catalyst compositions comprising small size molecular sieve crystals deposited in a porous material

专利摘要:
CATALYST COMPOSITIONS UNDERSTANDING SMALL SIZE MOLECULAR SCREEN CRYSTALS PLACED IN A POROUS MATERIAL. Catalyst compositions comprising a porous inorganic material with pore diameters of at least 2 nm and molecular sieve crystals, characterized by the fact that the molecular sieve crystals have an average diameter, measured by scanning electron microscopy, not greater than 50 nm, and the catalyst composition has a concentration of acid sites ranging from 50 to 1200 μmol / g, measured by TPD NH3 adsorption; and the XRD pattern of said catalyst composition is the same as the X-ray diffraction pattern of said inorganic porous material.
公开号:BR112016000038B1
申请号:R112016000038-2
申请日:2014-07-03
公开日:2021-03-16
发明作者:Hawk Kok-Giap；Goupil Jean-Michel；Gilson Jean-Pierre；Valtchev Valentin；Nesterenko Nikolai；Minoux Delphine；Dath Jean-pierre
申请人:Total Research & Technology Feluy；Centre National De La Recherche Scientifique (Cnrs)；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[0001] The invention relates to catalyst compositions for hydrocarbon conversion comprising molecular sieves, such as crystalline metallosilicate or zeolite. In particular, the invention relates to catalyst compositions comprising molecular sieve crystals and porous material. The invention also relates to the preparations and uses of said catalyst compositions. DESCRIPTION OF THE STATE OF THE TECHNIQUE
[0002] Molecular sieves such as crystalline metallosilicates or zeolites have been shown to have catalytic properties for various types of hydrocarbon conversion. More precisely, zeolites have been used as adsorbents, catalysts, and catalyst carriers for various types of hydrocarbon conversion processes, and other applications. They exhibit unique properties with respect to both catalytic activity and selectivity.
[0003] The catalytic activity of molecular sieves is related to their acidic properties and reflects the amount of reagent converted per unit time.
[0004] Selectivity is the molar fraction of a particular product desired in relation to all products formed. It is dependent on micropores that vary in size from 3Â to 12Â. The shape and size of the micropores induce various types of shape selectivity. In addition to the highly favorable role of providing format selectivity, the presence of micropores can also, in some cases, limit the catalytic performance of molecular sieves, such as zeolites. The cause for this is the restricted molecular transport rate inside the molecular sieve crystal, induced by the similarity between the size of the hydrocarbons involved and the diameter of the micropore. In addition, because the molecular sieves exhibit small pores of the microporous type (i.e., less than 2 nm), the accessibility of the active sites to bulky molecules is limited to the active sites present on the surface of the molecular sieve crystals. In transformations of bulky molecules, the low effective diffusivity in crystals of molecular sieve limits the reaction speed and yields. Only the outer surface of the molecular sieve crystal and the acidic sites located in the pore mouths are accessible to react with bulky molecules. The use of crystals of small molecular sieves, such as zeolite, allows, for a given mass of crystals, to increase the external surface and, thus, to increase the number of accessible sites to react with bulky molecules. In other words, the smaller the size of the crystal, the larger the surface area (BET) and the more important the number of active sites. Unfortunately, small size molecular sieve crystals are difficult to manipulate as they tend to clump when used to catalyze reactions. In addition, they do not have sufficient mechanical and frictional resistance to be used as a catalyst.
[0005] To overcome this inconvenience, it is known to produce catalyst compositions by depositing a molecular sieve, such as a zeolitic coating, on a carrier. The carrier provides the necessary mechanical resistance and friction to the catalyst compositions. It also allows to disperse the active sites of the molecular sieve, preferably the zeolitic active sites, on its surface. The literature related to such catalyst compositions is relatively abundant in the field of catalysts for fluid catalytic cracking (“fluid catalytic cracking” - FCC). In this field, the carrier used is usually non-porous.
[0006] GB 1 060 749 refers to a catalyst comprising two components, one of which is used as a carrier and is a solid particle-shaped material, which is catalytic or catalytically inert, with the diameter generally varying from 200 mesh up to 0.1 inch, the second component comprising a zeolitic molecular sieve conversion catalyst. The zeolitic molecular sieve in the form of particles with a diameter ranging from 15 microns or less, having at least some material no more than 5 microns in diameter and sufficient amount of said second component to substantially coat the particles of the first named component and to adhere to the particle surfaces of the first named component. The specific surface of the prepared catalyst is 132 m2 / g.
[0007] US 2005/0181933 discloses a method for producing a zeolite of the type ZSM-5 which consists of reacting calcined microspheres of kaolin with silicate and a seed solution used to form zeolite Y under conditions of pH, temperature, and time to obtain ZSM-5 crystals formed in-situ in the aforementioned calcined kaolin microspheres. The carrier used are calcined kaolin microspheres containing a minimum of reactive alumina. The presence of ZSM-5 crystals is evidenced via X-ray diffraction (“X-ray diffraction” - XRD).
[0008] WO 95/12454 discloses a process for producing improved FCC zeolitic catalysts by spray-drying a mixture of kaolin and spinel. The mixture is essentially metakaolin-free. The resulting microspheres are calcined to convert hydrated kaolin to metakaolin. They are then placed to react with an alkaline solution of seeded sodium silicate to form zeolite crystals. The carrier used is metakaolin, which is not a porous material. The presence of faujasite-Y zeolite crystals is evidenced via X-ray diffraction. In the examples, the surface area ranges from 230 m2 / g to 330 m2 / g.
[0009] US 4,493,902 describes a catalyst for fluid catalytic cracking (FCC) consisting of microspheres containing more than about 40%, preferably 50-70% by weight of Faujasite-Y zeolite. The document also describes the method for producing such catalysts. The catalyst is prepared via crystallization of faujasite-Y zeolite, originating from zeolite initiator, in microspheres from a mixture of metakaolin clay and kaolin clay. This document describes a large amount of zeolite coated in a material that has no porosity. The presence of faujasite-Y zeolite crystals is evidenced via X-ray diffraction pattern.
[0010] Jacobsen C. J. H. et al. in “Zeolites by confined space synthesis characterization of the acid sites in nanosized ZSM-5 by ammonia desorption and 27Al / 29Si MAS NMR spectroscopy” Microporous and Mesoporous Materials vol. 39 n ° 1-2, 1 September 2000 pages 393-401 described the preparation of zeolite crystals of the type ZSM-5 in confined space. They crystallized small-sized zeolite crystal within the porosity of a carbon black matrix. The carbon black matrix is completely removed by calcination in order to obtain finely dispersed crystals of ZSM-5. The crystals obtained are finally characterized by X-ray diffraction and they exhibit a clear XRD pattern signature of ZSM-5 crystals.
[0011] Schmidt I. et al. in: "Confined space synthesis. A novel route to nanosized zeolites” Inorganic chemistry, vol. 39 n ° 11, 1 November 1990 pages 2279-2283 similarly described the preparation of zeolite crystals using a carbon black matrix to limit growth The black carbon matrix is removed by calcinations.The crystals obtained are characterized by their X-ray diffraction patterns and they exhibit a clear XRD pattern of crystallized zeolite.
[0012] Srivastava R. et al. in: “Synthesis of nanocrystalline MFI-zeolites with intracrystal mesopores and their application in fine chemical synthesis involving lager molecules” Chemistry - A European Journal vol. 14 n ° 31, 29 October 2008, pages 9507-9511 describes the preparation of zeolite type ZSM-5 by controlling the size and mesoporosity of the nanocrystal by adding alkyl alkoxysilanes within a conventional synthetic composition. The zeolite crystals obtained have a spherical / egg-shaped nanocrystalline morphology with a clear XRD pattern.
[0013] Xu X. et al in: “micrometer scale macroporous silica alumina composites with spheric and lathy MFI-type crystals via seed-induced in-situ and layer-by-layer synthetic methods” Materials Letters vol. 64, n ° 15, 15 August 2010 pages 1660-1663 prepared a macroporous silica-alumina composite material. They first prepared an amorphous silica-alumina monolith which they then impregnated with a PDDA before being impregnated with a solution containing silica seeds (silicalite-1 solution). The silica-coated matrix was finally converted to MFI using a vapor phase treatment (VPT) with the aid of a TPAOH template. The MFI structure was evidenced with an XRD and the SEM analysis of the obtained crystal showed the presence of spherical particles with the size of about 100 nm.
[0014] Mavrodinova V. et al. in: “Beta zeolite colloidal nanocrystal supported on mesoporous MCM-41” Journal of colloid and interface science, vol. 286, n ° 1, 1 June 2005 used a preformed mesoporous molecular sieve of MCM-41, in which they impregnated a beta zeolite nanophase. Beta zeolite was directly impregnated in the molecular sieve of MCM-41 without the aid of any other component. Once deposited, beta zeolite was evidenced via XRD and the acidity (measured via NH3 TPD) of the obtained solid was in the range of 2.01 to 2.97 mmol / g (that is, 2010 to 2970 μmol / g).
[0015] WO 2006/105771 refers to a membrane for gas separation prepared by impregnating 4, 6 and / or 8 rings zeolite on a porous substrate via impregnation (ie zeolites with a maximum pore diameter) 4.4 Â - 0.44 nm). The impregnation is performed directly on the porous substrate without the aid of any other components. Only zeolites with small pores are deposited on the materials because the main application of the membrane is gas phase separation. There is no application of the possible use of the membrane for catalytic reaction.
[0016] FR 2 981 943 describes the use of a hydrocracking catalyst prepared by zeolithizing a porous mineral matrix. Zeolithization is defined as putting the matrix in contact with the source of element required to form the zeolite followed by the crystallization of those elements under conditions to form the zeolite. The zeolite thus formed coated the surface of the matrix. Zeolithization can be understood more as a coating than a deposition of zeolite crystals. In particular, on page 9, lines 19-21, it is stated that beta zeolite forms a layer on the outer surface of the porous mineral matrix or, otherwise, fills the porosity of the matrix. Therefore, it can be understood that zeolithization leads to a coating on the matrix surface and that a clearly defined crystallization of zeolite is formed. Additionally, in example 2, page 15, line 5, it is stated that the crystallinity rate is 95%.
[0017] The state of the art provides us with catalyst compositions obtained by crystallization of a zeolite in different carriers, demonstrating the formation of the zeolitic phase by XRD pattern signatures. This usually means the formation of zeolite with a crystal size in the range of 50 nm or more.
[0018] Alternatively, the state of the art describes the deposition of zeolite seeds or precursor elements of zeolite on a carrier followed by a crystal growth step, such as transition in vapor phase. The zeolite crystals thus formed are shown via XRD.
[0019] The formation of zeolite crystals in a carrier such as kaolin using a zeolite precursor solution is known in the art. The carrier is used to bring mechanical resistance to the catalyst. The carrier is generally made up of small particles that do not have porosity but that clump together. The catalyst is then made up of that carrier coated with a zeolite coating. The zeolite coating consists of covering the surface of the carrier with a layer of crystalline zeolite. The uniform coating of the carrier with a layer of zeolite is evidenced, among other ways, via X-ray diffraction (XRD). The strong acidic sites of the zeolite present at the top of the zeolite layer are accessible to small, bulky molecules. The accessibility of acidic sites located within the zeolytic layer is prevented by limiting diffusion to small molecules; for bulky molecules those acidic sites are not accessible.
[0020] An object of the invention is to provide catalyst compositions that have an increased number of acidic sites accessible to both bulky and small molecules.
[0021] Furthermore, it is a particular objective of the present invention to provide a catalyst composition with an improved surface area. It is also a particular object of the present invention to provide catalyst compositions with improved activity and selectivity.
[0022] Another object of the invention is to provide a method for producing such a catalyst composition.
[0023] There is also a need to stabilize small particles of molecular sieve crystals while carrying out the catalyzed reactions. BRIEF DESCRIPTION
[0024] In the following passages, different aspects of the invention are defined in more detail. Each aspect thus defined can be combined with any other aspect or aspects, unless clearly indicated to the contrary. In particular, any aspect indicated as being preferred or advantageous can be combined with any other aspect or aspect indicated as being preferred or advantageous.
[0025] Catalyst compositions that have an increased number of acidic sites and also have acidic sites accessible to both bulky and small molecules have been discovered.
[0026] The invention provides a catalyst composition comprising an inorganic porous material with pore diameters of at least 2 nm and molecular sieve crystals, notable because: the molecular sieve crystals have an average diameter of no more than 50 nm, measured using Scanning Electron Microscopy; the catalyst composition has a concentration of acid sites ranging from 50 to 1200 μmol / g, measured by Desorption with Programmed Temperature of ammonia (“Temperature-Programmed Desorption of ammonia” - TPD NH3); concentration of Bronsted acid sites of at least 10 μmol / g measured by pyridine desorption at 150 ° C; and the X-ray diffraction pattern of said catalyst composition is the same X-ray diffraction pattern of said inorganic porous material. This final characteristic means that there is no change in the X-ray diffraction pattern when the molecular sieve crystal is being deposited in the porous inorganic material, it remains substantially the same. The deposition of molecular sieve crystal is evidenced via indirect methods. For example, the deposition of the molecular sieve crystal is evidenced by an increase in surface area, an increase in acidity or a change in MAS NMR of 27Al.
[0027] The catalyst composition according to the invention is additionally notable because the inorganic porous material is amorphous. The use of an amorphous material yields more accessible molecular sieve crystals present in the catalyst composition because of its open porosity.
[0028] The catalyst composition according to the invention is additionally remarkable because it contains up to 30% by weight of molecular sieve crystals in relation to the total weight of the catalyst composition.
The catalyst compositions according to the invention are notable because the molecular sieve crystals have an average diameter of no more than 40 nm, preferably below 30 nm, more preferably still below 15 nm.
[0030] The presence of molecular sieve crystals is also evidenced by an increase in the microporous volume of the catalyst composition, compared to that of the carrier only. In fact, the microporous volume of the catalyst is caused mainly by the molecular sieve crystals.
[0031] Such an acid concentration is high enough to carry out a reaction such as, for example, cracking or oligomerization reactions.
The catalyst compositions according to the invention comprise a porous material with pore diameters of at least 2 nm and containing Al2O3 and SiO2 with an Al / Si atomic ratio greater than 1, and up to 30% by weight of crystals molecular sieve in relation to the total weight of the catalyst composition.
The catalyst composition comprises at least 1% by weight, preferably 5% by weight, more preferably 10% by weight of molecular sieve crystal on the total weight of the catalyst composition.
[0034] The size of the crystals is such that they are not detectable by X-ray diffraction. However, their presence is evidenced by the acidity of the catalyst compositions, which is greater than the acidity of the porous material used as a carrier only. The acidity increases by at least 5%, preferably 10%, more preferably 20%, as measured by TPD NH3.
[0035] Preferably, the catalyst compositions have a concentration of acid sites ranging from at least 200 μmol / g, measured by TPD NH3, preferably at least 350 μmol / g.
[0036] Preferably, the catalyst compositions have a concentration of acid sites ranging from a maximum of 1000 μmol / g, measured by TPD NH3, preferably a maximum of 800 μmol / g.
[0037] The presence of molecular sieve crystals is also evidenced by an increase in the microporous volume of the catalyst composition, compared to that of the carrier only. In fact, the microporous volume of the catalyst is caused mainly by the molecular sieve crystals.
[0038] The catalyst compositions comprise microporous molecular sieves, but they remain substantially meso-macroporous. This means that the porous material that has pores with a mesoporous volume and / or macroporous volume and the molecular sieve crystals that have pores with a microporous volume, the ratio of the aforementioned microporous volume to the mesoporous and / or macroporous volume varies from 0, 2 cm3 / g 0.005 cm3 / g, the aforementioned volumes being determined using ASTM D4365 (95-2008).
[0039] The surface area (measured using ASTM D3663) of the catalyst compositions is greater than the surface area of the porous material by at least 5%, preferably 10%, more preferably 20%, most preferably 30%. The surface area is at least 250 m2 / g, preferably at least 300 m2 / g, more preferably still at least 350 m2 / g using ASTM D3663 - 03 (2008).
[0040] The catalyst compositions being substantially meso-macroporous, this means that the catalyst compositions have a Vtotal / Vmicro ratio of at least 5, more preferably greater than 10, with Vtotal meaning the total porous volume (in cm3 / g) of catalyst compositions and Vmicro meaning the microporous volume (in cm3 / g) of the catalyst compositions, both being measured via ASTM D4365 (95-2008).
[0041] An important increase in the external surface area with a limited increase in the microporous volume has the advantage that all the added surface area is accessible to bulky molecules and not to microporosity.
[0042] The concentration of acidic sites in the catalyst compositions is at least 10 μmol / g of acidic sites as measured by pyridine adsorption. The acidity of the catalyst composition measured via pyridine adsorption at 150 ° C is advantageously increased by at least 5%, preferably 10%, more preferably 20%, most preferably 30%, compared to the only inorganic porous material.
Preferably, the catalyst compositions have a concentration of Bronsted acid sites of at least 15 μmol / g, more preferably at least 20 μmol / g, measured by pyridine desorption at 150 ° C.
[0044] According to another embodiment, the catalyst composition is amorphous XRD. This means that the X-ray diffraction pattern of the catalyst compositions does not have the characteristic bands of the molecular sieve crystal, but it does have the amorphous DRX pattern of the porous material used as a carrier. In fact, in the preferred embodiment, the porous material is amorphous, more preferably the porous material contains a silica-alumina, and more preferably, the porous material is a high-purity silica-alumina material.
[0045] In another embodiment, the catalyst composition according to the invention is notable because the inorganic porous material is a silica-alumina, a SiO2, an Al2O3 or a mixture thereof; or an amorphous inorganic material containing Al2O3 and SiO2 with an atomic ratio Al / Si> 1, preferably the porous material contains elements other than Si, O, Al with a concentration below 500 ppm by weight.
[0046] In another embodiment, the catalyst composition according to the invention is also notable because the said molecular sieve crystals are of the MFI type, preferably of the ZMS-5 type.
[0047] In another embodiment, the catalyst composition is a body molded into a shape, which is directly suitable for the catalytic application in fixed, mobile, batch or fluidized bed reactors.
[0048] In another embodiment, the catalyst compositions further comprise one or more of: - phosphorus; - at least one metal selected from the group: B, Cr, Co, Ga, Fe, Li, Mg, Ca, Mn, La, Ti, Mo, W, Ni, Ag, Sn or Zn, Pt, Pd, Ru, Re , Os, Au or any combination thereof; - at least one binder selected from silica, silica-alumina, metal silicates, metal oxides such as ZrO2 and / or metals, amorphous aluminum phosphate or silica aluminum phosphates, gels including mixtures of silica and metal oxides, amorphous aluminum phosphate or any combination of these .
[0049] In the preferred embodiment, the catalyst compositions contain molecular sieve crystals with a pore diameter of less than 2 nm, preferably in the range of 0.3 to 1.2 nm, more preferably from 0.4 to 0.9 nm .
[0050] In another embodiment, the catalyst compositions contain molecular sieve crystals with a pore diameter greater than 0.3 or more preferably 0.5 nm and up to 0.9 nm, preferably up to 1.1 nm, more preferably up to 1.2 nm.
[0051] The catalyst compositions described above can be prepared by the following preparation process which includes the following steps: a) providing a porous inorganic material; b) optionally, calcining said porous material at a temperature of 400 ° C to 1200 ° C; c) providing a solution containing at least one charge surface modifying agent; d) contacting the solution of step c) and the material obtained in step b) to obtain an inorganic porous amorphous material modified with a charge surface modifying agent; e) provide a solution containing precursors for the molecular sieve; f) react the molecular sieves by: i) maturing the solution of step e) for a period of time from 0 to 50h, the maturation process being followed by DLS and interrupted when the molecular sieve crystals have a maximum size of 50 nm , or, preferably, when the molecular sieve crystal has a size in the range of 15 nm and exposes a modified porous material in contact with the matured solution to deposit the molecular sieve crystals on the surface of the modified porous material obtained in step d); and / or ii) put the modified porous material obtained in step d) in contact with the solution in step e) and mature the mixture obtained for a period of time from 0 to 50h until the acidity of the catalyst composition measured by TPD of ammonia has increased by at least 10%, compared to the acidity of the porous inorganic material; maturation is stopped before the molecular sieve crystal appears in the X-ray diffraction pattern of the catalyst composition.
[0052] The maturation time is adapted so that the X-ray diffraction pattern of the inorganic porous material remains unchanged; that is, the maturation time is increased to achieve the desired acidity of the catalyst composition, but maturation is stopped before the molecular sieves appear in the X-ray diffraction pattern. g) separate the solid from the liquid, if any, the mixture obtained after step f); h) calcining the solid obtained in step g).
[0053] Advantageously, the preparation method presented above does not particularly require a drastic operational condition to form the molecular sieve crystals. In fact, the solution of step e) contains the entire element required for the preparation of the molecular sieve and there is no need for a drastic condition for the leaching of the inorganic porous amorphous material element necessary to form the molecular sieve. There is no need for an autoclave to increase the temperature and pressure to develop the molecular sieve crystals. There is no need to perform deposition under vapor phase transition (VPT) conditions.
[0054] In another embodiment, steps e) to g) are repeated at least twice before executing h) in order to increase the content of molecular sieve crystals deposited in the porous materials.
[0055] When steps e) to g) are repeated at least twice before h) is performed, preferably the maturation of the solution is carried out for at least 30 min and at most 100h each time, preferably at most 30h, more preferably at maximum 20h.
[0056] In another embodiment, steps e) to g) are repeated at least twice before executing h), preferably the maturation of the solution is carried out for at least 30 min and at most 100h each time, preferably at most 30h , more preferably at most 20h, more preferably at most 10h.
[0057] In another embodiment, steps e) to g) are performed once and the maturation of the solution is conducted for at least 10h and, preferably at least 30h and, more preferably at least 100h.
[0058] In another embodiment, steps e) to g) are performed once and the maturation of the solution is carried out for a maximum of 10h and, preferably a maximum of 30h, and more preferably a maximum of 20h, more preferably still a maximum of 50h.
[0059] In another embodiment, the porous material contains Al2O3 and SiO2 with an atomic ratio Al / Si> 1, preferably the porous material contains elements other than Si, O, Al with a concentration below 500 ppm by weight .
[0060] In another embodiment, the catalyst compositions have the X-ray pattern of the porous material, preferably the porous material is amorphous XRD.
[0061] In another embodiment, the process of preparing catalyst compositions according to the invention can include one or more of the following steps, the aforementioned steps being performed after step h) in any order: - introduction of phosphorus by impregnating the catalyst composition by a solution containing phosphorus, the aforementioned step being optionally followed by additional steps of calcination and / or steam treatment; - addition of at least one metal selected from the group: B, Cr, Co, Ga, Fe, Li, Mg, Ca, Mn, La, Ti, Mo, W, Ni, Ag, Sn or Zn, Pt, Pd, Ru , Re, Os, Au or any combination thereof, by impregnating the catalyst compositions with a solution containing the selected metal salts; - addition of at least one binder selected from silica, silica-alumina, metal silicates, metal oxides such as ZrO2 and / or metals, amorphous aluminophosphate or aluminophosphates, gels including mixtures of silica and metal oxides, amorphous aluminophosphate or any combination thereof, drying by spraying, extrusion or any suitable method known to a person who is a technician in the field; - molding the catalyst composition by extrusion.
[0062] In another embodiment, in the preparation of catalyst compositions according to the invention, the porous material used is a high purity silica-alumina.
[0063] Advantageously, the method of preparing the catalyst can be carried out directly on the molded catalyst or on the support or precursor. In fact, the solution containing the molecular sieve crystals can be impregnated in the catalyst being molded in the form, for example, of extrudates, spray dried pearls, spheres, tablets etc. In contrast to other techniques for the synthesis of micro-mesoporous materials, for example, desilication, this modification leads to an increase in the surface area and acidity of the molded bodies without destroying them. In addition, it simplifies the overall catalyst manufacturing process and represents significant economic advantages.
[0064] Examples of the reactions in which the catalyst compositions can be used, include but are not limited to: Fluid Catalytic Cracking, hydrocracking of heavy molecules, olefin oligomerization, isomerization, gasoline reform, alkylation, conversion of oxygenates to hydrocarbons (methanol to olefins ("methanol to olefins" - MTO), methanol to gasoline ("methanol to gasoline" - MTG), methanol to hydrocarbons ("methanol to hydrocarbons" - MTH)), dehydration of alcohols to the corresponding olefins, cracking of olefins, conversion of biomass to olefins, conversion of biomass to BTX (benzene, toluene, xylenes), conversion of biomass to fuel, transformation of waste to fuel, hydrocracking of extremely heavy raw materials, monomers, chemicals, any types of catalytic pyrolysis or any reactions that imply an organic component and that require an acidic site or bifunctional catalyst site (acidic and metallic functions) .
[0065] The catalyst compositions according to the invention have an improved stability over time yet with a high conversion and they are more selective.
[0066] The catalyst compositions according to the invention are also useful for the conversion of bulky molecules, for the transformation of small molecules to bulky molecules, as in the oligomerization for the transformation occurred via bulky transition intermediates.
[0067] The invention is also related to the catalyst compositions obtained by the process described above.
[0068] Another objective of the invention is the use of catalyst compositions in fluid catalytic cracking reactions, catalytic pyrolysis of biomass, waste, plastic derivatives or their co-processing with conventional fossil raw materials, hydrocracking of heavy hydrocarbons or extra-heavy raw materials, olefin oligomerization reactions, conversion of oxygenated molecules to olefins, gasoline, aromatics or distillates, olefin cracking into lighter olefins, catalytic cracking of C4-C12 paraffins, isomerization reactions, gasoline reform, alkylation reactions, dehydration reactions from alcohols to matching olefins and / or dehydrogenation reactions. DETAILED DESCRIPTION
[0069] Regarding the meaning of mesoporous, microporous and macroporous, as recommended by the International Union of Pure and Applied Chemistry (“International Union of Pure and Applied Chemistry” - IUPAC) in Pure & Appl. Chem., Vol. 66, No. 8, pp. 1739-1758, 1994, the term micropore refers to the pore that is less than 2 nm wide; the term mesopore refers to pores with widths between 2 and 50 nm; the term macropore refers to pores with widths greater than 50 nm. Detailed description of the prepared catalyst compositions
[0070] With respect to the catalyst compositions, they contain molecular sieve crystals at a content ranging from 0.1 to 50% by weight of molecular sieve crystals in relation to the total weight of the catalyst compositions, more preferably in the range of 1 to 40% by weight, more preferably still in the range of 1 to 30% by weight. The catalyst compositions are characterized by the fact that the molecular sieve crystals are small in size. The term "small" is to be understood as referring to particles having an average diameter less than 50 nm, preferably less than 40, more preferably less than 30 nm, more preferably about 15 nm or less. The diameter of the molecular sieve crystals is measured via scanning electron microscopy (“scanning electron microscopy” - SEM).
[0071] The present invention has the advantage that the amount of molecular sieve crystal dispersed in the porous material can be adapted in order to adjust the acidity of the solid for a given reaction. Therefore, the acidity of a given porous material can be increased to achieve the desired activity to perform a given reaction. The determination of the appropriate amount of molecular sieve crystals to carry out the reaction can be determined simply by testing the catalyst compositions prepared with the reaction under consideration.
[0072] Preferably, the molecular sieve crystal according to the invention is dispersed on the carrier surface, and does not form a uniform layer covering the carrier as is common in the prior art. In fact, with a coating, the only accessible sites are the sites present at the top of the layer. With the molecular sieve crystals dispersed, the sites present on the side faces of the crystal are additionally accessible. Consequently, the dispersion of the molecular sieve crystals leads to both an increase in surface area, as well as microporous volume and acidity or any combination of these. The dispersion of the molecular sieve crystals is facilitated by their small size, that is, by a diameter not larger than 50 nm.
[0073] With respect to molecular sieve crystals, they can consist of any microporous materials that have molecular sieve properties and, advantageously, that have acidic active sites. More precisely, they consist of crystallized material that has a pore diameter of less than 2 nm, preferably a pore diameter in the range of 1.2 to 0.3 nm. As a non-limiting example, aluminosilicate, metallosilicate, metalaluminophosphates (MeAlPO4) or crystalline microporous silicate can be mentioned.
[0074] They can consist of a realization of zeolite, which according to the invention is selected from the group MOR, FAU, EMM, MWW, BETA, ZSM-21, ZSM-42, AEI, CHA, ERI, LEV, OFF , ZSM-34, AFI, AEL, LTL, MFI (ZSM-5, silicalite, TS-1), MEL (ZSM-11, silicalite-2, TS-2), MTT (ZSM-23, EU-13, ISI -4, KZ-1), MFS (ZSM- 57), HEU (Clinoptilolite), FER (ZSM-35, Ferrierite, FU-9, ISI-6, NU-23, Sr-D), TON (ZSM-22 , Theta-1, ISI-1, KZ-2 and NU-10), LTL (L), MAZ (mazita, Omega, ZSM-4) or a mixture of these. These zeolites and their isotypes are described in the related literature. The structure types are provided by IUPAC and can be found in Pure Appl. Chem., Vol. 73, No. 2, pp. 381-394, 2001.
[0075] In one embodiment, the zeolite structure is an intergrowth structure in two or more phases, which, according to the invention could be selected from a group ZSM-34 (OFF / ERI), AEI / CHA, MFI / AEL etc.
[0076] Crystalline silicates are microporous crystalline inorganic polymers based on a framework of XO4 tetrahedrons linked together by sharing oxygen ions, where X can be trivalent (for example, Al, B, ...) or tetravalent (for example, Ge, Si, ...). The crystal structure of a crystalline silicate is defined by the specific order in which a network of tetrahedral units are linked together. The size of the crystalline silicate pore openings is determined by the number of tetrahedral units, or, alternatively, oxygen atoms, required to form the pores and the nature of the cations that are present in the pores. They have a unique combination of the following properties: large internal surface area; uniform pores with one or more different sizes; ion exchange capacity; good thermal stability; and the ability to adsorb organic compounds. As the pores of these crystalline silicates are similar in size to many organic molecules of practical interest, they control the ingress and egress of reagents and products, resulting in particular selectivity in catalytic reactions. For example, crystalline silicates with the MFI structure have a bi-directional interconnect pore system with the following pore diameters: a direct channel along [010]: 0.53-0.56 nm and a sinusoidal channel along [ 100]: 0.51-0.55 nm. Crystalline silicates with the MEL structure have a two-way interconnected direct pore system with direct channels along [100] having pore diameters of 0.53-0.54 nm.
[0077] The metallosilicates obtained by the process of the present invention may comprise a load-balancing M-cation selected from the group consisting of hydrogen, ammonium, monovalent, divalent and trivalent cations and mixtures thereof.
[0078] Molecular sieves, particularly zeolitic and zeolitic molecular sieves, preferably have a molecular frame of one, preferably two or more tetrahedral TO units that share angles, more preferably, two or more SiO4, AlO4 and / or PO4 tetrahedral units. In particularly preferred embodiments, the molecular sieve frame may have two tetrahedral units of SiO4 and AlO4, or three tetrahedral units of SiO4, AlO4, and PO4. These latest molecular sieves based on silicon, aluminum, and phosphorus and molecular sieves based on silicon, aluminum, and phosphorus containing metal have been described in detail in numerous publications, including, for example, US Patent No. 4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), US Patent No. 4,440,871 (SAPO), European Patent Application No. EP-AO 159 624 (ELAPSO where El is As, Be, B, Cr, Co, Ga, Ge , Fe, Li, Mg, Mn, Ti or Zn), US Patent No. 4,554,143 (FeAPO), US Patent No. 4,822,478, 4,683,217, and 4,744,885 (FeAPSO), European Patent Application No. EP -AO 158 975 and US Patent No. 4,935,216 (ZnAPSO), European Patent Application No. EP-A- O 161 489 (CoAPSO), European Patent Application No. EP-AO 158 976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti or Zn), US Patent No. 4,310,440 (AlPO4), European Patent Application No. EP-A-0 158 350 (SENAPSO), US Patent No. 4,973,460 (LiAPSO ), US Patent No. 4,789,535 (LiAPO), US Patent No. 4,992,250 (GeAPSO), US Patent No. 4,888,167 (GeAPO), Patent and US No. 5,057,295 (BAPSO), US Patent No. 4,738,837 (CrAPSO), US Patent No. 4,759,919 and 4,851,106 (CrAPO), US Patent Nos. 4,758,419, 4,882,038, 5,434,326, and 5,478,787 (MgAPSO), US Patent No. 4,554,143 (FeAPO), US Patent No. 4,894,213 (AsAPSO), US Patent No. 4,913,888 ( ASAPO), US Patent Nos. 4,686,092, 4,846,956, and 4,793,833 (MnAPSO), US Patent No. 5,345,011 and 6,156,931 (MnAPO), US Patent No. 4,737,353 (BeAPSO), US Patent No. 4,940,570 ( BeAPO), US Patent Nos. 4,801,309, 4,684,617, and 4,880,520 (TiAPSO), US Patent Nos. 4,500,651, 4,551,236, and 4,605,492 (TiAPO), US Patent Nos. 4,824,554 and 4,744,970 (CoAPSO), US Patent No. 4,735,806 (GaAPSO), European Patent Application No. EP-AO 293 937 (QAPSO, where Q is the frame oxide unit [QO2]), as well such as US Patent Nos. 4,567,029, 4,686,093, 4,781,814, 4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164, 4,956,165, 4,973,785, 5,241,093, 5,493. 066, and 5,675,050, all of which are incorporated herein by reference in their entirety.
[0079] In one embodiment, the molecular sieves of the invention can be combined with one or more other molecular sieves. In another embodiment, the silicoaluminophosphate or aluminophosphate molecular sieves, or a combination thereof, can be combined with one of the following non-limiting molecular sieves examples, described in the following references: Beta (US Patent No. 3,308,069), ZSM -5 (US Patent Nos. 3,702,886, 4,797,267, and 5,783,321), ZSM-II (US Patent No. 3,709,979), ZSM-12 (US Patent No. 3,832,449), ZSM- 12 and ZSM-38 (US Patent No. 3,948,758), ZSM-22 (US Patent No. 5,336,478), ZSM-23 (US Patent No. 4,076,842), ZSM-34 (US Patent No. 4,086 .186), ZSM-35 (US Patent No. 4,016,245, ZSM-48 (US Patent No. 4,397,827), ZSM-58 (US Patent No. 4,698,217), MCM-I (US Patent No. 4,639,358), MCM-2 (US Patent No. 4,673,559), MCM-3 (US Patent No. 4,632,811), MCM-4 (US Patent No. 4,664,897), MCM-5 (US Patent No. 4,639,357), MCM-9 (US Patent No. 4,880,611), MCM-10 (US Patent No. 4,623,527), MCM-14 (US Patent No. 4,619,818), MCM-22 ( US Patent No. 4,954,325), MCM-41 (US Patent No. 5,098,684), M-41S (US Patent No. 5,102,643), MCM-48 (US Patent No. 5,198,203), MCM-49 (US Patent No. 5,236,575), MCM-56 (US Patent No. 5,362,697), ALPO-II (US Patent No. 4,310,440), titanium aluminosilicates (TASO), TASO-45 (European Patent Application No. EP-AO 229 295), boron silicates (Patent US No. 4,254,297), titanium aluminum phosphates (TAPO) (US Patent No. 4,500,651), mixtures of ZSM-5 and ZSM-II (US Patent No. 4,229,424), ECR-18 (US Patent No. 5,278,345), ALPO-5 linked to SAPO-34 (US Patent No. 5,972,203), International Publication No. WO 98/57743 published on December 23, 1988 (molecular sieve and Fischer-Tropsch), Patent US No. 6,300,535 (MFI-linked zeolites), and mesoporous molecular sieves (US Patent Nos. 6,284,696, 5,098,684, 5,102,643, and 5,108,725), all of which are incorporated herein by reference in their entirety.
[0080] With regard to the size of molecular sieve crystals, it is not greater than 50 nm, preferably it is not greater than 40 nm, more preferably not greater than 30 nm, more preferably it is still in the range 15 nm or not greater than 15 nm. Such a small size of crystals cannot be evidenced by X-ray diffraction, because the crystals are very small. The crystals are believed to have a size that is below the detection limit of the X-ray diffraction technique. The XRD detection limit being in the 50 nm range, it is believed that the crystals are smaller than 50 nm. Therefore, the catalyst composition of the present invention does not have the characteristic X-ray bands of the molecular sieve. However, the presence of such crystals can be evidenced by indirect technique. In particular, the presence of such a crystal can be evidenced by an increase in the surface area with a small increase in the microporous volume. It can also be evidenced by the presence of the characteristic NMR 13C signal of the model inside such a crystal if the model is present during the synthesis. It can also be evidenced by the presence of increased acidity and the detection of acidic sites by FTIR of adsorbed Pyridine. Finally, it can be evidenced by the presence of Al coordinated tetrahedrally via MAS NMR of 27Al.
[0081] On the other hand, the minimum size attainable while maintaining the crystallographic structure is the size of a single crystal cell. Considering the crystallographic structure of a unit cell, it is possible to estimate the minimum size. In the case of FAU, a minimum size to form tetrahedrally coordinated Al was estimated at about 15 nm to have at least one unit cell. Consequently, the minimum achievable size of a molecular sieve is expected to be in the range of 15 nm or from 15 nm to a maximum of 50 nm.
[0082] When referring to the “average size” of the molecular sieve crystal, it should be interpreted as referring to the maximum particle diameter. In fact, molecular sieve particles are not necessarily spherical; therefore, the term size refers to its longest length. Since all particles are not exactly the same size, the term "average" must refer to the position of the maximum of a Gaussian curve obtained while counting the particles as a function of their size. When the particles are deposited in the porous inorganic material, they retain their size. However, when the number of particles increases, they can at least partially agglomerate to form a coating. In this case, the average particle size merely refers to the thickness of the coating which must remain below 50 nm to avoid having an XRD pattern. In fact, the length of the coating can be greater than 50 nm as long as the thickness remains below 50 nm and does not lead to an XRD signature. Detailed description of, process, preparation of the catalyst compositions
[0083] The preparation method described in that part is to be used to prepare the catalyst composition described in the part above. All the achievements of the catalyst composition described in the part above are connected and must be considered in combination with all the achievements of the preparation method and everything is related to the achievements described in that part.
[0084] The preparation process includes the following steps: a) providing a porous inorganic material;
[0085] A porous inorganic material is used as a carrier for the crystal of molecular sieves. It has at least a mesoporosity, that is, pores of at least 2 nm. Advantageously, the porous inorganic material has a macroporosity, that is, pores of at least 50 nm. Preferably, the carrier pore diameters are at least 100 nm, more preferably at least 200 nm. The large pore diameter makes it possible to grant an additional accessible surface area inside the carrier itself to receive molecular sieve crystals.
[0086] The carriers used in the state of the art are small particles of material that do not have mesoporosity. In this case, the interior of the carrier particles cannot be used to catalyze the reaction. In contrast, a porous inorganic material is used in an invention to disperse the molecular sieve crystals. Using a porous material allows to increase the available surface to disperse the molecular sieve crystals and, therefore, allows to increase the overall activity of the catalyst composition.
[0087] Additionally, dispersing the molecular sieve crystals in porous material allows the crystals to stabilize. In fact, molecular sieve crystals that have a diameter of less than 50 nm are not stable and have a tendency to agglomerate when catalyst reactions are carried out. The catalyst compositions according to the invention make it possible to stabilize crystals of small size by fixing them on the surface of a carrier.
[0088] The porous material is preferably amorphous and has porosity with pore diameters of at least 2 nm (both a macroporosity and a mesoporosity). It must contain Al2O3 and SiO2 with an atomic ratio Al / Si> 1. It must be inert or not for the reaction in which the catalyst composition is used. Preferably, the material has some acidic sites, which could be measured, for example, by TPD NH3. When the porous material is amorphous, the catalyst compositions do not exhibit any crystallinity detectable by X-ray diffraction. As an alternative, the porous material is crystalline and the catalyst compositions exhibit an X-ray pattern identical to the X-ray pattern of the said porous material. cystaline.
[0089] In one embodiment, the porous material is an inorganic material selected from silica-doped alumina, metal aluminosilicates, mixed metal oxides, or gels including mixtures of silica, alumina and metal oxides, amorphous, or amorphous aluminophosphates silica.
[0090] In addition to silicon and aluminum, the porous material may contain O, Na, Ca, Mg, Li, La, Ti, Zr, P, As, Be, B, Cr, Co, Ga, Ge, Fe, Ni , Mo, W, Ag, Sn, Mn, S, C or Zn.
[0091] If the porous material is amorphous, it contains a silica-alumina, and more preferably the porous material is a silica-alumina material of high purity. High purity means that the impurity content (elements other than Si, O, Al) is below 500 ppm by weight.
[0092] In the preferred embodiment, the porous materials have a very low S, Cl, Br, F, I content, below 100 ppm by weight.
[0093] In the preferred embodiment, the precursors of porous materials were obtained by the alkoxide route or by using the alumina precursors obtained by the alkoxide route.
[0094] In the preferred embodiment, porous materials have a pore volume of at least 0.25 cm3 / g measured using ASTM D4365. b) optionally, calcining said porous material at a temperature of 400 ° C to 1200 ° C;
[0095] Calcination consists of treating a solid at an elevated temperature, that is, at least 400 ° C in an oven without gas circulation or under air flow, oxygen flow or N2 flow. This optional first calcination considered in the preparation of the catalyst composition is used to stabilize the porous material. By stabilization, it must be understood that this calcination allows to improve the surface stability during contact with a solution containing precursors for the molecular sieve f). A person who is a technician in the subject understands the effect of calcination via limiting the further dissolution of the elements that make up the material. As a matter of example, calcination is used in the first stage to limit the dissolution of aluminum during the other stages, when the porous material is brought into contact with the solution containing the surface modifying agent or the molecular sieve precursors. c) providing a solution containing at least one charge surface modifying agent;
[0096] The loading surface modifying agent can consist of any type of component allowing the modification of the loading surface of the porous material. Without wishing to be attached to any theory, it is believed that during the crystallization of a molecular sieve, very small crystals are formed. These small crystals are electrically charged and these charges are compensated by counter ions present in the solution. Because of these charges, small size crystals cannot easily be deposited directly on the porous inorganic support. It has been found that impregnation of the inorganic porous material with a charge surface modifying agent before depositing the small crystals allows those small crystals to be deposited on the porous surface with good dispersion. It is believed that during the maturation stage, the charge modifying agent deposited on the surface of the inorganic porous material facilitates the deposition of small particles on the surface of the porous material by limiting the electrostatic repulsion between the small crystals and the surface of the porous material.
[0097] Such components can be organic or inorganic. Organic charge modifying agents are generally water-soluble polymers, which can be both non-ionic and ionic. Ionic polymers can be of the anionic, cationic or amphoteric type.
[0098] As a non-limiting example of inorganic load-modifying agents, one can mention aluminum, aluminum chloride and derivative components, such as aluminum polychloride or sodium silicate (silica fume). Advantageously, the inorganic compounds used are the same as the compounds used to prepare the solution containing the source of the elements for the molecular sieve.
[0099] In another embodiment, charge-modifying surface agents are organic molecules that have a charge compensated by a counter-anion. Water-soluble polymers that have surfactant properties (ionic or non-ionic surfactant), anionic polymers, cationic polymers or polymers used in the flocculation process are preferred. As a non-limiting example, any polymer from the poly (diallyldimethylammonium chloride) family (“poly diallyl dimethyl ammonium chloride” - PDDA) can be used. In addition other polymers such as polyacrylamide [9003-05-8]; poly (ethylene oxide) [25322-68-3]; sodium polyacrylate [9003-04-7]; poly [2- (N, N, N-trimethylamino) ethyl acrylate] (chloride salt) [5407697-0]; polyethylenimine [26913-06-4]; poly [N- (dimethylaminomethyl) acrylamide] [25765-484]. Other non-ionic homopolymers of 1-vinyl-2-pyrrolidone [88-12-0], N-vinylformamide [13162-05-5], methoxyethylene [107-25-5], etc. poly (vinyl alcohol) [9002-895] are synthesized by hydrolysis of poly (vinyl acetate). Very high molecular weight poly (ethylene oxide) [25322-68-3] is obtained by polymerizing ethylene oxide on special catalysts, for example, alkaline earth carbonates or aluminum (C1-C4) alcoholates.
[0100] As a non-limiting example, ionic charge modifying agents are copolymers from acrylamide [79-06-1] and a charged comonomer. Anionic polymers are synthesized as homopolymers or copolymers of alkali metal acrylamide or ammonium salts of acrylic acid [79-10-7]. Methacrylic acid [79-41-4], maleic acid [6915-18-0], ethylene sulfonic acid [1184-84-4], 4-styrenesulfonic acid [98-70-4], and 2-methyl-2- [(l-oxo-2-propenyl) amino] -1- propanesulfonic [15214-89-8] can also be used as comonomers in acrylamide copolymers. Other water-soluble cationic polymers can be used for the production of cationic polymers, for example: substituted salts of acrylamide and methacrylamide [16-19]; N-vinylformamide [13162-05-5] and N-vinylacetamide [5202-78-8], which are polymerized and hydrolyzed in alkaline or acidic media to “vinylamine” copolymers [593-67-9] [20-23 ]; and salts of N-vinylimidazole [1072-63-5], 2-vinylpyridine [100-69-6] or 4-vinylpyridine [100-43-6].
[0101] The efficiency of the modification of the loading surface of the mesoporous material can be easily verified by measuring the zeta potential of the material obtained in step d). A comprehensive list of components that have the ability to neutralize the surface of the charge can be found in Ullmann’s Encyclopaedia of Industrial Chemistry, 6th edition completely revised, volume 14 pages 201-212, incorporated herein by reference. d) putting in contact the solution of step c) and the material obtained in step b) to obtain a porous material modified with a load surface modifying agent;
[0102] Bringing the solution in contact and the material can consist of any of the common impregnation techniques used to prepare catalyst compositions. For example, it may consist of a moisture impregnation technique, in which the solid is placed in contact with the exact amount of solution that fills its porosity. It may consist of a balancing impregnation technique in which the solid is brought into contact with a large excess of solution. Then, the solid can be separated either via filtration or the excess liquid can be evaporated. In one embodiment, the impregnation can be carried out at room temperature. In another embodiment, the impregnation can be carried out at a temperature ranging from room temperature to 150 ° C. The optimization of the impregnation step is known in the state of the art. In the case of impregnation of the load surface modifying agent, the good dispersion of that agent on the surface of the porous support can be verified by measuring the load surface of the porous material. In particular, the zeta potential of the porous material can be monitored. Additional references and details about the zeta potential can be found in Ullmann’s Encyclopaedia of Industrial Chemistry, 6th Edition, volume 11, pages 702-703 incorporated herein by reference. e) provide a solution containing precursors for the molecular sieve;
[0103] The solution containing molecular sieve precursors or molecular sieve seeds consists of the elements in any form as long as they are soluble in the solution and as long as they can be used to prepare the corresponding molecular sieve. In the preferred embodiment, the preparation of the solution containing molecular sieve precursors comprises mixing appropriate amounts of sodium silicate, sodium aluminate, sodium hydroxide and, optionally, an organic model. In a more preferred embodiment, mixing is carried out in a controlled manner and heating the resulting mixture for a time sufficient for the seeds to mature, but insufficient for turbidity to occur.
[0104] In one embodiment, the sources of the various elements of the metallosilicate can be any of those found on the market or prepared for that purpose. For example, the source of silicon may be a silicate, for example, a tetraalkylorthosilicate, pyrogenic precipitated (smoked) silica, or preferably a colloidal aqueous silica suspension.
[0105] Preferably, the inorganic silicon source has a limited solubility in water prior to the addition of alkaline medium.
[0106] When the metallosilicate is an aluminosilicate zeolite, the aluminum source is preferably hydrated alumina dissolved in an alkaline solution or aluminum metal, a water-soluble aluminum salt, for example, aluminum sulphate or aluminum chloride, aluminum chloride sodium or an alkoxide, for example, aluminum isopropoxide. When the metallosilicate is a borosilicate zeolite, the boron source is preferably hydrated boron oxide dissolved in an alkaline solution or a water-soluble boron salt, for example, boron chloride or an alkoxide. When the metallosilicate is a ferrosilicate or galossilicate, the source of iron or gallium can be almost any iron or gallium salts that are readily soluble in water. When the metallosilicate is titanosilicate, the source of titanium can be titanium halides, titanium oxyhalides, titanium sulfates or titanium alkoxides. The atomic ratio of silicon to metal depends on the metal and the use of the metallosilicate and is at least 2/1 to about 10,000/1, preferably from 5/1 to about 5000/1 and most preferred from about 10 / 1 to 1000/1.
[0107] In another embodiment, the molecular sieve is preferably obtained without the direct addition of a model according to a method known to a person who is a technical subject.
[0108] Optionally, one or more modeling agent (or directing agent), such as organic or inorganic compounds containing nitrogen, oxygen, sulfur, or phosphorus can be introduced into the synthesis mixture. When the driving agent is a cation, it can also be introduced in the form of a mixture of hydroxide and salt, for example, a halide. The agent used will depend on the metallosilicate prepared by the process. The amount of the steering agent depends on the metallosilicate prepared by the process. The source of M cations can be hydroxides or alkaline or alkaline earth salts. M can also be hydroxide or ammonium salts. Together with the managing agent (s), the M-cation will impact the pH of the medium that is crystallizing,
[0109] The mixing order of the metal and silicon precursors is not essential and will depend on the molecular sieve being prepared. Optionally, the crystallization medium can be aged at a temperature at which no crystallization occurs, optionally, nucleation can be initiated. The person skilled in the art knows the equipment used to prepare molecular sieve crystals of the type used in the present invention. Generally, silosilicates can be prepared using autoclaves, which have sufficient agitation to homogenize the crystallization mixture during heating until the effective nucleation and the crystallization temperature of the mixture is reached. The crystallization vessel can be made of metal or metal alloys that resist crystallization conditions or, optionally, can be coated with a fluorocarbon such as Teflon® ™. Other means of introducing agitation known to one skilled in the art can be employed, such as pumping the mixture of synthesis from one part of the autoclave to another.
[0110] In the preferred embodiment, the solution containing the precursor for the molecular sieve of step e) contains small crystals of molecular sieves and is amorphous XRD, that is, it does not exhibit any crystallinity by X-ray diffraction. F) reacting the sieves molecular by: i) maturing the solution of step e) for a period of time from 0 to 50h in order to obtain molecular sieve crystal with a maximum size of 50 nm, preferably 10 nm, measured by DLS and exposing a porous material modified in contact with the matured solution under appropriate conditions to form the molecular sieve crystals on the surface of the modified porous material obtained in step d); and / or ii) put the modified porous material obtained in step d) in contact with the solution in step e) and mature the mixture obtained for a period of time from 0 to 50h under conditions to increase the acidity of the catalyst composition without modifying it. its X-ray diffraction pattern and / or to form the molecular sieve crystals;
[0111] Maturation consists of treating the mixture made up of porous material with the solution containing the precursor of crystal molecular sieve. This step is performed to allow the deposition and / or crystallization of the molecular sieve crystal in the porous material. In one embodiment, the solution containing the crystal molecular sieve precursor is first matured to initiate the crystallization of the molecular sieve (step f) i)). In another embodiment, the solution is placed in contact with the porous material impregnated with a load-modifying agent without having first been matured. In the latter case, crystallization is initiated directly in the porous material (step f) ii)). In yet another embodiment, the solution is first matured, then placed in contact with the porous material impregnated with a load modifying agent and the mixture obtained is finally matured.
[0112] Without wishing to be linked to any theory, it is believed that the maturation stage f) ii) consists of both the usual crystallization stage as known by the state of the art and a deposition stage in which the small crystals molecular sieves already present in the solution are deposited on the porous material.
[0113] The maturation steps can last from 10 min to up to 48 h, more preferably it lasts from 1 h to 24 h, most preferably it lasts from 2 h to 12 h.
[0114] In another embodiment, maturation is optional.
[0115] Putting the solution in contact with the solid in step f) i) or f) ii) is performed in a similar way to step d). g) separate the solid from the liquid, if any, from the mixture obtained after step f);
[0116] The separation of the solid from the liquid can be carried out by any means known in the art, for example, mention can be made of filtration, drying at least 100 ° C, nanofiltration etc. h) calcining the solid obtained in step g).
[0117] The calcination carried out in step h) is carried out to remove the organic compounds present in the solid by combustion under O2 or air or any oxidizing atmosphere. It can also consist of removing impurities (ie components other than organic components, for example, counter ions) that may be present on the surface. The calcinations are carried out at a temperature of at least 400 ° C. The calcination is preferably carried out in a temperature range of 400 ° C to 1200 ° C. Other comments on the process
[0118] This process allows to prepare a catalyst composition with small crystals of molecular sieve dispersed on its surface.
[0119] In one embodiment, the preparation of the described catalyst composition leads to a porous material in which molecular sieve crystals having an average diameter of not more than 50 nm, preferably not greater than 40 nm, more preferably not greater than 30 nm, more preferably still in the range of about 15 nm or less.
[0120] In another embodiment, steps e) to g) are repeated at least twice in order to increase the content of molecular sieve crystals deposited in the porous materials.
[0121] In another embodiment, the catalyst compositions could be further modified by metal deposition, phosphorus deposition, steam treatment, ion exchange, acid leaching, alumination, silication, graft surface functionalization, etc.
[0122] Acid leaching can be done with an organic acid such as citric acid, formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, acid fumaric acid, nitriloacetic acid, hydroxyethylenediaminetriacetic acid, ethylene diaminetetraacetic acid, trichloroacetic acid, trifluoroacetic acid or a salt of such an acid (for example, the sodium salt) or a mixture of two or more of such acids or salts. The other inorganic acids can comprise an inorganic acid such as nitric acid, hydrochloric acid, methanesulfonic acid, phosphoric acid, phosphonic acid, sulfuric acid or a salt of such an acid (for example the sodium or ammonium salts) or a mixture of two or more of such acids or salts.
[0123] In another embodiment, the process of preparing catalyst compositions according to the invention can include one or more of the following steps, the aforementioned steps being performed after step h) in any order: - introduction of phosphorus by impregnating the catalyst composition by a solution containing phosphorus, the aforementioned step being optionally followed by additional steps of calcination and / or steam treatment; - addition of at least one metal selected from the group: B, Cr, Co, Ga, Fe, Li, Mg, Ca, Mn, La, Ti, Mo, W, Ni, Ag, Sn or Zn, Pt, Pd, Ru , Re, Os, Au or any combination thereof, by impregnating the catalyst compositions with a solution containing the selected metal salts; - addition of at least one binder selected from silica, silica-alumina, metal silicates, metal oxides such as ZrO2 and / or metals, amorphous aluminophosphate or aluminophosphates, gels including mixtures of silica and metal oxides, amorphous aluminophosphate or any combination thereof, drying by spraying, extrusion or any suitable method known to a person who is a technician in the field; - molding the catalyst composition by extrusion.
[0124] Binding materials are typically effective in reducing the overall cost of the catalyst, acting as heat sinks assisting in the heat shielding of the catalyst composition, for example, during regeneration, densification of the catalyst composition, increasing the strength of the catalyst as well as strength crushing and friction resistance, and controlling the conversion rate in a particular process. The binder could be the same or different from the initial porous materials. The binder is an inorganic material selected from silica, metal silicates, metal oxides such as ZrO2 and / or metals, or gels including mixtures of silica and metal oxides. It is desirable to provide a catalyst that has good crushing strength. This is because in commercial use, it is desirable to prevent the catalyst from breaking down into powdered materials. Such oxide binders have been used normally only for the purpose of improving the crushing strength of the catalyst. A particularly preferred binder for the catalyst of the present invention comprises silica, alumina, amorphous aluminum phosphate, silica aluminum phosphate or silica-alumina. The relative proportions of the finely divided crystalline silicate materials and the inorganic oxide matrix of the binder can vary widely. Detailed description of the possible use of the catalyst compositions
[0125] Regarding the use of the catalyst, they can be used as a catalyst in any reaction that requires active acidic sites. They can also be used as a support where acidic properties for the support are required. They can also be used as a cocatalyst with another catalyst, for example, in a mechanical mixture or a formulation constituent; they can be added before formulation or as a part of the formulation. For example, they can be used as a catalyst in the FCC reaction or an additive catalyst for the FCC reaction.
[0126] The materials disclosed in the invention can also be useful as an adsorbent or a support for the adsorbent for different applications.
[0127] As the catalyst composition is characterized by a uniform spatial distribution of the molecular sieve of crystals in the porous material, this results in the presence of well-dispersed active catalytic sites (evidenced by SEM) in the porous material. The catalyst composition of the present invention alone or in combination with one or more catalytically active substances can have high activity, high selectivity, high stability, or combinations thereof when used as catalysts for a variety of hydrocarbon conversion processes.
[0128] The catalyst composition (as such or after modification with metals or metal oxides: Ga, Zn, Fe, Mo, Ni, Co) can be used for reaction as catalytic pyrolysis of hydrocarbonaceous material originating from biomass or different types of waste to produce fuel, aromatics or olefins. Catalytic improvement by pyrolysis vapors using the catalyst composition is a promising method for removing oxygen from organic compounds and converting them to hydrocarbons.
[0129] In a particular embodiment, catalytic pyrolysis with the catalyst composition is performed as a coprocessing of the raw biomaterial containing oxygen with the fossil raw materials. For example, the aforementioned coprocessing is performed at the FCC unit.
[0130] The hydrocarbonaceous material useful as a raw material for the invention may comprise, for example, a component such as xylitol, glucose (for example, α-D-glucose, β-D-glucose), cellobiosis, cellulose, hemicellulose , lignin, sugarcane bagasse, glucose, wood, and corn straw along with their pyrolysis products and combinations of such components and / or their pyrolysis products.
[0131] Other examples of hydrocarbonaceous materials include, for example, plastic waste, recycled plastics, municipal and agrarian solid waste, food waste, animal waste, carbohydrates, lignocellulosic materials (for example, wood chips or shavings, lignocellulosic biomass, etc.). ), or combinations of these, among others.
[0132] As used in this document, the term “biomass” is given its conventional meaning in the state of the art and is used to refer to any organic source of energy or chemicals that are renewable. Its main components can be (1) trees (wood) and any other vegetation; (2) agricultural products and waste (corn silage, fruit, garbage, etc.); (3) algae and other marine plants; (4) metabolic waste (manure, sewage); and (5) urban cellulosic waste.
[0133] The achievements described in this document also involve chemical process designs used to perform catalytic pyrolysis. In some cases, processes may involve the use of one or more fluidized bed reactors (for example, a circulating fluidized bed reactor, turbulent fluidized bed reactor, bubbling fluidized bed reactor, etc.), or batch reactors including circulating batch reactors (mud reactor).
[0134] The process may involve, in some embodiments, the pyrolization inside a reactor (for example, a fluidized bed reactor) of at least a portion of a hydrocarbonaceous material under sufficient reaction conditions to produce one or more products of the pyrolysis. In addition, the process may involve catalytically reacting at least a portion of the one or more pyrolysis products using a catalyst under sufficient reaction conditions to produce one or more fluid hydrocarbon products. In some embodiments, one or more fluid hydrocarbon products may be produced from said pyrolysis products by dehydration, decarbonylation, decarboxylation, isomerization, oligomerization, and dehydrogenation reactions. The pyrolysis and catalytic reaction processes can occur, in some cases, in a single reactor. Chemical processes can be used, in some cases, to produce a specific hydrocarbon fluid product (for example, aromatics and / or olefins). In some cases, a portion of the olefins produced by the chemical process can be recycled within the supply stream through which the hydrocarbonaceous material is fed to the reactor (for example, the pyrolysis reactor).
[0135] An extra-heavy oil hydrocracking process capable of obtaining light cracked oil with high yields. The process could be carried out in a fixed, fluidized, batch or mud reactor. In the preceding process, the reaction conditions in the reaction step are a reaction pressure of 25-300 Atm; a reaction temperature of 300-500 ° C. Characterization techniques
[0136] With regard to measurements of surface area and porous volume, they are measured via N2 adsorption using usual measurements of surface area. In particular, surface area measurements, such as “BET” measurement, can be used (ie ASTM D3663 for surface area and D4365 for porous volume). Other techniques well known in the prior art can also be considered, such as mercury adsorption techniques (ASTM D4284). All measurements and data plots as used in this document were produced with a Micromeritics® Tristar 3000® analyzer.
[0137] Regarding the measurement of acidity, it is measured by:
[0138] Pyridine adsorption quantified via infrared measurements. The IR spectra were recorded on a Nicolet Magna 550 FT-IR spectrometer with an optical resolution of 4 cm-1, with a zero filling level for the Fourier transform. Before measurements, the catalysts were pressed into self-supporting discs (diameter: 1.6 cm, 10 mg cm2) and activated in the IR cell (connected to a vacuum line) at 723 ° K for 4 h in up to 106 Torr (14132 , 17 Pa). The IR cell was equipped with KBr windows, which made it possible to record spectra in the spectral region below 400 cm-1. The pressure of the adsorbed gases was measured by two Barocel meters, one of which was connected directly to the sample containing the cell compartment. Another made it possible for us to measure the gas dose in the known volume before it was adsorbed inside the cell. The temperature of the sample during the treatment or recording of the spectra was monitored by a chromelalumel thermocouple inserted inside the heater or inside the cooling compartment of the cell. Pyridine adsorption: pyridine (“pyridine” - Py) was performed at 423 ° K. The excess molecules in the probe were additionally evacuated at 423 ° K. The adsorption-evacuation was repeated several times until no changes in the spectra were observed. The amount of Py adsorbed was measured using the extinction coefficient £ 1545 (B-pyridine) = 1.8 cm μmol-1 and £ 1455 (L-pyridine) = 1.5 cm μmol'1. The adsorption of pyridine allowed to quantify the acidic sites of Bronsted and Lewis.
[0139] Measurement of TPD ammonia (TPD NH3), is performed in a fully automated AutoChem II (Micromeritics) equipped with a TCD detector (but not equipped with an IR spectrometer). A Pyrex® ™ cell with approximately 0.4 g of sample to be characterized is placed in an oven and the following steps are performed:
[0140] Activation: this step is performed under a He flow rate of 50 cm3 / min. The temperature is increased from room temperature to 600 ° C with a temperature increase of 20 ° C / min. The temperature is then maintained at 600 ° C for 1h. The temperature is then reduced to 100 ° C with a cooling rate of 10 ° C / min.
[0141] Saturation: this step is performed at 100 ° C. During the first hour, the solid is placed in contact with a flow of 30 cm3 / min of a mixture of 10% by weight of NH3 diluted in He. Then, during the next 2 hours, the solid is brought into contact with a flow rate of 50 cm3 / min of He.
[0142] Analysis: this step is performed under a flow of 50 cm3 / min of He. The temperature is increased to 600 ° C with a temperature increase of 10 ° C / min. Once the temperature of 600 ° C has been reached, this temperature is maintained for 1 hour. The cell is then cooled and weighed. The amount of NH3 deposited on the solid is determined as μmol NH3 absorbed in the temperature range of 100 ° C to 600 ° C of the standardized sample by a weight of the sample taken after the measurement.
[0143] TPD measurements of ammonia can be used to quantify the Bronsted and Lewis acid sites. However, to do this, it is necessary to follow the IR spectra of NH3 adsorbed on the solid. In our case, the TPD measurement unit was not equipped with an IR spectrometer. The quantification of the Bronsted and Lewis sites was performed via measurements of pyridine adsorption.
[0144] With respect to X-ray diffraction measurements, powder X-ray diffraction (XRD) standards were obtained with a PANalytical X'Pert Pro diffractometer using Cu Kα radiation (X = 1.5418 Â, 45 kV, 40 mA). All analyzes were performed using ca. 20 mg of powder loaded on a silicon wafer. The samples were studied in the range of 5 - 50 ° 2θ with a scanning step of 0.0167 ° s-1.
[0145] Regarding the measurement of the quantity of crystal, the measurements of 13C MAS NMR were obtained using a Bruker spectrometer using the following conditions: cross polarization by 13C-1H, 13C (100.6 MHz), 1H (400.3 MHz); Rotation speed = 12.5 kHz, Number of scans = 30k; Spectra were normalized in 30k scans and 20 mg of sample.
[0146] Regarding the catalytic tests, the catalytic cracking of 1,3,5-triisopropyl benzene (TiPBz) was carried out with a conventional atmospheric flow reactor. 20 mg of catalyst was loaded into the center of a stainless steel tubular reactor (internal diameter 12.7 mm, ie ^ inch) and activated in-situ at 460 ° C (increasing from room temperature to 5 ° C / min) under air flow (50 ml / min) for 1 hour and under N2 flow (50 ml / min) for 0.5 hour. The partial pressure of TiPBz (Alfa Aesar ca. 97%) was set at 170 Pa in a saturator maintained at 70 ° C. The mass hourly space velocity (“weight hour space velocity” - WHSV) was kept constant at 8 h-1 for all tests. The activity of the catalyst was evaluated at 300 ° C, exposing it to food for 180 min. The reaction products, transferred through a line heated to 150 ° C to a gas sampling valve, were monitored online by a gas chromatograph equipped with an FID detector.
[0147] Regarding the molecular sieve content deposited in the porous material, it is determined based on the weight loss of the organic model via thermogravimetric analysis (TG-DTA). Once prepared, the catalyst compositions are first exchanged for Na + in order to eliminate loosely bound model molecules. Once exchanged, they are analyzed via thermogravimetry. The weight loss corresponding to the model located inside the molecular sieve is identified in comparison with the thermogravimetric analysis obtained with the corresponding molecular sieve impregnated with the same model. The molecular sieve concentration is obtained by subtracting the weight loss obtained with the catalyst composition, the weight loss obtained with the porous material impregnated with the same model and exchanged for Na + to remove the loosely bound model.
[0148] Regarding thermogravimetric analysis (TG-DTA), it is performed from 30 ° C to 600 ° C at an increase rate of 5 ° K / min under 40 mL / min of air flow, followed by a plateau at 600 ° C for 10 min. The amount of active phase grown in the carrier is determined based on the weight loss of organic models in the temperature range of 350-500 ° C. The actual weight loss was obtained by subtracting the amount adsorbed in the reference sample (that is, the carrier without crystal deposition of molecular sieves).
[0149] As far as Dynamic Light Scattering (DLS) measurements are concerned, they are performed on a Malvern Zetasizer Nano Series DLS instrument. The samples were diluted in excess distilled water in a test cell and all measurements were performed at 25 ° C for 30-180 s.
[0150] Regarding MAS NMR in solid state, it is performed on a Bruker DRX500 spectrometer (27Al at 132.32 MHz, Pulse: 0.1 μsec (pi / 100), relaxation delay: 0.5 sec ). Before measurements, the samples were saturated at room temperature and atmospheric pressure in desiccators for 24 hours with the steam of an aqueous solution of KCl. 27Al MAS NMR measurements were performed using a 4mm probe. Chemical shifts were referenced with a 0.1 M AlCl3 solution (0 ppm). The rotors were rotated at 14.5 kHz. At least 256 scans, depending on the concentration of Al, were acquired for each spectrum. Description of the figures
[0151] Figure 1 shows the XRD standards of the porous material prepared according to example 1.
[0152] Figure 2 shows the NMR 13C spectra of the catalyst composition according to example 1.
[0153] Figure 3 shows the pyridine adsorption measures of the catalyst compositions prepared according to example 1
[0154] Figure 4 shows the catalytic tests of the solids prepared according to example 1
[0155] Figure 5 shows the XRD standards of the materials prepared according to example 4.
[0156] Figure 6 shows the SEM micrographs of the materials prepared according to example 4 after three impregnations of the molecular sieve precursor in the porous material (sample “3 impregnations”).
[0157] Figure 7 shows the quantification of acidic sites measured using pyridine adsorption according to example 4.
[0158] Figure 8 shows the catalytic tests of the solids prepared according to example 1, 3 and 4.
[0159] Figure 9 shows the detailed selectivity of the catalytic tests of the solids prepared according to example 4.
[0160] Figure 10 Correlation of the number of acidic sites measured via pyridine adsorption as a function of crystallization time.
[0161] Figure 11 size of molecular sieve crystal in solution after several tests, measured via Dynamic Light Scattering (DLS).
[0162] Figure 12 Conversion of TiPBz as a function of the number of Bronsted acid sites measured by pyridine adsorption. The conversion was measured after 2 min in current and after 180 min in current (the catalyst slightly deactivated after 180 min in current). On the right side of the graph, TiPBz conversion is shown for Siralox 300 without deposition of the molecular sieve crystal. On the left side of the graph the conversion to commercial nanometer crystals of ZSM-5 is shown.
[0163] Figure 13 27Al MAS NMR spectra according to example 7 of the initial solution, the solution aged after 12h, the matrix in which the siralox 30 is deposited, the matrix being deposited three times with the solution containing the nanometer molecular sieve crystal (nanomolded composite 3). The “composite C144” spectra related to the preparation according to example 2 with a maturation time of 144h. The letter “t” stands for synthesis time. EXAMPLES
[0164] Example 1 (according to the invention) - Preparation of the catalyst composition with a precursor solution being matured before being impregnated in the modified porous material.
[0165] The catalyst composition with the porous material being Siralox TH 30 (Sasol, Al2O3 / SiO2 -70/30% w / w) in which ZSM-5 molecular sieve crystals are dispersed was prepared according to the following procedure.
[0166] The solution containing the molecular sieve precursor (ZSM-5 - 4.5 (TPA) precursor solution 2O: 25 SiO2: 0.25 Al2O3: 430H2O: Si / Al = 50) was prepared by mixing TPAOH (tetrapropylazane hydroxide; CAS [66082-78-8]), H2O, Aluminum sulfate [10043-01-3], and TEOS (tetraethoxysilane; CAS [9044-80-8]). The ingredients were added gradually according to the order mentioned and hydrolyzed at room temperature (RT) for 1 h with vigorous stirring and then closed and stirred for another 3 h. Before its use in the porous material, this solution was matured at 100 ° C for several maturities: 12 h, 36 h, 48 h, 72 h, 96 h, 120 h, 144 h, 168 h, 192 h.
[0167] The porous material used was Siralox TH 30 commercial a Sasol silica-alumina oxide in the spray dried form (~ 40-60 μm) with an AI2O3: SiO2 ratio of 70:30. Before use, it was calcined at 600 ° C for 2 h. This calcination did not alter Siralox 30's amorphous X-ray signature (see figure 1).
[0168] The size of the molecular sieve crystal formed was measured via Dynamic Light Scattering (DLS) after 12h of maturation at 100 ° C. The results are shown in figure 11. The measurement was reproduced for the same sample three times (runs 1, 2 and 3). It appears that the size of the measured crystal is less than 10 nm.
[0169] The 2.95g of Siralox TH 30 calcined at 600 ° C were then impregnated with 10 ml of 0.5% w / w PDDA (Poly (diallyldimethylammonium chloride)) solution. The mixture was stirred on a shaker at a speed of 175 rpm for 2 h at RT. Then the excess water was removed by evaporation overnight (over a 150 ° C oven). The resulting solid was further dried at 100 ° C for 15 min before being used in the synthesis. Then, the Siralox TH 30 impregnated with PDDA is added to the aged precursor solution (from 12h to 192h) and the crystallization is carried out at 100 ° C for 48h (2 days). During this step, the precursors of the zeolite crystals suspended in the solution are attracted and bonded to the surface of the Siralox TH 30 impregnated with PDDA.
[0170] The corresponding samples after the different crystallization times were separated from the solution by filtration followed by drying at 100 ° C and calcination at 550 ° C for 4h to remove the model. Table 1. Synthesis of ZSM-5 / Siralox TH 30 (600 ° C) composite
The samples are identified in this document as 12h, 36h, 48h, 72h, 96h, 120h, 144h, 168h, 192h. Table 2. Quantification of the molecular sieve crystals deposited on the porous material after several crystallization times (Zeolite / Siralox TH 30 (600oC) composite after exchange for Na + (TG data)).
Table 3. BET surface area of the catalyst composition
Such oela 4. TPD NH3 of the catalyst composition

[0171] The XRD spectra do not show any molecular sieve crystals. However, those crystals are evidenced by indirect techniques, in particular by measurements of surface area. An increase in the surface area is evident whereas there is only a very small increase in the microporous volume (from 0.03 to 0.05 cm3g-1). Such an increase in surface area is evidence of the presence of a small crystal in the porous material. It can be concluded, therefore, that the crystals are too small to be detected via XRD. The limit of detection of the crystal size by XRD being 50 nm, the molecular sieve crystals are less than 50 nm. NMR 13C spectra show that the model signature is similar to the model signature within the ZSM-5 crystal. Therefore, there is deposition of ZSM-5 crystals on the porous support.
[0172] Both Bronsted and Lewis acid site concentrations were measured using pyridine adsorption at 150 ° C. The results obtained are shown in figure 10. It appears that both the number of Bronsted and Lewis acid sites increases significantly with crystallization, that is, with the amount of molecular sieve crystal deposited on siralox 30. The concentration of acid site of Bronsted up to 20 μmol / g was obtained with a crystallization time of 144h. Example 2 (according to the invention) - Catalytic testing of materials prepared according to example 1
[0173] TiPBz cracking catalytic tests were performed on the prepared catalyst composition (see figure 4). It seems that the catalyst compositions prepared with a longer crystallization time (more than 36h) have a greater activity than that of the initial Siralox TH 30 (600oC). Without wishing to be linked to any theory, it was interpreted that catalysts with a longer crystallization time have more acidic sites and a more developed surface area (table 3-4). This greater acidity originates from the small molecular sieve crystals deposited on the surface of Siralox TH 30. The catalyst compositions prepared by depositing the crystal of the molecular crystals on Siralox TH 30 show a higher conversion than Siralox TH 30. Example 3 (Comparative) Preparation of the catalyst composition with a precursor solution being matured followed by drying and calcination. No contact with the porous material.
[0174] The molecular sieve precursor solution was prepared by mixing TPAOH (tetrapropylazane hydroxide; CAS [66082-78-8]), H2O, Aluminum sulfate, and TEOS (tetraethoxysilane; CAS [9044-80-8] ). The ingredients were added successively in the order mentioned and hydrolyzed at RT for 3 h with vigorous stirring. Before use, this solution was aged at 100 ° C for 12 h. Dynamic Light Scattering (DLS) shows that particles smaller than 10 nm with a narrow particle size distribution are present in the seed solution aged for 12 h at 100 ° C. The catalyst composition was prepared by evaporating the solution followed by drying at 100 ° and calcination at 550oC for 4h. The sample is identified in this document as Dried Seed. Example 4 (according to the invention) - Preparation of the catalyst composition with a precursor solution being matured before being impregnated in the modified porous material with one or more than one impregnation.
[0175] A series of catalyst compositions with the porous material being Siralox TH 30 (Sasol) in which molecular sieve crystals are dispersed by repeating the deposition step.
[0176] The ZSM-5 precursor solution was prepared by mixing TPAOH (tetrapropylazane hydroxide; CAS [66082-78-8]), H2O, aluminum sulfate, and TEOS (tetraethoxysilane; CAS [9044-80-8 ]). The ingredients were added successively in the order mentioned and hydrolyzed at RT for 3 h with vigorous stirring. Before use, this solution was aged at 100 ° C for 12 h. Dynamic Light Scattering (DLS) shows that particles smaller than 10 nm with a narrow particle size distribution are present in the seed solution aged for 12 h at 100 ° C.
[0177] The porous material used was Siralox TH 30 commercial a Sasol silica-alumina oxide with an Al2O3: SiO2 ratio of 70:30. Before use, it was calcined at 600 ° C for 2 h. This calcination did not alter Siralox 30's amorphous XRD signature (see figure 5).
[0178] In order to obtain Siralox 30 modified with PDDA, 2.95g of Siralox 30 calcined at 600oC were impregnated with 10 ml of 0.5% w / w PDDA solution (Poly (diallyldimethylammonium chloride)). The mixture was stirred on a shaker at a speed of 175 rpm for 2 h at RT. Then the excess water was removed by evaporation overnight (over a 150 ° C oven). The resulting solid was further dried at 100 ° C for 15 min before being used in the synthesis. Siralox TH 30, once impregnated with PDDA, was then impregnated with 1 g of ZSM-5 precursor solution added dropwise to 0.5 g of the impregnated Siralox 30. The obtained mixture was then dried overnight in the open air and then at 100 ° C for 2h.
[0179] Then, the impregnation of ZSM-5 precursor solution is repeated up to three times using the same procedure. Before characterization, the solid was calcined under air at 550 ° C for 4h.
[0180] The consequently prepared solids were characterized via XRD (see figure 5). XRD patterns show that the solid retains an amorphous pattern. Similarly, the dried seed also has an amorphous DRX pattern.
[0181] SEM micrographs of the prepared material (see figure 6) demonstrate that the Siralox TH 30 matrix is coated with seeds with an average diameter of about 10 nm. SEM research also shows random shape and size of aggregates obtained by drying the seed particles. The SEM micrograph in Figure 6 illustrates that after three impregnations with ZSM-5 precursor solution, the surface matrix of Siralox TH 30 (600 ° C) is coated with seed crystals.
[0182] Pyridine adsorption was also measured (see figure 7) demonstrating that the number of acidic sites increases with the number of impregnations. There is, therefore, an increase in the amount of active phase present.
[0183] The samples are identified in this document as “1 impregnation” or “3 impregnations”. Example 5 - catalytic testing of materials prepared according to example 3
[0184] TiPBz cracking catalytic tests were performed on the prepared catalyst composition (see figure 8). Even the material prepared by impregnating Siralox TH 30 exhibits greater activity than dried seeds (comparative example) and Siralox TH 30 without impregnation. The material prepared according to example 1 also exhibits greater activity than dried seeds (comparative example). The technical advantage of dispersing such seeds in a porous material is, therefore, the greater activity and the easy handling of the materials that contain seeds. In addition, having the active sites dispersed in such a matrix also allows for easier formulation of the material.
[0185] The selectivity of the catalysts in the cracking of TiPBz is shown in figure 9. With the catalyst impregnated three times (example 3), the selectivity for benzene and cumene is greater in relation to the sample prepared according to example 1. This means that the different preparation procedure allows to adjust the catalyst design in relation to the selectivity for secondary cracking reaction.
[0186] The impact of the amount of Bronsted acid sites on TiPBZ conversion is shown in Figure 12. It appears that when the concentration of Bronsted site increases, TiPBZ conversion increases. There is, therefore, an advantage in using the catalyst composition prepared according to the example compared to pure Siralox 30. When pure MFI-90 (ZSM-5) is used, the number of Bronsted acid sites is significantly higher, but the conversion decreases. This is due to the low accessibility of acidic sites when pure MFI-90 is used. The composition according to the invention therefore allows to increase the conversion of bulky molecules such as TiPBZ. Example 6 (according to the invention) - on the treatment of the extruded body.
[0187] The preparation of the catalyst composition with a precursor solution being matured before being impregnated in the modified porous material.
[0188] A catalyst composition with a porous material being extruded 1.5 mm Siralox 30 cylinders (Sasol, Al2O3 / SiO2 -70/30% w / w) in which ZSM-5 molecular sieve crystals are dispersed was prepared from according to the procedure described in example 1 using the 144h maturation time. The sample in which the ZSM-5 is impregnated has the suffix - C144. 5 g of sample was used for the synthesis and the amount of the reagent was adjusted proportionally to the amount of the support. The surface area and acidic sites measured in the obtained catalyst composition are summarized in Table 5. Table 5. Extruded Siralox 30 impregnated with ZSM-5 molecular sieve crystals.


[0189] It appears that the crystal impregnation of ZSM-5 according to the invention allows to increase the surface area of the already formed catalyst. Example 7 - characterization of the various catalysts by MAS NMR 27Al
[0190] The catalyst compositions were also characterized via MAS NMR 27 Al. In fact, the 27Al MAS NMR allows determining the coordination and local structure of aluminum species in zeolites since each 27Al site can be readily resolved based on its distinctly different chemical shifts (δ). Figure 13 shows the 27Al MAS NMR spectra of the composites and their precursors. The 27Al NMR spectrum of the initial solution shows a characteristic peak signal of 51.3 ppm aluminum tetrahedrally coordinated (AlIV) in which the aluminum atoms are integrated within the silicon tetrahedral structure with a quadruple coordination. After 12 h aging at 100 ° C, some octahedrally coordinated aluminum (AlVI) are also present in the aged precursor as indicated by the peak with a chemical shift of ca. -0.7 ppm.
[0191] The 27Al NMR spectrum of the parent matrix (Siralox 30; 600 ° C) displays signals at 6.6 and 63.4 ppm which are attributed to Al atoms octahedrically and tetrahedrically coordinated, respectively. The 27Al NMR spectra of the catalyst compositions (C144 and nanomolded composite 3) showed some differences when compared with the spectrum of the parent matrix; the tetrahedrally coordinated aluminum signal is shifted to a higher field.
[0192] Nanomolded composites exhibit a peak at δ = 53.4 ppm wide and of low intensity of AlIV, which expands with the crystallization time (that is, 6 days or 144 h), moving in the direction of δ = 55.4; the latter peaks have a stronger profile than the first peak, thus indicating a more defined coordination of the Al atom within the zeolite structure, which is a consequence of crystalline growth in the C144 composite.
[0193] The molecular sieve crystals deposited on the siralox matrix cannot be evidenced by XRD. They are, in fact, too small to be detected via XRD. However, they can be evidenced via 27Al NMR as the peak at δ = 53.4 ppm of AlIV demonstrates the presence of tetrahedrally coordinated Al aluminum characteristic of crystallized molecular sieve.
[0194] The increase in surface area, the absence of XRD signature and the presence of tetrahedric coordinated aluminum demonstrate that very small crystals of molecular sieve are deposited on the surface of the siralox matrix.

权利要求:
Claims (8)
[0001]
1. Catalyst composition comprising an amorphous porous inorganic material with pore diameters of at least 2 nm and containing Al2O3 and SiO2 with an atomic ratio Al / Si> 1, and molecular sieve crystals, where - the molecular sieve crystals have a maximum diameter not greater than 50 nm measured using Scanning Electron Microscopy; - the catalyst composition has a concentration of acid sites ranging from 50 to 1200 μmol / g measured by Desorption with Programmed Temperature of ammonia, TPD NH3 according to the measurement protocol indicated in the specification; and - a powder X-ray diffraction pattern of the aforementioned catalyst composition obtained using Cu Kα radiation is the same as the X-ray diffraction pattern of the said inorganic porous material, it does not have the characteristic X-ray bands of the molecular sieve; characterized by the fact that - the catalyst composition contains a concentration of Bronsted acid sites of at least 10 μmol / g measured by pyridine desorption at 150 ° C quantified by Infrared Spectroscopy according to the measurement protocol indicated in the specification; - the catalyst composition contains up to 30% by weight of molecular sieve crystals in relation to the total weight of the catalyst composition; - the catalyst composition has a surface area of at least 250 m2 / g, measured using ASTM D3663; - the catalyst composition has a Vtotal / Vmicro ratio of at least 5, with Vtotal meaning the total porous volume of the catalyst compositions and Vmicro meaning the microporous volume of the catalyst compositions, both being measured via ASTM D4365.
[0002]
2. Catalyst composition according to claim 1, further characterized by the fact that one or more of the following are true: - the surface area is at least 300 m2 / g, more preferably at least 350 m2 / g measured using ASTM D3663; - the Vtotal / Vmicro ratio is greater than 10, with Vtotal meaning the total porous volume of the catalyst compositions and Vmicro meaning the microporous volume of the catalyst compositions, both being measured via ASTM D4365.
[0003]
Catalyst composition according to any one of claims 1 to 2, further characterized by the fact that the said inorganic porous material has pores with a mesoporous volume and / or macroporous volume and the molecular sieve crystals that have pores with a microporous volume, the ratio of The mentioned microporous volume over the mesoporous and / or macroporous volume varies from 0.2 to 0.005, the mentioned volumes being determined using the ASTM D4365.
[0004]
Catalyst composition according to any of claims 1 to 3, characterized in that the catalyst compositions additionally comprise one or more of: - phosphorus; - at least one metal selected from the group: B, Cr, Co, Ga, Fe, Li, Mg, Ca, Mn, La, Ti, Mo, W, Ni, Ag, Sn or Zn, Pt, Pd, Ru, Re , Os, Au or any combination thereof; - at least one binder selected from silica, silica-alumina, metal silicates, metal oxides such as ZrO2 and / or metals, amorphous aluminum phosphate or silica aluminum phosphates, gels including mixtures of silica and metal oxides, amorphous aluminum phosphate or any combination of these .
[0005]
Catalyst composition according to any of claims 1 to 4, characterized in that the molecular sieve crystals have a pore diameter of less than 2 nm, preferably in the range of 0.5 to 0.12 nm.
[0006]
Catalyst composition according to any of claims 1 to 5, further characterized in that said molecular sieve crystals are of the MFI type, preferably of the ZMS-5 type.
[0007]
Catalyst composition according to any of claims 1 to 6, further characterized by the fact that said porous inorganic material contains elements other than Si, O, Al with a concentration below 500 ppm by weight.
[0008]
8. Use of catalyst compositions as defined in any one of claims 1 to 7 characterized by the fact that it is applicable in: - Fluid catalytic cracking reactions - catalytic pyrolysis of biomass, waste, plastic derivatives or their co-processing with conventional fossil raw materials - hydrocracking of heavy hydrocarbons or extra-heavy raw materials - olefin oligomerization reactions - conversion of oxygenated molecules to olefins, gasoline, aromatics or distillates - olefin cracking into lighter olefins - catalytic cracking of C4-C12 paraffins - isomerization reactions - reform gasoline - alkylation reactions - alcohol dehydration reactions to the corresponding olefins - dehydrogenation reactions.

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KR102262349B1|2021-06-08|

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法律状态:
2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-01-12| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-16| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13175185.1|2013-07-04|

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EP13175185|2013-07-04|

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PCT/EP2014/064149|WO2015001004A1|2013-07-04|2014-07-03|Catalyst compositions comprising small size molecular sieves crystals deposited on a porous material|

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