EP0169877A1 - Charge ou support pour substances d'action catalytique, procede de production de cette charge ou ce support, catalyseur produit a partir de ce support, et utilisation de ce catalyseur - Google Patents

Charge ou support pour substances d'action catalytique, procede de production de cette charge ou ce support, catalyseur produit a partir de ce support, et utilisation de ce catalyseur

Info

Publication number
EP0169877A1
EP0169877A1 EP85900814A EP85900814A EP0169877A1 EP 0169877 A1 EP0169877 A1 EP 0169877A1 EP 85900814 A EP85900814 A EP 85900814A EP 85900814 A EP85900814 A EP 85900814A EP 0169877 A1 EP0169877 A1 EP 0169877A1
Authority
EP
European Patent Office
Prior art keywords
particles
catalyst
support
spray
attapulgite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP85900814A
Other languages
German (de)
English (en)
Inventor
Jan-Erik Anders Otterstedt
José Aurelio BAEZA CALZADILLA
Per-Arne Dahlqvist
Sven Gunnar JÄRAS
Jan-Anders Olav RÖJ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Eka AB
Eka Nobel AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from SE8400427A external-priority patent/SE8400427L/xx
Priority claimed from SE8400429A external-priority patent/SE8400429L/xx
Priority claimed from SE8400433A external-priority patent/SE8400433L/xx
Priority claimed from SE8400432A external-priority patent/SE8400432L/xx
Application filed by Eka AB, Eka Nobel AB filed Critical Eka AB
Publication of EP0169877A1 publication Critical patent/EP0169877A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
    • 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
    • B01J37/024—Multiple impregnation or coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • FILLER OR A SUPPORT FOR CATALYTICALLY ACTIVE SUBSTANCES, A PROCESS FOR PRODUCING SAID FILLER OR SUPPORT, A CATALYST * PRODU ED FROM SAID SUPPORT, AND THE USE OF
  • catalytic processes In catalytic processes, one frequently has to rely on rapid mass transportation in combination with a high accessibility of the catalytically active sur ⁇ face in order to achieve high reaction yield, good 5 selectivity and thus satisfactory economy of process.
  • the refining of heavy oils into different fuels, such as gasoline and diesel, is carried out by means of catalytic processes, for example catalytic hydropro ⁇ cessing, hydrogenation or cracking.
  • catalytic hydropro ⁇ cessing, hydrogenation or cracking As a result of 10 .
  • catalytic hydropro ⁇ cessing, hydrogenation or cracking As a result of 10 .
  • catalytic hydropro ⁇ cessing, hydrogenation or cracking As a result of 10 .
  • the increased crude prices it is endeavoured to cata ⁇ lyse increasingly heavier starting materials, and this has made it difficult to achieve a satisfactory economy of process because a combination of rapid mass transportation and high accessibility of the 15 catalytically active surface is not readily accom ⁇ plished.
  • the heavy starting materials are characterised in that they have large molecules and aggregates of large molecules, for which reason it is difficult to achieve a rapid 20 transport of these molecules or molecule aggregates into and out of the catalysts which are being used today for catalytic hydroprocessing, hydrogenation or cracking.
  • Another problem encountered in connec ⁇ tion with catalytic cracking is that the most common 25 catalyst supports have but low resistance to the pro ⁇ cess conditions and the conditions during the rege ⁇ neration and like treatment processes to which the catalyst must be subjected.
  • catalytic automobile exhaust emission control i.e. a purification process in which it is desired to remove nitrogen oxides and non-burned hydrocarbon molecules from the exhaust gases from automobile engines and other internal combustion engines.
  • the difficulty lies not in large molecules, but instead in the need for very high exhaust throughflow rates in the catalytic reactor.
  • Great demands are therefore placed on the porosity in combination with a large catalytic area, such that the catalytic reactions which are necessary in order to eliminate nitrogen oxides and non-burned hydrocarbons, can take place in the very short time during which the exhaust gases are in contact with the catalyst mass.
  • Catalytic cracking of heavy oils to gasoline and diesel is an example of a refinery process in which the process economy to a high degree is affected by the presence of large molecules and aggregates of molecules in the oil *
  • One of the difficulties with heavy molecules and aggregates of molecules in the - oil is that these frequently contain metal impurities of the type vanadium and nickel which have an adverse effect on the activity and selectivity of the catalyst.
  • the above-mentioned problem in respect of rapid mass transportation of the large molecules or molecule aggregates into the interior of the catalyst structure causes in itself a further problem in connection with catalytic cracking.
  • the diffusion rates of the large molecules and aggregates of molecules can be so low that the molecules stay too long in the catalyst and thus are subjected to so-called overcracking into undesired products, such as gases and coke.
  • a further problem encountered in catalytic cracking of heavy oils of the type residual oils is that the largest molecules and molecule aggregates easily get stuck in the small pores of the catalyst and are not removed during the so-called stripping step which, in the refinery process, precedes the regeneration. As a result, many large molecules and molecule aggregates may be taken along by the catalyst to the regenerator where they are burned and thus will be lost, the tem ⁇ perature in the regenerator increasing to undesired high values.
  • the large molecules or molecule aggregates getting stuck in the pores within the outer parts of the catalyst may also have the effect that the activity and efficiency of the catalyst is reduced considerably because subsequent molecules, both large and small ones, are prevented from penetrating into the active surface of the catalyst for cracking.
  • catalysts which consist of aluminium oxide having pore sizes within a rather narrow range of 40-70 A.
  • the porous aluminium oxide usually is impregnated with a mixture of, for example, cobalt sulphide and molybdenum sulphide. This type of catalyst functions satisfactorily for the removal of sulphur from the light molecules pre- sent in the relatively light hydrocarbons in gasoline and diesel.
  • a conventional catalyst e.g. a desulphurisation cata ⁇ lyst, may have an average particle size of about 40
  • catalysts e.g. a hydropro ⁇ cessing catalyst, having an average particle size exceeding 200 A because one has found that the average pore size should be at least 10 times greater than, the average diameter of the large molecules or molecule aggregates which are to pass into and out of the pores.
  • the active component i.e. the zeolite, has a very regular pore structure and is characterised by pores in the order of 12 A with pore openings in the order of 7-8 A.
  • the matrix in which the active component is incorporated, may have a pore structure varying from some twenty Angstrom up to several thousand Angstrom.
  • a further technique of solving the problem in connection with the catalytic cracking of heavy oils is to use zeolitic structures of larger pores and pore openings than are available in zeolite Y. In this case, use is made of clays having a plate-like structure, such as montmorillonite clays (cf. US-A-4,238,364) . These plates have been bonded together by means of crosslinks in the order of 10 A.
  • the spacing between the crosslinks may be varied, but lies typically at about 20 A.
  • Mont- morillonite which is cross-linked in this manner is characterised by pore openings which are about 10 A in one direction and about 20 A in the other direction, i.e. considerably larger than in zeolite Y, but still rather small as compared to the dimensions of the largest molecules in heavy oils.
  • a catalyst material 5 is produced by first forming a gel by mixing together an inorganic aluminium salt and an alkali metal silicate as well as a water-soluble anionic polyacrylic amide. To this gel is then added an aqueous dispersion of a zeolitic crystalline aluminium silicate, whereupon
  • the catalyst material obtained is not, however, based on a mineral having fibrous structure.
  • cracking catalyst is produced by forming a slurry of clay material or silica/aluminium oxide and other materials, whereupon the zeolite material is admixed. ; After filtration and drying, an ion exchange is effected. Drying may be- done by spray-drying, but the resulting
  • catalyst material is not based on a mineral of fibrous structure.
  • GB-A-1485370 discloses a catalyst which is made from "KAOWOOL" which is a mineral fibre product having coarse fibres which presumably are at least 0.1 mm
  • Such a batting structure or fibre structure cannot be used for the production of a support or catalyst of the type here concerned.
  • GB-A-2090766 discloses a porous hydroprocessing catalyst based on halloysite.
  • This catalyst is produced by preparing two disper ⁇ sions of different mineral materials and then convert ⁇ ing these dispersions into catalyst support particles which are coated with a catalytically active substance. When catalyst support particles are being shaped,
  • the BET surface area lies about 50 m /g.
  • the halloysite fibres have a smooth surface structure.
  • One object of the present invention is to obviate the shortcomings of known hydrocarbon processing cata ⁇ lysts by providing a novel type of structure for the catalyst support.
  • Another object of the present inven ⁇ tion is to provide a hydrocarbon processing catalyst and a support therefor having a surface area of at
  • a further object of the invention is to provide a novel catalyst and a support therefor having higher mechanical, thermal and hydrothermal stability than the corresponding conventional catalyst, so that it can be used in ca ⁇ talytic processes, such as catalytic cracking, hydro- cracking, hydroprocessing, automobile exhaust emission control etc.
  • Another object of the invention is to provide a process for producing such a support or catalyst, and still another object of the invention is to provide a support or catalyst and a process for producing such a support or catalyst which has aggregate particles in the form of a coherent three- dimensional network of mineral particles having fibrous and strip-shaped structure.
  • Still another object of the invention is to provide, in the production of such a support or catalyst, a desired pore diameter by pretreating natural mineral particles having fibrous or strip-shaped structure.
  • a cracking catalyst of aggregate particles having the said coherent three- dimensional network of such mineral particles having fibrous or strip-shaped structure, granules of zeolite material being enclosed within said network.
  • a further object of the present invention is to provide such a filler having a new structure.
  • a filler or a support for catalytic substances according to the present invention consists of aggregate particles having a coherent three-dimensional network structure of mineral particles having fibrous or strip- shaped structure and a diameter of at least 100 A and a mechanical, thermal and hydrothermal stability required for the contemplated use or catalytic process.
  • the support has a surface area of at least 75 m /g and an average pore diameter of at least 100 A, at least 75% of the surface being present in pores having a diameter exceeding 100 A.
  • the zeolite particles may be distributed and locked.
  • aluminium silicate and magnesium silicate mineral particles having fibrous or strip-shaped structure use may preferably be made of attapulgite, sepiolite and chrysotile, separately or in mixture.
  • the filler or support for the catalytically active substance is produced by forming a well-dispersed slurry of in ⁇ dustrial mineral particles which have the requisite particle diameter in the natural state or to which this particle diameter has been imparted by modifica ⁇ tion.
  • Zeolite particles may, if necessary, be suspended in the said well-dispersed slurry which then either is spray-dried in order directly to form the aggre- gate particles, or is extruded or pelletised to form such aggregate particles, or is first spray-dried to aggregate particles which are then slurried and extruded or pelletised to the desired catalyst support particles.
  • a catalytic substance or a precursor thereof is applied as a surface coating on the fibrous or strip-shaped particles of the support prior to or after spray-drying, extrusion or pelletisation of the support particles.
  • the first step in the production of a catalyst support having the desired characteristics is to pro ⁇ quiz an extremely well-dispersed slurry of fibrous or strip-shaped industrial minerals, especially alumi- nium silicates or magnesium silicates, in water.
  • zeolite particles in this slurry.
  • extreme well-dispersed slurries is here meant that the mineral fibres or strips and the zeolite particles, if any, are to be suspended separately in the slurry and thus preferably should form no aggregates at all.
  • aluminium silicates having fibrous or strip-shaped structure are attapulgite and sepiolite.
  • An example of fibrous or strip-shaped magnesium silicates is chrysotile.
  • zeolites employed for cracking catalysts is faujasite, i.e. zeolite Y and zeolite X, mordenite and zeolites of the type ZSM.
  • the zeolite content may be from low contents of, for example, 0.5% by weight up to 75% by weight, based on the fi ⁇ nished catalyst.
  • a useful content range is 10-75% by weight, especially 25-60% by weight.
  • the zeolite particles preferably have a particle size of 0.1-5 ⁇ m, preferably 0.5-5 ⁇ m, or 0.5-3 ⁇ m.
  • dispersing agents such as water glass, aluminium hydroxy chloride, polyphosphates etc. are used.
  • the catalyst sup- port with a large surface area in combination with a large average pore size and high mechanical, thermal and hydrothermal stability is to spray-dry an extreme ⁇ ly well-dispersed slurry of, for example, attapulgite dispersed in water with water glass as dispersing * agent, zeolite particles also having been dispersed in the slurry when a cracking catalyst is to be pro ⁇ quizd.
  • a catalyst support with a large surface area in combination with a large average pore size and high mechanical, thermal and hydrothermal stability is to form an extremely well- dispersed slurry of, for example, attapulgite and, where appropriate, zeolite particles in water by means of water glass, whereupon this slurry is pelletised to support and catalyst particles, respectively.
  • a third possibility of producing, in the process according to the present invention, the support or the catalyst with a large surface area in combina- tion with a large average pore size and high mechani ⁇ cal, thermal and hydrothermal stability is first to spray-dry extremely well-dispersed slurries of, for example, attapulgite and, where appropriate, zeolite particles in water with water glass as a dispersing agent, and then to re-slurry these spray-dried par ⁇ ticles in water to a viscous mass which then is ex- truded or pelletised to form the final support and catalyst material, respectively.
  • the present invention also comprises the produc ⁇ tion of catalyst supports formed for mixtures of dif ⁇ ferent types of fibrous or strip-shaped mineral par- tides.
  • the invention comprises the pro ⁇ duction of catalysts or catalyst supports which, in their network structure of fibrous or strip-shaped mineral particles, contain other incorporated particles than zeolite particles, for example particles of alu ⁇ minium oxide.
  • Such a mixed structure of fibres and zeolite and/or other particles has a bimodal pore size di ⁇ stribution i.e. a first pore size distribution which is characteristic of, for example, the zeolite (e.g. about 12 A pores having a pore opening of 7-8 A) or of aluminium oxide (e.g. 40-100 A) as a support for desulphurisation catalysts, and a second pore size distribution within the range 100-1000 A which is characteristic of the support structure according to the present invention.
  • a bimodal pore size di ⁇ stribution i.e. a first pore size distribution which is characteristic of, for example, the zeolite (e.g. about 12 A pores having a pore opening of 7-8 A) or of aluminium oxide (e.g. 40-100 A) as a support for desulphurisation catalysts, and a second pore size distribution within the range 100-1000 A which is characteristic of the support structure according to the present invention.
  • spray-dried supports by modification of the surface of the fibrous or strip- shaped mineral particles included, a structure with acid seats, such that also the support proper will obtain cracking catalytic activity.
  • the fibrous or strip- shaped mineral particles may be modified prior to the production of the three-dimensional network struc- ture. Such modification may serve to increase the fibre diameter, thereby to increase the average pore size of the resulting network structure, or may serve to deposit catalytically active substances on the surface of the mineral particles.
  • catalytical ⁇ ly active substances may be supplied also after the desire network structure has been produced by extrusion, pelletisation and/or spray-drying.
  • the catalytically active substance may be supplied for example by im- pregnation with a precursor of the catalytic substance, such as platinum, palladium etc., which then is formed in situ on the fibres or strips of the support.
  • a dispersing agent In order positively to achieve the requisite high degree of dispersion in the slurry prior to spray- drying, extrusion or pelletisation, a dispersing agent should be used. Many conventional dispersing agents are in the form of sodium salts. If such dispersing agents are used for the production of the catalyst, support by spray-drying, extrusion or pelletisation in accordance with the present invention, the resulting catalyst support will in that case contain sodium in different amounts. If sodium is detrimental to the subsequent catalytic process, the sodium content must be reduced by washing and ion exchange. It may, however, be difficult to remove all of the sodium from the catalyst support. For some purposes, e.g.
  • sodium-free dispersing agents are aluminium hydroxy chloride, tetramethyl ammonium silicate, tetraethanol ammonium hydroxide, ammonium citrate, ammonium tartrate, ammonium glycolate etc., all of which are excellent dispersing agents for fibrous or strip-shaped aluminium silicates and magnesium silicates, such as attapulgite, sepiolite, chrysotile etc.
  • kaolin is admixed to a slurry of, for example, attapulgite
  • the admixture of kaolin which is a cheaper material than attapulgite implies that the spray- dried, pelletised or extruded structures will have a lower surface area and higher density, which in some cases may be disadvantageous.
  • the characteristics of the catalyst supports produced by spray-drying, extrusion or pelletisation of slurries of fibrous or strip-shaped mineral particles can be improved by different aftertreatments.
  • One way of improving the mechanical strength and fixing the pore structure is to thermally treat the spray- dried particles in the temperature range 100-700 C.
  • Another way of increasing the mechanical strength and fixing the pore structure is to coat the surface of the spray-dried, extruded or pelletised particles of the fibrous or strip-shaped mineral with silica according to prior art technique. After washing and drying, the spray-dried silica-coated particles are subjected to heat treatment in the temperature range 100-700°C.
  • the raw material i.e. the mineral having the fibrous structure
  • a pretreat- ment in order to modify the-mineral structure.
  • This modification is carried out as an acid treatment with an acid to remove some of the elements in the mineral structure.
  • the acid treatment must be carried out for such a short time or with an acid so diluted that the mineral will retain its basic structure.
  • the mineral in one embodiment, can be treated with a 20% sulphuric acid solu ⁇ tion in which the mineral is agitated for 1-3 hours at a temperature of 30-80 C. After separation of the mineral from the sulphuric acid solution, washing with deionised water is carried out, whereupon drying is effected, for example at 120 C.
  • An acid treatment with sulphuric acid involves that, for example, Na, K, Ca, Mg, Al and Fe are partly removed from the mineral structure. Furthermore, the removal of Al results in a change of the Si:Al ratio in the mineral structure, especially in the outer regions of the crystal complexes. Acid treatment may also be carried out with hydro ⁇ chloric acid in water in a concentration of 1:1 to 1:10.
  • a modification by means of weak acids results in but a slight leaching of Fe and K, and also the ' leaching of Al will be less strong. However, the leach ⁇ ing of Ca is still strong and Ca can be removed to almost 100% by leaching for 1 hour at 20 C. An increase of the leaching temperature will also increase the leaching of Al and Mg. If attapulgite is leached with 20% sulphuric acid in the manner described above, about 10% of the originally present Al and about 20% of the originally present Mg will be removed.
  • hydrochloric acid is less aggressive to the minerals than sulphuric acid.
  • various minerals are affected to different degrees and in different manners depending on the structure of the minerals.
  • the catalytically active material required in a hydroprocessing or hydro ⁇ genation catalyst according to the present invention can be supplied at different stages of the production process. Three different main processes may be distin ⁇ guished, viz. 1) coating before spray-drying, 2) coating after spray-drying, and 3) coating after extrusion or pelletisation of the slurry or the re-slurried spray-dried material.
  • the catalytically active substance is deposited on the fibrous or strip-shaped mineral particles while these are in the form of a slurry.
  • the slurry of the particles coated with cata ⁇ lytically active substance are then shaped into larger particles by spray-drying, extrusion or pelletisation.
  • the catalytically active substance is deposited on the support material after spray-drying thereof.
  • the spray-dried particles coated with cataly ⁇ tically active substances may, optionally, be mixed with spray-dried aluminium oxide particles which also - have catalytically active substances on their surface.
  • a support material in the form of larger aggregate particles is first pro ⁇ **d by extrusion or pelletisation of the well-dispersed slurry of fibrous or strip-shaped mineral particles, or by first spray-drying and then re-slurrying the slurry in water prior to extrusion or pelletisation.
  • the cata ⁇ lytically active substance may be deposited in dif- ferent ways on the fibrous or strip-shaped particles of the support material.
  • One possibility of producing active hydroprocessing catalysts is to deposit on the fibrous or strip-shaped mineral particles very small particles of catalytically active substances according to a microemulsion technique disclosed in the PCT publication WO81/02688 (PCT/SE81/00091) .
  • a microemulsion is first pro ⁇ claimed in which small particles of the contemplated ac ⁇ tive catalyst material, e.g. small particles of cobalt and molybdenum sulphide, are suspended.
  • microemul ⁇ sion is then mixed with the slurry of the fibrous or strip-shaped mineral material, the said fibrous or strip-shaped mineral particles being coated with a mono ⁇ layer of small particles of cobalt and molybdenum sul ⁇ phide. After that, the slurry is spray-dried or extruded.
  • a hydrogenation catalyst can be produced by first preparing a microemulsion in which small particles of metallic platinum are suspended.
  • Another possibility of depositing the catalytically active substance is to form first a colloidal slurry of par ⁇ ticles, the surface of which has been coated with a catalytically active substance, in accordance with Swedish patent application 8400426-6 of January 30, 1984.
  • This colloidal slurry is then mixed with the slurry of fibrous or strip-shaped mineral particles.
  • hydroprocessing catalysts it is thus possible first to produce a sol of silicic acid or aluminium silicate, the surface of which is coated with cobalt and molybdenum sulphide. Upon ad ⁇ mixture to the slurry of fibrous or strip-shaped mineral material, the fibres of this material will obtain a monolayer of colloidal sol particles.
  • the same tech ⁇ nique can be used for producing a hydrogenation cata ⁇ lyst, the silicic acid sol, aluminium silicate or alkali aluminium silicate sol particles having me ⁇ tallic platinum on their surface. Another possibility of applying catalytically active subtance is by precipitation.
  • a hydroprocessing catalyst may thus be produced by impregnating a spray- dried powder of the fibrous or strip-shaped mineral material (possibly in mixture with spray-dried aluminium oxide particles) with a solution of ammonium molybdate in water. After the water has been driven off, the spray-dried powder is impregnated with the solution of cobalt nitrate in water. After drying and calcining, cobalt and molybdenum are present as oxides on the surface of the individual fibres or strips of the support material.
  • the spray-dried powder can be impregnated correspond ⁇ ingly with a solution of chloroplatinic acid, whereupon the solvent is driven off and reduction to metallic platinum is effected so that the inner surfaces of the spray-dried particles are coated with metallic platinum.
  • the above-mentioned microemulsion technique may be employed for deposit ⁇ ing particles of cobalt and molybdenum sulphide or cobalt and molybdenum hydroxide. If the particles deposited according to the microemulsion technique- are in the form of oxide-hydroxides, such particles may be converted into sulphides by sulphidisation.
  • the main process 2 it is possible in the main process 2 to produce hydrogenation catalysts by first coating the individual particles of a silicic acid sol, aluminium silicate sol or an alkali aluminium silicate sol with metallic platinum, whereupon this modified sol is used for impregnating spray-dried particles of the fibrous or strip-shaped mineral particles which also in this instance may be mixed with a spray-dried pow ⁇ der of aluminium oxide.
  • the shaping of the support material into active catalysts may be carried out in different ways.
  • the support material in the main process 3 is in the form of an extrudate formed either of a slurry of fibrous or strip-like mineral particles, optionally in mixture with spray-dried particles of aluminium " oxide, or of a slurry formed of spray-dried particles of the fibrous or strip-shaped mineral material, optionally in mixture with spray-dried particles of aluminium oxide.
  • One possibility in the main process 3 thus is to impregnate the extrudates with solutions of the catalytically active substances or precursors thereof.
  • hydroprocessing catalysts it is thus pos- sible to impregnate the extrudate with a solution - of ammonium molybdate.
  • the extrudate After the water utilised as solvent has been driven off, the extrudate is impregnat ⁇ ed with a solution of cobalt nitrate. After calcining, the cobalt and the molybdenum are present as oxides.
  • the cobalt and molybdenum oxide can then be converted into the corresponding cobalt and molybdenum sulphides which are the catalytically active substances..
  • the extrudate can be * impregnated with chloroplatinic acid. After the water has been driven off and after reduction, the individual particles of the extrudate are coated with platinum which is the catalytically active substance in the hydrogenation catalyst.
  • a hydropro ⁇ cessing catalyst can be produced by impregnating the extrudate with a previously prepared microemulsion in which cobalt and molybdenum sulphide or cobalt and molybdenum oxide-hydroxide is suspended. If the particles applied according to the micr emulsion tech ⁇ nique are present as oxide-hydroxides, these can be converted into sulphides by sulphidisation.
  • Hydroprocessing or hydrogenation catalysts produced in accordance with the present invention are charac ⁇ terised by a high average pore size in combination with a high surface area.
  • Such catalysts may be used with advantage in processes in which large molecules or aggregates of molecules must be converted, such as the catalytic hydroprocessing of heavy fuel oils, in order to remove metallic impurities and heteroatoms, such as sulphur and nitrogen.
  • the cracking catalysts according to the present invention are characterised by a high average pore size in combination with a large catalytically active surface area accomplished by spray-drying and/or pelletisation of a well-dispersed slurry of zeolite particles and fibrous or strip-shaped aluminium silicate or magnesium silicate minerals.
  • the surfaces of the fibrous or strip-shaped particles included in the catalyst may be provided with a surface of aluminium silicate or alkali aluminium silicate converted into catalytically active form by ion exchange with hydrogen ions or ions of rare earth metals.
  • the cracking catalyst production according to the present invention may also be carried out in ac ⁇ cordance with three main processes, viz. 1.
  • a well-dispersed slurry is formed of zeolite particles and particles of fibrous or strip-shaped aluminium or magnesium silicates and is then spray-dried. If the zeolite is not in the desired form for catalytic cracking, the zeolite may be converted into such form by subjecting the spray-dried particles to a succession of ion exchange steps, for example ammonium ion exchange and ion exchange with rare earth metals.
  • Particles of fibrous or strip-shaped aluminium or magnesium silicates in a well-dispersed slurry are given a catalytically active surface or a precursor thereof.
  • the slurry of zeolite and fibrous or strip- shaped particles is then spray-dried to a struc ⁇ ture which is characterised by the above-mentioned high average pore size in combination with a large surface area. If the zeolite particles or the fibrous or strip-shaped particles are not in the final catalytic form, they can be converted thereto by a succession of ion exchange steps, such as an ammonium ion exchange and ion exchange with rare earth metals.
  • a slurry of zeolite particles and fibrous or strip-shaped aluminium silicate magnesium silicate mineral is spray-dried to particles of the above-mentioned structure having a high average pore size in combination with a large surface area. After that the spray-dried particles are impregnated with a catalytically active sub ⁇ stance or a precursor thereof. If the coating on the fibrous or strip-shaped particles consists of such a precursor or if the zeolite is not in the final catalytic form, the precursor and the zeolite, respectively, can be converted into this catalytically active form by a series of ion exchange steps with ammonium ions and ions of rare earth metals.
  • One way of producing a cracking catalyst accord ⁇ ing the main process 1 of the present invention is to prepare a slurry of zeolite, for example zeolite Y in sodium form, and fibrous or strip-shaped alu ⁇ minium or magnesium silicates.
  • the slurry is spray- dried, and the spray-dried particles are shaped into an active cracking catalyst by ion exchange.
  • ammonium ion exchange washing, drying and calcining, a cracking catalyst in hydrogen form is produced.
  • ion exchange of spray-dried particles first with ammonium and then with ions of rare earth metals, a catalyst in rare earth form is produced.
  • a particularly interest ⁇ ing way of producing a catalyst according to the main process 1 is to proceed from an acid-leached attapulgite and zeolite of the type ultrastable hydrogen Y.
  • a well-dispersed slurry of the attapulgite and this zeolite in water is formed with aluminium hydroxy chloride as dispersing agent, followed by spray-drying and calcining at 500-600 C, whereby a catalyst is obtained which has a very low sodium content and, thus, a very high hydrothermal stability.
  • One way of producing the cracking catalysts ac ⁇ cording to the main process 2 of the present invention is to coat in a slurry the particles or fibrous or strip-shaped aluminium of magnesium silicates with a monolayer of small sol particles.
  • the sol particles consist of aluminium silicate, preferably in ammonium form, or alkali aluminium silicate.
  • the sol particles may also consist of silicic acid, but then the particle surface must be modified by means of aluminate or alkali aluminate to an aluminium silicate and alkali aluminium silicate, respectively, which is converted into the ammonium form., If the surface area of the fibrous or strip-shaped aluminium or magnesium sili ⁇ cate is known, one can calculate the amount of sol that must be supplied to the slurry of fibrous or strip-shaped aluminium or magnesium silicate particles in order to coat each particle with a monolayer of sol particles.
  • particles of zeolite Y preferably in the ammonium form, the zeolite being supplied in the form of a powder or slurry.
  • the slurry of the zeolite particles and the coated fibrous or strip-shaped particles is spray-dried 5 to particles having an average particle size of about 70 ⁇ m. If the zeolite or the surface coating of the fibrous or strip-shaped particles is present in the ammonium form, this can be converted into the hydrogen form by calcining at about 500 C, whereby ammonia
  • ammonium ions may be replaced by ions of rare earth metals by slurry-
  • the spray-dried particles in the ammonium form are slurried in a solution of chlorides of rare earth metals. After filtration
  • the catalyst is obtained in the rare earth form.
  • Another way of producing an efficient cracking catalyst according to the main process 2 is to coat the fibrous or strip-shaped aluminium silicate or
  • each particle in the slurry is coated with an alkali aluminium silicate layer, the thickness of which may be varied from a few Angstrom to several hundred Angstrom.
  • the slurry of the particles thus coated is mixed with particles of zeolite NaY in the form 'of a powder or a slurry and is spray-dried to particles having an average particle size of 70 ⁇ m.
  • Alkali ions such as sodium or potassium ions, are replaced by ammonium ions in that the spray-dried particles are slurried in a solution of ammonium sulphate. After filtration and washing, the ammonium form may be converted into the hydrogen form by calcining of the spray-dried • particles at 500 C.
  • the fil ⁇ trate of the spray-dried particles which are present in the ammonium form is slurried in a solution of chlorides of rare earth metals.
  • a finished catalyst is obtained by filtration, washing and drying of the spray-dried particles.
  • One way of producing a cracking catalyst according to the main process 3 of the present invention is to spray-dry slurry of zeolite particles, such as zeolite Y in the ammonium form, and fibrous or strip- shaped aluminium or magnesium silicate to particles having an average particle size of 70 ⁇ m.
  • the surface of the spray-dried fibrous or strip-shaped particles is coated with a monolayer of aluminium silicate par ⁇ ticles or silicic acid particles, the surface of which has been modified with aluminium to aluminium silicate.
  • the particles of aluminium silicate preferably should be in the ammonium form.
  • ammonium can be driven off by calcining at 500 C, the zeolite being converted into the hydrogen form and a surface of aluminium silicate in the hydrogen form being established.
  • ammonium may be replaced by ions of rare eath metals by ion exchange with a solu ⁇ tion of chlorides of rare earth metals.
  • the cracking catalysts according to the present invention are characterised by a high average pore size in combination with a large surface area. These catalysts may be used with advantage for cracking heavy oils, especially heavy residual oils, whereby several of the problems encountered in the cracking of heavy oils in present-day refineries are avoided. Thus, large molecules and aggregates of molecules present in the heavy oils will have easy access to the catalytically active surface of fibrous or strip- shaped aluminium or magnesium silicates, while fragments of large molecules or smaller molecules will have easy access to the catalytically active surface of the zeolite for cracking.
  • the driving-off, the "stripping" of products from the catalyst preparatory to regene ⁇ ration of the catalyst will also be-more efficient so that no products or large molecules are carried along to the regenerator to be burned therein and to cause undesired high temperatures in the regene ⁇ rator.
  • extruded, pelletised or spray-dried supports according to the present invention may be used after impregnation with precious metals, such as platinum, palladium etc., as oxidation catalysts in, for example, automobile exhaust emission control.
  • precious metals such as platinum, palladium etc.
  • the extruded, pelle- tised or spray-dried supports according to the invention may be used, after impregnation with catalytically active substances, such as cobalt, molybdenum, nickel, tungsten etc., also as hydroprocessing catalysts.
  • catalytically active substances such as cobalt, molybdenum, nickel, tungsten etc., also as hydroprocessing catalysts.
  • Attapulgite having the trade name "ATTAGEL 50" and purchased from Engelhart Minerals, was utilised. This attapulgite contains 68% Si0 2 , 12% A1-0-, and 10.5% MgO.
  • soda water glass or sodium sili ⁇ cate solution from EKA Kemi AB was used.
  • the ratio of SiO- to a 2 0 was in this instance 3.3:1, the Si0 2 content being 26.6% and the density 1350 kg/m .
  • the aluminium hydroxy chloride employed had the formula Al 2 (OH) g Cl.3H-0 and was purchased from Hoechst under the trade name "KLORHYDROL ACH".
  • the spray drier utilised for the tests was a pilot spray drier from Niro A/S, Denmark, having a diameter of 9 feet (2.75 m) .
  • the spray drier had a rotating spreader wheel, variable air flow, variable speed of the spreader wheel, variable input and out- put temperatures, and variable inflow. Typical running conditions during the spray-drying of the slurries in the following Examples where:
  • the moisture content of the spray- dried particles varied between 10 and 30%
  • Pore sizes were determined by means of an appara ⁇ tus "DIGISORB 2600" from Micromeritics. If a catalyst or catalyst support according to the invention is produced by extrusion moulding, use may be made of conventional extrusion moulding machines for use in catalyst production or in the ceramic in- dustry. To obtain satisfactory results, it has been found to be extremely important to maintain a correct moisture content in the mass to be extruded, and in this respect it has been found that, for the object of this invention, the best results are obtained at moisture content of 30-50%. In those cases where extrusion moulding has been used in the following Examples, a moisture content within this range has been used. The diameter of the extrudates has been selected within the range 0.8-3.2 mm.
  • the extrudates are dried, and in the Examples this has been done by linearly increasing the tempera ⁇ ture of the extrudate from room temperature up to 200°C at a temperature increase rate of 85 C/hour, sometimes 100 C/hour, whereupon the extrudates have been maintained at 200 C for 2 hours. After heating, the extrudates where allowed to cool to room temperature in stationary air.
  • the fibrous clay minerals are pretreated by an acid treat- ment before the catalyst support is produced.
  • This acid treatment is carried out in the following manner: A. 35 g of fibrous material are mixed with 500 ml of 20% sulphuric acid (H 2 SO.) and agitated at 20-80°C for 1-3 hours. B. The mineral is separated from the solution.
  • the mineral is washed with deionised water.
  • the washed mineral is dried at 120°C.
  • the fibrous structure (basic structure) on the mineral is maintained, which can be confirmed by X-ray analysis.
  • some elements were removed from the mineral structure. In respect of attapulgite, about 20% of the aluminium and 20% of the magnesium normally present in the mineral were leached out.
  • EXAMPLE 1 Production of a support
  • 2.85 kg "ATTAGEL 50" are added to 10 litres of water containing water glass in a ratio of 3.3:1.
  • the water glass content of the slurry is made to correspond to 3.5 g Si0 2 from the water glass per 100 g of dry attapulgite.
  • the attapulgite is added under intense agitation; .
  • the final attapulgite content is 22% by weight of dry attapulgite.
  • the attapulgite slurry is then spray- dried under the above-mentioned conditions. Spray-dried particles have an average pore size of 426 A and a
  • Example 1 is repeated, but after spray-drying the spray-dried particles are calcined at 500 C for
  • the spray-dried particles After calcining, the spray-dried particles have an average pore size of 362 A and a surface area
  • Example 1 Production of a carrier Example 1 is repeated, but the spray-dried par ⁇ ticles are aged at 750 C in an atmosphere of 100% relative humidity for 18 hours. After aging, the spray- dried particles have an average pore size of 465 A
  • Example 1 is repeated, but the spray-dried par ⁇ ticles are calcined at 750°C for 1 hour. After cal ⁇ cining, the spray-dried particles have an average
  • EXAMPLE 7 Production of a support A well-dispersed slurry of sepiolite in water is dispersed with water glass and spray-dried. A three- dimensional network structure is obtained in the spray- dried particles.
  • EXAMPLE 8 Production of a support well-dispersed slurry of attapulgite with water glass is extruded to support particles having a three- dimensional network structure.
  • EXAMPLE 9 Production of a support A well-dispersed slurry of attapulgite in water is dispersed by means of water glass and spray-dried. The spray-dried particles are slurried in water to a viscous slurry which is extruded to catalyst sup ⁇ port particles.
  • EXAMPLE 10 Production of a support A well-dispersed slurry of attapulgite is dispersed with water glass and spray-dried. The spray-dried par ⁇ ticles are coated with silica. After the coating with silica, the spray-dried particles are heated at 500°C for 1 hour. EXAMPLE 11
  • a well-dispersed slurry containing 75% attapul ⁇ gite and 25% kaolin is dispersed with water glass and spray-dried.
  • the spray-dried particles have a structure in the form of a three-dimensional network " of attapulgite fibres, and the kaolin particles are mechanically retained in the three-dimensional net ⁇ work.
  • a well-dispersed slurry of attapulgite in water and water glass as dispersing agent is formed.
  • the fibre surfaces of the slurried particles are coated with a 200 A thick layer of aluminium silicate, fol- lowed by spray-drying.
  • Support particles of aluminium silicate-coated attapulgite fibres in a three-dimen ⁇ sional network structure are obtained.
  • EXAMPLE 13 Production of a support A well-dispersed slurry of 50% attapulgite and 50% chrysotile in water is formed, water glass being used as dispersing agent. During spray-drying of the slurry, support particles are formed which have a three-dimensional network with pores corresponding approximately to the diameter of the attapulgite and the chrysotile.
  • EXAMPLE 14 Production of hydroprocessing catalyst Attapulgite in an amount corresponding to 1.82 kg of dry attapulgite is added to 10 litres of water containing, as a dispersing agent, aluminium hydroxy chloride in an amount corresponding to 16 g A1 2 0 ⁇ per 100 g of dry attapulgite.
  • the attapulgite is added under intense agitation. When all attapulgite has been added, the well-dispersed slurry contains 15% by weight of attapulgite, calculated as dry attapulgite.
  • the re ⁇ sulting slurry is spray-dried. 100 g of the spray- dried attapulgite are slowly heated to 540 C for 3 hours and then calcined at 540°C for 16 hours. 10 g of the calcined attapulgite are then impregnated with a solu- tion of 1.06 g ammonium molybdate [(NH.)gMo_0 24 .4H 2 0] in 13.77 g of water.
  • the ammonium molybdate Before the ammonium molybdate is added to the water, the ammonium molybdate is mois ⁇ tened with 0.47 ml ammonium hydroxide consisting of 25% ammonia in water.
  • the ammonium molybdate-impregnated attapulgite is dried in an oven for 8 hours at 120 C.
  • the attapulgite is agitated every 10 minutes during the first hour of drying.
  • the attapulgite is impregnated with a solution of 0.58 g of cobalt nitrate [Co(N0 3 ) 2 .6H 2 0] in 15.27 g of water.
  • the im- pregnated attapulgite is dried for 8 hours at 120 C.
  • the catalyst is agitated every 10 minutes during the first hour of drying.
  • the attapulgite impregnated with cobalt and molybdenum salts is slowly heated to 540 C and calcined at this temperature for 10 hours.
  • the spray-dried attapulgite impregnated with cobalt and molybdenum salts has an average pore size of 360 A and a surface areaof 85 m 2/g. 76% of the surface area are in pores exceeding 100 A.
  • the dispersion degree of the molybdenum is 89%.
  • alumi ⁇ nium oxide (PURALSB) impregnated with cobalt and molybdenum in the same manner as the atta ⁇ pulgite above, will have an average pore size of 60 A and a surface area of 240 m 2/g. 5% of the surface area are in pores exceeding 100 A.
  • the dispersion degree of the molybdenum is in this case 31%.
  • the attapulgite catalyst produced in accordance with this Example and impregnated with molybdenum and cobalt may be used as a hydroprocessing catalyst.
  • Spray-dried particles have an average pore size of
  • spray-dried particles after spray-drying are calcined at 500 C for 1 hour, they will have, after calcining, an average pore size of 362 A and
  • an surface area of 111 m /g. 87% of the surface area are in pores exceeding 100 A.
  • the spray-dried particles are aged at 750°C in an atmosphere of 100% relative humidity for 18 hours, the spray-dried particles after aging will have an average pore size of 465 A and a
  • An aluminium silicate sol whose surface is coated with cobalt and molybdenum oxide-hydroxide is admixed to the attapulgite slurry which is then spray-dried.
  • the spray-dried particles have an average pore size of 410 A and a
  • the particles may be used a hydroprocessing catalyst.
  • EXAMPLE 17 Production of a hydrogenation catalyst A well-dispersed slurry of attapulgite is prepared and spray-dried in accordance with Example 14.. Conven- tional coating of the spray-dried material with pla ⁇ tinum is carried out, whereupon the material is ex ⁇ truded. The resulting extrudate may be used as a hydro ⁇ genation catalyst.
  • a well-dispersed slurry of attapulgite is prepared and spray-dried in accordance with Example 14, and the spray-dried material is coated in conventional manner with cobalt and molybdenum, followed by ex- trusion and sulphidisation.
  • the sulphidisation may be performed in situ in the catalytic reactor.
  • the resulting extrudate may be used as a hydroprocessing. catalyst.
  • a well-dispersed slurry of attapulgite is prepared and spray-dried in accordance with Example 14.
  • the spray-dried attapulgite is coated with aluminium oxide sol, the sol particle surfaces of which are coated with oxide-hydroxides of molybdenum and nickel. After extrusion and sulphidisation, the resulting extrudate may be used a hydroprocessing catalyst.
  • EXAMPLE 20 Production of a hydroprocessing catalyst A well-dispersed slurry of attapulgite is prepared and spray-dried in accordance with Example 14. The spray-dried attapulgite is mixed with spray-dried • aluminium oxide. Spray-dried attapulgate and aluminium oxide are coated in conventional manner with molybdenum and cobalt. After extrusion and sulphidisation the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 21 Production of a hydroprocessing catalyst - A well-dispersed slurry of attapulgite is prepared and spray-dried in accordance with Example 14. The spray-dried attapulgite is mixed with the spray-dried alumium oxide and coated with sulphides of molybdenum and nickel according to microemulsion technique. After extrusion, the resulting material may be used as a hydroprocessing catalyst.
  • a well-dispersed slurry of attapulgite is prepared and spray-dried in accordance with Example 14 and mixed with the spray-dried aluminium oxide.
  • Spray-dried attapulgite and aluminium oxide are coated with alumi ⁇ nium oxide sol whose sol particle surfaces are coated with oxide-hydroxides of tungsten and nickel. After extrusion and sulphidisation, the resulting material may be used as a hydroprocessing catalyst.
  • a well-dispersed slurry of attapulgite and mont- morillonite is prepared and spray-dried.
  • Spray-dried attapulgite and montmorillonite are coated in conven- tional manner with tungsten and cobalt. After extru ⁇ sion and sulphidisation, the resulting material may be used a hydroprocessing catalyst.
  • EXAMPLE 25 Production of a hydroprocessing catalyst A well-dispersed slurry of attapulgite and chry ⁇ sotile is prepared and spray-dried. Spray-dried atta ⁇ pulgite and chrysotile are coated in conventional manner with molybdenum and nickel. After extrusion and sulphidisation, 'the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 26 Production of a hydrogenation catalyst An extrudate of attapulgite and aluminium oxide is formed from a well-dispersed slurry and coated in conventional manner with platinum. The resulting material may be used as a hydrogenation catalyst.
  • EXAMPLE 27 Production of a hydroprocessing catalyst An extrudate of attapulgite and aluminium oxide is formed from a well-dispersed slurry. This well- dispersed slurry is formed by mixing an aqueous slurry of 500 g attapulgite with such an amount of aluminium oxide that the dry content of the slurry will be above 30% and the aluminium oxide content 33%, based on the dry weight of the slurry. The extrudate is then coated in conventional manner with cobalt and molybdenum. After sulphidisation, the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 28 Production of a hydroprocessing catalyst An extrudate of attapulgite and aluminium oxide is formed from a well-dispersed slurry and coated with aluminium oxide sol whose surface is coated with molybdenum and nickel. After sulphidisation, the result ⁇ ing material may be used as a hydroprocessing catalyst.
  • EXAMPLE 29 Production of a hydroprocessing catalyst An extrudate of attapulgite and aluminium oxide is formed from a well-dispersed slurry and coated with aluminium oxide sol whose surface is coated with molybdenum and nickel. After sulphidisation, the result ⁇ ing material may be used as a hydroprocessing catalyst.
  • EXAMPLE 29 Production of a hydroprocessing catalyst An extrudate of attapulgite and aluminium oxide is formed from a well-dispersed slurry and coated with aluminium oxide sol whose surface is coated with molybdenum and nickel. After sulphidisation, the result ⁇ ing material may be used
  • Attapulgite in an amount correspond ⁇ ing to 0.50 kg of dry attapulgite is added to 1.6 litre of water which, as a dispersing agent, contains water glass in an amount corresponding to 3.0 g Si0 2 per 100 g of dry attapulgite.
  • the attapulgite is added under intense agitation in a Z-shaped blade kneader.
  • the slurry -contains 30% by weight of attapulgite, calculated as' dry atta- pulgite.
  • the resulting mass is extruded in the above- mentioned manner to extrudates having a diameter of 1.6 mm and a length of 3-5 mm.
  • the finished extrudates are slowly heated to 200 C during 2 hours and then held at 200 C for a further 2 hours for drying. 100 g of the dried extrudate are then slowly heated to 540 C during 3 hours and then calcined at 540 C during a further 2 hours.
  • the attapulgite extrudate impreg ⁇ nated with cobalt and molybdenum salts has an average pore size of 360 A and a surface area of 108 m 2/g,
  • the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 30 Production of a hydroprocessing catalyst An extrudate of spray-dried attapulgite is formed from a well-dispersed slurry and coated with particles of molybdenum sulphide and nickel sulphide prepared by microemulsion technique. The resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 31 Production of a hydroprocessing catalyst An extrudate of spray-dried attapulgite is formed from a well-dispersed slurry and coated with aluminium oxide sol whose sol particle surfaces are coated with oxide-hydroxides of tungsten and nickel. After sulphi ⁇ disation, the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 32 Production of a hydroprocessing catalyst An extrudate of spray-dried chrysotile is " formed from a well-dispersed slurry and coated with aluminium * oxide sol, the sol particle surfaces of which are coated with oxide-hydroxides of molybdenum and co ⁇ balt. After sulphidisation, the resulting material may be used as a hydroprocessing catalyst.
  • An extrudate of slurries of attapulgite and ont- morillonite is formed from a well-dispersed slurry and coated in conventional manner with tungsten and cobalt. After sulphidisation, the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 34 Production of a hydroprocessing catalyst An extrudate of slurries of attipulgite and chry ⁇ sotile is coated in conventional manner with molybdenum and nickel. After sulphidisation, the resulting material may be used as a hydroprocessing catalyst.
  • EXAMPLE 35 Production of a hydrogenation catalyst Attapulgite in an amount corresponding to 1.82 kg of dry attapulgite is added to 10 litres of water containing "KLORHYDROL ACH" as a dispersing agent in an amount corresponding to 16 g Al 2 0., per 100 g of dry attapulgite. The attapulgite is added under intense agitation.
  • the slurry contains 15% by weight of attapulgite, calculated as dry attapulgite.
  • the slurry of attapulgite in water is spray-dried.
  • 100 g of spray-dried atta ⁇ pulgite are slowly heated to 540 C for 3 hours and then calcined at 540°C for 16 hours.
  • 10 g of the cal ⁇ cined attapulgite are impregnated with a suspension of platinum particles in a microemulsion of heptane.
  • the platinum particles in the microemulsion are of the order 25 A.
  • the attapulgite particles are impreg ⁇ nated with a platinum content of 1%.
  • the calcined spray-dried particles have an average
  • EXAMPLE 36 Production of a cracking catalyst 2.85 kg “ATTAGEL 50" are added to 10 litres of water containing water glass in a ratio of 3.3:1.
  • the water glass content in the slurry is made to cor ⁇ respond to 3.5 g SiO- from the water glass per 100 g of dry attapulgite.
  • the attapulgite is added under intense agitation.
  • the final attapulgite content is 25% by weight of dry attapulgite.
  • the attapulgite in the well-dispersed slurry is coated with particles of a sol of ammonium aluminium silicate.
  • the attapulgite slurry is then spray-dried under the above-mentioned conditions, whereupon the spray-dried particles are calcined at 500°C for 1 hour, whereby the hydrogen form of the catalyst is obtained. After calcining, the spray-dried particles have an average pore size
  • EXAMPLE 37 Production of a cracking catalyst Example 36 is repeated, but the spray-dried par- tides are aged at 750 C in an atmosphere of 100% relative humidity for 18 hours. After aging, the spray- dried particles have an average pore size of 465 A
  • Example 36 Production of a cracking catalyst Example 36 is repeated, but the spray-dried par ⁇ ticles are subjected to ion exchange with rare earth metals, followed by calcining at 750°C for 1 hour. After calcining, the spray-dried particles have an average pore size of 380 A and a surface ar •ea' of 91 m2/g.
  • Example 36 is repeated, but sepiolite is used instead of attapulgite. Equivalent results are ob ⁇ tained.
  • Attapulgite in an amount corresponding to 263 g of dry attapulgite is added to an aqueous solution of water glass in a ratio of 3.3:1.
  • the water glass content corresponds to 4% Si0 2 , based upon dry atta- pulgite.
  • the attapulgite is added under intense agita ⁇ tion. When all attapulgite has been added to the slurry, the well-dispersed slurry has a dry content correspond- ing to 20% of dry attapulgite.
  • 1 litre of a solution of potassium aluminium silicate is prepared by mixing 56% by volume of potassium silicate which is in the ratio of 2:1 and which is 3-molar with regard to SiO ⁇ , with 25% by volume of 2-molar potassium aluminate and 19% by volume of water.
  • To 1 litre of attapulgite slurry 840 ml of the solution of potassium aluminium silicate are added for 1 hour.
  • the temperature of the slurry is maintained at 80-85 C, and the pH of the slurry at 10-11.5 by the addition of acetic acid. In this manner, the attapulgite particles are coated with a homogeneous layer of aluminium silicate.
  • the slurry is spray-dried.
  • the spray-dried attapulgite is slurried in water and ion exchanged with ammonium ions by adding ammonium sulphate to the slurry at pH 4.5 and a temperature of 80 C.
  • the spray-dried particles are filtered, and the ion exchange procedure is. epeated twice. After the last ion exchange step, the spray-dried particles are filtered and washed.
  • the spray-dried particles are then aged for 18 hours at 750°C and in 100% water vapour.
  • the catalytic activi ⁇ ty of the aged aluminium silicate-coated attapulgite is measured with a Micro Activity Testing apparatus (MAT testing is a technique described in literature). The test gave a yield of 50%, which should be com ⁇ pared to the yield obtained with an equilibrium catalyst in a commercial cracking plant.
  • the selectivity of gasoline and diesel is excellent.
  • the yield of gas and carbon is low.
  • EXAMPLE 41 Production of a cracking catalyst A well-dispersed slurry of attapulgite is prepared and spray-dried to particles having an average pore size of 70 ⁇ m. The surface of the spray-dried particles is coated with a layer of sol particles of aluminium silicate in the ammonium form.
  • EXAMPLE 42 Production of a cracking catalyst A well-dispersed slurry of attapulgite is prepared and spray-dried to particles having an average pore size of 70 ⁇ m. The surface of the spray-dried particles is coated with a layer of sol particles of aluminium silicate in the ammonium form.
  • Example 41 is repeated, but the ammonium form of the aluminium silicate is converted into RE form.
  • EXAMPLE 43 is repeated, but the ammonium form of the aluminium silicate is converted into RE form.
  • Example 41 Production of a cracking catalyst Example 41 is repeated, but a mixture of chrysotile and attapulgite is used as support material.
  • Example 38 Production of a cracking catalyst Example 38 is repeated, but instead of attapulgite a mixture of 70% attapulgite and 30% bentonite is used.
  • a well-dispersed slurry is prepared from zeolite NaY and attapulgite, utilising water glass as dispers ⁇ ing agent.
  • the slurry is spray-dried, and the spray- dried particles are then subjected to ammonium ion exchange and then to ion exchange with ions of rare earth metals.
  • EXAMPLE 46 Production of a cracking catalyst A well-dispersed slurry is prepared from attapul- gite and zeolite RE-Y, using aluminium hydroxychloride as dispersing agent. The slurry is spray-dried to particles which are calcined at 600 C.
  • Example 46 Production of a cracking catalyst Example 46 is repeated, but instead of zeolite RE-Y the highly stable zeolite US-Y is used.
  • a well-dispersed slurry is prepared from attapul- gite, kaolin and zeolite NH ⁇ -Y, use being made of aluminium hydroxychloride as dispersing agent.
  • the slurry is spray-dried, and the spray-dried particles are subjected to ion exchange with ions of rare earth metals.
  • EXAMPLE 49 Production of a cracking catalyst Attapulgite is added to an aqueous solution of chloroaluminium hydroxide under intense agitation. When all attapulgite has been added to the slurry, a sodium aluminium silicate sol is added, such that the attapulgite fibres are provided with a monolayer of sol particles. To this well-dispersed slurry the zeolite NA-Y is then added. The resulting slurry of zeolite NA-Y and attapulgite is spray-dried, and the resulting particles are first subjected to ammonium ion exchange and then to ion exchange with ions of rare earth metals.
  • Attapulgite is dispersed under intense agitation in an aqueous solution of aluminium hydroxychloride, whereupon an ammonium aluminium silicate sol is added for coating the surface of the attapulgite fibres with a monolayer of sol particles.
  • an ammonium aluminium silicate sol is added for coating the surface of the attapulgite fibres with a monolayer of sol particles.
  • a well-dispersed slurry of the zeolite US-Y is added under intense agitation. After that, spray-drying is effected to particles which finally are calcined at 500 C.
  • EXAMPLE 53 Production of a support material having high crushing strength Attapulgite ("ATTAGEL 50") in an amount correspond- ing to 1.82 kg of dry attapulgite is added to 10 litres of water which, as a dispersing agent, contains alumi ⁇ nium hydroxy chloride in an amount corresponding to 16 g Al p O, per 100 g of dry attapulgite.
  • Attapulgite A support material having high crushing strength Attapulgite
  • the attapulgite is added under intense agitation to form a well-dispersed slurry.
  • the slurry contains 15% by weight- of attapulgite, calculated as dry attapulgite.
  • the resulting slurry is spray-dried.
  • 200 g of spray-dried attapulgite are mixed in the dry state with 100 g attapulgite which has not - been sprayed.
  • This attapulgite mixture is added under intense agitation in a 2-blade kneader to 1.2 litre of water which, as a dispersing agent and binder, contains 3 g Si0 2 per 100 g of attapulgite that has not been spray-dried.
  • the well-dispersed mass contains 29% weight of dry -material.
  • Example 29 has a BET surface area of 130 m /g and an average pore size of 380 A.
  • This extrudate has high crushing strength and can be used as a sup- port for catalyst material.
  • the catalyst material can be supplied in the manner previously mentioned.
  • Attapulgite Production of a catalyst support of attapulgite and aluminium oxide Attapulgite (“ATTAGEL 50”) is mixed with water and a dispersing agent in accordance with Example 53 and is spray-dried.
  • 500 g (calculated as dry attapulgite) of the spray-dried attapulgite are mixed with 88 g aluminium oxide ("PURAL SB").
  • This dry mixture is added under in ⁇ tense agitation in a Z-shaped blade kneader to 1.3 litre of water to form a mass containing 30% by weight of dry material.
  • This mass is extruded in the manner mentioned above and dried by being slowly heated to and maintained at 200 C in the manner stated in Example 29. After drying at 200 C, the temperature of the mass is immediately and slowly heated to 540 C for 3 hours and held at this temperature for a further 2 hours for calcining.
  • the resulting calcined product has a BET surface 2 area of 173 m /g and an average pore size of 260 A and may be used as a catalyst support.
  • the resulting calcined product has a BET surface 2 area of 130 m /g and an average pore size of 284 A and may be used a catalyst support.
  • ACH ACH" water glass is used in an amount corresponding to 3.0% Si0 2 , calculated on the dry weight of the attapulgite and bentonite present.
  • the resulting calcined product has a BET surface 2 area of 136 m /g and an average pore size of 300 A and may be used as catalyst support.
  • EXAMPLE 57 Production of a catalyst support of attapulgite and cross-linked smectite 100 g of cross-linked smectite are prepared by adding 100 g of bentonite to a solution of 90 g "KLOR ⁇ HYDROL ACH" in 1340 g water at 90°C. The suspension is kept under gentle agitation for 5 hours at 90 C. The filtered material is then washed three times with deionized water at 90°C. After the removal of the last wash water the material is dried at 105 C for
  • Example 55 is then repeated, use being made of the said cross-linked smectite instead of the bentonite.
  • the resulting calcined product has a BET surface 2 area of 123 m /g and an average pore size of 380 A and may be used as a catalyst support.
  • Example 57 is repeated, but instead of "KLORHYDROL
  • ACH use is made of water glass in an amount correspond- ing to 3.0% Si0 2 , calculated on the dry weight of attapulgite and smectite present.
  • the resulting calcined product has a BET surface 2 area of 136 m /g and an average pore size of 370 A and may be used as a catalyst.
  • ion exchange is carried out by means of 5% by weight solution of ammonium sulphate. This ion exchange treatment is effected 3 times in all. After ion exchange, the extrudate is washed 3 times with water. Both the ammonium sulphate solution and the wash water have a temperature of 60 C. Ion exchange and washing are carried out on the one hand in order to remove Na in the extrudate by ion exchange and, on the other hand, to remove any residual ash from the burning of CMC.
  • the extrudate After the last washing with water and after filtra ⁇ tion of the extrudate, the extrudate is heated from room temperature to 150 C for 2 hours, whereupon the temperature is maintained at 150 C for a further 2 hours for drying. After that, the temperature is raised at a rate of 115 C/hour to 500 C, and the extrudate is maintained at this temperature for one further hour for calcining.
  • the resulting product has a BET surface area 2 of 133 m /g and an average pore size of 300 A, 77% of the surface area being in pores exceeding 100 A.
  • Example 59 is repeated, but in step b) 80 g of the spray-dried material are mixed with 300 g of attapul- gite that has not been spray-dried and 19 g of CMC, whereby a mixture is obtained which, calculated on the dry weight, contains 74% of attapulgite that has not been spray-dried, 20% of spray-dried attapulgite and 6% of CMC, said mixture being added to 670 g of water under intense agitation to form the well-dispersed slurry.
  • the product obtained after calcining has a BET
  • Example 59 is repeated, but step a) is omitted and in step b) 350 g of "ATTAGEL 50" are mixed with 6 g of CMC and 41 g of aluminium oxide (“PURAL SB”), the mixture being added to 660 g of water to form the well-dispersed slurry. Calculated on a dry basis, this well-dispersed slurry contains 88% attapulgite,
  • EXAMPLE 62 A well-dispersed attapulgite slurry as prepared and spray-dried according to Example 1.
  • the present invention provides a support or catalyst structure having an unusually high pore diameter coupled with a large surface area.
  • the large surface area is concentrated to the pores having a diameter exceeding 100 A.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Une charge ou support pour des substances d'action catalytique consiste en des particules d'agrégat ayant une structure cohérente d'un réseau tridimensionnel de particules minérales ayant une structure fibreuse ou en bande et un diamètre d'au moins 100 Ao et une stabilité mécanique, thermique et hydrothermique nécessaire à un hydrotraitement ou une hydrogénation. Le support possède une surface spécifique d'au moins 75 m2/g et un diamètre de pore moyen d'au moins 100 Ao, au moins 75% de la surface spécifique présentant des pores d'un diamètre supérieur à 100 Ao. Dans un catalyseur de crackage, hydrogénation ou hydrotraitement, la substance d'action catalytique est déposée sous la forme d'un revêtement superficiel sur les particules minérales fibreuses ou en forme de bande du support. L'attapulgite, la sépiolite et la chrysotile peuvent être utilisées comme particules minérales fibreuses ou en bande. La charge ou support est produit en formant une boue de particules minérales bien dispersée qui, dans leur état naturel, possèdent le diamètre de particule requis ou à qui l'on a donné ce diamètre de particule en les modifiant, après quoi la boue bien dispersée est soit séchée par atomisation de manière à former directement les particules d'agrégat soit extrudée ou mise en forme de pastilles pour former de telles particules d'agrégat, soit elle est d'abord séchée par atomisation en particules d'agrégat qui sont ensuite transformées en boue et extrudées ou mises en pastilles sous la forme de particules désirées du support catalyseur, la substance d'action catalytique étant appliquée, dans la production du catalyseur, sous la forme d'un revêtement superficiel appliqué sur les particules fibreuses ou en forme de bande du support avant ou après le séchage par atomisation, l'extrusion ou la mise en forme de pastilles des particules du support.
EP85900814A 1984-01-30 1985-01-29 Charge ou support pour substances d'action catalytique, procede de production de cette charge ou ce support, catalyseur produit a partir de ce support, et utilisation de ce catalyseur Ceased EP0169877A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
SE8400427A SE8400427L (sv) 1984-01-30 1984-01-30 Berare for katalytiskt aktiva emnen och sett att framstella en sadan berare
SE8400429A SE8400429L (sv) 1984-01-30 1984-01-30 Vetebehandlings- eller hydreringskatalysator och sett att framstella denna
SE8400427 1984-01-30
SE8400429 1984-01-30
SE8400432 1984-01-30
SE8400433 1984-01-30
SE8400433A SE8400433L (sv) 1984-01-30 1984-01-30 Krackningskatalysator och sett att framstella en sadan
SE8400432A SE8400432L (sv) 1984-01-30 1984-01-30 Krackningskatalysator och sett att framstella en sadan

Publications (1)

Publication Number Publication Date
EP0169877A1 true EP0169877A1 (fr) 1986-02-05

Family

ID=27484645

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85900814A Ceased EP0169877A1 (fr) 1984-01-30 1985-01-29 Charge ou support pour substances d'action catalytique, procede de production de cette charge ou ce support, catalyseur produit a partir de ce support, et utilisation de ce catalyseur

Country Status (6)

Country Link
EP (1) EP0169877A1 (fr)
BR (1) BR8504994A (fr)
DK (1) DK437385A (fr)
FI (1) FI853778L (fr)
NO (1) NO853819L (fr)
WO (1) WO1985003241A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59914480D1 (de) * 1998-04-08 2007-10-11 Basf Ag Verfahren zur herstellung eines formkörpers unter verwendung eines metalloxidsols, formkörper, seine verwendung bei der herstellung eines alkenoxids
JP3855994B2 (ja) * 2003-12-25 2006-12-13 日産自動車株式会社 触媒及びその製造方法
CN101791556B (zh) * 2010-03-23 2012-01-25 北京科技大学 一种辛醇加氢精制催化剂及其制备方法
DE102019200180A1 (de) * 2018-07-25 2020-01-30 Audi Ag Filterelement für einen Partikelfilter, Abgaspartikelfilter, Verfahren zum Herstellen eines Filterelements sowie Verwendung eines Beschichtungsmaterials
CN110683690A (zh) * 2019-11-01 2020-01-14 安徽绿金生态环境科技有限公司 一种小型生活污水处理设备
CN111569908A (zh) * 2020-06-04 2020-08-25 深圳市汇德丰控股集团有限公司 一种加氢脱氮催化剂及其制备方法与应用
CN114100616B (zh) * 2020-08-31 2023-10-20 中国石油化工股份有限公司 烃类蒸汽转化催化剂及其制备方法
CN112877322B (zh) * 2021-02-22 2022-06-21 杭州楠大环保科技有限公司 基于微生物相变的易腐垃圾生物降解方法
CN116139873A (zh) * 2022-11-30 2023-05-23 中国石油大学(华东) 一种空间限域型镍钼柴油加氢催化剂的制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1161053A (en) * 1965-09-28 1969-08-13 Grace W R & Co Preparation of Hydrocarbon cracking catalyst.
NL143139B (nl) * 1967-04-14 1974-09-16 Stamicarbon Werkwijze voor het bereiden van een dragerkatalysator door behandelen van een drager met een oplossing van een zout van een katalytisch actief element.
NL6816777A (fr) * 1968-11-23 1970-05-26
NL6818337A (fr) * 1968-12-20 1970-06-23
JPS568080B1 (fr) * 1971-04-23 1981-02-21
GB1485370A (en) * 1974-12-06 1977-09-08 Atomic Energy Authority Uk Catalysts and catalytic burners
US4215015A (en) * 1979-02-02 1980-07-29 Uop Inc. High octane FCC catalyst
FR2449474A1 (fr) * 1979-02-26 1980-09-19 Rhone Poulenc Ind Billes d'alumine a double porosite, leur procede de preparation et leurs applications comme supports de catalyseurs
US4425261A (en) * 1980-03-24 1984-01-10 Ytkemiska Institutet Liquid suspension of particles of a metal belonging to the platinum group and a method for the manufacture of such a suspension
JPS5919072B2 (ja) * 1980-04-04 1984-05-02 株式会社日本自動車部品総合研究所 コ−ジエライト体の製造方法
CA1168210A (fr) * 1981-01-12 1984-05-29 Chevron Research And Technology Company Catalyseur de traitement des hydrocarbures residuaires
US4477492A (en) * 1983-04-22 1984-10-16 E. I. Du Pont De Nemours And Company Process for preparing superficially porous supports for chromatography and catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8503241A1 *

Also Published As

Publication number Publication date
BR8504994A (pt) 1986-01-21
FI853778A0 (fi) 1985-09-30
WO1985003241A1 (fr) 1985-08-01
NO853819L (no) 1985-09-27
DK437385D0 (da) 1985-09-27
DK437385A (da) 1985-09-27
FI853778L (fi) 1985-09-30

Similar Documents

Publication Publication Date Title
US3518206A (en) Supported catalysts composed of substrate coated with colloidal silica and catalyst
KR880001778B1 (ko) 촉매지지체 코우팅용 알루미나 조성물에 의한 촉매지지체의 코우팅 방법 및 이와같이 수득된 촉매지지체
US3565830A (en) Coated film of catalytically active oxide on a refractory support
CA1090536A (fr) Particules spheriques d'aluminium
JPH0513702B2 (fr)
CA1160200A (fr) Preparation d'un agent de catalyse
US4111846A (en) Hydrosol and catalyst preparation
US2280650A (en) Manufacture of catalysts
EP0169877A1 (fr) Charge ou support pour substances d'action catalytique, procede de production de cette charge ou ce support, catalyseur produit a partir de ce support, et utilisation de ce catalyseur
US4843052A (en) Acid-reacted metakaolin catalyst and catalyst support compositions
JP3949778B2 (ja) 接触分解触媒
US3923692A (en) Hydrotreating catalyst
US3391075A (en) Catalytic conversion of hydrocarbons with the use of a steam treated y type of crystalline aluminosilicate
US4940531A (en) Catalytic cracking process employing an acid-reacted metakaolin catalyst
US5160032A (en) Hydrocarbon conversion process using alumina clay compositions
US3472791A (en) Method of spherical catalyst preparation
US2763622A (en) Craking catalyst preparation
US2280649A (en) Manufacture of catalysts
US3193491A (en) Preparation of a hydrocracking catalyst and hydrocracking therewith
EP0153911A1 (fr) Catalyseur de purification des émissions de gaz d'échappement d'automobiles et son procédé de fabrication
JPH01266853A (ja) 触媒の製法
US2381825A (en) Catalytic conversion process
US2964480A (en) Manufacture of platinum metalcontaining catalyst
US2278746A (en) Manufacture of catalysts
US2744057A (en) Catalytic conversion process with the use of a base-exchanged silica-alumina catalyst

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19850726

AK Designated contracting states

Designated state(s): BE DE FR GB LU NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EKA NOBEL AKTIEBOLAG

17Q First examination report despatched

Effective date: 19870120

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19871004

RIN1 Information on inventor provided before grant (corrected)

Inventor name: JAERAS, SVEN, GUNNAR

Inventor name: ROEJ, JAN-ANDERS, OLAV

Inventor name: DAHLQVIST, PER-ARNE

Inventor name: BAEZA CALZADILLA, JOSE, AURELIO

Inventor name: OTTERSTEDT, JAN-ERIK, ANDERS