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    • 专利摘要:
    The present disclosure relates to a method for preparing a zeolitic core-shell catalytic composite for use in hydroisomerization of linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms, the core-shell catalytic composite comprising spheres of carrier material, of at least 90 wt% gamma alumina, and a shell surrounding the carrier material spheres, wherein the shell comprises mordenite, alumina and at least one platinum or palladium component.
    公开号:ES2732235A2
    申请号:ES201990004
    申请日:2018-01-23
    公开日:2019-11-21
    发明作者:Arechederra José María Mazon；Jimenez María Del Mar Bermejo；Delgado Juana María Frontela；Mora Rafael Domingo Larraz；Pascual Miguel Antonio Perez
    申请人:Espanola De Petroleos S A U Cepsa Cia；
    IPC主号:
    专利说明:

    [0001]
    [0002] Core-bark catalyst for hydroisomerization reactions of linear hydrocarbons
    [0003]
    [0004] The present disclosure relates to the field of hydrocarbon hydroisomerization reactions by catalysis.
    [0005]
    [0006] State of the art
    [0007]
    [0008] Hydrocarbon hydroisomerization is a process for hydroconverting to convert wax-like normal chain paraffins of the CnH 2n + 2 form into branched paraffins. This process is a fundamental industrial process, used in the petroleum and petrochemical industries, to improve the physical properties of lubricating and combustible oils at cold temperatures and to produce iso-pentane from n-pentane, with iso-pentane being an enhancer of octane in gasoline formulations. The process is generally carried out on molecular sieve catalysts, such as zeolites. The product selectivity depends on the acidity of the catalyst, the dimensions and topology of pores, and the size of the crystalline unit.
    [0009]
    [0010] The use of supports for catalysts is well known in the art. Traditionally, the support is a very small particle that provides a basis for the active catalytic material. A supported catalyst of this type is then agglomerated to provide a tablet, or an extruded product, having an essentially uniform catalyst composition throughout. Another type of supported catalysts are the so-called "core-crust" catalysts, which do not have a uniform catalyst composition, but are composed of an internal non-catalytic part (the core) and an external catalytically active part (the cortex). They are generally used in:
    [0011]
    [0012] • strongly exothermic reactions (for example, oxidation reactions such as:
    [0013] oxidation reaction of acrolein to maleic anhydride, oxidative dehydrogenation of 2-butene, propylene ammoxidation, etc.) to alleviate problems due to the heat generated during the reaction, hot spots, temperature control;
    [0014]
    [0015] • reactions in which only the external part of the catalyst plays a role and precious materials are used (for example Pt, Pd, Au, Ag, etc.) (for example, reaction of heterogeneous vinyl acetate monomers);
    [0016]
    [0017] • reactions with high LHSV (liquid hourly space velocity), to avoid unwanted side reactions, and that it is necessary to regenerate “ex situ” (for example, selective dehydrogenation of n-paraffins);
    [0018]
    [0019] EP0542528B1 discloses a process for the hydroisomerization of wax or waxy feeds, through the use of a catalyst comprising an inert, catalytically inactive core material such as alpha or gamma alumina, which is coated with a mixture of boehmite / pseudoboehmite containing catalytically active material (platinum on fluoride-gamma alumina); The catalytically active material may be, among others, metals of the group VIB, VIIB or VIII, metal oxides or metal sulphides, as well as alumina-silicate such as natural or synthetic zeolites. Once coated, the coated core material is calcined, in order to convert the boehmite / pseudoboehmite into gamma alumina, thereby resulting in a catalyst comprising an inert core material, coated with a gamma alumina bark that includes the catalytically active material. Alternatively, the catalytically inactive core material can be coated with boehmite / pseudoboehmite and the latter calcined in order to convert it to gamma alumina, and then loaded with catalytically active material such as group VIB, VIIB or VIII metals. It is important to note that in the present disclosure the composition of the crust layer differs from that disclosed in EP0542528B1 since it is made of a mixture of a specific type of zeolite (NH4-mordenite) and crystalline alumina, and there is no fluoride. alumina on it. In fact, the catalyst of the present disclosure is the result of different sequential specific steps (see Figure 6) to obtain an environmentally friendly core material (non-corrosive) with mechanical wear resistance and high density of the catalytically active material (metal (s) platinum and / or palladium) in the crust for the hydroisomerization of short linear hydrocarbon chains in the range of 5 to 12 carbon atoms.
    [0020]
    [0021] EP0547756B1 discloses a catalyst comprising a catalytically inert core (y-alumina or a-alumina) coated with a layer of boehmite or pseudoboehmite comprising a catalytically active material comprising oxide, sulfide, group VIB, VIIB or VIII metal or mixtures thereof, and at least one selected phosphorus, halogen and boron activator. The boehmite or pseudoboehmite layer is subjected to a calcination step in order to produce y-alumina. This catalyst can be used for the hydroisomerization of waxes and for the improvement of distillates and refined.
    [0022] Stratified catalytic compositions have also been disclosed for different types of reactions, for example aromatic alkylation processes. US2002 / 0049132A1, US6710003B2 and US6376730B1 disclose a process for preparing a laminated catalyst composition comprising an inner core and an outer layer. The outer layer, which comprises a zeolite and a binder, is attached to the inner core through the use of an organic bonding agent. This provides the catalyst composition with sufficient resistance to mechanical wear so that it is suitable for use in aromatic alkylation processes (for example alkylation of benzene to ethylbenzene).
    [0023]
    [0024] GB2451863A discloses core-cortex catalysts comprising a zeolite crust and a crust comprising silicalite-1, or alternatively perovskite, as metal oxide. Platinum is mentioned in the description.
    [0025]
    [0026] Despite the development of supports for catalysts over the years, there is still a need to be able to carry out hydroisomerization reactions in an economical way.
    [0027]
    [0028] Brief Description of the Invention
    [0029]
    [0030] The present disclosure relates to core-crust catalytic spheres, which are resistant to mechanical wear, and are useful for catalyzing the hydroisomerization reaction of light normal paraffins, such as C5-C12 paraffins, C5-C10 paraffins, C5-C9 paraffins , C5-C8 paraffins, preferably C5-C7 paraffins, more preferably C5-C6 paraffins.
    [0031]
    [0032] In one aspect of the present disclosure there is provided a method for preparing a core-crust catalyst composite, comprising the steps of:
    [0033]
    [0034] to. provide spheres of carrier material with a BET surface area of 70 to 90 m2 / g, as measured by ASTM D3663-03, and a total pore volume of 0.8 cc / g or less, as measured by ASTM D6761-07, which contain at least 90% by weight of crystalline gamma alumina;
    [0035] b. surrounding the spheres with a crust comprising NH4-mordenite and pseudoboehmite, by application to the spheres of a dispersion or powder comprising the dispersed NH4-mordenite and pseudoboehmite, by a selected process of fluidized bed coating, fogging method, method of bearing, powder coating bearing on damp balls, peptized aqueous suspension, sol-gel process, by using a suspension spheronizer or an air spray system, containing the crust at least 70% by weight NH4 -mordenite and up to 29.99% by weight of pseudoboehmite, based on the formulation by weight of the initial combination, in which NH4-mordenite is an NH4-mordenite with a molar Si / Al ratio of 15 to 20;
    [0036]
    [0037] c. subject the core-crust spheres obtained to a calcination stage at a temperature of 625-650 ° C;
    [0038]
    [0039] d. subject the calcined core-bark spheres to a steam treatment stage and an acid leaching stage;
    [0040]
    [0041] and. dry at a temperature between 90 ° C and 300 ° C;
    [0042]
    [0043] F. calcine or oxidize at a temperature between 300 ° C and 590 ° C; Y
    [0044]
    [0045] g. incorporating a platinum or palladium component in the cortex comprising zeolite, by ion exchange or impregnation;
    [0046]
    [0047] h. dry at a temperature between 90 ° C and 300 ° C;
    [0048]
    [0049] i. calcine or oxidize at a temperature between 300 ° C and 590 ° C; Y
    [0050]
    [0051] j. reduce the platinum or palladium component with dry hydrogen that has a maximum water content of 3 vol. ppm.
    [0052]
    [0053] In the present disclosure, the adhesion of the zeolite to the inner core sphere is due to the addition of amorphous pseudoboehmite, which after calcination changes to crystalline alumina to provide adhesion of the NH4-mordenite-pseudoboehmite mixture to the spheres. The maximum amount of pseudoboehmite in the bark is up to 29.99% by weight of the initial combination of the fogging stage (see Figure 6).
    [0054]
    [0055] In a further aspect of the present invention there is provided a core-crust catalytic composite material that can be obtained by the method of the present invention.
    [0056]
    [0057] In another aspect, the present invention relates to a method for hydroisomerizing normal paraffins, which comprises contacting a hydrocarbon feed containing linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms, with hydrogen in the presence of a Catalytic corecortex composite material according to the present invention.
    [0058]
    [0059] In still a further aspect, the present invention relates to the use of a core-crust catalytic composite material according to the present invention for the hydroisomerization of linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms.
    [0060]
    [0061] Brief description of the drawings
    [0062]
    [0063] Figure 1a illustrates the cross section of spent hydroisomerization catalyst produced by extrusion.
    [0064]
    [0065] Figure 1b shows a cross section of a core-crust sphere catalyst.
    [0066]
    [0067] Figure 2 shows an embodiment, in which a fogging system is used to create the crust layer on the spherical refractory inorganic core. After cutting the catalysts of the present disclosure in half, it was observed that the alumina spheres were not impregnated with the metal solution, but only contained an active catalyst coating on the surface. After 4000 hours of hydroisomerization reaction, this external coating was still retained without diffusion of the active material.
    [0068]
    [0069] Figure 3 illustrates the conversion of i-C5 / EC5, in% by weight, versus temperature (° C), for a catalyst according to the present disclosure, (catalyst 2012-121), at different pressures. This figure illustrates that when the working pressure is reduced, the conversion increases.
    [0070] Figure 4 illustrates the conversion of i-C5 / EC5, in% by weight, against the number of cycles, at low pressure, for the catalyst 2012-121. The figure illustrates the high stability of the catalyst and its ability to maintain a stable conversion for at least 48 cycles, equivalent to 4,032 hours of operation.
    [0071]
    [0072] Figure 5 illustrates the conversion of i-C5 / EC5, in% by weight, versus temperature, in ° C, for catalyst 2012-121) at low pressure against other alternative hydroisomerization catalysts. This figure illustrates that the use of catalyst 2012-121) provides greater conversion than alternative hydroisomerization catalysts.
    [0073]
    [0074] Figure 6 shows the manufacturing steps of the core-crust catalyst of the present disclosure.
    [0075]
    [0076] Detailed description of the invention
    [0077]
    [0078] Definitions
    [0079]
    [0080] In the context of the present invention, the term "approximately" means / - 10%.
    [0081]
    [0082] In the present invention, the term "crystalline alumina" is understood as the change of amorphous aluminum oxide, also called pseudoboehmite, to an ordered phase, called crystalline alumina. Its specific crystalline structure is normally confirmed by the X-ray powder diffraction method (ASTM D4926-06 [reapproved in 2011]).
    [0083]
    [0084] In the context of the present disclosure, the term "normal paraffins" or "n-paraffins" refers to saturated, linear hydrocarbon chains having from 5 to 12 carbon atoms (C5, C6, C7, C8, C9, C10 , C11, C12), preferably from 5 to 10 carbon atoms, more preferably from 5 to 8 carbon atoms, even more preferably from 5 to 7 carbon atoms and most preferably, 5 or 6 carbon atoms. The normal paraffins of the present disclosure may be a mixture of hydrocarbon chains of different lengths. The overall n-pentane content is preferably at least 80% by weight.
    [0085]
    [0086] The term "fluidized bed coating" describes a process in which support particles are placed in a container that has a porous plate at the bottom through the which passes an inert gas. At a given gas velocity, the bed is fluidized, gas bubbles are no longer visible and the volume increases considerably. In this situation, the support bed is still well defined, with a differentiated gas phase above it. In this phase, the suspended particles are coated by the use of an air spray system. (Julian RH Ross (2012). Heterogeneous Catalysis Fundamentals and Applications. Elsevier BV ISBN: 978-0-444-53363-0).
    [0087]
    [0088] The term "nebulization method" in the context of the present disclosure describes a process of coating the spheres of carrier material with a suspension comprising zeolite, pseudoboehmite and additives by means of an air spray system.
    [0089]
    [0090] The term "rolling method" describes the process by which a coated catalyst is prepared by partially moistening the inert support, such as spheres of carrier material, with a liquid such as water. The partially wet support is contacted with a powder of the composition of active components, and the inert support is rolled in the active components.The contact between the powder and the inert support can be achieved by placing the support in a closed container, rotating the container in an inclined plane and adding portions of the Powder Preferably, substantially the entire portion of the powder is coated onto the support before another optionally added (Procedure for the preparation of unsaturated acids from unsaturated aldehydes, US Patent 4,910,369, August 29, 1978).
    [0091]
    [0092] The phrase "powder coating bearing on wetted balls" describes the process used for coating by spinning wetted spherical balls using powder coating particles by mixing with air in a powder gun. The powder coatings are crushed to 20-100 micrometers The powders adhere to the moistened surface of the spherical balls forming a thin layer after the temperature treatment (calcination stage) (Kansai Paint Co., Ltd., Japan, Coating Terms, March 2015).
    [0093]
    [0094] The term "peptized aqueous suspension" describes the process by which zeolite, together with other components, does not remain in suspension in the water, an acid (for example, NO3H) can be added to obtain a so-called "peptized aqueous suspension" which will be used as a feed for the air spray system.
    [0095] The term "sol-gel process" describes the process in which solid nanoparticles dispersed in a liquid (a sun) agglomerate together forming a continuous three-dimensional network that extends throughout the liquid (a gel). (Gel Catalysts and Methods for their Use in Dehydrogenation Processes (US Patent 7,071,371 B2, July 4, 2006)).
    [0096]
    [0097] The term "suspension spheronizer coating" describes the process of converting wet extruded cylindrical granules into smooth, uniform spheres. When coated with a spheronizer, the preformed spherical balls are fed to the spheronator bowl, forming a "twisted rope" . An aqueous suspension comprising NH4-mordenite and pseudoboehmite is poured onto the spherical balls in motion to coat them. The thickness of the coating depends on the time and the formulation suspension. Finally the spherical coated balls are collected to undergo a dry calcination step. (Wolfgang Pietsch (2008), Agglomeration Processes: Fenomena, Technologies, Equipment. Wiley-VCH Verlag GmbH, ISBN: 3-527-30369-3).
    [0098]
    [0099] The term "air spray system" describes the process of breaking and spraying a liquid suspension into tiny droplets (20-50 micrometers in diameter) using pressurized air to rotate the spherical balls. Spray application is performed using a gun of air spraying using pressurized air at 2.5-5.5 atm. The feeding of the suspension to the gun is achieved either by gravitational forces from a cuvette placed above the gun, or by suction from a cuvette placed under the gun, or by pressurizing the suspension.The liquid suspension adheres to the moistened surface of the spherical balls to form a thin layer after progressive elevations of vacuum and temperature.
    [0100]
    [0101] The term "calcining" or "calcination stage" describes a commonly known process, which in the context of the present disclosure describes the stage of converting amorphous alumina (boehmite / pseudoboehmite) into the crust of the corecortex catalyst composite material in crystalline alumina . Crystalline alumina serves as a permanent adhesive agent to adhere the crust of the core-crust catalyst composite material to the core. (Hydroisomerization of Wax or Waxy Feeds (European Patent 0542528B1, January 24, 1996).
    [0102]
    [0103] The term "steam treatment" or "hydrothermal stage" as used herein describes the desalumination of zeolites without destruction of the crystalline structure. using mild hydrotreatment (Scherzer, J., chapter 10, The Preparation and Characterization of Aluminum-Deficient Zeolites, of Catalytic Materials: Relationship Between Structure and Reactivity, ACS Symposium Series, American Chemical Society, 1984). Example 1 illustrates the specific conditions that can be used to carry out the steam treatment step.
    [0104]
    [0105] The terms "acid leaching" and "EFAL acid leaching", also described as a "chemical treatment" stage describe the zeolite desalumination process and consist of leaching with mineral acid solutions (Scherzer, J., Chapter 10, The Preparation and Characterization of Aluminum-Deficient Zeolites, of Catalytic Materials: Relationship Between Structure and Reactivity, ACS Symposium Series, American Chemical Society, 1984). This is exemplified in example 1.
    [0106]
    [0107] In the context of the present invention, the term "ion exchange" is understood as the adsorption process of one or more ionic species in which adsorption is accompanied by simultaneous desorption (displacement) of an equivalent amount of one of more species. , used to prepare supported metal catalysts.
    [0108]
    [0109] In the context of the present invention, the term "impregnation" is understood as a process for the introduction of a metal into a porous support by adsorption of a metal salt from the solution on the surface of the support.
    [0110]
    [0111] Preparation method
    [0112]
    [0113] In one aspect of the present disclosure there is provided a method for preparing a core-crust catalyst composite, comprising the steps of:
    [0114]
    [0115] to. provide spheres of carrier material with a BET surface area of 70 to 90 m2 / g, as measured by ASTM D3663-03, and a total pore volume of 0.8 cc / g or less, as measured by ASTM D6761-07, which contain at least 90% by weight of crystalline gamma alumina;
    [0116]
    [0117] b. surrounding the spheres with a crust comprising NH4-mordenite and pseudoboehmite, by applying to the spheres a dispersion comprising the dispersed NH4-mordenite and pseudoboehmite, by means of a Selected process of fluidized bed coating, fogging method, bearing method, powder coating bearing on damp balls, peptized aqueous suspension, sol-gel process, by using a suspension spheronizer or an air spray system , the cortex containing at least 70% by weight of NH4-mordenite and up to 29.99% by weight of pseudoboehmite, based on the formulation by weight of the initial combination, in which NH4-mordenite is an NH4-mordenite with a Si / Al molar ratio of 15 to 20;
    [0118]
    [0119] c. subject the core-crust spheres obtained to a calcination stage at a temperature of 625-650 ° C;
    [0120]
    [0121] d. subject the calcined core-bark spheres to a steam treatment stage and an acid leaching stage;
    [0122]
    [0123] and. dry at a temperature between 90 ° C and 300 ° C;
    [0124]
    [0125] F. calcine or oxidize at a temperature between 300 ° C and 590 ° C; Y
    [0126]
    [0127] g. incorporating a platinum or palladium component in the cortex comprising zeolite, by ion exchange or impregnation;
    [0128]
    [0129] h. dry at a temperature between 90 ° C and 300 ° C;
    [0130]
    [0131] i. calcine or oxidize at a temperature between 300 ° C and 590 ° C; Y
    [0132]
    [0133] j. reduce the platinum or palladium component with dry hydrogen that has a maximum water content of 3 vol. ppm.
    [0134]
    [0135] The carrier material sphere has a BET surface area (ASTM D3663-03 [2008]) of 70 to 90 m2 / g, more preferably 72 to 88 m2 / g, still more preferably about 77 m2 / g. The carrier material sphere has a total pore volume (ASTM D6761-07 [2012]) of 0.8 cc / g or less, preferably 0.7 cc / g or less, preferably 0.6 cc / g or less.
    [0136]
    [0137] Preferably the sphere of carrier material comprises at least 80% by weight of crystalline alumina Preferably the sphere of carrier material comprises at least 90% by weight of crystalline alumina. Preferably the sphere of carrier material comprises at least 95% by weight of crystalline alumina.
    [0138]
    [0139] The crystalline alumina of the sphere of carrier material is gamma alumina. Gamma alumina spheres have a relatively small diameter (i.e., usually an average diameter of 1.6 mm or less), an apparent density d
    [0140]
    [0141] The bark comprises a zeolite, more particularly NH4-mordenite. As shown in example 3, surprisingly the use of NH4-mordenite in step b provides superior conversion. More preferably, as shown in example 1, the zeolite is NH4-mordenite with a molar Si / Al ratio of 15.3, in which, as shown in example 4, such a specific type of mordenite provides a higher conversion than other forms of NH4-mordenite with a lower Si / Al ratio.
    [0142]
    [0143] In the context of the present invention, NH4-mordenite is understood as the basic form of mordenite (MOR), aluminosilicate zeolite having an orthorhombic crystalline structure, characterized by its pseudomonodimensional pore system (12MR channels).
    [0144]
    [0145] In the context of the present invention, the molar Si / Al ratios are at least 15, preferably in the range of 15 to 20, based on the ICP method (inductively coupled plasma). In one embodiment, the Si / Al molar ratio is in the range of 15-18. In a further embodiment, the Si / Al molar ratio is in the range of 15-17. In still a further embodiment, the Si / Al molar ratio is in the range of 15-16.
    [0146]
    [0147] The cortex comprising NH4-mordenite may have a thickness of between 50 and 300 micrometers, preferably between 100 and 300 micrometers, more preferably between 200 and 300 micrometers.
    [0148]
    [0149] To form said crust comprising NH4-mordenite, one or more additives may be added, preferably selected from the group consisting of alumina, colloidal alumina, polyvinyl alcohol (PVA), 1,2,3-propanediol, hydroxypropylcellulose, methylcellulose and carboxymethyl cellulose.
    [0150]
    [0151] In one embodiment, the dispersion or powder comprising the dispersed NH4-mordenite and pseudoboehmite is a dispersion and is applied by a selected fluidized bed coating process, nebulization method, peptized aqueous suspension, sol-gel process, by the use of a suspension spheronizer or an air spray system.
    [0152]
    [0153] According to a preferred embodiment, step b) is performed by the nebulization method. According to this method, the spheres are rotated in an open container, and NH4-mordenite, pseudoboehmite and optionally additives (1,2,3-propanediol) are dispersed, dispersed in a liquid, by means of an air spray system. Once the nebulization stage is over, the alumina spheres, coated with a thin layer rich in NH4-mordenite, continue to rotate for a certain period of time. Then, the core-crust spheres are transferred to a rotary rotary evaporator where excess liquid, used during the fogging stage, is removed by means of some heat and vacuum. After this, the dried core-crust spheres are subjected to a stirring process in order to check the adherence of the crust layer to the core spheres. Fine particles (<0.425 mm) can be obtained by sieving, and weighed to quantify the performance of the fogging process.
    [0154]
    [0155] Preferably, in step b), the weight ratio of the carrier / shell material sphere is between 1 and 6, preferably between 2 and 5, more preferably between 2.5 and 4.
    [0156]
    [0157] The calcination step c) is preferably performed in a rotary dryer. At this stage, the zeolite-rich layer crust is allowed to adhere substantially permanently to the core spheres due to the transformation of the pseudobohemite into gamma-alumina which takes place at temperatures above 625 ° C. The so-called "core-crust" spheres are ready for the next stages.
    [0158]
    [0159] Mordenite is a zeolite that has an orthorhombic crystalline structure. It is highly sensitive to pore blockage due to its pseudomonodimensional pore system (12MR channels).
    [0160]
    [0161] Desalumination generally aims to reduce this characteristic by generating a mesopore system and modifying its acidic properties (number, type and strength of acid sites) with the aim of optimizing selectivity, catalytic activity. In addition, the diffusion process improves and the tendency to coke formation, through dehydrogenation and cyclization reactions, decreases. The first reported method for mordenite desalumination was leaching with strong acids (Scherzer, J., Chapter 10, The Preparation and Characterization of Aluminum-Deficient Zeolites, of Catalytic Materials: Relationship Between Structure and Reactivity, ACS Symposium Series, American Chemical Society, 1984). It was observed that high degrees of desalumination led to partial destruction of the crystalline structure and that stabilization of the crystalline structure could be achieved through hydrothermal treatments. To achieve the desalumination without destruction of the crystalline structure, gentle hydrotreatment of the core-crust was used followed by leaching with mineral acid solutions. Hydrotreatment generates a certain amount of out-of-network alumina (EFAL) and leaching with acid is responsible for the extraction of EFAL. The end result is the formation of mesoporos in the crust, helping to diffuse reactants (n-paraffins), hydrogen and products, and therefore increasing the activity and stability of the catalyst by reducing gas production and the tendency to accumulate coke. at high temperatures
    [0162]
    [0163] The objective of step d) is to modify the composition of the cortex, in order to increase the activity, selectivity and stability of the alumina-NH4-mordenite corecortex catalyst.
    [0164]
    [0165] The drying stage e), according to a particular embodiment, is carried out for a period of from 2 to 24 hours or more. In another embodiment, the drying step h) is performed over a period of from 10 to 24 hours. In yet another embodiment, the drying step h) is performed over a period of from 18 to 24 hours.
    [0166]
    [0167] In step f), the core-crust sphere is calcined or oxidized at a temperature of 300 ° C to 590 ° C, preferably at a temperature of 350 ° C to 500 ° C, preferably in an air atmosphere, preferably during a period of 0.5 to 10 hours, more preferably for 1 to 5 hours, in order to convert substantially all metal components into the corresponding oxide form.
    [0168]
    [0169] Preferably the at least one platinum and / or palladium component is present in a total amount of from 0.01 to 2% by weight, preferably from 0.05 to 1.5% by weight, more preferably from 0.05 0.5% by weight based on the total weight of platinum and / or elemental palladium in the at least one component of platinum and / or palladium with respect to the total weight of the core-crust catalyst.
    [0170]
    [0171] Preferably at least 0.1% by weight, preferably at least 90% by weight, more preferably essentially all the platinum and / or palladium component is present as platinum and / or palladium in the elemental metal state with respect to the Total weight of platinum or palladium component. Preferably from 0.1 to 95% by weight of the platinum and / or palladium component is present as platinum and / or palladium in the elemental metallic state with respect to the total weight of the platinum and / or palladium component. Preferably from 5 to 95% by weight, preferably from 10 to 95% by weight, preferably from 20 to 95% by weight, preferably from 30 to 95% by weight, preferably from 40 to 95% by weight, preferably from 50 to 95 % by weight, preferably 60 to 95% by weight, preferably 70 to 95% by weight, preferably 80 to 95% by weight, preferably 85 to 97% by weight, preferably 90 to 97% by weight, preferably 95 to 100% by weight of the platinum and / or palladium component is present as platinum and / or palladium in the elemental metallic state with respect to the total weight of the platinum or palladium component.
    [0172]
    [0173] Preferably in step g) the platinum and / or palladium component is incorporated into the cortex comprising zeolite by coprecipitation, cogelification, ion exchange or impregnation.
    [0174]
    [0175] Preferably step g) is carried out so that the crust in the core-crust catalytic composite resulting from the process according to the present disclosure comprises at least one platinum and / or palladium component from 0.01 to 2% by weight , based on the content of platinum and / or elemental palladium with respect to the total weight of the core-crust catalyst composite.
    [0176]
    [0177] Preferably, the platinum and / or palladium component is selected from chloroplatinic acid, chloropaladic acid, ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, hydrated platinum tetrachloride, platinum dichlorocarbonyldichloride, dinitrodiaminoplatin, sodium tetranitroplatin (II) chloride (II) palladium, palladium nitrate, palladium sulfate, diamine palladium hydroxide (II) and tetraamine palladium (II) chloride. Preferably, the platinum or palladium component is chloroplatinic acid or chloropaladic acid. The core-crust catalyst composite will generally comprise 0.01 to 2% by weight of the platinum or palladium component; Preferred contents are 0.05 to 0.5% by weight of platinum or palladium metal.
    [0178] To perform step g), for example, a water-soluble platinum and / or palladium compound, which can be decomposed, can be incorporated into the bark material in a relatively uniform manner by impregnation. This component can be added for example using an aqueous solution of chloroplatinic and / or chloropaladic acid. Other water-soluble platinum and / or palladium compounds may be used in impregnating solutions and include ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, hydrated platinum tetrachloride, platinum dichlorocarbonyldichloride, sodium dinitrodiaminoplatin, sodium tetranitroplatin (ll), chloride palladium, palladium nitrate, palladium sulfate, diamine palladium hydroxide (ll), tetraamine palladium chloride (ll), etc. The use of a compound of platinum chloride and / or palladium chloride, such as chloroplatinic and / or chloropaladic acid, is preferred.
    [0179]
    [0180] The drying stage h), according to a particular embodiment, is carried out for a period of from 2 to 24 hours or more. In another embodiment, the drying step h) is performed over a period of from 10 to 24 hours. In yet another embodiment, the drying step h) is performed over a period of from 18 to 24 hours.
    [0181]
    [0182] In step i), the core-crust sphere is calcined or oxidized at a temperature of 300 ° C to 590 ° C, preferably at a temperature of 350 ° C to 500 ° C, preferably in an air atmosphere, preferably during a period of 0.5 to 10 hours, more preferably for 1 to 5 hours, in order to convert substantially all metal components into the corresponding oxide form.
    [0183]
    [0184] According to a particular embodiment, a strong acid is present in step g), which has a dissociation constant of acid pKa <-1,60, for example, but not limited to, hydrochloric acid HCl, nitric acid HNO3, hydroiodic acid HI , hydrobromic acid HBr, perchloric acid HClO4, sulfuric acid H2SO4, p-toluenesulfonic acid or methanesulfonic acid, that is to say in the step of incorporating the platinum or palladium component. This facilitates the uniform distribution of metal components throughout the crust material.
    [0185]
    [0186] According to a further particular embodiment, the method comprises an additional step, which can be carried out after the incorporation of the platinum or palladium component in step g and before, during or after the calcination or oxidation stage i of Figure 6), in the that any acid component is removed by treatment with steam or with a mixture of steam and air, at a temperature of 300 ° C to 590 ° C. Preferably, the temperature is 350 ° C to 500 ° C.
    [0187] It is necessary to carry out the reduction step j) before the use of the composite material as a catalyst, and under conditions substantially free of water. This stage is designed to selectively reduce platinum or palladium components to the corresponding metal. It is a good practice to dry the oxidized catalyst before this reduction stage by passing a stream of dry nitrogen or air through it at a temperature of 250 ° C to 590 ° C. Preferably, a substantially pure and dry hydrogen stream is used (eg H2 Premier Plus from Air Products, 99.9995% purity, <5 vol. Ppm of nitrogen, <3 vol. Ppm of H2O, <1 vol. Ppm of O2) as a reducing agent at this stage of reduction. The reducing agent is contacted with the oxidized catalyst under conditions that include a temperature of 200 ° C to 650 ° C, preferably 400 ° C to 510 ° C, and a time period of 0.5 to 10 hours effective for substantially reduce all platinum or palladium to the elemental metal state, preferably 3 to 7 hours.
    [0188]
    [0189] This reduction treatment can be carried out in situ in the reactor as part of a starting sequence if precautions are taken to dry the plant previously to a substantially water-free state and if hydrogen vapor substantially free of water (<3 vol. ppm H2O).
    [0190]
    [0191] Catalytic Composite Material
    [0192]
    [0193] The core-crust catalytic composite materials resulting from the method of preparation of the invention are useful in the hydroisomerization of linear saturated hydrocarbon chains. Therefore, a further aspect of the invention relates to a core-crust catalyst composite that can be obtained by the method of preparation according to the present invention. The corecortex catalytic composite materials of the present invention are characterized by having different improved properties compared to the prior art. For example, as demonstrated in Examples 1 and 3 below, carrying out the method of preparing the invention with NH4-mordenite instead of H-mordenite leads to a composite material that has a higher conversion in the reaction of hydroisomerization Even if the method of preparation of the invention includes several calcination steps and despite the fact that the calcination of NH4-mordenite per H-mordenite is provided (as exemplified in Example 3), the method of preparation of the invention leads however to different products for NH4-mordenite and H-mordenite, respectively.
    [0194] Hydroisomerization method
    [0195]
    [0196] In another aspect, the present invention relates to a method for hydroisomerizing normal paraffins, which comprises contacting a hydrocarbon feed containing linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms, with hydrogen in the presence of a Catalytic corecortex composite material according to the present invention. According to a particular embodiment, the normal paraffins that are hydroisomerized are C5-C12 normal paraffins, preferably C5-C10 normal paraffins, more preferably C5-C8 normal paraffins, even more preferably C5-C6 normal paraffins. For example, the hydroisomerization of n-pentane provides iso-pentane, an octane enhancer in gasoline formulation.
    [0197]
    [0198] The hydroisomerization method of the present invention can be carried out in a fixed bed system, a moving bed system, a fluidized bed system or in a batch operation. According to a particularly preferred embodiment, it is preferred to carry it out in a fixed bed. In this system, the hydrocarbon feed stream is preheated by any suitable heating means to the desired reaction temperature and then passed to a fixed bed of the previously reduced catalyst. The reactants may contact the catalyst bed in upward, downward or radial flow; radial flow is preferred.
    [0199]
    [0200] The reactants, that is the hydrocarbon feed stream and hydrogen, may be in the liquid phase, a mixed vapor-liquid phase or a vapor phase when contacted with the catalyst. According to a particular embodiment, the reactants are in the vapor phase.
    [0201]
    [0202] The presence of hydrogen substantially suppresses the formation of hydrogen-deficient carbon deposits on the catalytic composite. Usually, hydrogen is used in sufficient amounts to guarantee a molar ratio of hydrogen to hydrocarbon of 1: 1 to 20: 1, preferably 1.5: 1 to 10: 1.
    [0203]
    [0204] In still a further aspect, the present invention relates to the use of a core-crust catalytic composite material according to the present invention for the hydroisomerization of linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms. Preferably, the linear saturated hydrocarbon chains have from 5 to 9 carbon atoms, more preferably from 5 to 7 carbon atoms. carbon.
    [0205]
    [0206] The following working examples are introduced to illustrate the core-crust catalytic composite material of the present disclosure and the hydroisomerization process through the use of the composite material. These examples of the present disclosure are intended to be illustrative and should not be used to limit the scope of the disclosure.
    [0207]
    [0208] Examples
    [0209]
    [0210] The examples are all carried out in a laboratory scale hydroisomerization pilot plant comprising a syringe pump (Isco, DM500 model), a preheater, a reactor, a dry hydrogen feed, a gas-liquid separator, a flow meter of gas (Ritter) and a collection tank.
    [0211]
    [0212] In this plant, the feed stream (n-pentane or n-hexane) is combined with a dry hydrogen stream (<3 vol. Ppm H2O) and the resulting mixture is preheated to 100-175 ° C. The heated mixture is then passed down in contact with the core-crust catalyst (7.69 g), which is maintained as a fixed bed of catalytic core-crust spheres (14 cc) in the pressure reactor and desired conversion temperature (below 30 bar). The effluent stream is then removed from the reactor, cooled to 100 ° C and sent to a six-way valve connected to the injection inlet of a Bruker GC-FID instrument for continuous analysis. The remaining effluent stream was passed to the hydrogen separation zone where a hydrogen-rich gas phase separates from a liquid phase rich in hydrocarbons containing isomerized hydrocarbon (s), unconverted feed, and a minor amount of secondary products of the hydroisomerization reaction (gases, C1-C4, and C5 + or C6 +) that are collected in a pressurized tank. The portion of the hydrogen-rich phase is sent through a gas flow meter to a combustion system for environmental safety reasons.
    [0213]
    [0214] The conversion numbers reported in this document are all calculated based on the disappearance of the supply current and are expressed as a percentage by weight. The desired conversion temperature refers herein to the average temperature of three internal thermocouples located along the catalyst bed. The pressures reported in this document are recorded at the reactor outlet.
    [0215] All catalysts used in these examples are prepared according to the following preferred method, described in example 1, with suitable modifications notified in each example.
    [0216]
    [0217] Example 1: Preparation of the catalytic composite material "2012-121"
    [0218]
    [0219] 1/16 inch gamma-alumina spheres (1.6 / 80, BET surface area (ASTM D3663-03 [2008]): 77 m2 / g, total pore volume (ASTM D6761-07 [2012] ) of 0.74 cc / g, 95% crystallinity) [50 g], provided by Sasol Germany, is spun in an open container, and the NH4-mordenite is nebulized with a molar Si / Al ratio of 15, 3 (Conteka) [14 g], pseudoboehmite (SaSol Ger) [2.5 g] and glycerol (Merck AG Ger) [2.0 g] finely dispersed in deionized water [30 g], by means of a spray system of air ( stages a and b). Once the nebulization stage is over, the alumina spheres, covered by a layer rich in thin NH4-mordenite, continue to rotate for a certain period of time. Then, the core-crust spheres are transferred to a rotary evaporator (rotary evaporator), where the excess liquid used during the fogging stage is removed, by means of heat and vacuum. Subsequently, the dried bark core spheres are subjected to a stirring process, in order to check the adherence of the crust layer to the core spheres. Fine particles (<0.425 mm) are obtained by sieving and weighed to quantify the performance of the fogging process [96.8% by weight]. Finally, the bark core spheres are calcined in a rotary dryer at a temperature of 650 ° C ( step c), so that the zeolite-rich layer bark adheres permanently to the core spheres. The corecortex spheres obtained are placed in a tubular reactor and subjected to steam treatment at a temperature of 350 ° C and for a period of one hour C ( step d). The amount of out-of-network alumina (EFAL) generated during steam treatment is extracted by subjecting the steam-treated core-bark spheres to an acid leaching procedure at a temperature of 60 ° C and for a period of time of 2 C hours ( still stage d). The steam-treated core-bark spheres are dried, in a rotary kiln, drying at 300 ° C for 3 hours ( stage e) and calcined, at 590 ° C for 6 hours ( stage f). Then the metal impregnation ( step g) is achieved in a rotary evaporator, by contacting the calcined core-bark spheres with a chloroplatinic aqueous solution at a temperature of 45 ° C and for a period of 60 min. At the end of the impregnation process, the aqueous solution becomes transparent and the bark core spheres are yellow. The resulting composite material is dried at a temperature of 110 ° C for a period of 24 hours ( stage h) and finally calcined or oxidized at a temperature of 450 ° C in an air atmosphere for a period of 5 hours ( stage i), in order to convert substantially all metal components in the corresponding oxide form. The platinum metal content is 0.2% by weight (atomic absorption analysis) based on the total weight of elementary platinum with respect to the total weight of the core-cortex catalyst composite. The wear resistance of the catalysts was determined by weighing the catalyst and then vigorously stirring the catalyst prepared above on a 20 mesh screen for three minutes. Weight loss was considered lost in active material. The percentage of active catalyst loss was determined by subtracting the final weight of active catalyst material in the catalyst from the original weight of the active catalyst, dividing by the original weight of the active catalyst and multiplying by 100.
    [0220]
    [0221] Once the catalytic composite is inside the reactor, before reduction ( step j), the oxidized catalyst is dried by passing a stream of dry nitrogen or air through it at 300 ° C. Then, a stream of dry hydrogen is used (e.g. H2 Premier Plus from Air Products, purity of 99.9995%, <5 vol. Ppm. Of nitrogen, <3 vol. Ppm of H2O, <1 vol. Ppm of O2 ) as a reducing agent. The reducing agent is contacted with the oxidized catalyst at 500 ° C and a period of 5 hours to reduce all platinum oxide to its elemental metal state.
    [0222]
    [0223] Figure 3 illustrates the conversion of i-C5 / EC5, in% by weight, versus temperature (° C), for the catalytic composite "2012-121" at different pressures. This figure illustrates that the conversion increases with decreasing working pressure
    [0224]
    [0225] With respect to the stability behavior, Figure 4 illustrates the conversion of i-C5 / EC5, in% by weight, versus the number of cycles, at low pressure, for the "2012-121" catalytic composite. The figure shows that "2012-121” has a high stability, its conversion remaining stable for at least 48 cycles, equivalent to 4,032 hours.
    [0226]
    [0227] Example 2: Preparation of the catalytic composite material "2012-123"
    [0228]
    [0229] The catalytic composite material "2012-123" was prepared following the same procedure as described in example 1 for the catalytic composite material "2012-121", with the exception that ethano alumina spheres were used (BET surface area : 11 m2 / g; total pore volume: 0.4 cc / g), obtained by calcination of gamma-alumina spheres from 1.6 / 80 (Sasol, Ger) at 1095 ° C, as internal core. Its conversion is less than in the case of example 1 (see Figure 5).
    [0230]
    [0231] The preparation of this catalytic composite material is as follows:
    [0232]
    [0233] 1/16 inch ethae alumina spheres (1.6 / 80, BET surface area (ASTM D3663-03 [2008]): 11 m2 / g, total pore volume (ASTM D6761-07 [2012] ) of 0.50 cc / g [50 g], are rotated in an open container, and the NH4-mordenite is nebulized with a molar Si / Al ratio of 15.3 (Conteka) [14 g], pseudoboehmite ( SaSol Ger) [2.5 g] and glycerol (Merck AG Ger) [2.0 g] finely dispersed in deionized water [30 g], by means of an air spray system ( steps a and b). Nebulization stage, the alumina spheres, covered by a layer rich in thin NH4-mordenite, continue to rotate for a certain period of time.Then, the core-crust spheres are transferred to a rotary evaporator (rotary evaporator), where it is removed the excess liquid used during the nebulization stage, by means of heat and vacuum, subsequently, the dried bark core spheres are subjected to a stirring process, in order to check the adhesion of the crust layer to the core spheres. Fine particles (<0.425 mm) are obtained by sieving and weighed to quantify the performance of the fogging process [95.1% by weight]. Finally, the bark core spheres are calcined in a rotary dryer at a temperature of 650 ° C ( step c), so that the zeolite-rich layer bark adheres permanently to the core spheres. The core-crust spheres obtained are placed in a tubular reactor and subjected to steam treatment at a temperature of 350 ° C and for a period of time of one hour C ( step d). The amount of out-of-network alumina (EFAL) generated during steam treatment is extracted by subjecting the steam-treated core-bark spheres to an acid leaching procedure at a temperature of 60 ° C and for a period of time of 2 C hours ( still stage d). The steam-treated core-bark spheres are dried, in a rotary kiln, drying at 300 ° C for 3 hours ( stage e) and calcined, at 590 ° C for 6 hours ( stage f). Then the metal impregnation ( step g) is achieved in a rotary evaporator, by contacting the calcined core-bark spheres with a chloroplatinic aqueous solution at a temperature of 45 ° C and for a period of 60 min. At the end of the impregnation process, the aqueous solution becomes transparent and the bark core spheres are yellow. The resulting composite material is dried at a temperature of 110 ° C for a period of 24 hours ( step h) and finally calcined or oxidized at a temperature of 450 ° C in an air atmosphere for a period of 5 hour period ( step i), in order to convert substantially all the metal components into the corresponding oxide form. The platinum metal content is 0.2% by weight (atomic absorption analysis) based on the total weight of elementary platinum with respect to the total weight of the core-cortex catalyst composite. The wear resistance of the catalysts was determined by weighing the catalyst and then vigorously stirring the catalyst prepared above on a 20 mesh screen for three minutes. Weight loss was considered lost in active material. The percentage of active catalyst loss was determined by subtracting the final weight of active catalyst material in the catalyst from the original weight of the active catalyst, dividing by the original weight of the active catalyst and multiplying by 100.
    [0234]
    [0235] Once the catalytic composite is inside the reactor, before reduction ( step j), the oxidized catalyst is dried by passing a stream of dry nitrogen or air through it at 300 ° C. Then, a stream of dry hydrogen is used (e.g. H2 Premier Plus from Air Products, purity of 99.9995%, <5 vol. Ppm. Of nitrogen, <3 vol. Ppm of H2O, <1 vol. Ppm of O2 ) as a reducing agent. The reducing agent is contacted with the oxidized catalyst at 500 ° C and a period of 5 hours to reduce all platinum oxide to its elemental metal state.
    [0236]
    [0237] Example 3: Preparation of the catalytic composite material "2012-124"
    [0238]
    [0239] The catalytic composite material "2012-124" was prepared following the same procedure as described in example 1 for the catalytic composite material "2012-121", with the exception that H-mordenite was used, obtained by calcination thereof. NH4-mordenite used in example 1, as a zeolite component of the outer shell layer. This is an indication that the use of NH4-mordenite in the fogging stage provides greater conversion (see Figure 5).
    [0240]
    [0241] The preparation of this catalytic composite material is as follows:
    [0242]
    [0243] 1/16 inch gamma-alumina spheres (1.6 / 80, BET surface area (ASTM D3663-03 [2008]): 77 m2 / g, total pore volume (ASTM D6761-07 [2012] ) of 0.74 cc / g, 95% crystallinity) [50 g], provided by Sasol Germany, is rotated in an open container, and the H-Mordenite is nebulized with a molar Si / Al ratio of 15, 3 (calcined Conteka NH4-mordenite) [14 g], pseudoboehmite (SaSol Ger) [2.5 g] and glycerol (Merck AG Ger) [2.0 g] finely dispersed in deionized water [30 g], through of a air spray system ( stages a and b). Once the nebulization stage is over, the alumina spheres, covered by a layer rich in thin NH4-mordenite, continue to rotate for a certain period of time. Then, the core-crust spheres are transferred to a rotary evaporator (rotary evaporator), where the excess liquid used during the fogging stage is removed, by means of heat and vacuum. Subsequently, the dried bark core spheres are subjected to a stirring process, in order to check the adherence of the crust layer to the core spheres. Fine particles (<0.425 mm) are obtained by sieving and weighed to quantify the performance of the fogging process [95.4% by weight]. Finally, the bark core spheres are calcined in a rotary dryer at a temperature of 650 ° C ( step c), so that the zeolite-rich layer bark adheres permanently to the core spheres. The core-crust spheres obtained are placed in a tubular reactor and subjected to steam treatment at a temperature of 350 ° C and for a period of time of one hour C ( step d). The amount of out-of-network alumina (EFAL) generated during steam treatment is extracted by subjecting the steam-treated core-bark spheres to an acid leaching procedure at a temperature of 60 ° C and for a period of time of 2 C hours ( still stage d). The steam-treated core-bark spheres are dried, in a rotary kiln, drying at 300 ° C for 3 hours ( stage e) and calcined, at 590 ° C for 6 hours ( stage f). Then the metal impregnation ( step g) is achieved in a rotary evaporator, by contacting the calcined core-bark spheres with a chloroplatinic aqueous solution at a temperature of 45 ° C and for a period of 60 min. At the end of the impregnation process, the aqueous solution becomes transparent and the bark core spheres are yellow. The resulting composite material is dried at a temperature of 110 ° C for a period of 24 hours ( step h) and finally calcined or oxidized at a temperature of 450 ° C in an air atmosphere for a period of 5 hours ( stage i), in order to convert substantially all metal components into the corresponding oxide form. The platinum metal content is 0.2% by weight (atomic absorption analysis) based on the total weight of elementary platinum with respect to the total weight of the core-cortex catalyst composite. The wear resistance of the catalysts was determined by weighing the catalyst and then vigorously stirring the catalyst prepared above on a 20 mesh screen for three minutes. Weight loss was considered lost in active material. The percentage of active catalyst loss was determined by subtracting the final weight of active catalyst material in the catalyst from the original weight of the active catalyst, dividing by the original weight of the active catalyst and multiplying by 100.
    [0244] Once the catalytic composite is inside the reactor, before reduction ( step j), the oxidized catalyst is dried by passing a stream of dry nitrogen or air through it at 300 ° C. Then, a stream of dry hydrogen is used (e.g. H2 Premier Plus from Air Products, purity of 99.9995%, <5 vol. Ppm. Of nitrogen, <3 vol. Ppm of H2O, <1 vol. Ppm of O2 ) as a reducing agent. The reducing agent is contacted with the oxidized catalyst at 500 ° C and a period of 5 hours to reduce all platinum oxide to its elemental metal state.
    [0245]
    [0246] Example 4: Preparation of the catalytic composite material “2012-125”
    [0247]
    [0248] The catalytic composite material "2012-125" was prepared following the same procedure as described in Example 1 for the catalytic composite material "2012-121", with the exception that a different NH4-mordenite was used (Si / ratio At 14.9 molar and wider particle size distribution) from an alternative supplier (Zeolyst USA) as a zeolite component of the outer cortex layer. Its conversion is less than in the case of example 1 (see Figure 5).
    [0249]
    [0250] The preparation of this catalytic composite material is as follows:
    [0251]
    [0252] 1/16 inch gamma-alumina spheres (1.6 / 80, BET surface area (ASTM D3663-03 [2008]): 77 m2 / g, total pore volume (ASTM D6761-07 [2012] ) 0.74 cc / g, 95% crystallinity) [50 g], provided by Sasol Germany, is spun in an open container, and the NH4-mordenite is nebulized with a molar Si / Al ratio of 14.9 (Zeolyst USA) [14 g], pseudoboehmite (SaSol Ger) [2.5 g] and glycerol (Merck AG Ger) [2.0 g] finely dispersed in deionized water [30 g], by means of a spray system of air ( stages a and b). Once the nebulization stage is over, the alumina spheres, covered by a layer rich in thin NH4-mordenite, continue to rotate for a certain period of time. Then, the core-crust spheres are transferred to a rotary evaporator (rotary evaporator), where the excess liquid used during the fogging stage is removed, by means of heat and vacuum. Subsequently, the dried bark core spheres are subjected to a stirring process, in order to check the adherence of the crust layer to the core spheres. Fine particles (<0.425 mm) are obtained by sieving and weighed to quantify the performance of the nebulization process [94.8% by weight]. Finally, the bark core spheres are calcined in a rotary dryer at a temperature of 650 ° C ( step c), so that the zeolite-rich layer bark adheres permanently to the core spheres. The spheres of The crust core obtained is placed in a tubular reactor and subjected to steam treatment at a temperature of 350 ° C and for a period of one hour C ( step d). The amount of out-of-network alumina (EFAL) generated during steam treatment is extracted by subjecting the steam-treated core-bark spheres to an acid leaching procedure at a temperature of 60 ° C and for a period of time of 2 C hours ( still stage d). The steam-treated core-bark spheres are dried, in a rotary kiln, drying at 300 ° C for 3 hours ( stage e) and calcined, at 590 ° C for 6 hours ( stage f). Then the metal impregnation ( step g) is achieved in a rotary evaporator, by contacting the calcined core-bark spheres with a chloroplatinic aqueous solution at a temperature of 45 ° C and for a period of 60 min. At the end of the impregnation process, the aqueous solution becomes transparent and the bark core spheres are yellow. The resulting composite material is dried at a temperature of 110 ° C for a period of 24 hours ( step h) and finally calcined or oxidized at a temperature of 450 ° C in an air atmosphere for a period of 5 hours ( stage i), in order to convert substantially all metal components into the corresponding oxide form. The platinum metal content is 0.2% by weight (atomic absorption analysis) based on the total weight of elementary platinum with respect to the total weight of the core-cortex catalyst composite. The wear resistance of the catalysts was determined by weighing the catalyst and then vigorously stirring the catalyst prepared above on a 20 mesh screen for three minutes. Weight loss was considered lost in active material. The percentage of active catalyst loss was determined by subtracting the final weight of active catalyst material in the catalyst from the original weight of the active catalyst, dividing by the original weight of the active catalyst and multiplying by 100.
    [0253]
    [0254] Once the catalytic composite is inside the reactor, before reduction ( step j), the oxidized catalyst is dried by passing a stream of dry nitrogen or air through it at 300 ° C. Then, a stream of dry hydrogen is used (e.g. H2 Premier Plus from Air Products, purity of 99.9995%, <5 vol. Ppm. Of nitrogen, <3 vol. Ppm of H2O, <1 vol. Ppm of O2 ) as a reducing agent. The reducing agent is contacted with the oxidized catalyst at 500 ° C and a period of 5 hours to reduce all platinum oxide to its elemental metal state.
    [0255]
    [0256] With respect to performance, Figure 5 illustrates the conversion of i-C5 / EC5, in% by weight, versus temperature, in ° C, for catalyst 2012-121, at low pressure compared to other alternative hydroisomerization catalysts ( examples II, III and IV). This figure illustrates that The 2012-121 catalyst (example 1) provides a higher conversion than alternative hydroisomerization catalysts.
    权利要求:
    Claims (15)
    [1]
    Method for preparing a core-crust catalytic composite, comprising the steps of:
    to. provide spheres of carrier material with a BET surface area of 70 to 90 m2 / g, as measured by ASTM D3663-03, and a total pore volume of 0.8 cc / g or less, as measured by ASTM D6761-07, which contain at least 90% by weight of crystalline gamma alumina;
    b. surrounding the spheres with a crust comprising NH4-mordenite and pseudoboehmite, by application to the spheres of a dispersion or powder comprising the dispersed NH4-mordenite and pseudoboehmite, by a selected process of fluidized bed coating, fogging method, method of bearing, powder coating bearing on damp balls, peptized aqueous suspension, sol-gel process, by using a suspension spheronizer or an air spray system, containing the crust at least 70% by weight NH4 -mordenite and up to 29.99% by weight of pseudoboehmite, based on the formulation by weight of the initial combination, in which NH4-mordenite is an NH4-mordenite with a molar Si / Al ratio of 15 to 20;
    c. subject the core-crust spheres obtained to a calcination stage at a temperature of 625-650 ° C;
    d. subject the calcined core-bark spheres to a steam treatment stage and an acid leaching stage;
    and. dry at a temperature between 90 ° C and 300 ° C;
    F. calcine or oxidize at a temperature between 300 ° C and 590 ° C; and
    g. incorporating a platinum or palladium component in the cortex comprising zeolite, by ion exchange or impregnation;
    h. dry at a temperature between 90 ° C and 300 ° C;
    i. calcine or oxidize at a temperature between 300 ° C and 590 ° C; Y
    j. reduce the platinum or palladium component with dry hydrogen that has a maximum water content of 3 ppm vol.
    [2]
    2. A method according to claim 1, wherein the NH4-mordenite of step b) is an NH4-mordenite with a molar Si / Al ratio of 15 to 18.
    [3]
    3. The method of claim 2, wherein the NH4-mordenite of step b) is an NH4-mordenite with a molar Si / Al ratio of 15.3.
    [4]
    4. A method according to any one of claims 1 to 3, wherein the dispersion or powder comprising the dispersed NH4-mordenite and pseudoboehmite is a dispersion and is applied by a selected process of fluidized bed coating, nebulization method, suspension Peptized aqueous, solgel process, by using a suspension spheronizer or an air spray system.
    [5]
    5. The method according to claim 4, wherein the dispersion comprising the dispersed NH4-mordenite and pseudoboehmite is applied by the nebulization method.
    [6]
    6. The method according to any one of claims 1 to 5, wherein the dispersion or powder comprising NH4-mordenite and pseudoboehmite further comprises one or more additives selected from colloidal alumina, 1,2,3-propanotriol, polyvinyl alcohol ) (PVA), hydroxypropyl cellulose, methyl cellulose and carboxymethyl cellulose.
    [7]
    7. A method according to any one of claims 1 to 6, wherein in step g) the platinum or palladium component is selected from chloroplatinic acid, chloropaladic acid, ammonium chloroplatinate, bromoplatinic acid, platinum trichloride, hydrated platinum tetrachloride , platinum dichlorocarbonyldichloride, sodium dinitrodiaminoplatin, tetranitroplatinate (II), palladium chloride, palladium nitrate, palladium sulfate, diamine palladium hydroxide (II) and tetraamine palladium (II) chloride, or a mixture thereof.
    [8]
    8. A method according to any one of claims 1 to 7, wherein it is present in step g), hydrochloric acid, nitric acid, iohydric acid, hydrobromic acid, perchloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, or any other acid that has an acid dissociation constant pKa <-1,60.
    [9]
    9. A method according to any one of claims 1 to 8, wherein the platinum and / or palladium component is incorporated into the cortex comprising zeolite by impregnation.
    [10]
    10. A method according to any one of claims 1 to 9, wherein in step j) the reducing agent is contacted with the oxidized catalyst at a temperature of 200 ° C to 650 ° C.
    [11]
    11. Method according to any one of claims 1 to 10, wherein in step j) the reducing agent is contacted with the oxidized catalyst for a period of 0.5 to 10 hours.
    [12]
    12. Method according to claim 11, wherein in step j) the reducing agent is contacted with the oxidized catalyst for a period of 3 to 7 hours.
    [13]
    13. Catalytic core-crust composite material that can be obtained by the method as defined in any one of claims 1 to 12.
    [14]
    14. Method for hydroisomerizing normal paraffins, comprising contacting a hydrocarbon feed containing linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms, with hydrogen in the presence of a core-shell catalyst composite material according to the claim 13.
    [15]
    15. Use of a core-crust catalyst composite according to claim 13 for the hydroisomerization of linear saturated hydrocarbon chains, having from 5 to 12 carbon atoms.
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    同族专利:
    公开号 | 公开日
    WO2018134441A8|2018-09-20|
    ES2732235R1|2019-11-22|
    WO2018134441A1|2018-07-26|
    ES2732235B2|2020-10-05|
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    PCT/EP2018/051598|WO2018134441A1|2017-01-23|2018-01-23|Preparation method for core-shell catalysts used in linear alkane hydroisomerisation|
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