EP1337329A1 - Composition catalytique en couches et procedes de preparation et d'utilisation de la composition - Google Patents

Composition catalytique en couches et procedes de preparation et d'utilisation de la composition

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Publication number
EP1337329A1
EP1337329A1 EP00980270A EP00980270A EP1337329A1 EP 1337329 A1 EP1337329 A1 EP 1337329A1 EP 00980270 A EP00980270 A EP 00980270A EP 00980270 A EP00980270 A EP 00980270A EP 1337329 A1 EP1337329 A1 EP 1337329A1
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EP
European Patent Office
Prior art keywords
composition
catalyst
alumina
inner core
metal
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.)
Withdrawn
Application number
EP00980270A
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German (de)
English (en)
Inventor
Robert H. Jensen
Jeffrey C. Bricker
Quianjun Chen
Masaru Tatsushima
Kenji Kikuchi
Masao Takayma
Koji Hara
Isao Tsunokuma
Hiroyuki Serizawa
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.)
Honeywell UOP LLC
Original Assignee
UOP LLC
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Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of EP1337329A1 publication Critical patent/EP1337329A1/fr
Withdrawn legal-status Critical Current

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/321—Catalytic processes
    • C07C5/324—Catalytic processes with metals
    • C07C5/325—Catalytic processes with metals of the platinum group
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/12—Silica and alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/20—Carbon compounds
    • C07C2527/22—Carbides
    • C07C2527/224—Silicon carbide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays

Definitions

  • the inner core is now coated with a layer of a refractory inorganic oxide which is different from the inorganic oxide which may be used as the inner core and will be referred to as the outer refractory inorganic oxide.
  • This outer refractory oxide is one which has good porosity, has a surface area of at least 20m 2 /g, and preferably at least 50m 2 /g, an apparent bulk density of 0.2g/ml to 1.0g/ml and is chosen from the group consisting of gamma alumina, delta alumina, eta alumina, theta alumina, silica/alumina, zeolites, non-zeolitic molecular sieves (NZMS), titania, zirconia and mixtures thereof.
  • NZMS non-zeolitic molecular sieves
  • the catalyst composition is reduced under hydrogen or other reducing atmosphere in order to ensure that the platinum group metal component is in the metallic state (zero valent). Reduction is carried out at a temperature of 100°C to 650°C for a time of 0.5 to 10 hours in a reducing environment, preferably dry hydrogen.
  • the state of the promoter and modifier metals can be metallic (zero valent), metal oxide or metal oxychloride.
  • the layered catalyst composition can also contain a halogen component which can be fluorine, chlorine, bromine, iodine or mixtures thereof with chlorine and bromine preferred. This halogen component is present in an amount of 0.03 to 1.5 wt. % with respect to the weight of the entire catalyst composition.
  • the modifier metal can be present both in the outer layer and the inner core. This is owing to the fact that the modifier metal can migrate to the inner core, when the core is other than a metallic core.
  • Preferred olefins are ethylene, propylene and those olefins which are known as detergent range olefins.
  • Detergent range olefins are linear olefins containing from 6 up through 20 carbon atoms which have either internal or terminal double bonds. Linear olefins containing from 8 to 16 carbon atoms are preferred and those containing from 10 up to 14 carbon atoms are especially preferred.
  • the particular conditions under which the monoalkylation reaction is conducted depends upon the aromatic compound and the olefin used.
  • One necessary condition is that the reaction be conducted under at least partial liquid phase conditions. Therefore, the reaction pressure is adjusted to maintain the olefin at least partially dissolved in the liquid phase.
  • the reaction may be conducted at autogenous pressure. As a practical matter the pressure normally is in the range between 200 and 1 ,000 psig (1379-6985 kPa) but usually is in a range between 300-600 psig (2069-4137 kPa).
  • a benzene-to-olefin ratio of between 5:1 up to as high as 30:1 is generally sufficient to ensure the desired monoalkylation selectivity, with a range between 8:1 and 20:1 even more preferred.
  • the zeolites of this invention can also be used to catalyze transalkylation which is included in the general term "alkylation".
  • transalkylation is meant that process where an alkyl group on one aromatic nucleus is intermoleculariy transferred to a second aromatic nucleus.
  • a preferred transalkylation process is one where one or more alkyl groups of a polyalkylated aromatic compound is transferred to a nonalkylated aromatic compound, and is exemplified by reaction of diisopropylbenzene with benzene to give two molecules of cumene.
  • transalkylation often is utilized to add to the selectivity of a desired selective monoalkylation by reacting the polyalkylates invariably formed during alkylation with nonalkylated aromatic to form additional monoalkylated products.
  • the polyalkylated aromatic compounds are those formed in the alkylation of alkylatable aromatic compounds with olefins as described above, and the nonalkylated aromatic compounds are benzene, naphthalene, anthracene, and phenanthrene.
  • reaction conditions for transalkylation are similar to those for alkylation, with temperatures being in the range of 100 to 250°, pressures in the range of 100 to 750 psig, and the molar ratio of unalkylated aromatic to polyalkylated aromatic in the range from 1 to 10.
  • polyalkylated aromatics which may be reacted with, e.g., benzene as the nonalkylated aromatic include diethylbenzene, diisopropylbenzene, dibutylbenzene, triethylbenzene, triisopropylbenzene etc.
  • the layered compositions of this invention contain catalytic metals and optionally promoters and modifiers, they can be used in hydrocarbon conversion processes such as alkylation of isoparaffins, hydrocracking, cracking isomerization, hydrogenation, dehydrogenation and oxidation.
  • hydrocarbon conversion processes such as alkylation of isoparaffins, hydrocracking, cracking isomerization, hydrogenation, dehydrogenation and oxidation.
  • the conditions for carrying out these processes are well known in the art and are presented here for completeness.
  • Hydrogen circulation rates are in the range of 178 to 8,888 standard cubic meters per cubic meter of charge (1 ,000 to 50,000 standard cubic feet (scf) per barrel of charge) preferably between 355 to 5,333 std. m 3 /m 3 (2,000 and 30,000 scf per barrel of charge).
  • Catalytic cracking processes are preferably carried out with the catalyst composition using feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc. with gasoline bei ⁇ g the principal desired product.
  • feedstocks such as gas oils, heavy naphthas, deasphalted crude oil residua, etc.
  • gasoline bei ⁇ g the principal desired product.
  • Temperature conditions 454°C to 593°C (850° to 1100°F.)
  • LHSV values of 0.5 to 10 hr "1 and pressure conditions of from 0 to 345 kPag (50 psig) are suitable.
  • dehydrogenatable hydrocarbons are contacted with the catalyst of the instant invention in a dehydrogenation zone maintained at dehydrogenation conditions.
  • This contacting can be accomplished in a fixed catalyst bed system, a moving catalyst bed system, a fluidized bed system, etc., or in a batch-type operation.
  • a fixed bed system is preferred.
  • the hydrocarbon feed stream is preheated to the desired reaction temperature and then flowed into the dehydrogenation zone containing a fixed bed of the catalyst.
  • the dehydrogenation zone may itself comprise one or more separate reaction zones with heating means there between to ensure that the desired reaction temperature can be maintained at the entrance to each reaction zone.
  • the hydrocarbon may be contacted with the catalyst bed in either upward, downward or radial flow fashion. Radial flow of the hydrocarbon through the catalyst bed is preferred.
  • the hydrocarbon may be in the liquid phase, a mixed vapor-liquid phase or the vapor phase when it contacts the catalyst. Preferably, it is in the vapor phase.
  • Hydrocarbons which can be dehydrogenated include hydrocarbons with 2 to 30 or more carbon atoms including paraffins, isoparaffins, alkylaromatics, naphthenes and olefins.
  • a preferred group of hydrocarbons is the group of normal paraffins with 2 to 30 carbon atoms.
  • Especially preferred normal paraffins are those having 2 to 15 carbon atoms.
  • Dehydrogenation conditions include a temperature of from 400°C to 900°C, a pressure of from 1 to 1013 kPa and a liquid hourly space velocity (LHSV) of from 0.1 to 100 hr "1 .
  • LHSV liquid hourly space velocity
  • the effluent stream from the dehydrogenation zone generally will contain unconverted dehydrogenatable hydrocarbons, hydrogen and the products of dehydrogenation reactions.
  • This effluent stream is typically cooled and passed to a hydrogen separation zone to separate a hydrogen-rich vapor phase from a hydrocarbon-rich liquid phase.
  • the hydrocarbon-rich liquid phase is further separated by means of either a suitable selective adsorbent, a selective solvent, a selective reaction or reactions or by means of a suitable fractionation scheme.
  • Unconverted dehydrogenatable hydrocarbons are recovered and may be recycled to the dehydrogenation zone. Products of the dehydrogenation reactions are recovered as final products or as intermediate products in the preparation of other compounds.
  • the dehydrogenatable hydrocarbons may be admixed with a diluent material before, while or after being flowed to the dehydrogenation zone.
  • the diluent material may be hydrogen, steam, methane, ethane, carbon dioxide, nitrogen, argon and the like or a mixture thereof. Hydrogen is the preferred diluent. Ordinarily, when hydrogen is utilized as the diluent it is utilized in amounts sufficient to ensure a hydrogen to hydrocarbon mole ratio of 0.1:1 to 40:1 , with best results being obtained when the mole ratio range is 1 :1 to 10:1.
  • the diluent hydrogen stream passed to the dehydrogenation zone will typically be recycled hydrogen separated from the effluent from the dehydrogenation zone in the hydrogen separation zone.
  • Water or a material which decomposes at dehydrogenation conditions to form water such as an alcohol, aldehyde, ether or ketone, for example, may be added to the dehydrogenation zone, either continuously or intermittently, in an amount to provide, calculated on the basis of equivalent water, 1 to 20,000 weight ppm of the hydrocarbon feed stream. Adding 1 to 10,000 weight ppm of water gives best results when dehydrogenating paraffins having from 2 to 30 or more carbon atoms.
  • Hydrogenation processes can be carried out using reactors and hydrogenation zones similar to the dehydrogenation process described above.
  • hydrogenation conditions include pressures of 0 kPag to 13,789 kPag, temperatures of 30°C to 280°C, H 2 to hydrogenatable hydrocarbon mole ratios of 5:1 to 0.1 :1 and LHSV of 0.1 to 20 hr "1 .
  • the layered compositions of this invention can also be used in oxidation reactions. These oxidation reactions include:
  • the layered sphere catalyst will be of most benefit to processes where the activity or selectivity of the catalyst is limited by intraparticle diffusional resistance of product or reactants.
  • the conditions for the oxidation process depend on the individual process application but are generally 350°C to 800°C, 40 kPa to 2030 kPa, with a diluent present in the feedstream such as N 2 , C0 2 , HO to control the reaction.
  • Hydrogen may also be present as a diluent and also a reactant.
  • the molar ratio of oxygen to H 2 may vary from 0.05 to 0.5.
  • the diluent level is generally from 0.1 to 10 moles of diluent per mole of hydrocarbon.
  • the steam to ethylbenzene molar ratio may be from 5:1 to 7:1 during the dehydrogenation of ethylbenzene.
  • Typical space velocity for oxidation is between 0.5 to 50 hr "1 LHSV.
  • Alumina spheres were prepared by the well known oil drop method which is described in U.S.-A- 2,620,314 which is incorporated by reference. This process involves forming an aluminum hydrosol by dissolving aluminum in hydrochloric acid. Hexamethylene tetraamine was added to the sol to gel the sol into spheres when dispersed as droplets into an oil bath maintained at 93°C. The droplets remained in the oil bath until they set and formed hydrogel spheres. After the spheres were removed from the hot oil, they were pressure aged at 135°C and washed with dilute ammonium hydroxide solution, dried at 110°C and calcined at 650°C for about 2 hours to give gamma alumina spheres.
  • This slurry (1 ,000 g) was sprayed onto 1 kg of alpha alumina cores having an average diameter of 1.05 mm by using a granulating and coating apparatus for 17 minutes to give an outer layer of 74 microns. At the end of the process, 463 g of slurry were left which did not coat the cores.
  • This layered spherical support was dried at 150°C for 2 hours and then calcined at 615°C for 4 hours in order to convert the pseudoboehmite in the outer layer into gamma alumina and convert the tin chloride to tin oxide.
  • the calcined layered support (1150 g) was impregnated with lithium using a rotary impregnator by contacting the support with an aqueous solution (1 :1 solution: support volume ratio) containing lithium nitrate and 2 wt.% nitric acid based on support weight.
  • the impregnated catalyst was heated using the rotary impregnator until no solution remained, dried, and then calcined at 540°C for 2 hours.
  • the tin and lithium containing composite was now impregnated with platinum by contacting the above composite with an aqueous solution (1 :1 solution: support volume ratio) containing chloroplatinic acid and 1.2 wt.% hydrochloric acid (based on support weight).
  • the impregnated composite was heated using the rotary impregnator until no solution remained, dried and calcined at 540°C for 2/2 hours and reduced in hydrogen at 500°C for 2 hours. Elemental analysis showed that this catalyst contained 0.093 wt.% platinum, 0.063 wt.% tin and 0.23 wt.% lithium with respect to the entire catalyst.
  • This catalyst was identified as catalyst A.
  • the distribution of the platinum was determined by Electron Probe Micro Analysis (EPMA) using a Scanning Electron Microscope which showed that the platinum was evenly distributed throughout the outer layer only.
  • EXAMPLE 2 Electron Probe Micro Analysis
  • Example 2 The procedure of Example 1 was repeated, except that a slurry was prepared by mixing 275 g of an alumina sol into 431 g of deionized water with sufficient agitation, and then adding 289 g of gamma alumina powder, 5.36 g of a 50% aqueous solution of tin chloride was used, and after granulation and coating, the layered spherical support had an outer layer of 99 microns in thickness. There were 248 g of slurry left after the coating was carried out. Elemental analysis (wt.% based on the entire catalyst) showed that this catalyst contained 0.09 wt.% platinum, 0.09 wt.% tin and 0.23 wt.% lithium and was identified as catalyst B. Catalyst B was analyzed by EPMA which showed that the platinum was evenly distributed throughout the outer layer only.
  • a catalyst was prepared in a similar way to that of example ⁇ of U.S.-A- 4,786,625 except that the solution was sprayed onto the support.
  • the catalyst was analyzed and found to contain 0.43 wt.% platinum, 1.7 wt.% tin and 0.62 wt.% lithium. This catalyst was identified as catalyst C.
  • Catalyst C was analyzed by EPMA which showed that the platinum was on the surface of the support.
  • a catalyst was prepared according to example I of U.S.-A- 4,786,625. This catalyst was analyzed and found to contain 0.43 wt.% platinum, 0.48 wt.% tin and 0.58 wt. % lithium. This catalyst was identified as catalyst D. All the metals were evenly distributed throughout the support.
  • a gamma alumina slurry (1000g) was prepared as in example 1 except that no tin chloride was added to the slurry. This slurry was applied to 1000g of alpha alumina cores having a diameter of 1.054mm as in example 1 and calcined as in example 1 to give a layered support with an outer gamma-alumina layer of 74 microns in thickness.
  • the layered support (202g) was contacted with an aqueous solution prepared by diluting a 50% tin chloride solution (Sn content: 0.144g based on metal) and nitric acid (HN0 3 content: 18.2g) with deionized water to a volume of 150 ml.
  • the mixture was dried in a rotary evaporator at a temperature of 150°C for 2 hours, following by calcination at a temperature of 615°C for 4 hours.
  • the impregnated catalyst composition was heated in the rotary evaporator until no solution remained, calcined at 540°C for 2 A hours and then reduced in hydrogen at 500°C for 2 hours.
  • the platinum and tin were determined by EPMA to be evenly distributed throughout the outer layer. Elemental analysis showed that this layered catalyst composition contained 0.093 wt.% platinum, 0.071 wt.% tin and 0.268 wt. % lithium calculated as the metal and based on the entire catalyst weight. This catalyst was identified as catalyst E.
  • a sample of 600 ml. of spherical alumina was prepared as in example 1. This alumina was impregnated using a rotary impregnator with an aqueous solution prepared by diluting 9.55 g of a 50% tin chloride solution and 49.6 g of a 61% nitric acid solution with deionized water to a volume of 420 ml. The impregnated alumina spheres were dried in the rotary evaporator and then calcined at 540°C for 2 ⁇ A hours.
  • the resulting tin-containing catalyst was impregnated with an aqueous solution containing platinum and lithium, prepared by diluting a chloroplatinic acid solution (Pt content: 1.71 g), a lithium nitrate solution (Li content: 1.16 g) and 6.61 g of a 61% nitric acid solution with deionized water to a volume of 420 ml.
  • the obtained spherical catalyst was dried in a rotary evaporator until no solution remained and then calcined at a temperature of 540°C for 2.5 hours.
  • the platinum and tin were evenly distributed throughout the sphere.
  • a slurry was prepared by mixing 600 ml of the above spherical catalyst with 4.0 g of P-salt (dinitrodiammineplatinum in nitric acid) 0.641 g of meta stannic acid and 202 g of alumina sol (20 wt.% Al 2 0 3 ) with 1204 g of deionized water and ball milling the mixture for 4 hours.
  • This slurry was now used to apply a layer onto an alpha-alumina core having a diameter of 1.054 mm as in example 1.
  • a layered catalyst was obtained which had a layer of 50 microns. This layered catalyst composition was dried at 150°C for 2 hrs.
  • the catalysts of examples 1 -4 and comparative examples 1 and 2 were tested for dehydrogenation activity.
  • 10 cc of catalyst was placed and a hydrocarbon feed composed of 8.8 wt. % n-C 10 , 40.0 wt. % n- C ⁇ , 38.6 wt. % n-C ⁇ 2 , 10.8 wt. % n-C ⁇ 3) 0.8 wt. % n-Cu and 1 vol.
  • % non- normals was flowed over the catalyst under a pressure of 138 kPa (20 psig), a H 2 : hydrocarbon molar ratio of 6:1 and a liquid hourly space velocity (LHSV) of 20 hr "1 . Water at a concentration of 2000 ppm based on hydrocarbon weight was injected. The total normal olefin concentration in the product (% TNO) was maintained at 15 wt. % by adjusting reactor temperature.
  • the layered catalysts of the invention have both lower deactivation rates and increased selectivity to normal olefins versus catalysts of the prior art. Specifically, comparing catalysts A, B, E and F with catalyst C (platinum on the surface), it is observed that the deactivation rate is smaller for catalysts A, B, E and F. Additionally, selectivity is better for the layered catalysts of the invention. It must be pointed out that when selectivities are this high, one must look at the residual amount left or the non-TNO selectivity. Here, the amount of non-TNO for catalysts A and E are 17 wt.% and 14 wt. % less, respectively, than for catalyst C which is a substantial improvement.
  • catalysts B and F have a much lower deactivation rate than catalyst D, while catalysts A and E have a much higher selectivity (39 and 37 wt.% less non-TNO make, respectively) than catalyst D. Again, this shows a marked improvement in stability and selectivity.
  • Example 1 The procedure in example 1 was used to prepare a catalyst with a layer thickness of 90 microns. This catalyst was identified as catalyst I.
  • Catalysts G, H and I were tested for loss of layer material by attrition using the following test.
  • a sample of the catalyst was placed in a vial which in turn was placed in a blender mill along with two other vials containing the same amount of catalyst sample.
  • the vials were milled for ten (10) minutes, the vials removed and then sieved to separate the powder from the spheres.
  • the powder was weighed and an attrition loss (wt.%) was calculated.

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  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Cette invention concerne une composition catalytique en couches, un procédé de préparation et des procédés d'utilisation de cette composition. Cette composition catalytique comprend un noyau intérieur, tel qu'une alpha-alumine, et une couche extérieure liée au noyau intérieur et composée d'un oxyde inorganique réfractaire extérieur, tel qu'une gamma-alumine. La couche extérieure comporte éventuellement un métal du groupe platine, tel que le platine, et un métal promoteur, tel que l'étain, dispersés de manière uniforme sur ladite couche. En outre, la composition contient éventuellement un métal modificateur, tel que le lithium. La composition catalytique présente une durabilité et une sélectivité accrues s'agissant de la déshydrogénation des hydrocarbures.
EP00980270A 2000-11-27 2000-11-27 Composition catalytique en couches et procedes de preparation et d'utilisation de la composition Withdrawn EP1337329A1 (fr)

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PCT/US2000/030160 WO2002041990A1 (fr) 2000-11-27 2000-11-27 Composition catalytique en couches et procedes de preparation et d'utilisation de la composition
US30160 2000-11-27

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EP1337329A1 true EP1337329A1 (fr) 2003-08-27

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EP (1) EP1337329A1 (fr)
JP (1) JP4772270B2 (fr)
KR (1) KR100773666B1 (fr)
CN (1) CN1297341C (fr)
AU (2) AU2001217555B2 (fr)
CA (1) CA2429492C (fr)
MX (1) MXPA03004640A (fr)
NZ (1) NZ526222A (fr)
WO (1) WO2002041990A1 (fr)

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CN102463143B (zh) * 2010-11-17 2014-03-26 中国石油化工股份有限公司 制备薄壳形催化剂的复合载体
CN102463145B (zh) * 2010-11-17 2013-09-18 中国石油化工股份有限公司 用于氢气氧化催化剂涂层的浆料及其制备方法
CN102463146B (zh) * 2010-11-17 2013-12-04 中国石油化工股份有限公司 喷涂用的氧化铝浆料及其制备方法
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CN103755127B (zh) * 2014-01-14 2016-04-20 海南大学 一种锡槽脱氧的方法
CN105013481B (zh) * 2014-04-15 2018-02-06 中国石化扬子石油化工有限公司 一种C‑SiC复载型铂基催化剂其及制备方法和应用
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CN112892612B (zh) * 2019-12-03 2023-01-17 中国石化集团金陵石油化工有限责任公司 一种用于烃类转化反应的催化剂
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CN113426478A (zh) * 2021-06-25 2021-09-24 润和催化材料(浙江)有限公司 一种脱氢催化剂及其制备方法
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KR20030061409A (ko) 2003-07-18
AU2001217555B2 (en) 2006-01-05
CA2429492A1 (fr) 2002-05-30
MXPA03004640A (es) 2003-09-05
AU1755501A (en) 2002-06-03
JP4772270B2 (ja) 2011-09-14
WO2002041990A1 (fr) 2002-05-30
CN1297341C (zh) 2007-01-31
JP2004513778A (ja) 2004-05-13
KR100773666B1 (ko) 2007-11-05
CN1479649A (zh) 2004-03-03
NZ526222A (en) 2005-02-25
CA2429492C (fr) 2009-11-17

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