RU2777362C2 - Controlled alkaline treatments on molecular sieves - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: group of inventions relates to a method for performing controlled alkaline treatments of inorganic porous solid particles, in particular to a method for increasing the meso-porosity of zeolite, which consists of one treatment followed by a solid separation stage, such as a filtration stage, zeolite treated by the specified method, a method for preparing a technical catalyst, and the use of treated zeolite or a technical catalyst prepared using the specified method in catalysis processes or in adsorption or ion exchange processes. The method for increasing the meso-porosity of zeolite includes stages of: a) preparation of zeolite in the amount m _s ; b) preparation of a base in the total amount m _b,total ; and c) contact and interaction of this zeolite with the base in the amount of m _b (t) in an aqueous solution at a temperature from a room temperature to 100°C and pH from at least 10 to at most 14, wherein the base is continuously added to zeolite for a period of time Δt for the total amount of the base m _b,total of at least 15 s, thereby obtaining treated zeolite. Moreover, the maximum value m _b,max /m _s of the amount of the base m _b (t) brought into contact with inorganic porous solid m _s at any time t at the stage c) is less than m _b,total /m _s , wherein the total amount of the base m _b,total is provided in the form of solid alkali or alkaline solution, and where the maximum value m _b,max of the amount of the base m _b (t) at any given time t at the stage c) is at most 0.75*m _b,total . The method for preparing a technical catalyst contains stages of: preparation of treated zeolite by the specified method; addition of one or more additional ingredients to form a mixture, and molding of this mixture into a macroscopic mold in order to obtain a technical catalyst.

EFFECT: development of an efficient process leading to excellent physicochemical and catalytic properties and not adversely affecting the size of particles and crystals.

16 cl, 5 tbl, 41 ex, 11 dwg

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

The present invention relates generally to a process for performing controlled alkaline treatments on inorganic porous solids resulting in excellent physicochemical and catalytic properties and without adversely affecting particle and crystal size. Accordingly, the solid particles thus obtained can be easily recovered from the alkaline solution.

BACKGROUND OF THE INVENTION

Zeolites are microporous oxide aluminosilicate structures that have well-defined porous structures due to the high degree of crystallinity. Crystalline aluminosilicate zeolites can be of natural or synthetic origin. In protonic form, crystalline aluminosilicate zeolites are usually represented by the formula H _x Al _x Si _1-x O ₂ where "H" is the (exchange) proton that balances the electrovalence of the tetrahedron. The number of exchangeable protons is referred to as the cation exchange capacity (CEC). The exact type of aluminosilicate zeolite structure is usually identified by the specific molar ratio of silicon to aluminum (Si/Al) as well as the pore sizes of the cell structures. The micropore size (usually in the range of 0.4-1 nm) can be indicated by the number of T-atoms at the smallest diameter of the so-called "multi-membered rings" (MR). Using this definition, the most common industrial zeolites have 8-MR, 10-MR or 12-MR micropores. Zeolite structure can also be obtained using phosphates in addition to silica and alumina, giving rise to the crystalline microporous silicoaluminophosphate (SAPO) class. In addition to this, when silica is absent, crystalline microporous aluminophosphates (AlPO) are formed. SAPO and AlPO have, like zeolites, unique porous and acidic properties that provide them with large-scale industrial applications in catalysis, adsorption and ion exchange.

Recently, hierarchical (mesoporous) zeolites, SAPO and AlPO have received much attention due to their potential advantages in catalysis due to their high external surface area, reduced diffusion lengths, and open active sites. The introduction of a secondary network of mesopores (typically in the range of 2-50 nm) leads to significant changes in material properties that affect the performance of zeolites in traditional applications such as catalysis and separation. The number of available active sites increases rapidly with increasing material porosity. Additionally, hierarchical zeolite crystals have reduced diffusion paths compared to conventional microporous zeolites, AlPO or SAPO. Accordingly, these materials have achieved excellent performance in many catalytic reactions such as cracking, alkylation and isomerization.

Hierarchical zeolites can be made using a wide variety of ascending and descending procedures. Bottom-up procedures imply a change in the hydrothermal synthesis of zeolites, for example through the use of organic templates or an increase in crystallization time. However, the most commercially attractive option is the (downward) postsynthetic modification of conventional commercially available microporous zeolites. The key treatment in this category is the application of basic (alkaline) treatment, the so-called "desiliconization". This approach entails contacting zeolites in alkaline aqueous solutions to give hierarchical zeolites by removing a portion of the solid to create intracrystalline or intercrystalline mesopores. Basic processing allows you to convert almost any ordinary zeolite into its more advanced hierarchical counterpart. In addition, for SAPO and AlPO, basic treatments lead to better catalysts.

In addition to the goal of forming mesopores and thereby creating hierarchical crystalline materials, alkaline treatments can also be performed to wash out unwanted phases from two-phase materials. For example, NaOH leaching can be used to remove unwanted ZSM-5 impurities from ZSM-22 zeolites. In addition, basic leaching can be used to selectively leach elements from materials containing a wide variety of elements. For example, when applied to zeolites, the main leach is selective for silicon. On the other hand, when applied to SAPO, the main leach is selective mainly for phosphorus. Thus, the basic treatments make it possible to adjust, in addition to (meso)porosity, other physicochemical properties of the resulting material, such as the overall composition, the distribution of elements in crystals and acidity.

Basic treatments are performed by direct addition of the zeolite to an aqueous base solution, typically at a high pH (>12), and hence a high base concentration (eg >0.1 M NaOH). This procedure is followed by filtration, usually performed by Buchner filtration. For 10-MR zeolites, for example, with a framework topology such as MFI, FER, TON, using only an inorganic base (usually NaOH) is usually sufficient in alkaline treatment. However, for 12-MR zeolites, such as FAU or BEA topology zeolites, it may be necessary to add an organic such as tetrapropylammonium bromide (TPABr) or diethylamine to the alkaline solution to maintain the intrinsic properties of the zeolite, such as crystallinity, acidity, and microporosity. SAPO and AlPO are in most cases more sensitive than zeolites and require the use of (inorganic) salt-free alkaline solutions prepared with amines or TPAOH in order to obtain better solids.

Alkaline (basic) treatments are often performed as one treatment within a sequence of postsynthetic modifications. For example, to prepare a hierarchical Y zeolite with higher catalytic properties, a sequence of 3 consecutive acid-base-acid treatments can be performed. Alternatively, for clinoptilolite (natural zeolite), a sequence of 6 successive treatments (acid 4 times, base, acid) is known. Additionally, two treatments (base-acid) are known for ZSM-5 and ZSM-22. After each individual treatment, filtration and drying steps are required. In most cases, an acid treatment prior to the main treatment effectively removes aluminum from the zeolite framework, thereby improving the efficiency of the subsequent main treatment. On the other hand, the acid treatment performed after the main treatment has been described as a mild acid wash aimed primarily at removing aluminum contaminants from the outer surface. These aluminum contaminants are formed during the previous caustic treatment. The efficiency of the acid wash is therefore closely related to the efficiency of the previous alkaline treatment.

In addition to the aforementioned advantages of basic leaching, several serious disadvantages of basic leaching should be emphasized. First, the use of organic matter should be avoided whenever possible, as it must be removed by incineration. Not only does this process destroy expensive organics, but it is also necessary to carefully take care of the resulting combustion products, which in itself is an expensive procedure. Simple amines, such as diethylamine, used as a base for leaching 12-MR zeolites (beta and USY), AlPO and SAPO, can be easily recovered due to their high volatility, which increases their industrial appeal. However, the use of tetraalkylammonium (TAA) cations such as TPABr and cetyltrimethylammonium bromide (CTABr) is preferably avoided because they are more expensive and must be removed by heat treatment generating unwanted fluxes such as CO ₂ , NO _x , H ₂ O and /or explosive organics. Therefore, it is necessary to reduce the use of organics in every possible way, especially TAA.

Secondly, base leached zeolites, even under optimal conditions described in the literature with organic molecules, generally show greatly improved mesoporosity. However, quite often they can also show an undesirable decrease in zeolite properties. Representative examples of this are crystallinity, Brønsted acidity and microporosity. This reduction has been reported for most hierarchical or mesoporous zeolites, as shown in Table A in the Examples section.

An important recent development has been the realization that, in addition to the amount of secondary porosity, the quality of the pores is also of paramount importance. It has been observed that especially in zeolites with a high silica content (Si/Al> about 10) the main leach can produce mesopores that are (partially) cavitated. In this case, the greater the cavitation, the smaller the catalytic benefits. Therefore, at a constant surface or volume of mesopores, the smallest degree of their cavitation is desirable.

Finally, the main treatment can give a pronounced reduction in the size of the zeolite crystal. This decrease is due to fragmentation, which can give rise to fragments in the size range of 5-100 nm. They are colloidally stable particles that are very difficult to separate using conventional porous membrane filtration techniques and require the use of expensive commercial separation techniques such as high speed commercial centrifuges. Accordingly, zeolite slurries after the main leach are often extremely difficult to filter, as shown in Table A in the Examples section.

Therefore, it is desirable to provide a more efficient process that would give the same basic leaching effect (improved mesoporosity) but would produce solids with higher zeolitic properties, reduced cavitation, reduced organic additives and/or retained crystal size. . In addition, such an improved process would preferably have the same or reduced number of associated steps, overall process time, and amount of wastewater generated. The resulting materials may have improved properties for the preparation of technical catalysts or for use in catalysis, adsorption or ion exchange processes.

SUMMARY OF THE INVENTION

In accordance with the purpose of the present invention, it broadly refers to a method for performing alkaline treatment of inorganic porous solids, giving excellent physico-chemical (zeolite) and catalytic properties. These superior properties can be a combination of improved mesoporosity with higher Brønsted acidity, higher microporosity, higher mesoporosity, higher crystallinity, higher aluminum framework fraction, reduced mesopore cavitation, larger crystal size, and/or combinations of the above.

In one aspect, the present invention relates to a process for preparing a treated inorganic porous solid comprising a series of separate treatments (z) that are separated by a solid separation step, such as a filtration step, with each of the z treatments comprising the steps of:

a) preparing an inorganic porous solid in the amount of m _s ;

b) preparation of the base in the total amount m _b,total ; and

c) contacting and reacting this inorganic porous solid with a base in an amount m _b (t) in solution for a time Δt for a total amount of base m _b,total ;

thereby obtaining a treated inorganic porous solid;

wherein the maximum amount of base m _b,max m _b (t) brought into contact with the inorganic porous solid m _s at any time t in step c) is less than m _b,total /m _s . The total amount of base may be provided in the form of solid alkali or alkaline solution, preferably alkaline solution.

In some preferred embodiments, the maximum amount of base m _b,max m _b (t) at any particular time t in step c) is at most 0.75* m _b,total , preferably at most 0.50* m _b,total , and even more preferably at most 0.25* m _b,total .

In some preferred embodiments, the implementation of the inorganic porous solid contains a molecular sieve, such as zeolite or SAPO.

In some preferred embodiments, step a) comprises:

a') preparation of an inorganic porous solid in the amount of m _s suspended in a solution, preferably in water.

In some preferred embodiments, the method comprises a number (x) of base additions per treatment that are not separated by a solids separation step, such as a filtration step, and the amount of base added per addition ( m _b,i, where i=1.. .x ) is characterized in that x is at least 2, preferably at least 3, and even more preferably at least 4.

In some preferred embodiments, z is equal to 1.

In some preferred embodiments, the rate of addition of this amount of base is at most 3.0 mmol/g/min, preferably at most 1.0 mmol/g/min, and even more preferably at most 0.5 mmol/g/min.

In some preferred embodiments, the base is continuously added to the inorganic porous solid during the time interval Δt, the time interval Δt for adding the total amount of base m _b,total is at least 15 seconds.

In some preferred embodiments, this method is followed by sequential acid treatment.

In one aspect, the present invention relates to a treated inorganic porous solid obtained using a method in accordance with any of the aspects and embodiments described herein.

In one aspect, the present invention relates to a zeolite with a faujasite topology, preferably prepared according to the method in accordance with any of the aspects and embodiments described herein, with a unit cell size in the range from 24.375 Å to 24.300 Å, with a mesopore volume of at least 0 .35 ml/g, and also characterized by one or more of the following features:

- Brønsted acidity, measured with pyridine, at least 400 µmol/g;

- the proportion of Al in the frame is at least 0.5; and/or

- crystallinity of at least 75% compared to standard NaY zeolite, and at least 90% compared to standard NIST alumina (SRM 676).

In one aspect, the present invention relates to a zeolite with a faujasite topology, preferably prepared according to the method in accordance with any of the aspects and embodiments described herein, with a unit cell size of at most 24,300 Å, with a mesopore volume of at least 0.35 ml / d, and also characterized by one or more of the following features:

- micropore volume of at least 0.22 ml/g;

- crystallinity of at least 95% compared to commercial NaY zeolite, and at least 130% compared to standard NIST alumina (SRM 676);

- mesopore cavitation ratio, measured by nitrogen adsorption, at most 1.6; and/or

- with a particle size D _eff of at least 350 nm.

In one aspect, the present invention relates to an MFI topology zeolite, preferably prepared according to the method according to any of the aspects and embodiments described herein, with a Si/Al molar ratio of at most 400, with a mesopore volume of at least 0.30 ml /g and a crystallinity of at least 330% compared to standard NIST alumina (SRM 676).

In one aspect, the present invention relates to a process for preparing a technical catalyst comprising the steps of:

- preparing a treated inorganic porous solid according to any of the aspects and embodiments described herein, or preparing a porous solid according to any of the aspects and embodiments described herein;

- adding one or more additional ingredients to form a mixture, in which, preferably, one or more additional ingredients are selected from the group including: fillers, pyrogens, binders, lubricants, and combinations thereof; and

- shaping this mixture into a macroscopic form in order to obtain an industrial catalyst, where the macroscopic form preferably has a minimum size of at least 1 μm to at most 10 cm.

In one aspect, the present invention relates to the use of a treated inorganic porous solid in accordance with any of the aspects and embodiments described herein in catalysis, adsorption, or ion exchange processes.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from the detailed description which follows and the accompanying drawings, which are given by way of illustration only and thus are not intended to limit the present invention, and in which:

Fig. 1 depicts a general process diagram. Typically, a base is first added to a fixed volume of water, after which a porous solid is added and the reaction is carried out with vigorous mechanical agitation. On FIG. 1, however, shows multiple additions and/or multiple treatments. On FIG. 1 x is the number of base additions per reaction, m ₁ ( m _b ) is the amount of base added at one time, y is the number of solid additions per reaction, m ₂ (m _s ) is the amount of solid added per once, and z is the number of treatments. In the prior art, x, y, and z are 1. In additional embodiments, y and m ₂ ( m _s ) are not modified in this detailed description.

Fig. 2 shows the implementation of the contact of the porous solid with the base using a longitudinal arrangement. In this configuration, a porous solid is located on the membrane and a (diluted) base solution comes into contact with it as it passes (f) through the solid-coated membrane.

Fig. 3 shows a plug flow reactor in which a suspension of solid in water (f1) is fed together with a base (f2) into a tubular reactor. This configuration results in base contact as in a batch reactor, hence in accordance with the prior art.

Fig. 4 shows a plug flow reactor in which a suspension of solid (f1) is passed through a tube. However, unlike the prior art (described in Fig. 3), the base (f2) is added in several stages (x) as a function of position (and thus time), allowing the solid to react with the base gradually or step by step.

Fig. 5 shows a continuously stirred reactor in which the solid remains in the reactor where it reacts with a constant flow of base (f) in and out.

Fig. 6 illustrates a graph that shows a) the DLS-determined effective diameter ( D _eff ) of alkali-treated USY zeolites versus the amount of NaOH used per amount of zeolite ( m _b,total/ m _s ) according to the prior art (squares) and the present invention (circles); and b) filtration time ( t _F ) of alkali-treated USY zeolites as a function of DLS-determined effective diameter ( D _eff ) in accordance with the prior art and the present invention.

Fig. 7(a) shows a general flow diagram of a process in accordance with one embodiment of the present invention. The total mass of the solid m _s is added to the water. Then the total base mass m _b,total is added, where:

x=number of base additions during processing,

z=number of treatments (for example 1),

m _b =mass of base added per addition,

m _b,total = total mass of base to react with solid,

m _s = m _s,total = total mass of solid to react with base,

C=constant.

Fig. 7(b) shows the maximum amount of base ( m _b,max ) in contact with the porous solid ( m _s ) at any time (t) during treatment with the total amount of base ( m _b,total ). In the current state of the art, the zeolite is added one time to the alkaline solution, giving a theoretical value of m _b,max / m _s equal to m _b,total / m _s . However, the zeolite cannot be instantly and uniformly suspended in an alkaline solution. Accordingly, the experimental values of m _b,max / m _s significantly exceed the values of m _b,total / m _s . By gradually adding a base to an aqueous solution containing zeolite, in accordance with the embodiments of the present invention, the theoretical values of m _b,max / m _s become significantly smaller compared to the values of m _b,total / m _s . In addition, since the base is thus slowly and uniformly dissolved in the zeolite slurry, the experimental values of m _b,max / m _s are even lower than theoretical ones.

Fig. 8 illustrates the effect of alkaline treatments on mesopore volume ( Vmeso ), _Brönsted acidity, crystallinity and _micropore volume ( Vmicro ) in accordance with the state of the art (SA) and the present invention (IP).

Fig. 9 illustrates the effect on zeolite properties as a function of the desired introduction of secondary porosity ( V _meso ) using the current state of the art (SA) or technology in accordance with the present invention (IP).

Fig. 10 illustrates mesoporosity cavitation after introduction of secondary _{porosity ( Vmeso} ) using the state of the art (SA) or base leaching technology in accordance with the present invention (IP).

Fig. 11 illustrates BJH mesopore distributions obtained from nitrogen adsorption isotherms for standard untreated ZSM-5 zeolite (original) as well as base-contacted ZSM-5 zeolites derived from it in accordance with Comparative Example 11 (SA) and Example 22 (IP ). The pore width is indicated using a logarithmic scale.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE PRESENT INVENTION

The following detailed description is exemplary in nature and is not intended to limit the present invention, its application or use. In addition, the present invention is not bound by any theory presented in the previous section "prior art" or in the subsequent section "Detailed Description".

The following detailed description of the present invention refers to the accompanying drawings. Like reference numerals throughout the various drawings identify the same or like elements. In addition, the following detailed description does not limit the present invention. Instead, the scope of the present invention is defined by the appended claims, as well as their equivalents.

Several documents are cited throughout the text of this specification. Each of these documents (including any manufacturer's specifications, instructions, etc.) is hereby incorporated by reference into this document; however, there is no guarantee that any document cited is indeed prior art of the present invention.

The present invention will be described with reference to specific embodiments and with reference to some drawings, but the present invention is not limited to this, but only by the claims. The drawings described are only schematic and are not limiting. In the drawings, some of the elements may be exaggerated and not to scale for illustrative purposes. Sizes and relative dimensions are shown not to scale.

In addition, the terms "first", "second", "third", etc. in the description and in the claims are used to distinguish between like elements, and not necessarily to describe sequential or chronological order. It should be understood that the terms used in this way are interchangeable under appropriate circumstances, and that the embodiments of the present invention described herein may operate in other sequences than those described or illustrated herein.

In addition, the terms "top", "bottom", "above", "under", etc. in the description and in the claims are used for descriptive purposes and not necessarily to describe relative positions. It should be understood that the terms used in this manner are interchangeable under appropriate circumstances, and that the embodiments of the present invention described herein may operate in other orientations than those described or illustrated herein.

It should be noted that the term "comprising"/"comprising" used in the claims should not be interpreted as being limited to the means listed after it; it does not exclude other elements or steps. Thus, it is to be interpreted as defining the presence of the claimed features, integers, steps, or components, as mentioned, but does not preclude the presence or addition of one or more of the other features, integers, steps, or components, or groups thereof. Thus, the scope of the expression "device containing means A and B" should not be limited to devices consisting only of components A and B. It only means that for the present invention, the only relevant components of the device are A and B.

Reference in the text of this specification to "one embodiment" and the like. means that a particular feature, structure, or characteristic described in connection with that embodiment is included in at least one embodiment of the present invention. Thus, the phrase "in one embodiment" throughout this specification does not necessarily refer to the same embodiment, although it may. In addition, specific features, structures, or characteristics may be combined in any suitable manner, obvious to a person skilled in the art from this disclosure, in one or more embodiments.

Similarly, it should be understood that in the description of exemplary embodiments of the present invention, its various features are sometimes grouped in one embodiment, drawing or description for the purpose of simplifying the disclosure and facilitating understanding of one or more different aspects of the present invention. This mode of disclosure, however, should not be interpreted as reflecting that the claimed invention requires more features than are expressly stated in each claim. Instead, as the following claims reflect, aspects of the present invention lie in less than all of the features of the single prior disclosed embodiment. Thus, the claims following the Detailed Description are hereby expressly included in this Detailed Description, and each claim stands on its own as a separate embodiment of the present invention.

In addition, while some embodiments described herein include some and not other features included in other embodiments, any combination of features of different embodiments are within the scope of the present invention and form different embodiments, which should be understood by those skilled in the art. For example, in the following claims, any of the claimed embodiments may be used in any combination.

Numerous specific details are set forth in the foregoing description. However, it is contemplated that embodiments of the present invention may be practiced without these specific details. In other cases, well-known methods, structures, and techniques are not described in detail in order not to complicate the understanding of this description.

Other embodiments of the present invention will be apparent to a person skilled in the art upon consideration of this description and implementation of the invention disclosed in this document.

This description and examples are exemplary only.

Each claim is included in the description as an embodiment of the present invention. Thus, the claims are an additional part of the description and are in addition to the preferred embodiments of the present invention.

Each of the claims formulates one particular embodiment of the present invention.

Specific and preferred aspects of the present invention are set forth in the independent and dependent claims of the appended claims. The features of the dependent claims may be combined with the features of the independent claims and with the features of other dependent claims, as the case may be, and not just as expressly stated in the claims.

Thus, the claims following the Detailed Description are hereby expressly included in this Detailed Description, and each claim stands on its own as a separate embodiment of the present invention.

The following terms are provided solely to facilitate understanding of the present invention.

Used in this application, the term "room temperature" means a temperature in the range of 12-30°C, preferably in the range of 16-28°C, more preferably in the range of 17-25°C and most preferably in the range of about 20-23°C.

Used in this application, the term "molecular sieve" refers to a solid substance with pores of the size of the molecules. This includes, but is not limited to, microporous and mesoporous materials, AlPO and (synthetic) zeolites, columnar or non-columnar clays, clathrasyls, clathrates, carbon molecular sieves, mesoporous silica, silica-alumina (e.g., type MCM-41 with ordered system pores), microporous titanosilicates such as ETS-10, urea and corresponding carrier substances, and porous metal oxides. Molecular sieves may have a multimodal pore size distribution, also referred to as ordered ultramicropores (typically less than 0.7 nm), supermicropores (typically in the range of about 0.7-2 nm), or mesopores (typically in the range of about 2-50 nm).

One specific type of molecular sieve suitable for the present invention are silica molecular sieves, more specifically silica zeolites, zeolites and/or amorphous microporous silica materials. Among the solids known to date, those with uniform channels, such as zeolites represented by porous crystalline aluminum silicates and porous crystalline aluminum phosphates (AlPO), are defined as molecular sieves because they selectively adsorb molecules smaller than the inlet size. into the channel, or allow molecules to pass through the channel. From the point of view of crystallography, zeolites are completely crystalline substances in which the atoms and channels are completely regular. These fully crystalline molecular sieves are naturally produced or synthesized through hydrothermal reactions. The number of varieties of fully crystalline molecular sieves obtained or synthesized to date is several hundred. They play an important role as catalysts or supports in the modern chemical industry due to their characteristics including selective adsorption, acidity and ion exchange capacity. Molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline silicates. These silicates can be described as a rigid three-dimensional framework of SiO ₄ and oxides of group 13 elements of the periodic table, such as AlO ₄ , in which the tetrahedra are crosslinked by sharing oxygen atoms, whereby the ratio of group 13 and group 14 atoms, such as silicon, to oxygen atoms becomes 1:2. Crystalline microporous silica polymorphs represent the composite end members of these families of composite materials. These silica molecular sieves do not have a cation exchange capacity.

A "zeolite" can be defined as a crystalline material whose chemical composition includes essentially aluminum, silicon and oxygen. Generally, zeolites are described as aluminosilicates with a three-dimensional framework and molecular-sized pores. It has previously been demonstrated that zeolites, both natural and synthetic, have catalytic properties for various types of hydrocarbon conversion. Some zeolite materials are ordered, porous, crystalline aluminosilicates having a well defined X-ray diffraction crystal structure, within which there are a large number of smaller cavities that may be interconnected by a series of even smaller channels or windows. These cavities and pores are uniform in size within a particular zeolite material. Since these pores are sized to adsorb certain sized molecules and not adsorb large sized molecules, these materials are known as "molecular sieves" and are used in a variety of ways to take advantage of these properties. As used in the disclosure of the present invention, the term "zeolite" can also mean any mineral from the group of structured aluminosilicate minerals containing cations such as sodium and calcium, or less often barium, beryllium, lithium, potassium, magnesium and strontium; characterized by the formula H _x Al _x Si _1-x O ₂ where H can be replaced by any other monovalent cation or (when the x factor of H is divided by the valency) by a multivalent cation. The term "zeolite" also refers to an open tetrahedral framework capable of ion exchange and low retention of water molecules, which provides reversible dehydration. The term "zeolite" also includes "zeolite-related materials" or "zeotypes", which are obtained by replacing Si ⁴⁺ or Al ³⁺ ions with other elements, as in the case of aluminophosphates (for example, MeAPO, SAPO, ElAPO, MeAPSO and ElAPSO ), gallophosphates, zinc phosphates, titanosilicates, etc. The zeolite can be a crystalline porous material with a framework as described in US2013/0118954 or provided in the IZA Structure Committee Zeolite Framework Types Database, where they are designated by the following framework types (from which framework density can also be derived) defined by the International Zeolite Association such as ABW type, ACO type, AEI type, AEL type, AEN type, AET type, AFG AFI type, AFN type, AFO type, AFR type, AFS type, AFT type, AFX type, AFY type, AHT type, ANA, APC type, APD type, AST type, ASV type, ATN type, ATO type, ATS type, ATT type, ATV type, AWO type, AWW type, BCT type, BEA type, BEC type, BIK type, BOG type, BPH type, BRE type, CAN type, CAS type, CDO type, CFI type, CGF type, CGS type, CHA type, CHI type, CLO type, CON type, CZP type, DAC type, DDR type, DFO type, DFT type , DOH type, DON type, EAB type, EDI type, EMT type, EON type, EPI type, ERI type, ESV type, ETR type, EUO type, EZT type, FAR type, FAU type, FER type, FRA type, GIS, GIU type, GME type, GON type, GOO type, HEU, IFR type, IHW type, IMF type, ISV type, ITE type, ITH type, ITW type, IWR type, IWV type, IWW type, JBW type, KFI type, LAU type, LEV type, LIO type, LIT type, type LOS, type LOV, type LTA, type LTL, type LTN, type MAR, type MAZ, type MEI, type MEL, type MEP, type MER, type MFI, type MFS, type MON, type MOR, type MOZ, type MSE , MSO type, MTF type, MTN type, MTT type, MTW type, MWW type, NAB type, NAT type, NES type, NON type, NPO type, NSI type, OBW type, OFF type, OSI type, OSO type, OWE, PAR type, PAU type, PHI type, PON type, RHO type, RON type, RRO type, RSN type, RTE type, RTH type, RUT type, RWR type, RWY type, SAO type, SAS type, SAT type, SAV type, SBE type, SBN type, SBS type, SBT type, SFE type, SFF type, SFG type, SFH type, SFN type, SFO type, SGT type, SIV type, SOD type, SOS type, SSF type, SSY type , STF type, STI type, STO type, STT type, SZR type, TER type, THO type, TOL type, TON type, TSC type, TUN type, UEI type, UFI type, UOZ type, USI type, UTL type, VET, VFI type, VNI type, VSV type, WEI type, WEN type, YUG type and ZON type. The term "zeolite" also includes "zeolite-related materials" or "zeotypes" obtained by replacing Si ⁴⁺ or Al ³⁺ ions with other elements, as in the case of aluminophosphates (for example, MeAPO, AlPO, SAPO, ElAPO, MeAPSO and ElAPSO), gallophosphates, zinc phosphates, titanosilicates, etc.

In general, porous substances are classified according to their pore size, for example, porous substances with a pore size of less than 2 nm are classified as microporous substances, porous substances with a pore size between 2 and 50 nm are classified as mesoporous substances, and porous substances with a pore size greater than 50 nm are classified as macroporous substances. Non-zeolitic mesoporous silicas such as MCM-41 and SBA-15 can have significant microporosity. This type of microporosity, however, is "random" and not well defined, and should not be considered zeolitic. The microporosity defined in the embodiments of the present invention results primarily from zeolite micropores related to the framework topologies. For example, for USY zeolites with faujasite topology, microporosity is obtained by well-defined micropores of 0.74 nm, for beta zeolite with BEA topology, microporosity is obtained by well-defined 0.6 nm pores, and for ZSM-5 zeolite with MFI topology, microporosity obtained by well-defined 0.55 nm pores.

Those porous materials that have uniform channels, such as zeolite, are defined as molecular sieves. To date, several hundred types have been found and synthesized. Zeolites play an important role as catalysts or carriers in the modern chemical industry due to their characteristics, including selective adsorption, acidity, and ion exchange.

A number of ordered mesoporous materials, including MCM-41 and MCM-48, have been described in US Pat. MCM-41 has a uniform structure having a hexagonal arrangement of straight mesopores, such as honeycombs, and has a specific surface area of approximately 1000 m ² /g, measured using the conventional Brunauer-Emmett-Teller (BET) method. Existing molecular sieves have been produced by using inorganic or organic cations as templates, while ordered mesoporous materials are synthesized with liquid crystal template using surfactants as templates. These ordered mesoporous materials have the advantage that their pore sizes can be controlled in the range of 1.6 nm - 10 nm by controlling the types of surfactants or synthesis conditions used during the manufacturing process. Ordered mesoporous materials, referred to as SBA-1, -2 and -3, have been described in Science (1995) 268:1324. Their channels are arranged regularly, while the constituent atoms have an arrangement similar to that of amorphous silica. Ordered mesoporous materials have regularly spaced channels larger than existing zeolites, thus allowing them to be used for adsorption, isolation, or catalytic transformation reactions of relatively large molecules.

In general, the present invention relates to a process for controlled alkaline treatment of inorganic porous solids, such as crystalline solids, without adversely affecting the size of the particles or crystals, to obtain an end product of solid particles with higher physicochemical and catalytic properties. The process of the present invention can produce solids that are easily recovered from the caustic solution after treatment. In one particular embodiment, this process comprises stepwise contacting of the solid with the base, which largely prevents fragmentation. As a result, particle and crystalline pore sizes can be obtained that are more similar to those in the initial solid. In addition to higher physicochemical properties, higher catalytic properties, and improved filtration behavior, the present invention reduces the amount of organics required to maintain microporosity, crystallinity, and acidity during alkaline leaching.

As used herein, the term "framework Al" refers to tetrahedral coordinated Al.

In the examples, the filtering time is referred to as " t _F ". It should be understood that this amount refers to the time it takes to separate the solid from the 97% by volume alkaline solution using standard Buchner filtration. More specifically, this refers to the filtration of a suspension of solids using a Buchner filtration with a paper filter (Whatman #4 or #5 filter with a diameter of 9 cm). Filtration time is affected by both process conditions (reaction time, reaction temperature, solid to liquid ratio, amount of base, type of base, additives such as TPABr, conventional alkali treatment or alkali treatment according to the present invention), processing scale, and filter used (Whatman #4 or #5). Accordingly, these parameters are specified for all these examples. Processing time ( t _P ) refers to the total time it takes to perform alkaline processing and subsequent filtration. In the case of multi-stage treatment, the total processing and filtration time is increased by the time of the drying stage between filtration and subsequent alkaline treatment.

The properties of solids can be assessed using nitrogen adsorption at 77K as it is a known technique for quantifying zeotype properties (relevant for crystalline microporous solids) as well as the amount of mesopores in a solid. The first characteristic that is obtained from the nitrogen isotherm is the total surface area ( S _BET ). It is obtained by using the BET model and reflects the total porosity (micropores and mesopores) of solids. The properties of the zeotypes can be examined using the microporosity ( V _micro ) that results from applying the t-plot to the adsorption branch of the isotherm, preferably applied within the thickness range of 0.35-0.50 nm. Since the active sites (Brønsted sites described below) are located in the micropores, it is preferable that after the alkaline postsynthetic modification, the micropore volume remains as close to the micropore volume of the original zeolite as possible.

Nitrogen sorption measurements were performed at -196°C using a Micromeritics TriStar 3000 instrument controlled by TriStar 3000 software (Micromeritics) version 6.03. Before the experiment, the samples were degassed overnight in a stream of N ₂ when heated to 300°C (5°C/min). The t-plot method described in Microporous Mesoporous Mater., 2003, 60, 1-17 was used to distinguish between micro- and mesopores (thickness range=0.35-0.50 nm, using the Harkins-Jur thickness equation and the coefficient density conversion=0.0015468). For accurate comparison of solids microporosity obtained from a t-plot, it is preferred that the same t-plot method, thickness range, and thickness equation be used. For example, if the t-plot is applied in a narrow range at high relative pressures (eg p / p ₀ =0.30-0.35), the resulting microporosity may be overestimated. The t-plot method simultaneously produces an outer surface (referred to as " S _meso ") which is used as an indication of the degree of secondary porosity.

For pore size distribution, the BJH model described in Microporous Mesoporous Mater. 2003, 60, 1-17, applied to the adsorption branch of the isotherm. The total volume of the pore space ( V _pore ) was determined at relative pressure ( p / p ₀ =0.98). The mesopore volume ( V _meso ) is defined as V _meso = V _pore - V _micro . The occlusion or cavitation ratio is defined as the ratio of the slopes of points measured on the adsorption and desorption branches of nitrogen isotherms (slope _ads /slope _des ) between relative pressures p / p ₀ 0.82 and 0.87. The further the desorption branch deviates from the adsorption branch, the higher this ratio becomes. Therefore, high hysteresis/occlusion may be associated with a high cavitation ratio, which is undesirable in catalytic applications. Therefore, it is desirable that the cavitation ratio be as small as possible.

When the inorganic porous solids are crystalline, zeolites, SAPO, or AlPO, property retention can be examined using X-ray diffraction (XRD). This technique produces topology-specific reflection patterns. Relative crystallinity, indicative of overall zeotypic properties, can be assessed by integrating several characteristic peaks using methods such as those described in ASTM D3906 (for faujasite zeolites) and ASTM 5758 (for ZSM-5 zeolites). It is preferred that the alkali treated sample show as high a crystallinity relative to the original crystalline inorganic solid as possible. In the case of faujasites, the relative crystallinity is compared to Zeolyst's industry standard NaY zeolite (supplier code "CBV 100"). In addition, the relative crystallinities of zeolites are quantified by comparison with NIST standard alumina (SRM 676). This is achieved by comparing the NIST standard 2θ 25.7° peak area with the 15.7° 2θ peak area for FAU zeolites, or with the 7.7° 2θ peak area for BEA zeolites, or peak area at an angle of 2θ in the range from 23.1 to 24.3° for ZSM-5 zeolites. XRD is also a useful research technique because it allows the unit cell size to be determined. Particularly in the case of faujasites, the unit cell size is relevant as it provides information on the composition (Si/Al atomic ratio) of the framework. The unit cell size is obtained using established methods as defined in ASTM 3942. X-ray diffraction was measured on a Siemens D5000 diffractometer with Bragg-Brentano geometry and nickel-filtered Cu Kα radiation (λ=0.1541 nm). The data were recorded in the range of 2θ angle values of 5-50° with a step of 0.05° and a counting time of 8 s per step.

Another way to control the influence of postsynthetic processing is the method of spectroscopy using magic angular scanning nuclear magnetic resonance (MAS NMR). This technique probes the coordination of T-atoms (Al and Si). In the case of aluminum, it is generally assumed that the tetrahedrally coordinated zeolite framework species are in the range of 40 ppm to 80 ppm, while the partially pentahedrally coordinated framework species are in the range of 10 ppm to 40 ppm, and octahedrally coordinated outside the framework species are contained in the range from 10 ppm to -40 ppm (AngewandteChemie, 1983, 22, 259-336). Accordingly, it is important that in order to achieve the highest degree of zeolite properties during postsynthetic modifications, the relative amount of tetrahedral coordinated species is the highest. In the case of silicon coordination, the MAS NMR technique makes it possible to estimate the number of Al atoms with which the average Si atom is coordinated (AngewandteChemie, 1983, 22, 259-336). This number ranges from 0 (a state in which there are no neighboring Al atoms, referred to as "Si(0Al)") to complete coordination of Al (a state with 4 neighboring Al atoms, referred to as "Si(4Al)"). In the alkaline treatment of USY zeolites, it is most preferable to maintain the highest amount of Si(0Al) species, since in this case the desired hydrothermal stability of the framework is maintained.

EXPERIMENTAL MAS NMR spectra for ²⁹ Si and ²⁷ Al were obtained on Bruker Avance III spectrometers with frequencies of 400 and 700 MHz, operating at 9.4 and 16.4 T, respectively, and with Larmor frequencies of ²⁹ Si and ²⁷ Al 139.1 and 182.4 MHz, respectively. All samples were packed in 4 mm ( ²⁷ Al) and 7 mm ( ²⁹ Si) ZrO ₂ rotors. MAS NMR spectra for ²⁹ Si were recorded with a dual resonant probe at a rotation speed of 5 kHz using a pulse width (with a deflection angle of 45°) of 3.4 μs, which corresponds to a radio frequency (rf) field of ~ 37 kHz. The recirculation delay was set to 60 s and the number of scans from 500 to 1000 was used in all samples. The MAS NMR spectra for ²⁷ Al were recorded using a double resonant probe at a rotation speed of 14 kHz. Quantitative spectra were obtained using a π/18 (~0.3 µs) radio frequency pulse calibrated with an aqueous solution of Al(NO ₃ ) ₃ corresponding to a 104 kHz radio frequency field. The recirculation delay was set to 1 s and the number of scans from 9000 to 15000 was used in all samples. Chemical shifts are reported in parts per million from octakis(trimethylsiloxy)silsesquioxane (-109.68 ppm, for the farthest downside frequency peak) and aqueous Al(NO ₃ ) ₃ (0 ppm) for ²⁹ Si and ^27Al , respectively.

Most of the uses of the inorganic porous solids described herein are acid-catalyzed transformations. In this case, the type and number of acid sites are extremely important. In order to quantitatively monitor the acidic properties of solid particles, a commonly used technique is Fourier transform infrared (FTIR) spectroscopy of pyridine adsorbed on these solid particles. This method makes it possible to determine the number of strong Brønsted sites (B) and weaker Lewis acid sites (L) existing within the solid. In zeolite and SAPO catalytic applications, the number of Brønsted acid sites is the key to their efficient performance. Since the main purpose of modification by alkali treatment is to improve porosity, maintaining the Brönsted center density after alkali treatment is mandatory. In addition, Brønsted acidity can be measured using temperature-programmed NH ₃ -TPD desorption.

FTIR measurements with pyridine were performed using a Nicolet 6700 spectrometer equipped with a DTGS detector. Before measurements, the samples were pressed into self-supporting plates and degassed at 400°C for 1 hour in a vacuum. Acid sites according to Brønsted and Lewis were analyzed using a pyridine probe. After evacuation, the samples were exposed to 4-5 pulses of pyridine at a pressure of at least 25 mbar at 50°C for 1 min (until saturation), after which the system was heated to 150°C for 40 min, followed by the acquisition of spectra at the same temperature. Absorption at wavelengths of 1550 and 1450 cm ^-1 corresponded to the number of acid sites according to Brønsted and Lewis, respectively. Attenuation coefficients were determined in accordance with Emeis, J. Catal. 1993, 141, 347-354.

Temperature programmed desorption (TPD) signals of NH ₃ from particulates were obtained using custom settings in which 100 mg of sample was first pretreated at 400°C in a helium atmosphere (20 cm ³ /min) for 1 hour (at a rate of 10° C/min). Then 5% NH ₃ in helium (20 cm ³ /min) was adsorbed at 200° C. for 30 minutes followed by helium purge for 30 minutes at the same temperature (20 cm ³ /min). Desorption was observed on a Pfeiffer Omnistar quadrupole mass spectrometer in the range of 200–700°C (10°C/min) in a helium flow (10 cm ³ /min). Catalytic efficiency was monitored in α-pinene isomerization as it is a suitable model reaction in which both a function of internal zeotypic properties and a function of external surface appear. In this reaction, activity (A) refers to the degree of conversion, while productivity (P) is the yield of useful products (limonene, camphene, α-terpinene, γ-terpinene, terpinoline, p-cymene). The P/A ratio makes it possible to compare selectivities: higher P/A values mean lower amounts of undesirable by-products such as cokes (α-pinene polymers and oligomers). The P/V _meso value is the ratio of productivity to secondary porosity. Accordingly, it is a measure of the effectiveness of the secondary porosity.

Experimental catalysis: The isomerization reactions were carried out in a 50 cm ³ Parr reactor with a sampler at 150° C. under nitrogen at a pressure of 6-8 bar with a stirring speed of 750 rpm. A mixture of substrate (20 g; α-pinene) and catalyst (0.1 g) was heated to 100°C, after which the first liquid sample was taken. The reaction mixture was then further heated to 150°C and samples were taken 10, 30 and 60 min after the first sample. These samples were then analyzed on a gas chromatograph (HP 5890, Hewlett Packard) equipped with an HP1 column and a flame ionization detector (FID). Tetradecane was used as an external standard. Unidentified products were analyzed by gas chromatography - mass spectrometry (GC-MS) (6890N instrument, Agilent Technologies). The activity of the samples was determined by using the slope of the linear part of the graph of the dependence of the conversion of α-pinene from contact time.

In addition to physicochemical properties and associated catalytic efficiency, the recoverability of zeolites from aqueous solutions is a key parameter for the economic viability of solid particles, especially when prepared (and modified) in aqueous solutions. Therefore, when applying post-synthetic modifications in aqueous solutions, such as alkali treatment, it is required that, in addition to the desired physico-chemical improvements, the particle size distribution is not impaired. To date, the effect of alkaline treatments on particle and crystal size distribution and associated recoverability is unknown in the current state of the art. The present inventors have found that alkaline treatments of porous inorganic solids such as zeolites, SAPO and AlPO, and ordered mesoporous materials such as MCM-41 and SBA-15 have a significant effect on particle and crystal size of the inorganic solid. Alkaline treatments greatly reduce the average size of particles and crystals, complicating their recovery. As a result, filtration of inorganic porous solids using membrane techniques such as Buchner devices can take up to 100 times longer. This is economically disadvantageous and limits the commercial potential of prior art alkali-treated zeolites.

Particle size measurements were performed by placing a portion of the suspension obtained after alkaline treatment in a standard polystyrene cuvette (2.5 ml) and subjecting it to dynamic light scattering (DLS) analysis. Accordingly, the supernatant of the centrifuged (15 min at 12,000 rpm) suspension was measured in polystyrene cuvettes on a 990Plus Particle Size Analyzer (Brookhaven) equipped with a 659 nm laser with a detection angle of 90°. The scattered light intensity fluctuations were correlated between 10 ms and 5 s. Correlation functions were analyzed using the Igor Pro 6.2 software, using the Clementine package for modeling decay kinetics based on the maximum entropy method. The damping time was converted to hydrodynamic diameters using the Stokes-Einstein equation. The resulting measure for size is expressed as an effective diameter ( D _eff ), which is a weighted average of the hydrodynamic diameter of the particles in the sample. They are calculated from the diffusion coefficient measured with DLS.

According to a first aspect, the present invention relates to a process for preparing a treated inorganic porous solid comprising a number of separate treatments (z) separated by a solid separation step, such as a filtration step, each of the z treatments comprising the steps of:

a) preparing an inorganic porous solid in the amount of m _s ;

b) preparing the total amount of base m _b,total ; and

c) contacting and reacting this inorganic porous solid with the amount of base m _b (t) in solution for a time Δt for the total amount of base m _b,total ;

thereby obtaining a treated inorganic porous solid;

wherein the maximum amount of base m _b,max m _b (t) in contact with the inorganic porous solid m _s at any time t in step c) is less than m _b,total /m _s . The total amount of base may be provided in the form of solid alkali or alkaline solution, preferably alkaline solution.

In some preferred embodiments, this process includes a process for preparing a treated inorganic porous solid that comprises a single treatment (z=1) comprising the steps of:

a) preparing an inorganic porous solid in the amount of m _s ;

b) preparing the total amount of base m _b,total ; and

c) contacting and reacting this inorganic porous solid with the amount of base m _b (t) in solution for a time Δt for the total amount of base m _b,total ;

thereby obtaining a treated inorganic porous solid;

wherein the maximum amount of base m _b,max m _b (t) in contact with the inorganic porous solid m _s at any time t in step c) is less than m _b,total /m _s . The total amount of base may be provided in the form of solid alkali or alkaline solution, preferably alkaline solution.

In some embodiments, this process comprises stepwise contacting of the solid with the base, which largely prevents fragmentation. As a result, particle and crystalline pore sizes can be obtained which are similar to those in the initial solid.

In addition to higher physicochemical properties, higher catalytic properties, and improved filtration behavior, the present invention reduces the amount of organics required to maintain microporosity and crystallinity during alkali leaching.

The ratio m _b,max / m _s can be considered as the maximum amount of base that comes into contact with the solid at any given time. In the current state of the art (where y, x, z=1) the addition of the base to the solvent during processing ( t _mb ) occurs before the addition of the inorganic porous solid ( t _ms ) to the solvent during the same processing. Therefore, in the current state of the art, t _mb < t _ms . The zeolite powder takes several minutes to be suspended in an aqueous solution. This means that when the zeolite is added after the base ( t _mb < t _ms ), the initially suspended zeolite fraction is exposed to the total amount of base, ie m _b,max /m _s >>m _b,total /m _s .

In some preferred embodiments, the maximum amount of base m _b,max m _b (t) at any time t in step c) is at most 0.75* m _b,total , preferably at most 0.50* m _b,total . and even more preferably at most 0.25* m _b,total .

In some preferred embodiments, the implementation of the inorganic porous solid contains a molecular sieve, such as zeolite or SAPO.

In some embodiments, the inorganic porous solid is a zeolite material, preferably with a structure like MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, RTH AEL, AFI, CHA, DON, EMT, CFI, CLO , TON, FER, ERI, MEL, MTW, MWW, HEU, EUO, RHO, LTL, LTA, MAZ, and most preferably with the topology MOR, MFI, BEA, FAU, and this zeolite material becomes mesoporous after processing. This method or process may start with crystalline silicates, in particular those having a zeolitic structure, which are subjected to an alkaline treatment, and a new material with zeolitic properties and mesoporosity is obtained without high speed commercial centrifuges or eliminating filtration steps between treatments. These mesoporous zeolite materials can thus be prepared in an environmentally and economically advantageous manner.

In some embodiments, this method or process may start with amorphous silicate, such as fumed silica, and/or ordered silicas, such as MCM-41 or SBA-15.

In some preferred embodiments, step a) comprises:

a') providing an inorganic porous solid in the amount of m _s suspended in solution, preferably in water.

Preferably this solvent is water. In some embodiments, other solvents are used, such as alcohols (methanol, ethanol, or isopropanol). Typical solutions are aqueous solutions with a pH value varying from at least 10 to at most 14, corresponding to NaOH concentrations of 0.0001 M to 1 M. The solid to liquid ratio (inorganic porous solid to liquid base) can vary from very low, 1 g/l, to very high, 100 g/l, but in the examples it is usually equal to 33 g/l. The temperature may vary from at least room temperature to at most 100°C, preferably from at least 50°C to at most 70°C.

When adding base to a suspension of zeolite, for example in water ( t _mb > t _ms ), non-instantaneous mixing/dissolution of the base implies that the initial value of m _b,max /m _s <m _b,total /m _s .

In some embodiments, the base is added in multiple discrete steps. The inorganic porous solid does not separate between these steps. In some preferred embodiments, this method comprises a number of base additions per treatment (x) that are not separated by a solid separation step, and the amount of base added per addition ( m _b,i where i=1..x ) is characterized by that x is not equal to 1 and preferably is at least 2, more preferably at least 3, and even more preferably at least 4.

In some preferred embodiments, z is 1. This means that there is only one treatment followed by a solid separation step, preferably a filtration step. During this processing, the base is added in multiple stages (x≠1), or gradually. In some preferred embodiments, z is greater than 1, such as at least 2, at least 3, or at least 4.

In some embodiments, the implementation of the base is added gradually or continuously. The inorganic porous solid does not separate during this gradual addition. In some preferred embodiments, the rate of addition of this amount of base is at most 3.0 mmol/g/min, preferably at most 1.0 mmol/g/min, and even more preferably at most 0.5 mmol/g/min.

The rate of base addition over time may depend on the processing used. However, very good solids can be obtained by maintaining this value below 3.0 mmol base per gram of zeolite per minute (mmol/g/min), preferably below 1.0 mmol/g/min, and most preferably below 0.5 mmol. /g/min

The base addition rate, as mentioned in some of the examples, may be scale sensitive as it is not normalized to the amount of zeolite. It can be normalized to a unit expressed in moles of base per gram of zeolite per hour. In some embodiments, for example as demonstrated in Example 17 (3.3 g of zeolite in 90 ml of solvent to which 10 ml of 2M NaOH is added using a syringe pump), a suitable range is 5-150 ml/h, the preferred range is 10- 50 ml/h, and the most preferred range is 15-30 ml/h.

In some preferred embodiments, the base is continuously added to the inorganic porous solid over a time interval Δt, wherein the time interval Δt for adding the total base m _b,total is at least 15 s, preferably at least 30 s, such as at least 60 seconds, such as at least 2 minutes, such as at least 4 minutes, such as at least 8 minutes, such as at least 15 minutes, such as about 30 minutes. In some embodiments, Δt is at least 8 minutes and at most 60 minutes, preferably at least 15 minutes and at most 45 minutes, such as about 30 minutes.

In some preferred embodiments, this method is followed by sequential acid treatment. This has the advantage that the mesopore surface and volume, micropore volume, crystallinity and acidity are improved much better than in the current state of the art.

In some embodiments, additives may be added gradually, like the base. Such additives may be metal salts such as Al(NO ₃ ) ₃ and Ga(NO ₃ ) ₃ as well as organic compounds such as TPABr.

The effect of the present invention compared to the current state of the art may depend on the nature of the samples. Among other things, the topology density of the zeolite framework can have the greatest influence. In this case, the lower topological density results in greater benefits. Therefore, the benefits on FAU framework zeolites (density 13.3 T atoms/1000 Å ³ ) are greater than those on BEA framework zeolites (density 15.3 T atoms/1000 Å ³ ). Similarly, the benefit on BEA backbone zeolites can be greater compared to MFI backbone zeolites (18.4 T-atoms/1000 Å ³ ).

In addition, in the case of zeolites, the Si/Al ratio in the framework (and in the bulk) may be important. For example, in the case of preventing fragmentation and the associated increase in filtration time, the effect will be optimal when the Si/Al atomic ratio is 5 or more, preferably 10 or more, and most preferably 20 or more. This is demonstrated in Table A, where the filtration time of alkali treated USY zeolites increases rapidly with increasing Si/Al ratio of the parent zeolite.

In some embodiments, the present invention comprises a process for performing an alkaline treatment of inorganic porous solids resulting in higher physicochemical and catalytic properties without adversely affecting (or with limited adversely affecting) particle or crystal size. The use of the present invention produces solid particles that can be easily recovered from the alkaline solution after treatment. In some embodiments, this process comprises stepwise contacting of the solid with the base, which largely prevents fragmentation. The result is particle and crystalline pore sizes that are similar to those in the initial solid. In addition to higher physicochemical properties, higher catalytic properties, and improved filtration behavior, the present invention reduces the amount of organics required to maintain microporosity and crystallinity during alkali leaching.

As illustrated by various examples, the process of the present invention can be carried out by multiple lower alkalinity treatments with base dosing steps during the alkaline treatment or by pumping a diluted alkaline solution through a solid-containing membrane. After such treatments, the filtration time can be significantly reduced, thereby improving the overall performance of the leaching process.

In some embodiments, the reactor is then rapidly cooled, the solid is filtered off (using a Buechner laboratory device) and washed. Fig. 1 depicts the general scheme of a process in which a base is usually added first, followed by a porous solid, and the reaction is carried out with vigorous mechanical agitation. On FIG. 1 x is the number of base additions per reaction, m _b is the amount of base added at one time, y is the number of solid additions per reaction, m _s is the amount of solid added at one time, and z is the amount processing. In the prior art, x, y, and z are 1. In additional embodiments, y and m _s are not modified in this detailed description.

In order to emphasize the significance of the present invention, it is important to describe the current state of the art in alkaline solids leaching experimental procedures. In the current state of the art, a fixed amount of a porous solid (typically 33 g/l) is contacted with an aqueous solution having a fixed alkalinity. This is achieved by direct immersion of the solid in a hot caustic solution (usually using NaOH, at _0.24 m _b,total / ms and 65°C) followed by reaction (usually within 30 min).

In some embodiments, the alkaline treatment is performed exactly as in the current state of the art, eg as described above, except that the alkalinity is reduced and the treatment is repeated to achieve the desired leaching effect. It is possible, for example, that instead of one reaction at a value of m _b,total / m _s 0.24, two reactions are performed at a value of m _b,total / m _s 0.12. The present inventors have found that the filtration time of these two combined treatments can be significantly shorter than the filtration time after a single higher concentration direct treatment. On FIG. 1 difference between the current state of the art is the value of x is equal to 1, while z is equal to 2 (or more). In addition, the value of x * m _b * z is the same in the present invention and in the current state of the art. This means that the same total amount of base is contacted with the porous solid as is recommended to provide the desired leaching effect.

In some embodiments, the base is slowly added in solid or highly concentrated form during processing. The present inventors have found that this can be easily achieved using a pump such as a syringe or peristaltic pump. On a larger scale, industrial pumps or solids dispersers may be used. This approach has the advantage that only one treatment is required for the same significantly reduced filter times. In particular, in this embodiment, the efficiency of using TPABr or DEA to maintain the internal zeolite properties is greatly improved. The present invention goes beyond the current state of the art, which is supported by several arguments. First, the solid is added before the base is added. Secondly (see Fig. 1), the value of z is equal to 1, while the value of x is equal to 2 (or more). Keeping x * m _b constant ensures that the same amount of base will react with the solid.

In some embodiments, the method comprises stepwise contacting a solid with a base using a continuous configuration. In this configuration, a porous solid can be located on the membrane and a (diluted) base solution is contacted while passing (f) through the solid-coated membrane (see FIG. 2). On a laboratory scale, such an experiment can be performed using a continuous microfiltration device. This configuration is not similar to the known linear synthesis (see Fig. 3) because in this work the base is pumped together with the solid, hence allowing them to react in a displacement mode, which gives the same materials as the batch reactor used in the prior art. However, if base is added in steps in this in-line setup (see FIG. 4), solid and base no longer react as in a batch reactor. Instead, it acts as described for the innovative process: the solid is staggered into contact with the base, resulting in higher quality solids. In addition, the base may be contacted with the zeolite in a continuous mixing reactor (see Fig. 5), or in any other configuration that provides gradual or incremental contact of the solid with the base.

In the second aspect, the present invention relates to an inorganic porous solid obtained using the method in accordance with the first aspect, or any variant of its implementation. Preferred embodiments of these treated inorganic porous solids have been defined above.

In a third aspect, the present invention relates to a zeolite with a faujasite topology, preferably prepared by the method according to the first aspect or any embodiment thereof, with a unit cell size ranging from 24.375 Å to 24.300 Å and a mesopore volume of at least 0.35 ml /G. Typically, the unit cell becomes smaller when the Al framework is removed. This type of zeolite is commonly referred to as USY-I zeolite.

In some preferred embodiments, the implementation of the zeolite in accordance with the third aspect has a Brönsted acidity of at least 400 μmol/g, measured with pyridine; preferably 425 µmol/g or more, and most preferably 500 µmol/g or more.

In some preferred embodiments, the zeolite according to the third aspect has an Al framework fraction of at least 0.5, preferably 0.55 or more, and most preferably 0.60 or more.

In some preferred embodiments, the zeolite according to the third aspect has a crystallinity of at least 70%, preferably 75% or more, and most preferably 80% or more relative to the standard NaY zeolite, and at least 80%, preferably 90% or more, and most preferably 100% or higher compared to NIST standard alumina (SRM 676).

In some preferred embodiments, the zeolite according to the third aspect has a microporosity of at least 0.18 ml/g, preferably 0.21 ml/g or greater, and most preferably 0.24 ml/g or greater.

In a fourth aspect, the present invention relates to a faujasite topology zeolite, preferably prepared by the method according to the first aspect or any embodiment thereof, with a unit cell size of at most 24,300 Å, preferably with a mesopore volume of at least 0.35 ml/g . This type of zeolite is commonly referred to as USY-III zeolite.

In some preferred embodiments, the zeolite according to the fourth aspect has a micropore volume of at least 0.21 ml/g, preferably 0.22 ml/g or greater, and most preferably 0.23 ml/g or greater.

In some preferred embodiments, the zeolite according to the fourth aspect has a crystallinity of at least 95%, preferably 100% or more, and most preferably 105% or more relative to the standard NaY zeolite, and at least 130%, preferably 137% or more, and most preferably 142% or higher compared to NIST standard alumina (SRM 676).

In some preferred embodiments, the zeolite according to the fourth aspect has a nitrogen adsorption-measured mesopore cavitation of at most 1.6, preferably 1.5 or less, most preferably 1.4 or less.

In some preferred embodiments, the implementation of the zeolite in accordance with the fourth aspect has a particle size D _eff at least 300 nm, preferably 350 nm and above, and most preferably 400 nm and above.

In a fifth aspect, the present invention relates to an MFI topology zeolite, preferably prepared according to the method of the first aspect or any embodiment thereof, with a Si/Al molar ratio of at most 400, with a mesopore volume of at least 0.30 ml/g and a crystallinity of at least 330%, preferably 340% or more, and most preferably 350% or more compared to NIST standard alumina (SRM 676).

In one aspect, the present invention relates to a BEA topology zeolite, preferably prepared according to the method of the first aspect or any embodiment thereof, with a mesopore volume of at least 0.50 ml/g and a crystallinity of at least 500%, preferably 515% and higher, and most preferably 530% and higher compared to standard NIST alumina (SRM 676).

For industrial large scale applications, zeolite powders (as described in the examples) typically need to be converted into commercial catalysts. Technical catalysts are typically designed to provide the required mechanical strength and chemical resistance in order to withstand the operating conditions in industrial catalytic equipment. The conversion of the zeolite powder into a technical catalyst is preferably accomplished by mixing the zeolite with several other ingredients (such as fillers, pyrogens, binders, lubricants, etc.) and then shaping into macroscopic shapes. The resulting technical catalysts can be multicomponent bodies with sizes ranging from micrometers to centimeters.

In a sixth aspect, the present invention relates to a process for preparing a technical catalyst, comprising the steps of:

- preparing a treated inorganic porous solid in accordance with the first aspect of the present invention and preferred embodiments thereof;

- adding one or more additional ingredients in order to form a mixture, in which preferably one or more additional ingredients are selected from the group containing: fillers, pyrogens, binders, lubricants, and combinations thereof; and

- shaping this mixture into a macroscopic form in order to obtain an industrial catalyst, in which the macroscopic form preferably has a minimum size of at least 1 μm to at most 10 cm.

The present inventors have found that the solid particles described above, in particular those of the second, third, fourth and fifth aspects, as well as their preferred embodiments, are ideal intermediates for the preparation of the technical catalyst described above.

In a seventh aspect, the present invention relates to the use of a treated inorganic porous solid in accordance with any of the aspects described herein, as well as embodiments thereof, in catalysis, adsorption or ion exchange processes. Preferred embodiments of this use have been defined above.

Some embodiments of the present invention are set forth below. These embodiments may also be combined with any of the embodiments described above.

In some embodiments, the present invention relates to a porous solid alkaline leaching process that comprises multiple additions of base per reaction (x), where the amount of base added at one time is ( m _b ), multiple additions of solid per reaction (y) where the amount of solid added at one time is ( m _s ), and multiple treatments (z), and is characterized in that x, y, and z are not equal to 1.

In some embodiments, when x is 1, z is 2 (or higher). In addition, the x * m _b * z value can be adapted to the total amount of base in contact with the porous solid so as to guarantee the desired leaching effect and at the same time avoid fragmentation.

In some embodiments, the process is designed by controlling the values of y, z, or x, preferably z or x, preferably x, such that despite the fact that the porous solid is exposed to the same total amount of base, or that the same total amount base is contacted with a porous solid (which is preferred in order to ensure the desired leaching effect), the alkaline leaching was less strong than subjecting the porous solid at a concentration of 20-40 g/l in aqueous solution to contact with a fixed alkalinity of 0.1- 0.2 M NaOH, usually for about 20-40 minutes.

In some embodiments, the process is designed by controlling the values of y, z, or x, preferably z or x, preferably x, such that even though the porous solid is exposed to the same total amount of base, the alkaline leach is less strong than subjecting the porous solid at a concentration of 20-40 g/l in an aqueous solution to contact with a fixed alkalinity of 0.1-0.2 M NaOH, typically for about 20-40 minutes at a temperature of 45-85°C.

In some embodiments, the process is designed by controlling the values of y, z or x, preferably z or x, preferably x, such that despite the fact that the porous solid is exposed to the same total amount of base, no fragmentation of the components of the porous solid occurs. substances.

In some embodiments, the process is designed by controlling the values of y, z, or x, preferably z or x, preferably x, such that although the porous solid is exposed to the same total amount of base, essentially no fragmentation of the components occurs. porous solid.

In some embodiments, the porous solid is crystalline and the process is designed by controlling the values of y, z, or x, preferably z or x, preferably x, such that despite the fact that the porous solid is exposed to the same total amount of base, basically no crystal fragmentation occurred.

In some embodiments, the process comprises alkaline leaching of the porous solid at a concentration of 5-60 g/l, preferably 20-40 g/l by subjecting the porous solid to several treatment reactions with moderate NaOH conditions at a temperature of 40-70°C, preferably 60- 75°C for 10-50 min, preferably 20-40 min, this treatment regimen containing z treatments of NaOH in the amount of m _b so as to have the same consumed amount of NaOH as one treatment with 0.15- 0.25M NaOH.

In some embodiments, the porous solid is a porous silicate solid.

In some embodiments, the silicate solid is a group topology material consisting of MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, RTH AEL, AFI, CHA, DON, EMT, CFI, CLO, TON, FER, ERI, MEL, MTW, MWW, HEU, EUO, RHO, LTL, LTA and MAZ.

In some embodiments, the silicate solid is a group topology material consisting of MOR, MFI, BEA, and FAU.

In some embodiments, the silicate solid is a porous crystalline silicate.

In some embodiments, the silicate solid is a porous crystalline silicate having a zeolite structure.

In some embodiments, the silicate solid is amorphous, such as fumed silica or silica gel.

In some embodiments, the porous solid is an amorphous aluminosilicate.

In some embodiments, the silicate solid is a porous ordered silicate (eg MCM-41 or SBA-15).

In some embodiments, the porous solid is an ordered aluminosilicate (eg MCM-41).

In some embodiments, the porous solid is a porous amorphous (silico)aluminophosphate.

In some embodiments, the porous solid is porous crystalline (silico)aluminophosphate (eg AlPO-5, SAPO-11, SAPO-34).

In some preferred embodiments, the implementation of the present invention contains any of the following numbered formulations. These numbered statements may be combined with any other embodiment in the claims and description. The reference to formulation 1 in formulations 2-43 may also be replaced by reference to the first aspect of the present invention. The reference to the wording 44 in the words 45-51 can also be replaced by a reference to the second, third, fourth and fifth aspects of the present invention. References in statements 52-55 may also be replaced by reference to the seventh aspect of the present invention.

1. A process for alkaline treatments of inorganic porous solids, characterized in that said process gives higher physicochemical properties and higher catalytic efficiency without adversely affecting particle and crystal size distribution.

2. The method according to formula 1, characterized in that the inorganic porous solids belong to the group consisting of an amorphous solid, an ordered mesoporous solid, a crystalline solid, a solid in the form of silicates, aluminate, phosphate, aluminosilicate, aluminophosphate, and silicoaluminophosphate .

3. Process according to Formula 1, characterized in that the inorganic porous solids are crystalline silicoaluminophosphates.

4. Process according to Formula 1, characterized in that the inorganic porous solids are crystalline aluminosilicates.

5. The method according to formula 1, characterized in that the inorganic porous material before alkaline treatment has a total surface area ( S _BET ) preferably greater than 100 m ² /g, and most preferably greater than 200 m ² /g.

6. The method according to formula 1, characterized in that the inorganic porous solid is a zeolite material or porous crystalline silicate or amorphous porous silicate.

7. Process according to formula 1, characterized in that the solid has a cation exchange capacity of less than 1 mmol/g, and most preferably less than 0.5 mmol/g.

8. The method according to formulation 1, characterized in that the solid has a framework density of less than 18 T-atoms/nm ³ , and most preferably less than 15 T-atoms/nm ³ .

9. Process according to formula 1, characterized in that the solid has an external surface ( S _meso ) before alkaline treatment of greater than 20 m ² /g, and most preferably greater than 50 m ² /g.

10. Process according to formula 1, characterized in that the solid is a zeolite and has a Si/Al atom ratio > 10, and most preferably > 20.

11. The method according to formula 1, characterized in that the solid has a frame topology of AEL, AFI, CHA, DON, EMT, CFI, CLO, TON, FER, ERI, MEL, MTW, MWW, HEU, EUO, RHO, LTL, LTA or MAZ.

12. The method according to formula 1, characterized in that the solid has a frame topology of MOR, MFI, BEA or FAU.

13. A process according to any one of Formulas 1-12, characterized in that the base is an inorganic base.

14. A process according to any one of Formulas 1-12, characterized in that the base is an inorganic base of the group consisting of NH ₄ OH, NaOH, KOH, and LiOH.

15. A process according to any one of Formulas 1-12, characterized in that the base is an organic base or an organic additive.

16. A process according to any one of Formulas 1-12, characterized in that the base is an organic base or an organic additive from the group TPAOH, TPACl, TPABr, DEA, DPA, TBAOH and TEAOH, or combinations thereof.

17. A process according to any one of formulas 1-16, characterized in that it comprises contacting the zeolite slurry step by step with a base, wherein the number of steps is at least 2, and preferably 4 or more.

18. A process according to any one of formulations 1-16, characterized in that it consists essentially of stepwise contacting a slurry of zeolite with a base, wherein the number of steps is at least 2, and preferably 4 or more.

19. A process according to any one of Formulations 1-18, characterized in that the zeolite is contacted with the base by pumping the base through a zeolite-coated membrane, or any other configuration that is not equal to a batch reactor or a displacement reactor, such as a continuous mixing reactor.

20. The method according to any of the preceding formulations 1-19, characterized in that the sequence of postsynthetic modifications can be performed without the need for filtering between individual treatments.

21. A method for alkaline leaching of a porous solid according to any of the preceding formulations 1-20, wherein the method comprises multiple additions of base per reaction (x), amount of base added at a time ( m ₁ ), multiple additions of solid per reaction ( y), the amount of solid added at one time ( m ₂ ), and multiple treatments (z), characterized in that x, y and z are not equal to 1.

22. The method for alkaline leaching of a porous solid according to any of the preceding formulations 1-21, which when the x value is 1, that is, the z value is 2, and the x*m ₁ *z value is adapted to the total amount of base in contact with porous solid, guarantees the desired leaching effect while avoiding fragmentation.

23. A process for alkaline leaching of a porous solid according to any of the preceding formulations 1-21, but designed by controlling y, z, or x such that despite the fact that the porous solid is exposed to the same total amount of base, or that the same total amount of base is contacted with the porous solid (which is preferable in order to ensure the desired leaching effect), the alkaline leaching was less strong than subjecting the porous solid with a concentration of 20-40 g/l in aqueous solution to contact with a fixed alkalinity 0.1-0.2 M NaOH, usually within about 20-40 min.

24. A method for alkaline leaching of a porous solid according to any of the preceding formulations 1-23, but designed by controlling y, z or x so that despite the fact that the porous solid is exposed to the same total amount of base, alkaline leaching was less severe than subjecting a 20-40 g/L porous solid in aqueous solution to contact with a fixed alkalinity of 0.1-0.2 M NaOH, typically for about 20-40 minutes at 45-85°C.

25. A process for alkaline leaching of a porous solid according to any of the preceding formulations 1-23, but designed by controlling y, z, or x such that although the porous solid is exposed to the same total amount of base, no no fragmentation of porous solid components.

26. A process for alkaline leaching of a porous solid according to any of the preceding formulations 1-23, but designed by controlling y, z, or x such that, despite the porous solid being exposed to the same total amount of base, essentially no fragmentation of the components of the porous solid occurred.

27. A method for alkaline leaching of a porous solid according to any one of the preceding formulations 1-23, but wherein the porous solid is crystalline, which is designed by controlling y, z, or x such that despite the fact that the porous solid is exposed to the same total amount of base, essentially no crystal fragmentation occurred.

28. A method for alkaline leaching of a porous solid according to any of the preceding formulations 1-23, wherein x is 1 while z is 2 (or greater).

29. The method of alkaline leaching according to any of the preceding formulations 1-23 of a porous solid at a concentration of 5-60 g/l, preferably 20-40 g/l, by subjecting the porous solid to several treatment reactions with moderate NaOH conditions at a temperature of 40 -70°C, preferably 60-75°C for 5-150 min, preferably 20-40 min, this treatment regime contains w NaOH treatments in the amount of z to have the same amount of NaOH so as to have the same the most consumed amount of NaOH, which is one treatment with 0.15-0.25 M NaOH.

30. The method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the porous solid is a porous silicate solid.

31. A method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the porous solid is a material with a typology of the group consisting of MWW, BEA, MFI, CHA, MOR, MTW, RUB, LEV, FER, MEL, RTH AEL, AFI, CHA, DON, EMT, CFI, CLO, TON, FER, ERI, MEL, MTW, MWW, HEU, EUO, RHO, LTL, LTA and MAZ.

32. The method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the silicate solid is a material with a typology of the group consisting of MOR, MFI, BEA and FAU.

33. The method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the silicate solid is a porous crystalline silicate.

34. The method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the silicate solid is a porous crystalline silicate having a zeolite structure.

35. The method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the silicate solid is a porous amorphous silicate.

36. A method for alkaline leaching of a porous solid according to any of the preceding formulations 1-29, wherein the silicate solid is a porous aluminosilicate (eg MCM-41 or SBA-15).

37. The method according to any of the preceding formulations 1-36, wherein the maximum concentration of hydroxyls in the solution does not exceed 20% of the maximum concentration of hydroxyls in the current state of the art alkaline leaching of the same solid, and most preferably when said concentration does not exceed 10% of the concentration used in this state of the art method.

38. Use of the method according to any of the preceding formulations 1-36 to more easily recover the produced solid from aqueous suspensions compared to the alkali-treated solid in the current state of the art.

39. the method according to any of the preceding formulations 1-36 for easier recovery of the produced solid from aqueous suspensions compared to the solid prior to the main treatment.

40. Use of the method according to any of the foregoing formulations 1-36 to improve the characteristics of the solid, namely the reduction of the cation exchange capacity, the reduction of the framework density and the reduction of the crystal size.

41. Use of a method according to any of the foregoing formulations 1-36 to improve solids performance in alkaline slurries, namely increasing the solid to liquid ratio and the presence of organics such as amine or tetraalkyl ammonium cations.

42. The use of a method according to any of the foregoing formulations 1-36 to improve the performance of a solid that is obtained, but not limited to, when separation is performed using membrane filtration techniques such as Buchner filtration.

43. Use of a method according to any of the foregoing formulations 1-36 to improve solids performance in Buchner-type devices by reducing the pore size of the filter media and increasing the height of the filter cake, that is, the amount of zeolite per unit surface area of the filter media.

44. A solid or particulate obtained using any of the preceding formulations 1-36, having a lower degree of fragmentation and a correspondingly larger particle size compared to the current state of the art.

45. A solid according to formula 44, characterized in that it contains mesopores.

46. A solid in accordance with formulation 44, characterized in that it allows to reduce the filtration time up to, but not limited to, 100 times compared with a similar solid substance of the prior art.

47. The solid according to formula 44, characterized in that, by moderate alkaline treatment, it makes it possible to reduce the loss of solid particles in the form of fines (fragmented particles) during the filtration step.

48. A solid according to formula 44, characterized in that it adapts to form mesopores with moderate alkaline treatment, but can also be used for other applications.

49. A solid according to formula 44, characterized in that, with moderate alkaline treatment, it adapts, changing the composition of the phases, changing the elemental composition, or changing both.

50. A solid according to formula 44, characterized in that it is a microporous crystalline material having superior physico-chemical properties in terms of (a combination of) higher surface area ( S _meso ), higher micropore volume ( V _micro ), higher relative crystallinity and higher Brønsted acidity compared to the current state of the art.

51. A solid according to formula 44, characterized in that it exhibits higher efficiency in catalyzed reactions, obtaining higher activity and selectivity, as well as longer catalyst life.

52. The use of a solid according to any of formulations 44-51 in additional postsynthetic modifications such as acidic or basic modifications, as well as in other steps such as bonding, molding and extrusion.

53. The use of a solid according to any of formulations 44-51 in catalysis, for example in the catalysis of acid and/or base catalyzed reactions such as isomerization, carbon-carbon bonding and cracking.

54. The use of a zeolite solid or zeolite according to any of the formulations 44-51 in catalysis, for example a solid having other secondary phases such as alumina, silica or metals and zeolites and giving better dispersion of these secondary phases due to said process .

55. The use of a solid according to any one of formulations 44-51 in adsorption or ion exchange processes.

EXAMPLES

The following Comparative Examples 1-15 are used to demonstrate the state of the art and serve as a comparison to highlight the value of the present invention. The starting zeolites did not dissolve or come into contact with any base prior to these Comparative Examples.

Comparative example 1: 3.3 g of USY (FAU topology, Si/Al ratio=30) were contacted with 100 ml of distilled water in which NaOH had previously been dissolved in an amount of m _b,total /m _s = 0.24 g/g ( 0.2M base). This was achieved by adding zeolite to a vigorously stirred caustic solution at 65°C followed by reaction for 30 minutes. This procedure is referred to as "normal processing". After the reaction, the suspension was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter (9 cm diameter, pore size 2.5 μm). The filtration time for this suspension was 119 minutes. Because the inorganic porous solid was added after the base, where it takes several minutes to completely slurry, this gives a high contact rate of at least 6 mmol/g/min.

Comparative Example 2: 6.6 g USY (FAU topology, Si/Al ratio=30) were subjected to the usual treatment, but with an m _b,total / m _s value of 0.48 g/g NaOH (0.4 M NaOH) instead of 0.24 g/g. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 420 minutes.

Comparative Example 3: 3.3 g USY (FAU topology, Si/Al ratio=30) were subjected to the usual treatment with an m _b,total / m _s value of 0.36 g/g NaOH (0.4 M NaOH) instead of 0, 24 g/g. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 390 minutes.

Comparative Example 4: 33 g of USY (FAU topology, Si/Al ratio=30) were subjected to conventional processing at a scale of 1 L using 0.2 M NaOH. After the reaction, the suspension was transferred to a Buchner apparatus under vacuum with a Whatman #4 filter (9 cm diameter, pore size 25 μm). The filtration time for this suspension was 384 minutes. This corresponds to a filtration time of 12 min/g of the original USY zeolite.

Comparative Example 5: 33 g of USY (FAU topology, Si/Al ratio=30) were suspended in 1 liter of water for 30 minutes with vigorous stirring. The slurry was then transferred to a Buchner apparatus under vacuum with a Whatman #4 filter (9 cm diameter, pore size 25 µm). The filtration time for this suspension was 170 minutes. This corresponds to a filtration time of 5 min/g of the original USY zeolite.

Comparative Example 6: 3.3 g of USY (FAU topology, Si/Al ratio=466) were subjected to conventional processing. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 285 minutes.

Comparative Example 7: 3.3 g of USY (FAU topology, Si/Al ratio=15) were subjected to conventional processing. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 12.5 minutes.

Comparative Example 8: 3.3 g of USY (FAU topology, Si/Al ratio=30) were subjected to the usual treatment with the addition of 0.2 M TPABr. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 252 minutes. The crystallinity of this sample was 81% compared to the untreated parent zeolite, 91% compared to reference NaY CBV100, and 124% compared to NIST standard alumina (SRM 676).

Comparative Example 9: 3.3 g of USY (FAU topology, Si/Al ratio=30) were subjected to the usual treatment with the addition of 0.01 M TPABr. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 195 minutes. The cavitation ratio of the obtained sample was 1.85.

Comparative Example 10: 3.3 g of beta (BEA topology, Si/Al ratio=255) were subjected to the usual treatment. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 62.7 minutes.

Comparative Example 11: 3.3 g of ZSM-5 (MFI topology, Si/Al ratio=140) were subjected to conventional processing. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 66.6 minutes. This sample showed a crystallinity of 87% compared to the original zeolite and 319% compared to the NIST standard alumina (SRM 676). In addition, this sample exhibited a microporosity of 0.06 ml/g, a mesopore surface of 288 m ² /g, and a unimodal mesoporosity centered around 10 nm, as illustrated in FIG. eleven.

Comparative Example 12: 3.3 g of silicalite (MFI topology, Si/Al ratio=940) were subjected to conventional processing. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 11 minutes. The crystallinity of this sample was 76% compared to the untreated original zeolite.

Comparative Example 13: 3.3 g of SAPO-11 (AEL topology, Al/Si=10 ratio, P/Si=9, Al/P=1.1) were subjected to conventional processing using 0.4 M DEA instead of 0, 2 M NaOH for 60 min instead of 30 min. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was >400 min.

Comparative Example 14: 10 g of clinoptilolite (HEU topology) were treated with acid 4 times according to the conditions described in the current state of the art (Chem. Mater., 2013, 25, 1947-1959). 3.3 g of this dealuminated clinoptilolite (with Si/Al=10) were subjected to conventional treatment using 0.1 M NaOH instead of 0.2 M NaOH. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 8.1 minutes.

Comparative Example 15: 3.3 g of USY (FAU topology, Si/Al ratio=30) was contacted according to the usual treatment with an aqueous NaOH solution, except that m _b,total / m _s =0.12 g/g was used instead of m _b,total / m _s =0.24 g/g. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 2.5 minutes. Thereafter, the resulting solid was dried (6 hours) at 100°C and then contacted again in accordance with the usual processing, except that m _b,total / m _s =0.12 g/g was used instead of m _b,total / m _s \u003d 0.24 g / g. After this second reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this slurry was 2.6 minutes and the total filtration time was 5.1 minutes. The resulting solid was completely amorphous, the total process time was 425 minutes, and as a result, an undesirable double amount of wastewater was formed.

The following examples correspond to preferred embodiments of the present invention. The starting zeolites did not dissolve or come into contact with any base prior to running these examples.

Example 16: 3.3 g of USY (FAU topology, Si/Al ratio=30) were contacted in accordance with the usual treatment, except that the NaOH concentration was 0.05 M instead of 0.2 M NaOH. During the treatment, NaOH powder (0.05 mol/l solution) was added 3 times every 7.5 minutes in order to reach a value of m _b,total / m _s =0.24 g/g. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 1.9 minutes. In addition, there was no negative effect on the duration of the process, the number of stages and the amount of waste water, as in Example 15.

Example 17: 3.3 g of USY (FAU topology, Si/Al ratio=30) were contacted with the same amount of base for the same time and at the same temperature as in the conventional treatment. The base was gradually added to the zeolite suspended in 90 ml of vigorously stirred water using a syringe pump filled with 2 M NaOH solution at a rate of 20 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 2.3 minutes. NaOH was added in the amount of m _{b, total} /m _s =0.24 g/g. The addition rate was respectively 0.2 mmol/g/min.

Example 18: 3.3 g of beta (BEA topology, Si/Al ratio=255) was contacted with the same amount of base for the same time and at the same temperature as in the conventional treatment. The base was gradually added to the zeolite suspended in 90 ml of vigorously stirred water using a syringe pump filled with 2 M NaOH solution at a rate of 20 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 10.1 minutes.

Example 19: 3.3 g of USY (FAU topology, Si/Al ratio=30) were subjected to the same treatment as in Example 17, except that 3 M NaOH was used instead of 2 M NaOH. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time of this suspension was 149 minutes, which is less than 50% compared to the current state of the art shown in Comparative Example 3.

Example 20: 33 g of USY (FAU topology, Si/Al ratio=30) were subjected to the same treatment as in Example 17 ( m _b,total / m _s =0.24 g/g), but in tenfold volume, using 5 M NaOH instead of 2 M NaOH and at an addition rate of 80 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #4 filter. The filtration time for this suspension was 115 minutes. This refers to a filtration time of 3 min/g of the initial USY zeolite, which shows that the filtration was faster compared to the experiment performed on the same scale using the technology of the current state of the art (Example 4). In addition, this filtration time shows that the separation is even easier compared to placing the same amount of zeolite in the same amount of a non-alkaline solution consisting only of distilled water (Example 5). This accordingly indicates that the main leaching technique according to the present invention can even be used to improve the recovery of zeolites from solutions and therefore clearly represents an improvement on the current state of the art.

Example 21: 33 g of USY (FAU topology, Si/Al ratio=30) were subjected to the same treatment as in Example 17, however in tenfold volume, using 2.5 M NaOH solution in a syringe pump running at 40 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #4 filter. The filtration time for this suspension was 120 minutes. This refers to a filtration time of 3.6 min/g of the initial USY zeolite, which indicates that the filtration was faster compared to the experiment performed on the same scale using the technology of the current state of the art (Example 4). In addition, this filtration time shows that the separation is even easier compared to placing the same amount of zeolite in the same amount of a non-alkaline solution consisting only of distilled water (Example 5). This accordingly indicates that the main leaching technique according to the present invention can even be used to improve the recovery of zeolites from solutions and therefore clearly represents an improvement on the current state of the art.

Example 22: 3.3 g of ZSM-5 (MFI topology, Si/Al ratio=140) was contacted with the same amount of base for the same time and at the same temperature as in conventional processing. The base was gradually added to the zeolite suspended in 90 ml of vigorously stirred water using a syringe pump filled with 2 M NaOH solution at a rate of 20 ml/h. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 39.4 minutes. This sample showed a crystallinity of 96% compared to the original zeolite and 353% compared to the NIST standard alumina (SRM 676). In addition, this sample exhibited a microporosity of 0.07 ml/g, a mesopore surface of 262 m ² /g, and bimodal mesoporosity (with mesopore sizes of 8 nm and 20 nm) as illustrated in FIG. 11, which differs significantly from the unimodal mesoporosity of the sample synthesized in Comparative Example 11.

Example 23: 3.3 g SAPO-11 (AEL topology, Al/Si=10 ratio, P/Si=9, Al/P=1.1) was contacted with the same amount of base for the same time and at the same temperature as in Example 13. The base was gradually added to the zeolite suspended in 90 ml of vigorously stirred water using a syringe pump filled with 4 M DEA solution at a rate of 20 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 82 minutes.

Example 24: 3.3 g of USY (FAU topology, Si/Al ratio=30) were subjected to the same treatment as in Example 17, with 0.01 M TPABr added to the aqueous solution. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 2.0 minutes. The cavitation ratio of the obtained sample was 1.51.

Example 25: 10 g of clinoptilolite (HEU topology) were treated with acid 4 times according to the conditions described in the current state of the art (Chem. Mater., 2013, 25, 1947-1959). From this dealuminated clinoptilolite (Si/Al=10), 3.3 g were subjected to the same treatment as in Example 17, except that 1 M NaOH was used instead of 2 M NaOH. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 6.2 minutes.

Example 26: The porous properties of selected samples, evaluated using conventional nitrogen adsorption at 77 K, are shown in Table 1. In this document, it becomes apparent that the samples prepared using the present invention have a larger surface area and are better retained, and therefore more volume. micropores. It is also apparent from Table 1 that the present invention gives the lowest filtration and processing times. More detailed information about these materials is contained in the drawings of FIG. 8, 9, 10, 11 and in Tables B, C, and D. It should be emphasized that the retention of intrinsic properties may depend on the type of zeolite, as well as the nature and amount of base and organics used. Accordingly, the comparison between the current state of the art and the present invention should be made primarily between samples prepared in the same way, except for the method of adding the base. This can be done, for example, using comparative Example 9 and Example 24 on USY-III zeolite, where in both cases the zeolite is treated at m _b,total / m _s = 0.24 g/g using 0.01 M TPABr . In this case, it can be observed that the conventional technique results in a microporosity of 0.09 ^cc /g using 0.17 g TPABr per gram of final zeolite (see Table 1). Performing the same treatment using the technology in accordance with the present invention results in a value of 0.15 cm ³ /g using 0.17 g TPABr per gram of final zeolite (see Table 1). Therefore, using the technique of the state of the art, a microporosity of 0.53 cm ³ /g TPABr is obtained (Example 9). However, for the procedure in accordance with the present invention, this value is equal to 0.88 cm ³ /g TPABr (Example 24), which suggests that organics are used at least 50% more efficiently.

Comparative Example 27: The suspension obtained by the conventional processing in Example 1, as well as other samples prepared in the conventional manner, were subjected to dynamic light scattering (DLS) testing. Accordingly, the supernatant of the centrifuged (15 min at 12,000 rpm) alkali treated zeolites was measured in polystyrene cuvettes on a 990Plus Particle Size Analyzer (Brookhaven) equipped with a 659 nm laser with a detection angle of 90°. Fluctuations in scattered light intensity were correlated between 10 ms and 5 s. Correlation functions were analyzed using the Igor Pro 6.2 software, using the Clementine package for modeling decay kinetics based on the maximum entropy method. The damping time was converted to hydrodynamic diameters using the Stokes-Einstein equation. Fig. 6a shows the resulting effective diameter ( D _eff ). After contact of the USY-III zeolite with an increasing amount of NaOH, the value of D _eff decreased from 450 nm to 200 nm. In particular, below 250 nm, the filtration time starts to become extremely long (see Fig. 6b).

Example 28: The solution obtained after the treatment in Example 17 was subjected to the same study as in Example 27. FIG. 6a shows that the use of the present invention allows a much higher D _eff (>300 nm) to be achieved when the same amount of inorganic porous solid is contacted with a base. This indicates that defragmentation should be significantly reduced in the solids produced in Example 27.

Example 29: 1 g of USY (ratio Si/Al=30) was placed in a membrane filtration cell equipped with a Whatman #5 filter. Then, 200 ml of 0.4 M diethylamine (DEA) solution was added, after the mixture reached a temperature of 65°C, pressure was added to complete the filtration of the DEA solution through the zeolite bed in 1 hour. This step was repeated once with an overall yield of 52%. By flowing the base on the zeolite membrane, the zeolite is contacted with the base in a gradual manner. In this case, the value of x would be infinitely large. This was done according to the experimental configuration shown in FIG. 2.

Example 30: The acidity of the solid particles obtained in comparative Example 9 and Example 24 was determined using Fourier transform infrared spectroscopy after pyridine adsorption. These measurements were made using a Nicolet 6700 spectrometer equipped with a DTGS detector. Before measurements, the samples were pressed into self-supporting plates and degassed at 400°C for 1 hour in a vacuum. Acid sites according to Brønsted and Lewis were analyzed using a pyridine probe. After evacuation, the samples were subjected to 4-5 pulses of at least 25 mbar of pyridine at 50°C for 1 min (until saturation). Absorption at wavelengths of 1550 and 1450 cm ^-1 corresponded to the number of acid sites according to Brønsted and Lewis, respectively. The attenuation coefficients were determined in accordance with Emeis, J. Catal, 1993, 141, 347-354. The results (Table 1) demonstrate that although the same amount of TPABr was used in the preparation of both samples, the solid obtained in Example 24 contained more than twice as many Brønsted acid sites. This proves that the solid particles obtained using the present invention have a higher acidity compared to the prior art.

Example 31: The crystallinity of the solids obtained in Example 9 and Example 24 was evaluated. The results (Table 1) demonstrate that although the same amount of TPABr was used in the preparation of both samples, the solid obtained in Example 24 has twice higher crystallinity. This proves that the solid particles obtained using the present invention have a higher crystallinity compared to the prior art, and that TPABr was used more efficiently.

Example 32: The solid particles obtained after Example 1, Example 8, Example 9, Example 17 and Example 24 were converted to the proton form using standard ion exchange with 0.1 M NO ₃ NH ₄ (room temperature, 12 h, 3 repetition) followed by calcination (550°C, 5 hours, speed 5°C/min). Thereafter, these solids were evaluated for their catalytic ability in the α-pinene conversion reaction, which is a suitable model reaction to test activity and selectivity. The isomerization reactions were carried out in a 50 cm ³ Parr reactor with a sampler at 150° C. under nitrogen at a pressure of 6-8 bar with a stirring speed of 750 rpm. A mixture of substrate (20 g; α-pinene) and catalyst (0.1 g) was heated to 100°C, after which the first liquid sample was taken. The reaction mixture was then further heated to 150°C and samples were taken 10, 30 and 60 min after the first sample. These samples were then analyzed on a gas chromatograph (HP 5890, Hewlett Packard) equipped with an HP1 column and a flame ionization detector (FID). Tetradecane was used as an external standard. Unidentified products were analyzed by gas chromatography-mass spectrometry (GC-MS) (6890N instrument, Agilent Technologies). The activity of the samples was determined by using the slope of the linear part of the graph of the dependence of the conversion of α-pinene from contact time. The results shown in Table 1 show that, compared to the current state of the art, materials obtained using the present invention have higher activity and selectivity.

Table 1: Physico-chemical properties and catalytic efficiency of various USY zeolites.

Example S _meso ^a
(m ² /g) V _micro ^a
(cm ³ /g) Crystallinity ^b
(%) t _F ^c
(min) waste water ^d
(ml/g) t _P ^e
(min) B ^f
(µmol/g) ^Lf
(µmol/g) A ^g
(1 hour) ^Pg
(1 hour) P/A ^h
[-] raw 231 0.27 100 not applicable not applicable not applicable 158 26 48 47 0.98 Example 1 363 0.00 0 119 thirty 149 39 65 204 165 0.81 Example 8 436 0.20 not applicable 252 thirty 282 172 81 279 250 0.90 Example 9 211 0.09 thirty 195 thirty 225 63 40 201 180 0.90 Example 15 430 0.00 0 5 60 425 not applicable not applicable not applicable not applicable not applicable Example 16 607 0.00 not applicable 2 thirty 32 not applicable not applicable not applicable not applicable not applicable Example 17 405 0.00 not applicable 2 thirty 32 not applicable not applicable 215 190 0.88 Example 24 401 0.15 56 2 thirty 32 147 73 276 259 0.94

^a Mesoporosity ( S _meso ) and microporosity ( V _micro ) measured by nitrogen adsorption.

^b Crystallinity measured by XRD.

^c Filtration Time ( t _F ) after alkali treatment.

^d Effluent generated during alkaline treatment per gram of initial zeolite.

^e Processing time (t _P ) refers to the total time it takes to perform the alkaline treatment and subsequent filtration. In the case of multi-stage treatment, the total processing and filtration time is increased by the time of the drying stage between filtration and subsequent alkaline treatment.

^f Brønsted (B) and Lewis (L) acidity measured by pyridine adsorption.

^g Activity (A) and productivity (P) of the catalyst (after standard ion exchange and calcination) in the conversion of α-pinene. The unit of A is the number of grams of converted α-pinene per gram of catalyst per hour. The unit of P is the number of grams of useful products (limonene, camphene, α-terpinene, γ-terpinene, terpinoline, p-cymene) per gram of catalysts per hour.

^h P/A is a measure of the selectivity of zeolite catalysts for desired products.

Comparative Example 33 Conventional Base Leaching Techniques

Table A illustrates the physicochemical properties of conventional and base-treated zeolites using state of the art technology. The data are shown relative to the original zeolites.

Zeolite Mesoporosity ^a (%) Microporosity ^a (%) Crystallinity ^a (%) Brønsted acidity ^a (%) Filtration time ^b (%) USY-I (CBV 712, Si/Al=6) - regular 100 100 100 100 100 USY-I base leached 386 97 54 67 200 USY-II (CBV 720, Si/Al=15) - regular 100 100 100 100 100 USY-II base leached 297 81 64 57 3400 USY-III (CBV 760, Si/Al=30) - regular 100 100 100 100 100 USY-III base leached 296 78 76 93 4400 ZSM5 (CBV 8014, Si/Al=40) - normal 100 100 100 100 100 ZSM-5 base leached 700 57 72 84 600 beta (HSZ-940HOA, Si/Al=20) - normal 100 100 100 100 100 beta leached by base 313 90 61 76 500

^a Data for porosity, crystallinity and acidity were obtained from ACS Catalysis 2015 , 5 , 734;

^b Filtration times were obtained by reproducing experiments from ACS Catalysis 2015 , 5 , 734 at 100 ml scale and filtration using a Buchner device with Whatman #5 filter paper (9 cm diameter). Filtration times for untreated conventional zeolites were obtained by filtering a suspension of 3.3 g of zeolite in 100 ml of distilled water using a Buchner apparatus with Whatman #5 filter paper (9 cm in diameter).

Example 34: Comparison with Conventional Base Leaching Methods

Fig. 8 illustrates the effect of alkaline treatments on mesopore volume ( Vmeso ), _Brønsted acidity, crystallinity, and _micropore volume ( Vmicro ) relative to untreated (stock) zeolite. The treatments of the current state of the art (referred to as "SA") and in accordance with the present invention (referred to as "IP") were performed with the same total amount of base (NaOH) per amount of zeolite treated ( m _b,total / m _s =0.24 y/y). Treatments were performed as in the current state of the art (SA) as described in ACS Catalysis 2015 , 5 , 734: 3.3 g USY-I was contacted with 100 ml in which 0.8 g NaOH was dissolved at 65°C for 30 min in a round bottom flask with a stirrer. After the reaction, the solid was isolated from the suspension using Buchner filtration. For the present invention (IP): 3.3 g of USY-I was suspended in 90 ml of water, to which the base was added gradually over 30 minutes at a rate of 0.2 mmol NaOH per gram of starting zeolite per minute. After the reaction, the solid was isolated from the suspension using Buchner filtration. After alkaline treatments, these samples, following the protocols described in ACS Catalysis 2015 , 5 , 734, were subjected to a standard acid wash in 50 ml of water supplemented with Na ₂ H ₂ EDTA (0.55 g per gram of zeolite) at 95°C in for 6 hours, followed by three ion exchanges in 250 ml of water with addition (0.8 g per gram of zeolite), filtration and calcination at 550°C for 5 hours.

Fig. 9 illustrates the effect on zeolite properties as a function of the desired introduction of secondary porosity ( V _meso ) using the current state of the art (SA) or technology in accordance with the present invention (IP). Samples were prepared as described in Example 34. All data are relative to the untreated (initial) zeolite.

Table B illustrates the crystallinity, porosity, and acidity of conventional and base-treated USY-I zeolites.

Sample m _b,total / m _s ^a (y/y) V _meso ^b (ml/g) V _microb ⁽ ml/g) Crystallinity ^c (%) Acidity ^d
(µmol/g) Acidity ^e (%) P ^f
(1 hour) P ^/ Vmeso _g
a.u. initial NIST NaY USY-I-regular - 0.15 0.25 100 130 98% 346 100 31 207 USY-I Base Treated Comparative 0.24 0.42 (+180%) ^h 0.16 ( 36%) 66 (34%) 71 65 314 (-9%) 88 (12%) 202 (+552%) 481 (+132%) USY-I treated with base according to the present invention 0.24 0.37 (+147%) 0.24 (-4%) 87 (13%) 109 86 553 (+60%) 146 (+46) 254 (+719%) 686 (+231%)

^a Base treatments were performed according to Example 34. All base treated samples were then washed using the standard acid treatment as defined in Example 34;

^b Nitrogen adsorption;

^c Comparison by XRD of the original zeolite USY-I (“original”) with NIST standard alumina (SRM 676) (“NIST”) or standard NaY (CBV 100 manufactured by Zeolyst) (“NaY”);

^d FTIR of adsorbed pyridine;

^e NH ₃ -TPD;

^f Catalyst performance (after standard ion exchange and calcination) in α-pinene conversion, in grams of useful products (limonene, camphene, α-terpinene, γ-terpinene, terpinoline, p-cymene) per gram of catalysts per hour;

^g The P/ V _meso value is the ratio of productivity to secondary porosity. Accordingly, it is a measure of the effectiveness of the secondary porosity;

^h Values in parentheses indicate change from the original conventional USY-I zeolite.

Fig. 10 illustrates mesoporosity cavitation after introduction of secondary porosity ( V _meso ) using the current state of the art (black circles) or base leaching technology in accordance with the present invention (triangles). Samples obtained using the methods in accordance with the present invention show significantly lower cavitation ratios. They were obtained by leaching with base USY III at m _b,total / m _s =0.24 g/g with the addition of 0.2 M TPABr or 0.01 M TPABr. Similar protocols for SA and IP were used as in Example 34, except no acid wash was performed.

Example 35: 3.3 g of silicalite (MFI topology, Si/Al ratio=940) were contacted with the same amount of base for the same time and at the same temperature as in conventional processing. The base was gradually added to the zeolite suspended in 90 ml of vigorously stirred water using a syringe pump filled with 2 M NaOH solution at a rate of 20 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 9 minutes. The crystallinity of this sample was 107% compared to the untreated original zeolite.

Example 36: 3.3 g of USY (FAU topology, Si/Al ratio=15) was contacted with the same amount of base for the same time and at the same temperature as in the conventional treatment. The base was gradually added to the zeolite suspended in 90 ml of vigorously stirred water using a syringe pump filled with 2 M NaOH solution at a rate of 20 ml/hour. After the reaction, the slurry was transferred to a Buchner apparatus under vacuum with a Whatman #5 filter. The filtration time for this suspension was 2 minutes.

Example 37: 3.3 g of USY (FAU topology, Si/Al ratio=30) were subjected to the same treatment as in Example 17, with 0.2 M TPABr added to the aqueous solution. The microporosity of this sample was 0.24 ml/g. The crystallinity of this sample was 89% compared to the untreated parent zeolite, 100% compared to reference NaY CBV100, and 143% compared to NIST standard alumina (SRM 676).

Comparative example 38: 3.3 g of beta (BEA topology, Si/Al=12.5) was contacted with half the amount of base ( m _b,total / m _s =0.12 g/g) for the same time and at the same temperature as in conventional processing, with the addition of 0.2 M TPABr. After this reaction, standard acid washing, ion exchange and calcination were additionally performed as described in Example 34. The crystallinity of this sample was 86% compared to the untreated starting zeolite and 477% compared to the standard NIST alumina (SRM 676). This sample had a microporosity of 0.15 ml/g and a mesopore volume of 0.89 ml/g.

Example 39: 3.3 g of beta (topology BEA, Si/Al=12.5) were subjected to the same treatment as in Example 17, with the amount of base halved ( m _b,total / m _s = 0.12 g/g) and 0.2 M TPABr was added to the aqueous solution. After this reaction, standard acid washing, ion exchange and calcination were additionally performed as described in Example 34. The crystallinity of this sample was 95% compared to the untreated starting zeolite and 531% compared to the standard NIST alumina (SRM 676). This sample had a microporosity of 0.16 ml/g and a mesopore volume of 0.90 ml/g.

Comparative Example 40: USY-I zeolite was treated with base in NaOH (at m _b,total / m _s = 0.24 g/g) according to the state of the art as described in Example 34, except that the acid treatment in Na ₂ H ₂ EDTA was not performed. The resulting sample showed a Brønsted acidity measured with pyridine of 247 µmol/g. Accordingly, based on the information presented in Table B, the acid wash performed after the state of the art alkaline treatment in Example 34 caused an increase in Brønsted acidity to 67 µmol/g.

Example 41 USY-I zeolite was base treated in NaOH (at m _b,total / m _s = 0.24 g/g) according to the present invention as described in Example 34, except that the acid treatment in Na ₂ H ₂ EDTA was not performed. The resulting sample showed a Brønsted acidity measured with pyridine of 393 µmol/g. Accordingly, based on the information presented in Table B, the acid wash performed after the alkaline treatment according to the present invention in Example 34 caused an increase in Brønsted acidity to 160 µmol/g. This proves that acid washing becomes (over two times) more effective when alkaline treatment is carried out in accordance with the present invention.

New materials

The following new materials have been prepared using methods in accordance with embodiments of the present invention. The properties of these materials are shown in Fig. 8-11 and in Tables A-D.

For USY-I: Crystallinity (Fig. 8, 9, Table B), microporosity (Fig. 8, 9, Table B), acidity (Fig. 8, 9, Table B), Al and Si coordination (MAS NMR, Table C and Table D). For USY-III: Microporosity (Example 37), crystallinity (Example 37), cavitation (Fig. 9) and particle/crystal size (Fig. 6). For ZSM-5: Crystallinity (Example 22) and mesoporosity (Example 22, Fig. 11). For beta: Crystallinity (Example 39).

Table C: Coordination of aluminum in the original and base-treated USY-I, measured using ²⁷ AlMAS NMR spectroscopy.

Sample Tetrahedral framework varieties ^a (%) Pentahedral varieties of additional framework ^a (%) Octahedral varieties of additional framework ^a (%) USY-I-regular 46 twenty 34 Conventional USY-I treated with base (comparative) ^b 44 24 31 Conventional USY-I treated with base (according to the present invention) ^b 61 16 23 ^a Tetrahedral varieties (80 to 40 ppm), pentahedral varieties (40 to 10 ppm), and octahedral varieties (10 to -40 ppm).
^b Base treatment (m _b,total /m _s = 0.24 g/g) was supplemented with a standard acid wash as described in Example 34.

Table D: Silicon coordination in stock and base-treated USY-I measured using ²⁹ SiMAS NMR spectroscopy.

Sample Si(2Al)+Si(3Al) ^a (%) Si(1Al) ^a (%) Si(0Al) ^a (%) USY-I-regular 7 fourteen 79 Conventional USY-I treated with base (comparative) ^b eighteen 32 fifty Conventional USY-I treated with base (according to the present invention) ^b eleven 28 61 ^a Si(0Al) at -108 ppm, Si(1Al) at -102 ppm, Si(2Al) at -96 ppm, Si(3Al) at -92 ppm.
^b Base treatment (m _b,total /m _s = 0.24 g/g) was supplemented with a standard acid wash as described in Example 34.

Faujasite Difference (USY): Among the available USY zeolites, the most critical difference is the Si/Al framework ratio. It is quite different from the Si/Al ratio measured by elemental analysis (due to the presence of Si and Al varieties of additional frameworks trapped in the samples). The Si/Al ratio of the framework unambiguously determines its acidity, stability, and the type and nature of the postsynthetic protocol used. Because the Si/Al backbone ratio is difficult to measure by elemental analysis, it is obtained from the XRD pattern (using the standardized methods described in ASTM 3942). Since an increase in the amount of Al in the framework causes the framework of the zeolite to expand, the amount of Al in the framework can be obtained from an estimate of the unit cell size. The unit cell dimensions of the starting materials can be readily obtained from the zeolite supplier (Zeolyst). For USY-I (CBV 712) they are 24.35 Å, while for USY-III (CBV 760) they are 24.24 Å.

The new USY-I material can be unambiguously described as:

- (based on unprecedented acidity, see Figs. 8 and 9 and Table B) faujasite topology zeolite with unit cell size ranging from 24.375 Å to 24.300 Å, with a mesopore volume of at least 0.35 ml/g and with acidity according to Brønsted at least 400 µmol/g (measured with pyridine);

- (based on improved Al coordination, see Table C) a faujasite topology zeolite with a unit cell size ranging from 24.375 Å to 24.300 Å, with a mesopore volume of at least 0.35 ml/g, with an Al content in the framework, and hence with a tetrahedral coordination of at least 0.5 (measured by ²⁷ Al MAS NMR);

- (based on the retention of crystallinity during the formation of mesopores, see Fig. 8, 9 and Table B) zeolite with faujasite topology with a unit cell size ranging from 24.375 Å to 24.300 Å, with a mesopore volume of at least 0.35 ml / g and a crystallinity of at least 75% relative to standard NaY zeolite and at least 90% compared to standard NIST alumina (SRM 676).

- (based on the retention of microporosity during mesopore formation, see Fig. 8, 9 and Table B) faujasite topology zeolite with a unit cell size ranging from 24.375 Å to 24.300 Å, with a mesopore volume of at least 0.35 ml/ g and a microporosity of at least 0.21 ml/g (measured by nitrogen adsorption); and/or

- (based on maintaining Si coordination during mesopore formation, see Table D) faujasite topology zeolite with unit cell size ranging from 24.375 Å to 24.300 Å, with a mesopore volume of at least 0.35 ml/g and a proportion of Si species (0Al), and therefore with silicon in the frame, tetrahedrally coordinated with 4 Si atoms, greater than 0.5 (measured using ²⁹ Si MAS NMR).

The new USY-III material can be unequivocally described as:

- (based on the unprecedented microporosity of mesoporous USY-III, Example 37) faujasite topology zeolite with a unit cell size of less than 24,300 Å, with a mesopore volume of at least 0.35 ml/g and a micropore volume of at least 0.22 ml/g (measured by nitrogen adsorption);

- (based on the unprecedented crystallinity of mesoporous USY-III, Example 37) faujasite topology zeolite with a unit cell size of less than 24,300 Å, with a mesopore volume of at least 0.35 ml/g and a crystallinity of at least 95% compared to commercial zeolite NaY and at least 130% compared to NIST standard alumina (SRM 676);

- (based on reduced cavitation of mesoporous USY-III, see Fig. 10) faujasite topology zeolite with a unit cell size of less than 24,300 Å, with a mesopore volume of at least 0.35 ml/g and a mesopore cavitation ratio of at most 1.6 (measured by nitrogen adsorption); and/or

- (based on crystal size retention of mesoporous USY-III, see Fig. 6) faujasite topology zeolite with a unit cell size of less than 24,300 Å, with a mesopore volume of at least 0.35 ml/g and a particle size D _eff of at least 350 nm.

The new MFI material can be unambiguously described as:

an MFI topology zeolite with a Si/Al molar ratio of at most 400, with a mesopore volume of at least 0.30 ml/g and a crystallinity of at least 330% compared to NIST standard alumina (SRM 676).

The new BEA material can be unambiguously described as:

a BEA topology zeolite with a mesopore volume of at least 0.50 ml/g and a crystallinity of at least 500% compared to NIST standard alumina (SRM 676).

Claims (25)

1. A method for increasing the mesoporosity of a zeolite which consists of a single treatment followed by a solid separation step such as a filtration step and includes the steps of: a) preparation of zeolite in the amount of m _s ; b) base preparation in total m _b,total ; and c) contacting and reacting this zeolite with a base in an amount of m _b (t) in an aqueous solution at a temperature from room temperature to 100 ° C and a pH from at least 10 to at most 14, and the base is continuously added to the zeolite for a period time Δt for the total amount of base m _b,total at least 15 sec; thereby obtaining a treated zeolite; in which the maximum value m _b,max /m _s of the amount of base m _b (t) brought into contact with the zeolite m _s at any time t in step c) is less than m _b,total /m _s , and the total the amount of base m _b,total is provided in the form of solid alkali or alkaline solution, and where the maximum value m _b,max of the amount of base m _b (t) at any particular time t in step c) is at most 0.75* m _{b, total} . 2. The method of claim. 1, in which the ratio of solid to liquid is in the range from 1 g/l to 100 g/l. 3. The method according to claim 1 or 2, wherein the time period Δt is at most 60 minutes. 4. The method according to any one of paragraphs. 1-3, wherein the maximum base value m _b,max of the amount m _b (t) at any particular time t in step c) is at most 0.50* m _b,total , preferably at most 0.25* m _{b ,total} . 5. The method according to any one of paragraphs. 1-4, in which step a) comprises: a') preparation of m _s zeolite suspended in an aqueous solution, preferably water. 6. The method according to any one of paragraphs. 1-3, which includes a number (x) of base additions per treatment that are not separated by a solids separation step, such as a filtration step, in which the amount of base added per addition is m _{b, i} , where i=1. .x, and which is characterized in that x is at least 2, preferably at least 3, and even more preferably at least 4. 7. The method according to any one of paragraphs. 1-6, wherein the base addition rate is at most 3.0 mmol/g/min, preferably at most 1.0 mmol/g/min, and even more preferably at most 0.5 mmol/g/min. 8. The method according to any one of paragraphs. 1-7, in which the base is continuously added to the zeolite during the time interval Δt, and this time interval Δt for adding the total amount of base m _b,total is at least 60 s. 9. The method according to any one of paragraphs. 1-8 followed by successive acid treatments. 10. The method according to any one of paragraphs. 1-9, in which the base is an inorganic base selected from the group including NH ₄ OH, NaOH, KOH and LiOH, or an organic base or organic additive selected from the group including TPAOH, TPACl, TPABr, DEA, DPA, TBAOH and TEAOH, or combinations thereof. 11. Treated zeolite obtained using the method according to any one of paragraphs. 1-10. 12. A method for preparing a technical catalyst, comprising the steps: - preparation of the treated zeolite by the method according to any one of paragraphs. 1-10; - adding one or more additional ingredients to form a mixture; and - molding this mixture into a macroscopic form in order to obtain a technical catalyst. 13. The method of claim 12 wherein the one or more additional ingredients are selected from the group consisting of: fillers, pyrogens, binders, lubricants, and combinations thereof. 14. The method according to claim 12 or 13, wherein the macroscopic shape has a minimum size of at least 1 µm to at most 10 cm. 15. The use of treated zeolite according to claim 11 or a technical catalyst prepared using the method according to any one of claims. 12-14, in catalysis processes. 16. The use of the treated zeolite according to claim 11 or a technical catalyst prepared using the method according to any one of claims. 12-14, in the processes of adsorption or ion exchange.

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