
  • Pore parameter harmonisation herein refers to the process of reducing/minimising the variations in pore parameters across the surfaces of said layers.
  • Pore engineering in the prior art has comprised treatment (such as calcination) of the carrier materia] such as to alter the surface area(BET area).
  • Pore engineering in the prior art has not extended to proposing or adoption of wide pore carrier materials. This invention finds that adoption of wide pore carrier material(s) yields a more harmonised layer and improved catalyst efficiency and performance particularly with regard to selectivity. This is novel and has apparently not been disclosed in the prior art.
  • the carrier material mixture of the invention comprises at least one carrier material component that, with or without a thermal treatment thereof, primarily imparts said wide pore characteristic to the layer.
  • a second component synergisticaliy provides better adherablility to the mixture as a whole.
  • said second component is also a carrier material that can provide support for the catalyst element(s). It may have other functions within the scope of the invention. Also, within the scope of the invention, said mixture may comprise other carrier material components, third, fourth and others that additionally provide carrier(support) function and one or more of the other functions listed herein.
  • the novel process of the invention for installing said layers is a dry spray process and the novel mixture of the invention comprises a mixture of a carrier material component having a wide pore characteristic and a carrier material component that synergisticaliy interacts with the first(and or with one or more of the others) to correct the low adherability associated with wide pore carrier materials and restores it to workable levels.
  • Said process and mixture are not apparently disclosed in the prior art.
  • the magnitude of said diffusional resistance(DR) and the said uniformity thereof is of particular relevance in petroleum refining, petrochemical and hydrocarbon processing operations wherein said resistances are high because of the large and long reactant molecules involved. The adverse impact of said non-uniformity can be high in such processes.
  • a further object of the invention is to devise a said process that offers a high degree of controllability of the layer forming operation so as to achieve highly uniform layers of any thickness.
  • the process of the invention is therefore capable of laying uniform layers of any thickness.
  • the process is particularly suitable for laying highly uniform layers of thicknesses 300 microns(micrometres) and below, a range that is not within the capability of conventional slurry- based processes.
  • a still further object of the invention is to substantially equalise and harmonise the said pore parameters such that the said diffusional resistances are low and substantially uniform across the said layer surfaces.
  • Said desirable features ensure that said diffusion resistances remain low and are substantially equalised over substantially the whole of said carrier layer surfaces.
  • the other purpose is to ensure that diffusion of the catalyst element and the carrier material across the layer-core boundaries during operation is prevented/minimised.
  • This invention is therefore apparently the first to develop a said dry spray process of carrier deposition that provides a high degree of controllability of the coating laying process.
  • the process offers precision in layer formation and reliability as regards the uniformity of thickness across the layer surfaces.
  • It is also apparently the first process that can provide precise layer thicknesses in the range 300 microns and below.
  • This invention is also apparently the first in achieving said pore parameter equalisation/ harmonisation objective by adoption of novel pore engineering steps such as provision of a novel carrier material mixture that preferably comprises two aluminas each obtained by a different process of formation and a novel heat treatment procedure for the same.
  • This invention provides a novel dry spray process wherein the carrier material, with or without the catalyst impregnated therein, is deposited by spraying the powdered carrier material on the spherical elements, in a dry condition.
  • the deposition is by a dry spraying operation utilising a gas as the dispersing medium.
  • a binder liquid(or binder solution) is applied on the inert cores to promote bonding of the carrier material on the core surfaces.
  • the quantity of binder solution applied is carefully controlled so as to ensure that at no time any free binder liquid is present in the core material. Ensuring absence of free liquid in and around the core material during the dry spraying of the carrier material leads to improved uniformity in layer thickness. Free binder liquid if present tends to disturb the carrier material layer(s) and cause variations in the thicknesses thereof.
  • binder is preferably by spraying.
  • a separate spraying system for the binder solution is provided on the pan coater or other coating equipment that may be used.
  • the binder is applied before each spraying of the dry carrier material powder.
  • This invention further provides a novel carrier material composition that minimises said diffusion resistances and offers said equalisation/harmonisation of the pore configurations and parameters.
  • the invention also offers a process of admixture for making said novel synergistic carrier material mixture (composition).
  • Said novel carrier material mixture of the invention comprises a mixture of a wide pore carrier material with at least one other component.
  • said second component synergistically enhances the adhesivity of the mixture and takes care of the adhesion deficit arising from the adoption of said wide pore carrier materials.
  • the use of the wide pore material results in larger dia. pores, the diffusional resistances whereof are more equalised/harmonised.
  • the use of said mixture is found by this invention to result in more uniformity in pore diameters.
  • 'RIO' is intended to include all materials, whether refractory inorganic oxide or otherwise, that are suitable for the respective application, that is, for the core or for the carrier. Examples of such materials are provided hereinabove.
  • the characteristics of the layer formed by such a mixture are: (i) larger dia pores, (ii) a greater degree of equalisation in pore diameters across the layer surface, and (iii) a greater degree of equalisation/harmonisation of the diffusion resistances and other pore parameters.
  • This combination of properties is not obtainable by adoption of single carrier materials.
  • This invention observes that the mixture offers an unexpected synergy in respect of pore properties. Said synergy is in respect of adherability(adhesiveness) and pore harmonisation.
  • the invention also additionally provides a process for treatment of said mixture that provides a greater degree of , pore parameter equalisation/harmonisation. Said additional procedure of the invention may be optionally adopted and applied to the said carrier material mixture of the invention.
  • a process for making layered catalyst carrier(s) such as for applications in petroleum refining, petrochemicals and hydrocarbon processing and other sectors, comprising particulate core material having one or more layers(coatings) of catalyst carriers provided on the surfaces thereof, said process comprising the steps of:
  • a layered catalyst carrier(s) such as for applications in petroleum refining, petrochemicals and hydrocarbon processing and other sectors, made by the process of the invention disclosed hereinabove as the first aspect of the invention.
  • a carrier material for application as catalyst-carrier layers(coatings) on the surfaces of inert core supports of layered catalyst carriers such as for applications in petroleum refining, petrochemicals and hydrocarbon processing and other sectors, comprising a mixture of at least a first, and a second carrier material component, said first component being a wide pore carrier material and the said second carrier material, being either peptisable or being in a col or sol form, or a mixture thereof.
  • a layered catalyst carrier(s) such as for applications in petroleum refining, petrochemicals and hydrocarbon processing and other sectors, comprising particulate core material having one or more layers(coatings) of catalyst carriers provided on the surfaces thereof, wherein the carrier material of at least one layer thereof comprises a mixture of first and second carrier material components, as disclosed hereinabove as the third aspect of the invention.
  • a layered catalyst carrier(s) such as for applications in petroleum refining, petrochemicals and hydrocarbon processing and other sectors, comprising particulate core material having one or more layers(coatings) of catalyst carriers provided on the surfaces thereof, at least one said layer thereof having a thickness not exceeding 300 microns.
  • the said particulate core material may be any RIO or other material.
  • Said material may be oxide, non-oxide, metallic or non-metallic or others. Examples of some suitable core materials have been given hereinabove.
  • the core material is either cordierite or indialite and more preferably the latter.
  • the inert core material is indialite.
  • the invention can be easily and simply adapted for use with other core materials including, and particularly cordierite.
  • Said core particles may be spherical or of any other shape.
  • Said shapes may be regular or irregular and may be hollow or otherwise. Within the scope of the invention, they may be fabricated by any known process including by any of the known agglomeration processes such as for example, granulation, pelletisation and others.
  • Said particulate core material may also be an extrudate having any of the many possible cross- sections.
  • Said core material may also be any mixture of the abovementioned variants within the scope of the invention.
  • Said core particle surfaces may be plain or of any other configuration within the scope of the invention. Shapes such as those used in absorption tower packings are also within the scope of the invention.
  • the said core particles are spherical in shape and possess generally plain surfaces.
  • said core particles are small in diameter(or effective diameter) not exceeding about 5 mm. As their surface areas are correspondingly small, it helps in minimising said catalyst site migration into the core material. Accordingly, the core spheres in the embodiments described hereinbelow are small.
  • the said core spherical elements are calcined at a temperature of about 500 C to about 1400 C before taking up dry spraying of the carrier material thereupon.
  • This invention observes that indialite is particularly adapted for small core diameters as low as 5 mm and below and for installing thin layers of 300 microns and below thereupon.
  • Indialite is a high temperature form of cordierite and has a different structure as established by x-ray crystollagraphic analysis. It has greater thermal stability in contrast to cordierite. The distortion index of indialite is also lower than that of cordierite.
  • the LCC of the invention incorporating indialite cores has excellent IB, abrasion resistance, CBD, CS and other properties. Said properties are controllable by varying the component ratio in the carrier material mixture of the invention.
  • Said carrier material may also be any material: a RIO or a non-RIO. It may be any of the oxides of the rare earth metals, alkali earth metals, transition metals or metals of the lanthanide series, or any mixture thereof within the scope of the invention.
  • Said carrier material may further comprise admixed therein one or more compounds with functional properties such as stabilisation of the carrier structure, catalysis
  • Said carrier material for the formation of said layers may be with or without catalyst element(s) dispersed/impregnated thereupon.
  • Carrier material containing the catalyst element(s) is referred to herein as loaded carrier material or loaded carrier for short.
  • Said loading may comprise one catalyst element or a plurality thereof.
  • a said layer of the layered catalyst carrier of the invention may comprise one catalyst element or more.
  • the layered catalyst carrier may comprise a plurality of said layers and the said different layers thereof may be loaded with different catalyst elements(or mixtures thereof) within the scope of the invention.
  • the said carrier material mixture of the invention is a mixture of at least two carrier material components.
  • said first component can be any wide pore carrier material.
  • the said wide pore characteristic may be inherent in said first component material or may be developed by suitable heat treatment thereof. In some cases, the wide pore characteristic may be partly of an inherent nature and partly developed by the treatment procedure adopted.
  • carrier materials has been discussed hereinabove. Any of these carrier materials that have the said wide-pore property or that can be heat treated to acquire the wide-pore characteristic can be adopted as the first component of the carrier material mixture of the invention.
  • the material of said first component may be any carrier material, the only requirement being that they are in the wide-pore form or are convertible to the wide-pore form by the heat treatment procedure described herein.
  • Typical carrier materials that possess, or that can be modified by thermal treatment to achieve said wide-pore characteristic are the various aluminas, the rare earth oxides and others. These materials are simply and easily converted into the wide-pore form by the said heat treatment procedure.
  • Said first component is preferably one of the aluminas, or ceria or zirconia. More preferably the material of construction of said first component is an alumina obtained by a process of precipitation from a suitable solution thereof. Still more preferably the first - component is either precipitated delta or theta alumina, or mixtures thereof.
  • the second component of the carrier material mixture can be any of the carrier materials enumerated hereinabove that are peptisable.
  • said second component is also an alumina but derived by the alkoxide route. More preferably, said second component alumina is either delta alumina or theta alumina or a mixture thereof.
  • Said second component can thus be any peptisable carrier material in the broadest aspect of the invention. It can alternatively be a col or sol of any one of the several suitable RIOs or other material that are listed hereinabove.
  • said delta or theta alumina or a mixture thereof for the said first component is derived by precipitation from a suitable solution thereof by physical or chemical means and the second obtained through the alkoxide route.
  • Use of mixtures of said carrier materials for the said first and second components is within the scope of the invention.
  • Said carrier material mixture of the invention may comprise additionally third, fourth and higher order components within the scope of the invention.
  • the said second component may be a col/sol of said aluminas or of mixtures thereof or of ceria, zirconia, silica or other metal oxides within the scope of the invention. Mixtures of the abovecited materials are within the scope of the invention.
  • the alumina obtained by the precipitation route is referred to further herein as Compound A and the other alumina derived through the alkoxide route as Compound B.
  • Compounds A and B have been adopted in the examples described hereinbelow.
  • the mixture of compounds A and B is subjected to a novel calcination procedure developed of the invention before spraying onto the core by means of the said dry process.
  • compositions of the said two alumina components, (Compounds A and B) in the carrier material mixture of the invention are within the scope of the invention.
  • the ratio of the two said alumina components(Compound A to Compound B) is upto about 10: 1 by wt.
  • the more preferred value of the said ratio of compound A to compound B is from about 2:1 by wt. to about 2.5: 1 by wt.
  • the alumina carrier material may be modified by the addition of stabilisers, promoters, and others as required by the specific process intended to be catalysed, within the scope of the invention.
  • the aluminas may be any of the following: gamma, delta, theta and eta or transitional alumina.
  • This invention has discovered through experimental work the surprising synergy exhibited by a mixture of a wide pore carrier material and a peptisable carrier material. Similar synergy is also observed in a mixture of the former with a carrier material in a col/sol form. At different compositions of the said mixture different mean pore diameters of the formed layers are found.
  • indicators of catalyst performance change with the composition of the carrier material mixture and exhibit a maximum corresponding to a maximum in said synergy.
  • the process of the invention further benefit in the form of lowered diffusion resistance and further equalisation thereof is realised.
  • Forming said layers by the novel dry spraying process of the invention further helps to reduce the said layer-core interface migration of catalyst element(s).
  • the optional adoption of the novel treatment procedure of the invention for said carrier materials enhances said harmonisation and lowers diffusion resistances
  • Said dry spraying may be carried out by any conventional method within the scope of the invention including by fluidisation procedures.
  • the process of spraying is by means of one or more suitable spray guns.
  • the propellant may be any gas but is preferably air.
  • the relative movement during said dry spraying passes may be provided by movement imparted to said spray gun(s) or to the platform holding the core particulate material to be sprayed or both.
  • said relative movement may be reciprocating, oscillatory, vibratory, rotatory or others.
  • said platform is a pan coater; the said motion is rotatory and the pan inclined at an angle.
  • Examples of other equipment that can be utilised to carry out the dry spray process of the invention are fluid bed dryers, tablet and capsule coaters and others. All such equipment are within the scope of the invention.
  • the alumina materials for the said first and second components are separately subjected to pore- modification by calcination procedures.
  • the temperature for said calcination ranges from about 400 C to about 1000 C.
  • the preferred temperature slot is about 500C to 900 C.
  • the calcination period may extend from about 1 to about 10 h and is preferably in the range of about 2 to 6 hours.
  • the carrier material for dry spraying is preferably ground and milled down to about 5 to about 80 microns, more preferably to about 5 to 20 microns.
  • dry milling, jet milling, ball/jar milling (wet or dry) or any of the other known processes may be employed.
  • ball/jar milling wet or dry
  • the jar milling option is adopted.
  • the preferred ratio of the alumina components and ball media is about 1 :0.15 to 1 :5 and more preferably about 1 : 1 to 1 :3.
  • the ball milling media may be any of the known ones but are preferably stainless steel, zirconia, or ceramic and more preferably ceramic.
  • the carrier material to be dry sprayed is charged into a pan-coater which is run preferably at about 40 to about 100 rpm and more preferably between about 40 to 60 rpm. Preferably the angle of inclination of the pan coater is maintained at about 30 degrees to 45 degrees.
  • the carrier material may be wetted before the commencement of the first said spray operation. Said spraying operations are also referred to herein as passes.
  • the wetting may be carried out using any liquid.
  • the wetting liquid is distilled water. The wetting process encourages bonding between the carrier layer and the core surfaces.
  • the non-wetting alternative offers other advantages.
  • the said preliminary wetting operation may be carried out on the cores before they are charged into the pan coater or after such charging.
  • said wetting may be continued for a duration of time such that a pre-determined amount of water is absorbed by the particulate core mass.
  • the range of targeted weight increase during this process is preferably from about 15% by wt to about 45% by wt. and more preferably from about 10% by wt to about 40% by wt.
  • the duration of said wetting is from about 3 to about 24 h, preferably from about 12 h to 15 h.
  • the spherical elements are dried by a process of contact drying wherein absorbent paper or other material is employed to remove water on the surface.
  • the said wetting of the core material is not carried out.
  • the layered carrier obtained by such a process was found to have better attrition resistance than the product obtained by adopting said wetting, all other parameters being the same.
  • the core spherical elements are subjected to contact drying to remove substantially all free water clinging to the surfaces thereof. This may be done by using absorbent paper or other means.
  • the spherical elements mass is now ready for the dry spraying operation. Other methods of removing said surface water are within the scope of the invention.
  • a said layer may be formed in a single said dry spraying operation or by a plurality thereof each such operation laying a thin deposit of the carrier material on the core surfaces.
  • binding and/or bonding agents may be employed during said spraying and layer building operation, or otherwise. Adoption of said binders is preferable.
  • a binder composition comprising three individual binder components is employed. The desired characteristics of the three said binder components are elaborated hereinbelow.
  • the known binder materials fall into three classes and each of the three binder components going into the mixture of the invention can be any member of the respective class within the scope of the invention.
  • any of the known binder materials may be employed.
  • the preferred binder of the invention is a composition.
  • Said composition comprises first, second and third components, each of which is an individual binder material,
  • Said first component comprises a colloidal solution of alumina or other metal oxide material.
  • Said second component is one that imparts or enhances the acid resistance of the LCC.
  • the preferred material for the second component is aluminium nitrate.
  • Said third component is an organic binder that enhances the viscosity of the composition.
  • the preferred organic binder of the invention is HPMC(hydroxypropyl methyl cellulose).
  • the application of the binder may also be carried out simultaneously with the spraying. All arrangements, simultaneous, sequential or hybrids of the two are within the scope of the invention.
  • Both said first and second classes of binder compounds are generally inorganic compounds.
  • An inorganic binder will fall into one of the said two classes but some inorganic binders may belong to both, the properties of these binder compounds being such that they provide binding action as also impart acid resistance to the LCC as a whole.
  • an individual member of a class may be adopted or a mixture of the said members of the class, within the scope of the invention.
  • the binder solution(composition) can also be looked upon as a mixture of one or more inorganic binder compounds and an organic binder compound.
  • the binder compound is dispersed or dissolved in a suitable solvent which may be water or a mixture of water and a lower alcohol(s).
  • the spraying of the binder solution is carried out by means of spray nozzles installed over the said pan coater.
  • the binder composition of the invention is preferably applied on the base material, said base material being either uncoated spherical core elements or partially coated spherical core elements that are in different stages of the coating process. Said application by spraying may be before each dry spraying operation or simultaneously therewith.
  • Said fixing operation is preferably by calcination of the deposited layer.
  • said fixing by calcination may be carried out at the completion of a layer or during the formation of the layer. In case of the latter, said fixing by calcination may preferably be done after each said spraying operation, that is, upon laying of each deposit of the carrier material.
  • the calcination process binds the carrier material to the core surface or to a previously laid layer or deposit. Said process also develops the said pores in the deposited layer.
  • the inorganic binder compounds preferred are, but not limited to, alumina, silica, aluminium nitrate, aluminium phosphate and colloidal alumina sol.
  • the selection of organic binder compounds suitable is from, but is not limited to, HPMC(hydroxypropyl methyl cellulose), starch and other polymers, PVA(poly vinyl alcohol), and PEG(polyethylene glycol) having considerable amount of cross-linking.
  • the proportion of the binder compound(s) in the binder solution depends on the carrier material loading in the layer.
  • the ratio of the binder compound(s) to the solvent is from about 10% by wt. to about 25% by wt. More, preferably said ratio is about 20% by wt.
  • the preferred range for inorganic binders with respect to the amount of carrier material is . about 1 % by wt to about 10% by wt and preferably from 1% to 6% by wt.
  • the corresponding figure for organic binder(s) is upto about 3% by wt. and preferably upto about 0.5% by wt.
  • the inorganic and organic binder components cited above are precursors that undergo decomposition on heating.
  • the preferred temperature range for said heating operation is from about 100 C to about 400 C and more preferably from about 100 C to 270 C.
  • the solvent for the binder solution is preferably either water or a water/lower alcohol mixture. If the latter is used the preferred ratio of water to alcohol is from about 0 to about 10 v/v, more preferably about 0 to 5 v/v.
  • the loading of the carrier material, with or without the catalyst thereof, on said spherical support may be from about 10% to 80% by wt of the support(core material/base material). Preferably, the loading is about 20% to 40% by wt.
  • the 'green' spherical carriers are subjected to a process of calcination at temperatures from about 100 C to 900 C, preferably in the temperature range from about 100 C to 500 C.
  • Any active catalyst metal(and/or compound) may be deposited on said carriers before said dry spraying and layer formation and/or on the carriers after they have been deposited in the form of coatings on said spherical supports. Commonly said active catalyst metals are from Group III to XII of the periodic table (IUPAC). Widely used active metals are Pt, Pd, Rh, Re, Ru, Os, Sn and Ir.
  • Preferred promoter / modifying /dispersing agents are elements/oxides of boron, barium, Li, Ca, Ba, Zn, Si, Sm, Ce and other alkali and alkaline earth metals. Any combination of these elements/oxides may be installed on the said carrier layer(s) of the invention. The factors affecting the choice of said elements are the reaction to be catalysed, the degree of catalysis desired and others.
  • the dry spray layering process of the invention is simple and for thin layers, if required, the operation can be reduced to a single spraying step.
  • the carrier material is dry sprayed on said spherical elements. After every carrier material spraying pass a binder solution is sprayed.
  • the operation is carried out in a pan coater whose rpm is set at about 40 to 100 rpm. Preferably, the rotation is kept at about 40 to 60 rpm. Agitation(pan rotation) may be continued from about 0.5 h to about 3 hours. Preferably, the agitation is continued for about 1 to 2 h per batch.
  • the pan angle is set at about 5 deg. to 70 degrees, preferably it is kept at about 30 deg to 45 deg.
  • Wetting of the core material prior to coating is adopted. Wetting is carried out by immersion in distilled water. The wetting period is preferably from about 3 h to about 24 h, preferably from about 12 h to 15 hours.
  • the wetted spherical elements are pat dried.
  • the weight increase of the core material is targeted at from about 5% to 25% by wt. More preferably the spherical elements where the weight increase is in the range of about 10% to 20% by wt is taken up for dry spraying of the carrier material. Most preferably said range is 15% to 20% by wt.
  • the "green" layered carriers are then calcined at temperatures ranging from about 100 C to about 900 C, preferably in the range of about 100 C to 500 C for a period of time from about 1 h to about 7 h, preferably from about 2 h to about 5 hours.
  • said wetting step is not included, all other steps being as in the abovementioned embodiment.
  • novel features of this invention are easily and simply adapted to any said catalyst assembl and are particularly relevant for catalyst situations where diffusion limitation subsists.
  • a said layer may be laid in a single pass(operation) of said dry spray or multiple passes may be employed to build up a layer.
  • the layered catalyst carriers and the processes of the invention are easily and simply adapted for continuous processing. Such continuous processes and products thereof are within the scope of the invention.
  • the 2.33: 1 mixture(of A:B) appears to show better physico-chemical properties with respect to IB in addition to the parameter of catalyst efficiency.
  • Values given in Table 1 are for layers comprising compound A alone, compound B alone and mixtures of A and B. Two different mixtures have been studied. The table demonstrates the synergy arising from the use of a mixture of compounds A and B.
  • a very high level of control over the properties of the final catalyst assembly is offered by the carrier material mixture and the dry spray procedure of the invention. It permits engineering of the layers to realise specific parametric values. This is unlike as in prior art methods.
  • the parameters that can be effectively controlled are the layer thickness and its uniformity, reduction of diffusion resistances, harmonisation of the said resistances, catalyst efficiency and selectivity, CS, IB, CBD and others.
  • the degree of loading of the carrier material on the cores as well as the ratio of the compound A to compound B was found to influence the IB, CS and other properties including performance.
  • Table II shows the effect of adopting five different binders on IB and other properties of the LCC of the invention.
  • the A.B ratio has been maintained the same over the five samples and is the optimum ratio of 2.33:1 by wt.
  • the results show that the effect of changing the binder is rather small.
  • the preferred binder in the examples described hereinbelow is HPMC. .
  • Table III shows the effect of carrier material loading on the LCC properties. All the samples investigated are mixtures of the two aluminas and have the same A:B ratio, that is, the optimum value of 2.33: 1 by wt. Material A and B are mixtures of theta and delta alumina in all the examples. The same binder(HPMC) has been used in all the three samples.
  • the layer thickness was established by means of SEM images.
  • Table IV displays the parameter values for two experiments carried out to ascertain the effect of wetting of the core particles before being subjected to the dry spraying of the carrier material thereupon.
  • the spherical cores were wetted with water prior to the dry spray operation for layer deposition.
  • said pre-wetting operation was not resorted to.
  • identical amounts of water were used with the binder.
  • the layer thickness observed in the image of the layer according to the invention is about 235 to 291 microns, that is, a spread of about + 28 units about the mean.
  • the layer thickness in the image of the prior art process based layer is from about 53 to 205 microns.
  • the variation in this case is about + 76 units about the mean.
  • this invention provides for lower diffusion resistance and the said harmonisation thereof by adoption of thin and uniform layers and a wide pore carrier material which is used in the form of a mixture with a said second carrier material component.
  • the efficacy of the LCC of the invention should therefore be evident from variations in catalyst performance such as product selectivity and stability.
  • Catalytic trials using the LCC of the invention were conducted in confidence jointly with an actual user organisation that carries out laying of catalyst elements on layered catalyst carriers. This was done at their research laboratory where a rig was set up to verify the increased efficacy of a catalyst assembly using the LCC of the invention. Suitable catalyst elements for catalysing a hydrocarbon dehydrogenation reaction were dispersed on the LCC of the invention and the catalyst assembly formed.
  • the catalyst assembly spherical particles were slurried in the hydrocarbon to be dehydrogenated. The progress of the reaction was observed by taking BN(Bromine Number) measurements at successive time points. Layered catalyst carriers of two different specifications were used in the investigation. One of the LCC sample used had a wider mean pore dia. than the other. The mean pore dia. data of the two samples are presented in Table V below.
  • the catalyst mounted on the wide-pore LCC of the invention exhibited higher selectivity, stability and durability than the catalyst mounted on the LCC with smaller pore dia.
  • Table V gives parametric details of the two catalyst assembly samples used in the investigations.
  • the higher activity and stability shown of the larger pore diameter sample is attributable to reduced formation of by-products such as aromatics, which are known precursors of coke formation on the catalyst, which can cause rapid deactivation thereof.
  • This invention observes that increased diffusion resistances such as found in thick layers tend to increase said DL problems.
  • the interior sites become difficult to access. It also causes increases in residence times. This increases the scope for Said side reactions which brings down the efficiency, selectivity and stability of the catalyst. This scenario can be expected to occur even where the thickness of the thick layers employed is quite uniform.
  • catalyst assemblies Nos. 1,2,3 and 4 were prepared with different carrier material loading of 20%, 25%, 33% and 40% by wt. respectively.
  • the carrier material used was a mixture of compounds A and B in accordance with the invention.
  • the loading % is: Wt. of the carrier material mixture x 100
  • the A:B ratio was the same for the four said assemblies. Increased loading results in increased layer thickness.
  • the four samples thus comprised increasingly thick layers going from sample 1 to sample 4.
  • the catalysts performance passes through a maximum at about 33% by wt. loading.
  • the maximum represents the optimum layer thickness. Beyond the maximum the diffusion resistance as also the variation in diffusion resistances across the layer surfaces increases bringing down the catalysts performance.
  • the carrier material mixture comprised a theta and delta alumina mixture obtained by a precipitation route( compound A) with a theta alumina-delta alumina mixture derived by the alkoxide route(compound B).
  • the carrier material mixture was subjected to calcination and other treatment according to the procedure of the invention.
  • IB [(Weight of fines in gm)/(Total weight of the layered catalyst carrier material)] x 100
  • CBD Compact Bulk Density in gm/cc
  • Example 1 Layer thickness in microns, pore diameter in deg. Angstrom and others.
  • Indialite spheres (1.8mm, lOOOg) were taken in a polypropylene beaker of capacity 5000 mL. To this was added distilled water (1500g) under stirring to ensure that the indialite is completely submerged. The mixture was allowed to stand for 12h. After the stipulated time, the wet indialite was spread on an adsorbent paper-lined tray. Adequate precaution to ensure that clumping did not occur was taken. Further the indialite spheres were gradually patted to semi-dryness with paper towels. An increase in weight of indialite by 15% was observed. The indialite was transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained.
  • the angle of the pan coater was maintained at 45° throughout the layering process.
  • the outer refractory oxide (400g) comprised a single alumina component [Component B] calcined to 900°C followed by jar-milling to desired PS(particle size) of 20 microns.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 16g), Al (N0 3 ) 3 9H 2 0 (5%; 20g) and hydroxypropyl methyl cellulose (0.2%, 0.8g) dispersed in 250g of distilled water.
  • the process of layering of indialite cores by outer refractory oxide (carrier material mixture-in this case component B) was as follows.
  • outer refractory oxide (6g) was sprayed through a dosing element on the wet indialite in the rotating pan. It was allowed to mix thoroughly.
  • binder solution (4.2g) was sprayed through another dosing element on the indialite. Care was taken to see that the alumina did not stick to the wall surface of the pan.
  • Post- binder spraying another batch of outer refractory oxide (6g) was again sprayed. The process was continued till all the outer refractory oxide and binder solution were exhausted simultaneously.
  • the IB for this sample was found to be 1.7%.
  • the outer refractory oxide loading percent of this sample was found to be 40%.
  • Example 2 Indialite spheres (1.8mm, lOOOg) were taken in a polypropylene beaker of capacity 5000 mL. To this was added distilled water (1500g) under stirring to ensure that the indialite is completely submerged. The mixture was allowed to stand for 12h. After the stipulated time, the wet indialite was spread on an adsorbent paper-lined tray. Adequate precaution to ensure that clumping did not occur was taken. Further the indialite spheres were gradually patted to semi-dryness with paper towels. An increase in weight of indialite by 15% was observed.
  • the indialite was transferred to the pan coater fitted with a baffle.
  • the pan of the pan coater was then set into motion and an rpm of 60 was maintained.
  • the angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 16g), Al (N0 3 ) 3 9H 2 0 (5%; 20g) and hydroxypropyl methyl cellulose (0.2%, 0.8g) dispersed in 250g of distilled water.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h
  • weighed, calcined, layered supports (lOOgms) were taken in the attrition apparatus, a hollow drum fitted with a baffle and rotated at 60 rpm for 30 minutes.
  • the fines were collected, weighed and the impact breakage (IB) was determined as the weight percent fines generated versus the total weight of the spheres.
  • the IB for this sample was found to be 1.8%.
  • the outer refractory oxide loading percent of this sample was found to be 40%.
  • Example 3 Indialite spheres (1.8mm, l OOOg) were taken in a polypropylene beaker of capacity 5000 mL. To this was added distilled water (1500g) under stirring to ensure that the indialite is completely submerged. The mixture was allowed to stand for 12h. After the stipulated time, the wet indialite was spread on an adsorbent paper-lined tray. Adequate precautions to ensure that clumping did not occur were taken. Further the indialite spheres were gradually patted to semi-dryness with paper towels. An increase in weight of indialite by 15% was observed.
  • the indialite was transferred to the pan coater fitted with a baffle.
  • the pan of the pan coater was then set into motion and an rpm of 60 was maintained.
  • the angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 8g), Al ( ⁇ 0 3 ) 3 ⁇ 2 0 (5%; lOg) and hydroxypropyl methyl cellulose (0.2%, 0.4 g) dispersed in 50g of distilled water.
  • the IB for this sample was found to be ⁇ 1.0%.
  • Indialite spheres (1.8mm, lOOOg) were taken in a polypropylene beaker of capacity 5000 mL. To this was added distilled water (1500g) under stirring to ensure that the indialite is completely submerged. The mixture was allowed to stand for 12h. After the stipulated time, the wet indialite was spread on an adsorbent paper-lined tray. Adequate precaution to ensure that clumping did not occur was taken. Further the indialite spheres were gradually patted to semi-dryness with paper towels. An increase in weight of indialite by 15% was observed. The indialite was transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 16g), Al (N0 3 ) 3 9H 2 0 (5%; 20g) and hydroxypropyl methyl cellulose (0.2%, 0.8g) dispersed in 250g of distilled water.
  • the process of layering of the indialite cores by the outer refractory oxide(carrier material mixture) was as disclosed under Example 1 hereinabove.
  • the IB for this sample was found to be ⁇ 1.0 %.
  • Dry indialite spheres (1.8mm, 1 OOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 12g), Al (N0 3 ) 3 9H 2 0 (5%; 15g) and hydroxypropyl methyl cellulose (0.2%, 0.6g) dispersed in 300g of distilled water.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h.
  • the IB for this sample was found to be 1.2%.
  • Dry indialite spheres (1.8mm, lOOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; lOg), Al (N0 3 ) 3 9H 2 0 (5%; 12.5g) and hydroxypropyl methyl cellulose (0.2%, 0.5g) dispersed in 250g of distilled water.
  • Example 1 The process of layering of the indialite cores by the outer refractory oxide(carrier material mixture) was as disclosed under Example 1 hereinabove.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h
  • the IB for this sample was found to be ⁇ 1 %.
  • Example 7 Dry indialite spheres (1.8mm, lOOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 8g), Al (N0 3 ) 3 9H 2 0 (5%; lOg) and hydroxypropyl methyl cellulose (0.2%, 0.4g) dispersed in 200g of distilled water.
  • the process of layering of the indialite cores by the outer refractory oxide(carrier material mixture) was as disclosed under Example 1 hereinabove.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h.
  • the IB value of the product was found to be ⁇ 1.
  • the outer refractory oxide loading percent of this sample was found to be 20%.
  • Dry indialite spheres (1.8mm, lOOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 10g ), Al (N0 3 ) 3 9H 2 0 (5%; 12.5g) and polyethylene glycol (0.2%, 0.5g) dispersed in 250g of distilled water.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h.
  • Accurately weighed, calcined, layered supports (lOOgms) were taken in the attrition apparatus, a hollow drum fitted with a baffle and rotated at 60 rpm for 30 minutes. The fines were collected, weighed and the impact breakage (IB) was determined as the weight percent fines generated versus the total weight of the spheres.
  • the IB value of the product was found to be 1.5.
  • the outer refractory oxide loading percent of this sample was found to be 25%.
  • Dry indialite spheres (1.8mm, lOOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; lOg ), Al (N0 3 ) 3 9H 2 0 (5%; 12.5g) and polyvinyl alcohol (0.2%, 0.5g) dispersed in 250g of distilled water
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h.
  • Accurately weighed, calcined, layered supports (lOOgms) were taken in the attrition apparatus, a hollow drum fitted with a baffle and rotated at 60 rpm for 30 minutes. The fines were collected, weighed and the impact breakage (IB) was determined as the weight percent fines generated versus the total weight of the spheres. The IB value of the product was found to be 1.8.
  • Dry indialite spheres (1.8mm, lOOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; lOg ), Al (N0 3 ) 3 9H 2 0 (5%; 12.5g) and starch (0.2%, 0.5g) dispersed in 250g of distilled water.
  • Example 1 The process of layering of the indialite cores by the outer refractory oxide(carrier material mixture) was as disclosed under Example 1 hereinabove.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C-for 3h.
  • the IB value of the product was found to be 1.2.
  • the outer refractory oxide loading percent of this sample was found to be 25%.
  • Example 11 Dry indialite spheres (1.8mm, lOOOg) were transferred to the pan coater fitted with a baffle. The pan of the pan coater was then set into motion and an rpm of 60 was maintained. The angle of the pan coater was maintained at 45° throughout the layering process.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; lOg ), Al (N0 3 ) 3 9H 2 0 (5%; 12.5g) and methyl cellulose (0.2%, 0.5g) dispersed in 250g of distilled water.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h.
  • the IB value of the product was found to be ⁇ 1.
  • the outer refractory oxide loading percent of this sample was found to be 25%.
  • the IB values in the examples as a whole were found be below about 5% by wt and in many cases below about 1 % by wt. The average was about 1 to 2% by wt.
  • Indialite spheres (1.8mm, lOOOg) were taken in a polypropylene beaker of capacity 5000 mL. To this was added distilled water (1500g) under stirring to ensure that the indialite is completely submerged. The mixture was allowed to stand for 12h. After the stipulated time, the wet indialite was spread on an adsorbent paper-lined tray. Adequate precaution to ensure that clumping did not occur was taken. Further the indialite spheres were gradually patted to semi-dryness with paper towels. An increase in weight of indialite by 15% was observed.
  • the indialite was transferred to the pan coater fitted with a baffle.
  • the pan of the pan coater was then set into motion and an rpm of 60 was maintained.
  • the angle of the pan coater was maintained at 45° throughout the layering process.
  • the outer refractory oxide (400g) comprised a single [Component A] alumina component calcined to 900°C followed by jar-milling to desired PS(particle size) of 5 microns.
  • the binder solution comprised colloidal alumina sol (20 wt% solution; 4%; 16g), Al (N0 3 ) 3 9H 2 0 (5%; 20g) and hydroxypropyl methyl cellulose (0.2%, 0.8g) dispersed in250g of distilled water.
  • the process of layering of the indialite cores by the outer refractory oxide(carrier material mixture) was as disclosed under Example 1 hereinabove.
  • the resulting 'green' coated spheres were unloaded from the pan coater into ceramic trays.
  • a single layer of 'green' coated indialite spheres taken in a ceramic tray was subjected to calcination at 550°C for 3h
  • Accurately weighed calcined, layered supports (l OOgms) were taken in the attrition apparatus, a hollow drum fitted with a baffle and rotated at 60 rpm for 30 minutes.
  • the fines were collected, weighed and the impact breakage (IB) was determined as the weight percent fines generated versus the total weight of the spheres.
  • the IB for this sample was found to be 21%.
  • the outer refractory oxide loading percent of this sample was found to be 40%.
  • material-in-process at various stages of the process.
  • Said material-in-process is also referred to as base material herein. No ambiguity arises from this as the meaning is apparent from the context. The meaning appropriate to the context may be adopted.

Abstract

L'invention concerne un procédé de séchage par pulvérisation pour le dépôt de matériau de support de catalyseur sur des noyaux particulaires inertes sphériques (ou autres), qui offre un meilleur contrôle du procédé de couchage pour donner de minces couches de support d'épaisseur uniforme. On décrit un nouveau matériau de support de catalyseur, comprenant un mélange d'alumine à large pore dérivé par précipitation avec une alumine dérivée par la voie de l'alkoxyde. De préférence, les deux alumines sont de l'alumine soit delta soit thêta ou des mélanges de celles-ci. D'autres de ces mélanges sont divulgués. Dans un essai de catalyseur dans lequel le catalyseur est dispersé/imprégné sur une couche de support de catalyseur mince et uniforme formé dudit mélange d'alumine et déposé par ledit procédé de séchage, le catalyseur se révèle être de sélectivité, stabilité et durabilité accrues.
PCT/IN2011/000243 2011-03-31 2011-04-08 Supports de catalyseur en couches et leur procédé de fabrication WO2012131687A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN104607197A (zh) * 2015-01-12 2015-05-13 北京三聚环保新材料股份有限公司 一种有机硫加氢催化剂及其制备方法
RU2809169C2 (ru) * 2019-08-23 2023-12-07 Юоп Ллк Композиция катализатора дегидрирования

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Publication number Priority date Publication date Assignee Title
US3145183A (en) 1958-12-16 1964-08-18 Norton Co Catalyst carrying balls
US5935889A (en) 1996-10-04 1999-08-10 Abb Lummus Global Inc. Catalyst and method of preparation
WO2001072415A1 (fr) * 2000-03-28 2001-10-04 Basf Aktiengesellschaft Catalyseurs a coque, leur procede de production et leur utilisation
EP1138385A1 (fr) * 1999-09-17 2001-10-04 Nippon Kayaku Kabushiki Kaisha Catalyseur
US20020049132A1 (en) * 1998-11-03 2002-04-25 Deng-Yang Jan Process for preparing attrition resistant zeolitic layered catalyst composition
WO2006127136A1 (fr) 2005-05-25 2006-11-30 Celanese International Corporation Composition multicouche et procédés servant à préparer et à utiliser la composition

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Publication number Priority date Publication date Assignee Title
US3145183A (en) 1958-12-16 1964-08-18 Norton Co Catalyst carrying balls
US5935889A (en) 1996-10-04 1999-08-10 Abb Lummus Global Inc. Catalyst and method of preparation
US20020049132A1 (en) * 1998-11-03 2002-04-25 Deng-Yang Jan Process for preparing attrition resistant zeolitic layered catalyst composition
EP1138385A1 (fr) * 1999-09-17 2001-10-04 Nippon Kayaku Kabushiki Kaisha Catalyseur
WO2001072415A1 (fr) * 2000-03-28 2001-10-04 Basf Aktiengesellschaft Catalyseurs a coque, leur procede de production et leur utilisation
WO2006127136A1 (fr) 2005-05-25 2006-11-30 Celanese International Corporation Composition multicouche et procédés servant à préparer et à utiliser la composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104607197A (zh) * 2015-01-12 2015-05-13 北京三聚环保新材料股份有限公司 一种有机硫加氢催化剂及其制备方法
CN104607197B (zh) * 2015-01-12 2017-07-25 北京三聚环保新材料股份有限公司 一种有机硫加氢催化剂及其制备方法
RU2809169C2 (ru) * 2019-08-23 2023-12-07 Юоп Ллк Композиция катализатора дегидрирования

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