Method for producing a zeolite body and zeolite body obtained through said method

Abstract

The present invention relates to a method for producing a zeolite body.

Description

Technical Field

[0001] The present invention relates to a method for producing a zeolite body.

Background Art

[0002] The present invention realizes an industrially significant production of a robust and high-performance zeolite body. The term "industrially significant" refers to a process that can produce zeolite bodies in amounts of multiple kilograms per day using cost-effective and readily available equipment. Thus, laboratory-based preparation protocols and procedures that produce gram amounts of samples, using, for example, beakers and test tubes, are typically not industrially significant.

[0003] Zeolites are inorganic crystalline material sorbents that are used to adsorb gases or other chemical species or are used in many catalytic processes. Zeolites are used as substrates for many catalysts or act as catalysts themselves. Zeolite bodies can be cation-exchanged or impregnated with metal species, such as metal oxides. The porosity of the zeolite body is clearly important for the body to act as a catalyst or sorbent. If the zeolite body is not sufficiently porous, reagents cannot reach the active catalytic sites. If there are too many large pores in the body, the volumetric performance will decrease, and unwanted reactants may reach the core of the zeolite body. The control of the pore size and level of porosity of the zeolite body is clearly important. The zeolites of interest have the chemical formula Na n Al n Si 96-n O 192There are aluminosilicate zeolites having ·16H2O (0 < n < 27), etc. Among the aluminosilicate zeolites having this chemical formula, there are widely used catalyst zeolites such as Zeolite Socony Mobil-5 or ZSM-5, which are known to be commercially available. Other useful zeolites include type A, zeolite beta, titanium silicate-1, faujasite (types X and Y), chabazite (SSZ-13 and SAPO-34), ferrierite, sodalite, and mordenite, etc.

[0004] Zeolites are typically synthesized as fine powders having an average particle size between 2 microns and 10 microns. They are typically produced following a sol-gel process, through filtration and washing steps, followed by drying. Typically, such zeolite crystal sizes are large enough so that the filtration and washing steps are industrially feasible. Even so, the treatment, washing, and subsequent separation and drying of such fine powders to remove residual reactants or to perform ion exchange certainly result in non-negligible costs and complexities. By being able to perform these steps on larger zeolite bodies, for example, the handling and separation of the zeolite bodies from the washing water can potentially be made simpler.

[0005] Zeolites are widely used as heterogeneous solid catalysts and as support media for other catalyst materials. Thus, fine zeolite powder typically needs to be formed into larger bodies, such as granules having a maximum inner diameter greater than 100 microns, or even bodies several millimeters in size, such as extrudates, when used in a "fixed bed". Forming the zeolite powder into such larger bodies helps to improve handling and avoid problems such as excessive pressure drop and "channeling", which often occurs when fine powders are used. The use of larger zeolite bodies improves fluid flow, which plays a role in improving the characteristics of both mass transfer and heat transfer under typical industrial process conditions. The zeolite body needs to be sufficiently robust to withstand the conditions of fabrication and use, particularly high temperatures and strong agitation from fluid flow and remain intact.

[0006] Robustness and strength are important requirements for such zeolite bodies. Many industrial processes use such zeolite bodies in large "fixed beds" and continuously flow a fluid, whether liquid or gas, through the fixed bed to bring the zeolite body into contact with reactants. The fluid can move and abrade the zeolite catalyst body, generating dust. The accumulation of this fine, dusty material can clog equipment and is one of the major factors limiting the useful life of such zeolite bodies.

[0007] Zeolite powder is not self - binding and, therefore, needs to be formed into mechanically stable larger bodies with different sizes and shapes. Very typically, this requires the use of a binder material at some stage of the process. This binder may be required to provide strength for the "green" article prior to any drying and / or firing steps and / or to provide strength to the final formed body. In this context, "green" refers to the body before it is passed through any subsequent firing steps. An organic binder can be burned out during the firing step if the body is to subsequently maintain sufficient strength, for example, due to firing. The binder can remain in the zeolite body after formation or can be chemically converted in - situ to another chemical species. The binder can be an organic material (e.g., an organic polymer), or an inorganic material such as alumina, silicates, or clays, and mixtures thereof. In the art, typically, levels of inorganic binder of 15 wt% to 30 wt% or higher are required to provide sufficient strength and wear resistance for large - scale and extensive use.

[0008] A further level of complication in using many zeolites is that they are constructed around "template" molecules or "structure - directing agents" so as to have specific sizes and pore sizes and shapes. These templates are organic molecules and must be removed from the zeolite for the zeolite to be functional. This is typically done by firing the zeolites at a temperature greater than 500 °C to burn out the template after synthesis. Clearly, this also removes any other organic materials present. This does not mean that an organic binder that helps provide green strength cannot be used. Some processes use an organic binder during the initial processing and also rely on firing the zeolite particles during firing to provide a robust body.

[0009] Such processes will necessarily introduce even larger macropores originating from the burned-out binder, which can result in a body with a lower density and a non-optimal porosity profile. Also, the use of binders such as alumina or boehmite, especially at relatively high levels that may be required to provide adequate robustness, can negatively impact parameters such as the zeolite level, porosity profile, and chemical behavior (e.g., Bronsted acidity) of the zeolite body as a whole. This can occur even when binders such as silica, alumina, and metakaolin are subsequently converted to zeolites (so-called " binderless" zeolite bodies) by post-hydrothermal treatment or dry gel conversion, because it is very likely that a 100% amorphous material such as metakaolin cannot be converted to a crystalline zeolite, resulting in low microporosity. Typically, the zeolites formed by the conversion of the inorganic binder in such " binderless" zeolite bodies will not be the same zeolites as those formed in the zeolite body. Additionally, or alternatively, the use of relatively high levels of binder also results in other negative effects, such as clogging of the entrances of the zeolite pores (resulting in poor mass transfer), especially at the pore openings of the catalyst, leading to a decrease in catalyst selectivity and undesirable chemical reactions such as coke formation, and combinations thereof.

[0010] The pore size distribution of the zeolite body affects catalyst selectivity and lifespan. Specifically, controlling and restricting the proportion of larger pores may help control the species accessible to the active catalyst sites. Larger pores, such as mesopores (2 nm - 50 nm) or macropores (> 50 nm), help admit reactants to the catalyst sites located inside the intrinsic micropores of the zeolite crystal. However, larger pores, especially macropores, can also allow overly easy ingress and egress of unwanted species, including unwanted by-products, to and from the material, increasing the risk of unwanted reactions. Specifically, macropores are often associated with the problem of carbon "coking", where carbon deposits accumulate over time inside the zeolite body, limiting performance and catalyst lifespan.

[0011] All current zeolite bodies are thus complex, compromising between competing and sometimes conflicting requirements. The use of a binder in forming such bodies is necessary but not desirable, as there are always negative consequences associated with the use of any type of binder. An ideal zeolite catalyst body could combine relatively high robustness, high density, high surface area, high catalytic activity, and selective and hierarchical porosity, all in a single zeolite body, without excessive macroporosity. These requirements are often conflicting.

[0012] Therefore, there is a need to develop an improved zeolite body and an improved manufacturing process for producing such a body, in particular a robust body that requires only a low level of binder or no binder at all throughout the forming process. The inventors have found that by drying the reaction mixture in a controlled manner to avoid powder formation, subsequently forming it into a body, and then firing it, a zeolite body with improved properties can be directly produced from a reaction mixture comprising submicron zeolite microcrystals. If these steps are carried out on the zeolite powder before the powder is formed into a larger body, subsequent washing and / or ion exchange can be carried out in a much easier manner than would otherwise be possible. Compared to producing a typical zeolite body from a pre-formed powder, the small zeolite particles in the reaction mixture allow for a more compact packing in the zeolite body (which increases the density and reduces the macropores), reduce or even eliminate the need for a binder material, and increase the robustness of the final zeolite body. A zeolite body formed directly from the reaction mixture can have improved robustness even compared to a zeolite body formed from submicron zeolite powder.

[0013] For extrusion or any other process of producing zeolite bodies to be industrially meaningful, extrudates / bodies that can be handled at an industrially meaningful rate using existing equipment must be producible. Much of the prior art regarding the extrusion of zeolites (or other particle formation steps) describes results obtained on a small scale, e.g., in a laboratory, which are not readily applicable to industrial processes. A mixture containing a liquid plasticizer / lubricant in addition to zeolite powder is typically made into a single extrudate strand, which is left to dry and subsequently cut, typically dried and calcined. To enable large-scale industrially meaningful processing, the physical properties required of the mixture that is extruded or otherwise formed into a body are rarely described in the art. However, successfully handling the formed zeolite body after extrusion or general manufacturing is essential for any further large-scale manufacturing rate.

[0014] In the extrusion process, it is necessary to break or cut the extruded strand into smaller lengths (“extrudates”). This can be done by mechanical cutting of longer extrudates or by relying on breakage during extrusion and subsequent handling. Extrudates are often formed by mechanical cutting of the extrudate strand using a die face-cutter during subsequent handling or by natural breakage of the strand. Extrudates are typically cut by a rotating blade that moves across the surface of the die plate. This means that the extrudate can be cut to a controlled length, and this length can be controlled by the rotational speed of the cutting tool. It may be preferable for such extrudates to be cut into various lengths, including small pieces, to promote bulk filling density. It may be preferable for the extrudates to be cut to a very consistent length.

[0015] For any body forming process based on an extrusion cutting process or a cutting or milling operation to work well, it is desirable that the material does not stick to any blade / tool used to break or cut the material. If a large amount of material actually sticks to the cutting blade / tool, this will result in a rapid accumulation of material on the cutting tool, and instead of individual extrudates or bodies, large chunks of material will be produced. It is also necessary that the bodies, such as extrudates, do not stick to each other or to the equipment side immediately after cutting or breaking. This is often a major problem with extrusion cutting processes, which is due to the extrudates concentrating in a small space and leading to frequent extrudate:extrudate collisions. If the extrudates or bodies are too soft and / or too sticky, they may stick to each other after a collision. Also, if the extruded strands are too soft or too sticky, processes that rely on mechanical breaking of the extrudate strands will not work well, of course.

[0016] The problem of preventing the material from sticking to the cutting tool / blade applies to other forms besides extrudates, such as flakes, sheets, tablets, or other larger bodies or chunks of material. Extrudates are a very convenient form, but it is also industrially significant that other larger bodies, such as larger zeolite chunks formed by tray drying, can be made into smaller, industrially significant zeolite bodies, for example, by cutting or otherwise breaking them using a flaker or other cutting tools. The formation of the smaller zeolite bodies is often followed by optional but highly preferred additional process steps such as spheronization in a spheronizer, controlled drying, firing, washing, ion exchange, and combinations thereof. The firing step can remove any template molecules from inside the pores.

[0017] Therefore, it can be seen that in order to successfully carry out the large-scale production of suitable zeolite bodies by extrusion or other particle forming processes, the zeolite mixture being processed is required to have specific physical properties. Any mixture should not be too soft when cut or broken, otherwise it will stick to itself, or to the equipment side, or to the cutting tool, which will immediately lead to the process becoming infeasible. If the mixture is too hard, it may be difficult to extrude the mixture.

[0018] For clarity, the term "zeolite body" describes a body, such as an extrudate, or milled / cut particles (also referred to as granular bodies), where in this case the majority of the body (i.e., > about 50 wt%) comprises one or more zeolites.

[0019] When the zeolite bodies are granular bodies, such as those formed by milling / cutting and sieving, they preferably have a d 50 average particle size greater than about 100 microns and up to about 3000 microns, such as from about 250 microns to about 1500 microns, or from about 350 microns to about 1200 microns, as measured by the methods described herein.

[0020] The zeolite bodies of the present invention can also contain catalyst species. Typically, these catalyst materials are present at very low levels and can be incorporated into the zeolite bodies either in the reaction mixture or in a post-formation chemical modification step.

[0021] The inventors have found that an optimized zeolite body is formed when the zeolite particles / microcrystals in the reaction mixture used to form the zeolite body are of a small size. Suitable sizes, as measured by the methods described herein, are less than about 1 micron, or less than about 900 nm, or less than about 800 nm, or less than about 600 nm, or less than about 400 nm, or even less than about 200 nm, or most preferably less than about 100 nm d 50 There are zeolite microcrystals having etc.

[0022] Separating such small microcrystals by filtration in the same way that larger zeolite particles can be separated is not industrially easy. Separating, washing, and concentrating the zeolite particles / microcrystals from the reaction mixture is generally done in the laboratory by using a high-speed centrifuge. This may be possible in the case of small zeolite microcrystals, but it is not industrially practical for large-scale operation due to the cost and complexity of high-speed centrifugation.

[0023] It is highly preferred that the zeolite reaction mixture containing these small zeolite particles / microcrystals does not undergo a powder-forming drying step, such as flash drying or spray drying, to remove water before being formed into a larger zeolite body. A rapid drying process produces zeolite powder. Thus, the production of zeolite powder typically may require the use of a high level of binder to make a robust zeolite body, which necessarily has negative consequences. In addition, such a rapid drying step typically causes small zeolite particles to aggregate into larger porous powder particles, and these powder particles will have low mechanical stability and bulk density in any resulting zeolite body.

[0024] In the method of the present invention, a zeolite reaction mixture comprising small zeolite particles / microcrystals is typically concentrated by controlled (and further slow) removal of water to form a mass of solid or very viscous paste-like or gel-like material rather than a powder, and then further formed into smaller zeolite bodies. Such solid or very viscous paste-like masses are referred to as "partially dried" zeolite masses. Typically, the zeolite microcrystals in the reaction mixture are not passed through a washing step before being formed into zeolite bodies. Instead, the zeolite bodies are typically washed after being formed to remove impurities. This simplifies the process. Typically, the smaller zeolite particles / microcrystals allow for a more compact packing and density in the final zeolite body.

[0025] Typically, adding an adsorbent binder powder to the partially dried zeolite mass can assist in the subsequent formation of the zeolite body, which is done, for example, by increasing the viscosity of the partially dried zeolite mass such that a partially dried zeolite mass that can be extruded without problems or is more easily formed into smaller bodies is produced. Suitable binders can be selected from silicas, aluminas, aluminosilicates including zeolites, and clays. Preferably, the adsorbent binder powder is silica. Silicas can also act as binders that promote the strength of the final zeolite body. The level of silica can be less than 15 wt% of the zeolite body, which helps to avoid problems with using high binder levels. Zeolite bodies with even lower levels of silica, such as less than 10 wt% or even 5 wt%, are preferred. Compared to typical prior art, the lower level of binder is made possible by the small size of the zeolite microcrystals and the direct formation of the zeolite body from the reaction mixture.

[0026] It is also possible to incorporate additional zeolite powder into the partially dried zeolite mass, under the condition that the level is restricted to (e.g., < about 40 wt%, or < about 30 wt%, or < about 20 wt%, or < about 10 wt% zeolite body), which helps to avoid some of the negative results of the zeolite powder. Preferably the zeolite powder is the same zeolite as that formed in the reaction mixture. A preferred option is that the adsorbent zeolite powder comprises recycled zeolite body material, typically after a milling step. It may be preferred that the partially dried zeolite body is classified (in any order) and further dried after formation, and that the dried but off-specification material is milled. Milling is made easier by milling off-specification material prior to calcination.

[0027] Typically, a "partially dried" zeolite mass retains sufficient water to be deformable and extrudable, but is solid enough to maintain its shape during handling if formed into a body. The partially dried zeolite mass is formed into a zeolite body by body-forming steps such as extrusion and / or cutting. The zeolite body is subsequently passed through subsequent process steps selected from washing, chemical modification, drying, calcination, and combinations thereof. The drying step can be integrated with the calcination step.

[0028] The reaction mixture can be dried under conditions typically avoiding the formation of zeolite powder, and partially dried zeolite lumps can be formed by various means. The reaction mixture can be dried by heating to a temperature of less than about 100 °C, or less than about 90 °C, or less than about 80 °C, or even less than about 70 °C. This can take several days, for example about 1 day, or about 2 days, or about 3 days, or about 4 days, or even longer than about 5 days. The reaction mixture can be dried by two or more different methods. A preferred technique is to concentrate the reaction mixture by using a wiped film evaporator. The concentrated reaction mixture obtained from the wiped film evaporator can be made into partially dried zeolite lumps, provided it is dried sufficiently, or can be further dried, for example by slow tray drying, to form partially dried zeolite lumps, or can be combined with an adsorbent material such as silica to form partially dried zeolite lumps. Typically, the partially dried zeolite lumps will retain some "free" water, although it is possible for the partially dried zeolite lumps to have no measurable level of free water. "Free" water refers to some of the water that can be removed from the material by drying at 35 °C for 5.0 hours. Free water is not tightly bound to the chemical species and can affect the rheology of the zeolite lumps. For example, water incorporated into the zeolite crystal structure is not considered free water. A sample size between 1.0 g and 2.0 g is generally used when measuring the free water level.

[0029] By controlling the physical properties of the partially dried zeolite mass, for example by controlling the level of free water in the partially dried zeolite mass, industrially significant processes such as extrusion molding / spheronization can be used successfully. If the level of free water is too high, the zeolite mass will become too soft to be processed into a zeolite body. The level of free water in the zeolite mass can also be evaluated not only by mass loss but also by the water activity of the mass. The water activity of a material at a given temperature is defined as the ratio of the humidity of the air in equilibrium with the sample at that temperature to the saturated humidity of the air at that temperature. The greater the level of free water, the greater the water activity. Thus, it is also possible to define a higher level of water activity such that the material is processable.

[0030] Firing the partially dried zeolite body, typically by removing any template material, increases the strength of those zeolite bodies. The small particle size of the zeolite microcrystals promotes the sintering effect of the firing step.

SUMMARY OF THE INVENTION

MEANS FOR SOLVING THE PROBLEM

[0031] The present invention provides a method for manufacturing a zeolite body, the method comprising: (a) forming a zeolite reaction mixture, wherein the zeolite reaction mixture comprises: (i) submicron-sized zeolite microcrystals; and (ii) water, and forming the step; (b) removing at least a portion of the water from the reaction mixture to form a partially dried zeolite mass; and (c) extruding and / or cutting the partially dried zeolite mass to form a partially dried zeolite body; (d) passing the partially dried zeolite body through one or more additional process steps selected from a spheronization step, a drying step, a classification step, and any combination thereof; (e) heating the partially dried zeolite body to a temperature greater than 400 °C to form a fired zeolite body; (f) contacting the fired zeolite body with water to form a water-exchanged zeolite body; (g) passing the washed zeolite body through a cation exchange step to form a cation-exchanged zeolite body; (h) heating the cation-exchanged zeolite body to a temperature greater than 200 °C to form a zeolite body, and comprising.

[0032] Preferably, the zeolite microcrystals can be selected from: ZSM-5; zeolite A; zeolite beta (aluminosilicate beta and Sn-beta); titanium silicate-1; faujasite (types X and Y); chabazite (SSZ-13, Cu-SSZ-13, Fe-SSZ-13, and SAPO-34); ferrierite; sodalite; mordenite; ZSM-11; ZSM-22; ZSM-23; zeolite L; MCM-22; and any combination thereof. Thus, the zeolite body can comprise ZSM-5; zeolite A; zeolite beta (aluminosilicate beta and Sn-beta); titanium silicate-1; faujasite (types X and Y); chabazite (SSZ-13, Cu-SSZ-13, Fe-SSZ-13, and SAPO-34); ferrierite; sodalite; mordenite; ZSM-11; ZSM-22; ZSM-23; zeolite L; MCM-22; and any combination thereof.

[0033] Step (e) will typically involve removing any template material from the fired zeolite body. Step (e) can be carried out at a temperature greater than about 400 °C, or greater than about 500 °C, for example about 550 °C. Step (h) can be carried out at a temperature greater than about 200 °C, for example about 250 °C, or about 300 °C, or about 350 °C, or about 400 °C, or about 450 °C, or about 500 °C, or about 550 °C, or even higher than that.

[0034] The adsorbent binder powder can be incorporated into the partially dried zeolite mass during step (b) and / or (c). It can be highly preferred to include the adsorbent binder powder in the partially dried zeolite mass either during or after step (b) so as to improve step (c). This can simplify step (b), for example, by reducing the amount of water that needs to be removed.

[0035] The partially dried zeolite mass is typically formed into a partially dried zeolite body, such as an extrudate of a predetermined length. Subsequently, they are typically passed through one or more further processing steps, such as drying, sizing, and / or spheronization. The partially dried zeolite body can also be further dried in a secondary drying step. The partially dried zeolite body is calcined to form a calcined zeolite body. Preferably, any drying step, typically step (b) and / or step (d), is carried out under controlled and restricted conditions, such as below about 100 °C, or below about 70 °C, or even below about 50 °C. If the water level in step (b) and / or step (d) is greater than about 70 wt%, it may be preferable for the initial drying step to be carried out at a temperature of about 100 °C, or greater than about 100 °C. If the water level in step (b) and / or step (d) is about 70 wt% or less than about 70 wt%, it may also be preferable for the drying step to be carried out at a temperature that is even less than about 100 °C, or less than about 70 °C, or less than about 50 °C. It may be preferable to manage the drying temperature as described above, as the material dries and the water level is reduced in step (b) and / or step (d). It may be preferable to integrate step (d) and step (e) by having a drying step as part of the calcination cycle. Any secondary drying step can also be integrated with the calcination step.

[0036] If the water level in the reaction mixture is high, for example, initially, a higher temperature may be used, but it needs to be reduced once the reaction mixture starts to solidify. The controlled drying of the partially dried zeolite mass and zeolite body is considered important for controlling the macro- and mesoporosity of the partially dried zeolite body. The faster the drying, the more macroporosity is introduced into the resulting body. If the drying is too rapid, the zeolite mass or body may even fragment.

[0037] The present invention also provides zeolite bodies made according to the processes disclosed herein, wherein the at least one zeolite body comprises greater than 85% zeolite; the at least one zeolite body comprises greater than 0.6 g / cm 3 and 1.4 g / cm 3 the at least one zeolite body has a macroporosity of less than 15% as measured by mercury porosimetry.

[0038] At least one zeolite body has a d between 100 microns and 3000 microns. 50 The at least one zeolite body may be in the form of granules having a particle size of greater than about 100 microns in thickness and less than about 10 cm in length. The at least one zeolite body may be in the form of extrudates having a minimum internal dimension (thickness) of greater than about 100 microns and a maximum internal dimension (length) of less than about 10 cm ... 3 It may have a greater bulk density. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0039] Throughout this specification, one or more aspects of the present invention may be combined with one or more features described herein to define distinct embodiments of the present invention.

[0040] Wherever a singular form of a noun is referred to herein, this includes the plural form of that noun, and vice versa, unless the context indicates otherwise. For example, the term zeolite body should be understood to also refer to zeolite bodies.

[0041] Throughout this specification, the term "comprise", or variations such as "comprises" or "comprising", are to be understood to imply the inclusion of the stated element, ingredient, or step, or group of elements, ingredients, or steps, but not the exclusion of any other element, ingredient, or step, or group of elements, ingredients, or steps. The term "comprising" includes within its scope the terms "consisting of" and "consisting essentially of".

[0042] The term "consisting" or variations thereof is to be understood to imply the inclusion of the stated element, ingredient, or step, or group of elements, ingredients, or steps, and the exclusion of any other element, ingredient, or step, or group of elements, ingredients, or steps.

[0043] The term "consisting essentially of" or variations thereof is to be understood to imply the inclusion of the stated element, ingredient, or step, or group of elements, ingredients, or steps, and that additional elements may be present, but that they only substantially do not affect the essential characteristics of the formulation, composition, or compound.

[0044] As used herein, the term "about", when quantifying a number or value, is used to refer to a value within ±5% of the specified value.

[0045] A method for producing a zeolite body. The method is: (a) forming a zeolite reaction mixture, wherein the zeolite reaction mixture is: (i) submicron-sized zeolite microcrystals and; (ii) water, and comprising the step of; (b) removing at least a portion of water from the reaction mixture to form a partially dried zeolite mass; (c) extruding and / or cutting the partially dried zeolite mass to form a partially dried zeolite body; (d) passing the partially dried zeolite body through one or more further process steps selected from a spheronization step, a drying step, a classification step, and combinations thereof; (e) heating the partially dried zeolite body to a temperature greater than about 400 °C to form a calcined zeolite body; (f) contacting the calcined zeolite body with water to form a water-exchanged zeolite body; (g) passing the washed zeolite body through a cation exchange step to form a cation-exchanged zeolite body; (h) heating the cation-exchanged zeolite body to a temperature of about 200 °C, or about 300 °C, or greater than about 400 °C to form a zeolite body, and comprising.

[0046] The present invention provides a method for producing a high-performance zeolite body from a zeolite reaction mixture comprising submicron zeolite microcrystals. The zeolite reaction mixture is concentrated by a controlled water drying step to form a partially dried zeolite mass. This has the form of a solid mass or a very viscous paste mass rather than a powder. An adsorbent binder powder can be incorporated into the partially dried zeolite mass. A preferred method is to add a low level of adsorbent powder, preferably silica, alumina, aluminosilicates, or clay, to the partially dried zeolite mass. This can assist in the formation of such zeolite bodies by increasing the green strength of the partially dried zeolite body and / or the ease of cutting the partially dried zeolite mass.

[0047] The partially dried zeolite mass is subsequently formed into a partially dried zeolite body by means of an extrusion and / or cutting process. The partially dried zeolite body is subsequently typically passed through one or more further process steps selected from classification, spheronization, drying, and combinations thereof, prior to firing. The fired zeolite body subsequently undergoes a washing step and, very typically, a cation exchange step to remove undesirable cations such as sodium. They are subsequently passed through a further high-temperature treatment step to form the final zeolite body.

[0048] Zeolite powder can also be incorporated into the partially dried zeolite mass. The zeolite powder may or may not be the same zeolite as that which forms the partially dried zeolite mass. Preferably the zeolite powder is recycled material from a later stage in this process. For example, the zeolite powder can be selected from: ZSM-5; zeolite A; zeolite beta (aluminosilicate beta and Sn-beta); titanium silicate-1; faujasite (types X and Y); chabazite (SSZ-13, Cu-SSZ-13, Fe-SSZ-13, and SAPO-34); ferrierite; sodalite; mordenite; ZSM-11; ZSM-22; ZSM-23; zeolite L; MCM-22; and any combination thereof.

[0049] The method of the present invention is believed to enable the use of even lower levels of binder material (e.g., less than about 15 wt% of the zeolite body) to minimize the negative results discussed above.

[0050] Step (a). Formation of a zeolite reaction mixture. Step (a) forms a zeolite reaction mixture.

[0051] Preferably, step (a) is: (i) (a) A zeolite precursor material, preferably two or more zeolite precursor materials, preferably three or more zeolite precursor materials; (b) Water, and are brought into contact together to form a dilute reaction mixture, wherein the dilute reaction mixture comprises: (a) Sub-micron sized zeolite particles / microcrystals; and (b) Water; and is carried out by comprising the above.

[0052] In other words, the sub-micron sized zeolite particles / microcrystals are formed by contacting a zeolite precursor material, for example two or more, or three or more zeolite precursor materials.

[0053] The sub-micron size is such that the zeolite microcrystals have a sub-micron d 50It means having an average particle size. Preferably, the microcrystals have a weight-average average particle size of from about 10 nm to about 1000 nm, or from about 10 nm to about 800 nm, or from about 12 nm to about 700 nm, or from about 15 nm to about 500 nm, or from about 20 nm to about 300 nm, or from about 25 nm to about 150 nm. Smaller microcrystals typically increase particle packing in the zeolite body, giving a higher bulk density and increasing the level of particle:particle sintering during the firing step. The method of measuring the particle size is described in more detail below. The particle size of the zeolite microcrystals is typically measured in the reaction mixture using dynamic light scattering, but can also be measured in the final zeolite body using SAXS techniques. The particle size of the zeolite microcrystals can be controlled by varying the concentration of the reactants (zeolite precursor materials), the temperature of the reaction mixture, and the time of the reaction. Preferably, the reaction is carried out at a lower temperature, for example less than about 80 °C, or less than about 70 °C, over a period of several days, for example from about 3 days to about 10 days, preferably about 5 days. For example, the zeolite precursor materials are brought into contact with each other at about 25 °C and subsequently heated at 70 °C for 5 days. Typically, the precursor materials comprise "template" molecules that govern the structure and pore size of the zeolite.

[0054] The zeolite precursor material can be, for example, a silica material (such as tetraethyl orthosilicate, sodium silicate, colloidal silica, fumed silica, silica gel, and / or amorphous silica), an aluminum material (such as alumina, aluminum sulfate, aluminum chloride, aluminum nitrate, aluminum hydroxide, and / or aluminum alkoxide), an alkali metal or alkaline earth metal material (such as sodium hydroxide, sodium aluminate, potassium hydroxide, and / or calcium hydroxide), and / or an organic structure-directing agent (such as tetraethylammonium hydroxide and / or tetrapropylammonium hydroxide). For example, the zeolite precursor material can be tetraethyl orthosilicate, tetrapropylammonium hydroxide, and aluminum sulfate.

[0055] Step (b). Formation of a partially dried zeolite mass. Step (b) removes water from the zeolite reaction mixture to form a partially dried zeolite mass.

[0056] Step (b) can be implemented in a plurality of ways. Preferably, exact process conditions are basically important. Preferably, the partially dried zeolite mass is not a particle. Typically, the partially dried zeolite mass is a very viscous paste-like mass. The partially dried zeolite mass can be made into an integrated mass. Without wishing to be bound by theory, it is believed that the formation of a powder material can be avoided by controlling the rate at which water is removed (e.g., by increasing and / or decreasing) (e.g., by controlling the drying temperature). This can potentially be done in a wiped film evaporator, and the resulting partially dried zeolite mass is subsequently formed into smaller partially dried zeolite bodies. Suitable equipment includes, for example, the D-Velpac Evaporator manufactured by LCI Corporation. The zeolite reaction mixture is left to dry at a moderate temperature for a long period of time, for example while spreading on a flat surface or in a reaction vessel, to form a partially dried zeolite mass, and then it can potentially be cut in a forming step, for example in a cutting mill or flaker, or other suitable cutting equipment. To avoid doubts, milling or flaking can be performed on the partially dried zeolite mass, the partially dried zeolite body, the fired zeolite body, the washed and fired zeolite body, the cation-exchanged zeolite body, or the zeolite body. After milling, the milled zeolite can be sieved to obtain a preferred particle size. The drying time can be made greater than about 48 hours at a drying temperature that is less than about 70 °C, or less than about 65 °C, or even less than about 60 °C.

[0057] The adsorbent binder powder can be added to the partially dried zeolite mass either during or after drying. This combination of steps can provide process advantages such as enabling the partially dried zeolite mass to be more easily formed into smaller, further partially dried zeolite bodies, for example by extrusion molding, while at the same time limiting the amount of water that has to be removed (thereby simplifying the process).

[0058] Step (b) can be carried out in different unit operations, for example, by removing some of the water in a wiped film evaporator and then adding the adsorbent binder powder in a mixer or extruder. The mixing of the partially dried zeolite mass and the binder powder can be carried out in the same extruder that is used to form the extrudate or in separate equipment. One option may be to mix the partially dried zeolite mass and the adsorbent binder powder and then carry out extrusion molding or form smaller bodies. Suitable equipment includes, for example, the Z Sigma Blade Extruder Mixer manufactured by Winkworth Machinery Ltd.

[0059] Silicas suitable for use as further adsorbent materials are precipitated silicas or fumed silicas, preferably fumed silicas or silica suspensions. Suitable fumed silicas include, for example, Cab-O-Sil® M-5 manufactured by Inoxia. Suitable precipitated silicas include the Sipernat product range manufactured by Evonik.

[0060] Typically, the partially dried zeolite mass prior to forming the partially dried zeolite body is at least > about 4.0×10 at 10 s -1 and 25 °C 5It has a viscosity of mPa·s. In one preferred embodiment, since the partially dried zeolite mass is deformable under pressure or impact, it can be spheronized, for example, in a spheronizer. It may be preferred that the partially dried zeolite mass can be milled in a mill to form a zeolite body if it is sufficiently dry and hard.

[0061] Step (c). Extruding and / or cutting the partially dried zeolite mass to form a partially dried zeolite body. Step (c) extrudes and / or cuts the partially dried zeolite mass to form a partially dried zeolite body having a size smaller than the partially dried zeolite mass. The choice of equipment clearly depends on the end use. Extrusion is preferred for making larger bodies. Suitable equipment includes extruders such as Caleva's Variable Density Extruder. The extrusion step can also potentially be used to incorporate an adsorbent binder powder into the partially dried zeolite mass immediately before forming the partially dried zeolite body. Cutting / milling equipment such as Retsch's SM Cutting Mill series may be suitable for other applications that require small bodies (e.g., granules). Small zeolite bodies include those formed by milling (e.g., granules) or having a particle size of greater than about 100 microns and up to about 3000 microns, such as from about 250 microns to about 1500 microns, or from about 350 microns to about 1200 microns, as measured by the methods described herein. 50 There are zeolite bodies having a particle size, etc.

[0062] Step (d). Pass the partially dried zeolite body through one or more further process steps selected from a spheronization step, a drying step, a classification step, and combinations thereof. Typically, after forming the partially dried zeolite body, e.g., by extrusion or cutting / milling, the partially dried zeolite body is typically not yet suitable for the firing step. They can be spheronized in a spheronizer or it may be necessary to sort them prior to firing to remove bodies that are too large or too small in size. Step (d) may also include options such as further drying the partially dried zeolite body, e.g., an extrudate, milling the further partially dried zeolite body, and classifying the milled further partially dried zeolite body. Suitable equipment for such a milling step includes, for example, the SM Cutting Mill from Retsch. By selecting only the bodies that are optimally sorted for the subsequent firing, off-specification material can be recycled more easily. The size and properties of the partially dried zeolite body depend on the application. Larger extrudates are suitable for some applications, while smaller milled granules are more suitable for other applications, and those skilled in the art will be well aware of such things. It may also be useful to further dry the partially dried zeolite body prior to firing. Suitable equipment for spheronization includes, for example, the Caleva spheronizer, such as the Caleva S500.

[0063] Step (e). Heating the partially dried zeolite body to a temperature greater than 400 °C to form a fired zeolite body. Step (e) activates the partially dried zeolite body, which is typically done by burning off any template material to form the fired zeolite body. Step (e) also typically causes the particles to sinter together partially to increase the robustness of the final zeolite body. Step (e) is typically carried out at a temperature greater than about 400 °C, such as about 500 °C or about 550 °C. Typically, step (e) maintains the zeolite body at a high temperature greater than about 500 °C for a time longer than about 1.0 hour, longer than about 2.0 hours, longer than about 3.0 hours, or even longer than about 4.0 hours.

[0064] Step (f). Contacting the fired zeolite body with water to form a water-exchanged zeolite body. Step (f) contacts the fired zeolite body with water. This promotes the removal of soluble residual reactants. Typically, this is carried out until the washing water in contact with the fired zeolite body has a pH between about 7 and about 8.

[0065] Step (g). Passing the washed zeolite body through a cation exchange step to form a cation-exchanged zeolite body. The fired and washed zeolite body is typically passed through a cation exchange by contacting the washed zeolite body with a solution of ammonium chloride. This exchanges free cations such as sodium for ammonium ions. Suitable ammonium chloride solutions include those having a concentration between about 0.25 M and about 5 M. Typically, the cation exchange is carried out for at least about 1.0 hour, and preferably at least about 1.0 hour to about 14 hours. Typically, the cation exchange is carried out at room temperature, or at an elevated temperature, such as about 60 °C to about 100 °C. The cation-exchanged zeolite body is subsequently typically washed. The cation exchange step can be repeated.

[0066] Step (h). Heating the cation-exchanged zeolite body to a temperature higher than about 200 °C, about 300 °C or about 400 °C to form a zeolite body. This step typically removes any remaining water and any ammonium chloride from the cation-exchanged zeolite body to form the completed zeolite body.

[0067] Binder. The binder may optionally be included in the zeolite mass. Preferably, the binder is silica. When used, the binder is typically added at a level of less than about 15 wt% of the zeolite body.

[0068] The zeolite body can also be subjected to a post-synthesis modification step, for example, a further ion exchange step or impregnation with a metal species selected from one or more of the following: Cu, Ag, Mg, Ca, Sr, Ti, Zr, Hf, Zn, Cd, B, Al, Ga, Sn, Pb, Pt, Pd, Re, Rh, V, P, Zn, Sb, Rb, Li, Cs, Ag, Ba, Cr, Mo, W, Mn, Re, Fe, Co, Ni, and noble metals.

[0069] Partially dried zeolite mass. The partially dried zeolite mass is formed in step (b). Typically, it is important to control the rheology of the partially dried zeolite mass. The mixture being cut needs to be sufficiently "solid" so that it can be cut successfully without damage. One measure of how "solid" the material is its viscosity. Typically, therefore, it is important that the viscosity of the partially dried zeolite mass is above a certain minimum value. The rheology of the partially dried zeolite mass can be changed by adding an adsorbent material and / or a binder, making the zeolite mass more suitable for forming a body.

[0070] In addition, a preferred option is for the partially dried zeolite bodies to be passed through a spheronization step after cutting or breaking, for example in a spheronizer. Spheronization of the partially dried zeolite bodies is preferred as a dust reduction step. However, for the extrudates to be spheronized, they need to be sufficiently deformable for this spheronization to occur. If the partially dried zeolite bodies are to be spheronized, there is preferably an upper limit on the viscosity value of the partially dried zeolite agglomerates.

[0071] Thus, the partially dried zeolite agglomerates in the preferred method of the present invention typically have a mass of about 3.0×10 5 mPa.s or approximately 4.0×10 5 Greater than mPa.s, or approximately 5.0×10 5 mPa.s or approximately 6.0×10 5 greater than mPa.s, or approximately 7.0×10 5 Greater than mPa.s or approximately 1.0 mPa.s x 10 6 mPa.s even greater than 10s -1 The preferred viscosity may be selected based on the nature and design of the cuts and subsequent processing steps. In a preferred method of the invention, the partially dried zeolite agglomerates typically have a viscosity of about 3.0×10 6 Less than mPa.s, or about 2.0 x 10 6 Less than mPa.s, or about 1.25 x 10 6 mPa.s, less than 10s -1 It has a viscosity of

[0072] Partially dried zeolite body. The partially dried zeolite body is formed in step (c). The partially dried zeolite body undergoes further process steps in step (d). The partially dried zeolite body can have various shapes and sizes. The partially dried zeolite body can be in the form of granules, or spheroidized pellets, or even larger extrudates. When the partially dried zeolite body is in the form of an extrudate, it typically has a minimum internal dimension (thickness) greater than about 100 microns and a maximum internal dimension (length) less than about 10 cm. The term "internal dimension" describes the length of a straight line drawn approximately perpendicular from one edge of the body to the opposite edge of the body without intersecting any external surface. These can be determined by optical microscopy techniques or by image analysis using a QicPic device. When the partially dried zeolite body is in the form of granules, for example, milled from a larger body, the size is typically described by 50 the average particle size. A preferred 50 size, measured by the method described herein, is from 100 microns to 1500 microns. When the granules are spheroidized extrudates, 50 can be as large as, or even larger than, typically 3000 microns, measured by the method described herein. The particle size can be measured by laser diffraction using an instrument such as a Mastersizer 3000 manufactured by Malvern Panalytical.

[0073] Fired zeolite body. The fired zeolite body is formed in step (e).

[0074] Water and cation-exchanged zeolite body. The water and cation-exchanged zeolite body is formed in steps (f) and (g).

[0075] Zeolite body or main body. The zeolite body is formed in step (h). The zeolite body comprises zeolite and optionally a binder, such as a silica binder. The binder, if present, is less than about 15 wt% of the zeolite body. Typically, the zeolite body has an envelope density between 0.6 g / cm 3 and 1.4 g / cm 3 and typically greater than about 1.0 g / cm 3 .

[0076] The zeolite body can be in the form of granules having a particle size between 100 microns and 3000 microns. The zeolite body can have a bulk density greater than 0.5 g / cm 50 . 3 Test method

[0077] Method for measuring viscosity. A suitable instrument for measuring the viscosity of an undried binder mass is the Anton Paar MCR 92 Rheometer, which has a 25 mm diameter plate, a 25-degree angle cone, and is measured at 25 °C using a 3.0 mm gap. Place a sample of about 2 g on the plate, lower the upper cone to the target gap distance, remove the excess sample from the side, and measure the rotational viscosity. Typically, the viscosity is measured over a range up to a shear rate of 50 s -1 . For the purposes of this specification, the viscosity of the material is the viscosity measured at 10 s -1 .

[0078] Method for measuring water activity. The water activity of a material is defined as the fractional relative humidity of the atmosphere in equilibrium with that material, i.e., the ratio of the partial pressure of water vapor above the material to the partial pressure of water vapor above pure water at the same temperature. The term "Relative Humidity" (or RH) is used to describe water in the atmosphere or gas phase in equilibrium with a solid and is expressed as a percentage, with the relative humidity of pure water in a closed system being 100%. Thus, for any material, the water activity value (aw) is defined as %RH / 100. ​

[0079] Suitable equipment includes, for example, the probe HC2-AW connected to the Hygrolab C1 display unit, both of which are manufactured by Rotronic Measurement Solutions. It is desirable to set up the equipment properly and operate it according to the manufacturer's instructions. The RH of the material is measured by placing a sample of the material inside the measuring chamber of the HC2-AW, making sure that a volume greater than 1 / 4 of the available volume is filled by the sample, sealing the chamber, and leaving it until the measured value reaches equilibrium as indicated on the display.

[0080] Unless otherwise specified, the water activity measurement is carried out at 25 °C.

[0081] A method for evaluating the particle size distribution of particles in a zeolite body by SAXS. The particle size distribution of zeolite particles forming the zeolite body can be evaluated by SAXS. In principle, in a SAXS experiment, light is scattered as a result of the contrast in electron density between two phases. Based on this, the size of spherical equivalent particles, or other shapes, can be calculated. The SAXS intensity at a specific angle depends on the electron density contrast. This also depends on the size of the particles. Large particles cause scattering at low angles, and small particles cause scattering at larger angles. To generate measurement results, a zeolite body sample piece is placed on a sample holder. For SAXS, X-rays are generated by synchrotron radiation. One or more sets of data are collected with the entire range of scattering angles as the target range. A Kratky instrument can be used to collect small-angle scattering at large scattering angles (from 1e-1 to 4e-0 degrees). A Bonse Hart instrument can be used to collect small-angle scattering at even smaller scattering angles (from 2.2e-3 to 5e-1 degrees). In this case, after background removal, the two data sets are combined into a single scan, and the data is subsequently sharpened. These sharpened data are then converted into a volume size distribution function by a regularization method. The volume distribution function is the final output of this procedure.

[0082] Measurement of the particle size of zeolite microcrystals. The particle size distribution of zeolite microcrystals can be measured by dynamic light scattering method if in a reaction mixture. Suitable instruments include NANO-flex II manufactured by Colloid Metrix, which is operated according to the manufacturer's instructions. The sample probe can be inserted directly into the reaction mixture. Dilution of the reaction mixture is usually not necessary.

[0083] d 50 Measurement of the average particle size. This can be measured by laser diffraction method using an instrument such as Mastersizer 3000 manufactured by Malvern Panalytical and operated according to the manufacturer's instructions.

[0084] Bulk density. The bulk density of a plurality of bodies can be measured by completely filling a suitable cylindrical container of known volume and measuring the mass. Since the appropriate size of the container will depend on the dimensions of the body being measured, the dimensions of the container are not fixed, and those skilled in the art will recognize that it is desirable for both the inner diameter and height of the container to be 10 times larger than the maximum internal dimension of the body, respectively. There is no restriction imposed on the upper limit of the volume of the container, provided that the larger the volume, the greater the amount of material required to fill them, which can be very expensive.

[0085] Measure the mass and volume of the empty container. Subsequently, fill the container by pouring the zeolite body into the container from 5 cm above the height of the container. The top of the poured zeolite body should be at the same height as the top of the container. Subsequently, measure the combined mass of the container and the contained zeolite body. The mass of the zeolite body is calculated by subtracting the mass of the empty container from the combined mass of the container and the zeolite body. The bulk density is subsequently calculated by dividing the mass of the zeolite body by the volume of the container. Method for measuring envelope density

[0086] The zeolite body made according to the present invention typically has an envelope density greater than 0.6 g / cm 3 or greater than 0.8 g / cm 3 or greater than 1.0 g / cm 3 or greater. Typically, the zeolite body has an envelope density less than 1.4 g / cm 3 or less.

[0087] The envelope density of the body is the weight of the body (in grams) divided by its envelope volume (in mm 3It can be measured by dividing by the unit). The envelope volume is defined in ASTM D3766 as "the ratio of the mass of the particles to the sum of the volume of the solids within each piece and the volume of the voids within the interior of each piece, i.e., within a close-fitting virtual envelope (the envelope) that completely surrounds each piece."

[0088] Depending on the size and properties of the zeolite body, multiple techniques are used. Measuring the volume of the body using an accurate 3D scanner is suitable for larger regular bodies such as extrudates, for example those with a diameter > 3 mm. Suitable equipment includes the BLK360 from Leika. The dimensions of well-formed extrudates can also be measured by caliper, taking multiple measurements of each extrudate and averaging the thickness and length. Since it is necessary to measure multiple (> 25) extrudates, this is a very laborious technique.

[0089] The envelope density of the body can be measured using a technique based on Archimedes' principle of volume exclusion. The envelope density can be measured by mercury porosimetry. At atmospheric pressure, mercury does not penetrate into the internal pores. Therefore, the volume of mercury excluded by the body under atmospheric pressure is the envelope volume of the object. Dividing the weight of the sample by this volume gives the envelope density.

[0090] The envelope volume and density of the body can also be measured using a powder pycnometer, for example the GeoPyc Model 1360 from Micrometrics Instrument Corp. If necessary, the envelope volume measured by these techniques can be used interchangeably with the envelope volume measured by mercury porosimetry. If there is a contradiction between the results, powder pycnometry and mercury porosimetry are preferred. Macroporosity

[0091] The macropores of the zeolite body produced according to the present invention preferably comprise less than 15% of the zeolite body. Preferably, the macropore ratio is less than 12%, or less than 10%, or less than 7%, or even less than 5% of the envelope volume measured by mercury intrusion porosimetry. Macropores are defined as pores larger than 50 nm according to the IUPAC convention.

[0092] The macropore ratio of the main body can be determined by the following method. The mercury porosimetry value can be measured in accordance with ASTM D4284-12. Suitable equipment for performing ASTM D4284-12 includes, for example, Micromeritics AutoPore VI 9510 of Micromeritics Corporation of the United States. Let the surface tension and contact angle of mercury be 485 mN / m and 130°, respectively. In ASTM D4284-12, mercury is pushed into the pores under pressure. A sample size of 1 g is preferably used. The zeolite body is fragmented and sieved between 710 microns and 250 microns, and the sieved material is used.

[0093] The pressure required to push mercury into the pores of the sample is inversely proportional to the pore size according to Washburn's equation. For the purpose of property evaluation, it is assumed that all pores are cylindrical. The porosimeter increases the pressure applied to the mercury in the sample holder to gradually infiltrate mercury into the small sample pores. AutoPore VI automatically converts the applied pressure into an equivalent pore diameter using Washburn's equation and the above contact angle and surface tension values.

[0094] The envelope volume of the sample can be determined by the volume of mercury excluded by atmospheric pressure. When the applied pressure is increased, mercury is pushed into the internal pores. Therefore, the % macropore ratio of the sample is shown as the ratio of the volume of mercury infiltrated into the sample as the pressure is increased from 1.001 atm to 292 atm to the exclusion volume at atmospheric pressure. The envelope volume can also be measured by other methods.

[0095] Embodiments of the present invention

[0096] The following are embodiments of the present invention.

[0097] 1. (a) A step of forming a zeolite reaction mixture, wherein the reaction mixture comprises: (i) Zeolite microcrystals having a submicron particle size; and (ii) water; and forming a step; (b) Removing water from the zeolite reaction mixture to form a partially dried zeolite mass; (c) Extruding and / or cutting / breaking the partially dried zeolite mass to form a partially dried zeolite body; (d) Passing the partially dried zeolite body through at least one further processing step selected from any combination of spheronization, drying, and classification; (e) Heating the partially dried zeolite body to a temperature greater than about 400 °C to form a fired zeolite body; (f) Contacting the fired zeolite body with water to form a washed and fired zeolite body; (g) Contacting the washed and fired zeolite body with an ammonium ion-containing solution to exchange sodium ions in the zeolite with ammonium ions to form a cation-exchanged zeolite body; (h) Heating the cation-exchanged zeolite body to a temperature of about 200 °C, or about 300 °C, or greater than about 400 °C to form a zeolite body; A method for producing a zeolite body, comprising:

[0098] 2. (i) (a) A zeolite precursor material, preferably two or more zeolite precursor materials, preferably three or more zeolite precursor materials; and (b) water; contacted together to form a dilute reaction mixture, the dilute reaction mixture being: (a) sub-micron sized zeolite microcrystals; and (b) water; The process according to embodiment 1, which is carried out by comprising.

[0099] 3. The process according to embodiment 2, wherein the zeolite precursor material and water are maintained at a temperature of less than about 100 °C, or less than about 80 °C, or less than about 70 °C, or less than about 60 °C.

[0100] 4. The process according to any one of embodiments 1 to 3, wherein step (b) is carried out by drying the reaction mixture at a temperature even less than about 100 °C, or less than about 90 °C, or less than about 80 °C, or less than about 70 °C, or less than about 60 °C.

[0101] 5. The process according to any one of embodiments 1 to 4, wherein step (b) is carried out in a wiped film evaporator.

[0102] 6. The process according to any one of embodiments 1 to 5, wherein the adsorbent binder powder is incorporated into the partially dried zeolite mass during any of steps (a), (b), or (c).

[0103] 7. The process according to embodiment 6, wherein the adsorbent binder powder comprises silica, alumina, aluminosilicates, clays, and combinations thereof.

[0104] 8. The process according to any one of embodiments 1 to 7, wherein additional zeolite powder is incorporated into the partially dried zeolite mass.

[0105] 9. The zeolite is: (i) ZSM-5; (ii) A-type zeolite; (iii) zeolite beta (aluminosilicate beta and Sn-beta); (iv) Titanium silicate-1; (v) Faujasite (X and Y types); (vi) Chabazite (SSZ-13, Cu-SSZ-13, Fe-SSZ-13, and SAPO-34); (vii) Ferrierite; (viii) Sodality; (ix) Mordenite; (x) ZSM-11; (xi) ZSM-22; (xii) ZSM-23; (xiii) Zeolite L; (xiv) MCM-22; and (xv) Any combination thereof, The process according to any one of Embodiments 1 to 8, selected from

[0106] 10. The process according to any one of Embodiments 1 to 9, wherein step (c) is carried out by using an extruder and step (d) involves the use of a spheronizer.

[0107] 11. The process according to any one of Embodiments 1 to 10, wherein the partially dried zeolite mass has a viscosity between about 3.0×10 5 mPa·s and about 3.0×10 6 mPa·s at 10 s -1 and 25 °C.

[0108] 12. The process according to Embodiment 6, wherein the level of the adsorbent binder powder is less than about 15 wt% of the zeolite body.

[0109] 13. The process according to any one of Embodiments 1 to 12, wherein non-zeolite catalyst species containing metal ions and metal-based nanoparticles are incorporated into the zeolite body.

[0110] 14. Use of a zeolite body produced according to the process according to any one of Embodiments 1 to 13 in the catalytic treatment of hydrocarbons or alcohols.

[0111] 15. (a) A step of forming a zeolite reaction mixture, wherein the reaction mixture comprises: (i) zeolite microcrystals having a submicron particle size; and (ii) water and forming a step; (b) removing water from the zeolite reaction mixture to form a partially dried zeolite mass; (c) heating the partially dried zeolite mass to a temperature greater than about 400 °C to remove residual organic material and form a calcined zeolite mass; (d) cutting / breaking the calcined zeolite mass to form a calcined zeolite body; (e) passing the calcined zeolite body through at least one further processing step selected from spheronization, drying, and classification; (f) contacting the calcined zeolite body with water to form a washed and calcined zeolite body; (g) contacting the washed and calcined zeolite body with an ammonium ion-containing solution to exchange sodium ions in the zeolite with ammonium ions and form a cation-exchanged zeolite body; (h) heating the cation-exchanged zeolite body to a temperature greater than about 200 °C, or greater than about 300 °C, for example about 400 °C, to form a zeolite body, and a method for producing a zeolite body.

[0112] 16. The process according to any one of embodiments 1 to 15, wherein the adsorbent binder powder and / or the zeolite powder material is incorporated into the partially dried zeolite mass by the use of an extruder or a Sigma mixer.

[0113] 17. As a result of passing the zeolite body through a further ion exchange step and / or impregnation step, a process according to any of embodiments 1 to 16 doped with a metal species selected from the following: Cu, Ag, Mg, Ca, Sr, Ti, Zr, Hf, Zn, Cd, B, Al, Ga, Sn, Pb, Pt, Pd, Re, Rh, V, P, Zn, Sb, Rb, Li, Cs, Ag, Ba, Cr, Mo, W, Mn, Re, Fe, Co, Ni, and noble metals.

[0114] 18. A zeolite body made according to the process of any of embodiments 1 to 17, wherein at least one zeolite body comprises zeolite greater than 85%; wherein at least one zeolite body has an envelope density between 0.6 g / cm 3 and 1.4 g / cm 3 ; wherein at least one zeolite body has a macroporosity of less than 15% as measured by mercury porosimetry, the zeolite body.

[0115] 19. At least one zeolite body according to embodiment 18, which is in the form of granules having a particle size between 100 microns and 3000 microns. 50

[0116] 20. At least one zeolite body according to embodiments 18 and 19 having a bulk density greater than 0.5 g / cm. 3

[0117] All references referred to herein are incorporated herein in their entirety as if the entire content of each reference were set forth herein in full.

[0118] Although specific embodiments and / or implementations of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications within the scope of the present invention be included within the scope of the subject matter of the appended claims.

Example

[0119] Examples 1 and 2 of the present invention Preparation of ZSM-5 zeolite material A zeolite reaction mixture was prepared as follows. All raw materials were laboratory-grade reagents from Sigma-Aldrich.

[0120] 72 g of 1M tetrapropylammonium hydroxide solution (Sigma-Aldrich) and 60 g of 98% active tetraethyl orthosilicate (Sigma-Aldrich) were mixed under ambient conditions to form Solution 1.

[0121] 15 g of 1M tetrapropylammonium hydroxide solution (Sigma-Aldrich), 0.21 g of NaOH (Sigma-Aldrich), and 6 g of distilled water were mixed under ambient conditions to form Solution 2.

[0122] Al(OH)3 gel was prepared by precipitation. 1.05 g of aluminum sulfate hydrate (Al2(SO4)3·18H2O) (Sigma-Aldrich) was dissolved in 15 mL of distilled water together with 4 mL of 25 wt% ammonia solution. This formed the gel material. The reaction mixture was placed in an Avanta J-15 centrifuge and centrifuged at 5000 rpm for 5 minutes, then washed, centrifuged, and redispersed until the supernatant had a pH of 7.4. Subsequently, all the washed Al(OH)3 gel was slowly added to Solution 2 with strong stirring. Subsequently, the mixture of Al(OH)3 gel and Solution 2 was added dropwise to Solution 1 with strong stirring under ambient conditions to form the zeolite reaction mixture.

[0123] The reaction mixture was kept at a temperature below 70 °C for 5 days under sealed conditions to crystallize the zeolite microcrystals of ZSM-5. The zeolite reaction mixture was measured to have a solid content of 27% by drying at 100 °C. The zeolite microcrystals had a particle size of less than 100 nm. Subsequently, the zeolite reaction mixture was poured equally into four separate 60 ml Falcon tubes.

[0124] Example 1 of the present invention. Two of the 60 ml Falcon tubes were placed in an oven at 140 °C for 1 hour and then slowly dried at 50 °C for 5 days to form solid, partially dried zeolite masses (Example 1). The partially dried zeolite masses were strong and could be easily handled without breaking.

[0125] Example 2 of the present invention. The remaining two tubes were also placed in an oven at 140 °C for 1 hour. Subsequently, 5 wt% (based on the zeolite content of the partially dried zeolite mass) of fumed silica (Cab-o-Sil) was added to each of the Falcon tubes and stirred to form a zeolite reaction mixture. As a result, the reaction mixture became much harder, and the reaction mixture could be easily formed into spherical bodies by hand, which was different from the reaction mixture without using silica.

[0126] Subsequently, the spheroidized zeolite masses obtained from Example 2 of the present invention were dried in the same manner as in Example 1 of the present invention to similarly form tough, partially dried zeolite bodies that could be easily handled without breaking.

[0127] Subsequently, the partially dried zeolite bodies of both Example 1 and Example 2 of the present invention were calcined in a muffle furnace at 550 °C for 6 hours at a heating rate of 1 °C / min to form calcined zeolite bodies.

[0128] Subsequently, the fired zeolite body was washed with distilled water until the surrounding water reached a pH of 7.3. Subsequently, the water-exchanged zeolite body was cation-exchanged by contacting it with a 1 M ammonium chloride solution at 80 °C overnight. This cation-exchange step was repeated using a fresh ammonium chloride solution, and then the cation-exchanged zeolite body was washed again with distilled water until the pH of the water reached 7.6.

[0129] Subsequently, the cation-exchanged zeolite body was dried at 50 °C and then calcined again in a muffle furnace at 550 °C for 6 hours at a heating rate of 1 °C / min to produce the final zeolite body.

[0130] Both sets of zeolite bodies (those with and without silica) were robust and did not form any visible dust when subjected to strong shaking in a glass vial. When tested, the zeolite body material of Example 1 of the present invention had a BET surface area of 442 m 2 / g, which was superior to that of commercially available ZSM-5 zeolite pellets and the extrudates known to the inventors. The material of Example 2 of the present invention had a BET surface area of 422 m 2 / g.

[0131] Comparative Example Comparative Example 1 2.7 g of commercially available ZSM-5 powder (CBV8014 from Zeolyst) was dispersed in 7.3 g of deionized water. CBV 8014 had a submicron particle size. This slurry was consistent in concentration (solid content) with the examples of the present invention. The slurry was dried and calcined in the same manner as the other examples. Subsequently, the fired body was not washed or ion-exchanged because these steps were performed on the zeolite powder. Unlike the examples of the present invention, the resulting body fragmented upon strong manual shaking to form visible dust.

[0132] Comparative Example 2 A similar slurry was prepared as in Comparative Example 1, except that the pH of the slurry was adjusted to pH 14 by adding 0.1 M NaOH. This was to verify whether the pH of the reaction mixture was related to the advantages in terms of consistency. Subsequently, the slurry was dried and fired in the same manner as the samples of the present invention. Again, the samples fragmented upon strong manual shaking, generating visible dust.

[0133] Comparative Examples 3 and 4 - Using a high level of binder together with pre-formed powder still shows a disadvantage compared to the examples of the present invention.

[0134] Comparative Example 3 3.5 g of CBV 8014 was mixed with 1.5 g of α-alumina (XFNano) in 40 mL of water and dried and fired as in the previous examples. The BET surface area of Comparative Example 3 was only 382 m 2 / g, indicating dilution from the binder, and the dried body broke apart upon strong manual shaking in the same manner as the other examples.

[0135] Comparative Example 4 3.5 g of CBV 8014 was mixed with 1.5 g of silica (Sipernat 22S) in 40 mL of water and dried and fired as in the previous examples. The BET surface area of Comparative Example 4 was only 386 m 2 / g, indicating dilution from the binder, and the dried body also broke apart upon strong manual shaking in the same manner as the other examples.

[0136] Example 3 of the present invention A zeolite reaction mixture having a solids content of 50% was prepared in the same manner as used in Examples 1 and 2 of the present invention using partial drying. The reaction mixture with 50% solids was too soft to form an extrudate. 5 wt% (based on the zeolite level) of Sipernat 22S was stirred into this mixture. The mixture could then be extruded and dried and calcined in the same manner as the previous samples.

[0137] Example 4 of the present invention - Preparation of silicate-1 zeolite body 20 g of tetraethyl orthosilicate (reagent grade, 98%) (Sigma-Aldrich) and 34 g of 1 M tetrapropylammonium hydroxide solution (Sigma-Aldrich) were hydrolyzed under ambient conditions with stirring overnight to form a clear solution. 0.63 g of water was added to this clear solution. The clear solution was kept in a furnace preheated to 120 °C under a sealed stainless steel autoclave with a Teflon lining for 3 days to crystallize the zeolite nanocrystals of silicate-1.

[0138] The zeolite nanocrystals had a particle size of about 100 - 120 nm. The colloidal zeolite suspension was poured into a 60 ml Falcon tube and dried at 140 °C for 1 hour, followed by slow drying at 60 °C for 5 days to form a solid zeolite body. The zeolite body was calcined at 550 °C, washed in distilled water, cation exchanged, dried at 60 °C, and calcined at 550 °C. The silicate-1 zeolite body had a BET surface area of 506 m 2 / g and did not fragment when strongly shaken and did not form dust.

[0139] Example 5 of the present invention: Preparation of a zeolite body comprising zeolite beta. 0.21 g of NaOH (97+%, ACS reagent, pellets, Acros Organics) was dissolved in 25.2 g of tetraethylammonium hydroxide (35 wt.% in H2O, Sigma-Aldrich) to form Solution 1. Subsequently, 0.17 g of aluminum isopropoxide (≧98%, Sigma-Aldrich) was dissolved in Solution 1 while vigorously stirring magnetically. 33.3 g of LUDOX® AS-30 colloidal silica (30 wt.% suspension in H2O, Sigma-Aldrich) was added dropwise to Solution 1 while stirring strongly for 2 to 15 hours to achieve a clear Solution 1. The clear synthesis solution 1 was allowed to stand quietly at room temperature for 48 hours and then heated in a synthesis furnace at 100 °C for 6 days. Subsequently, 1.13 g of aluminum isopropoxide (≧98%), Sigma-Aldrich was added to Solution 1 and stirred at room temperature for 2 hours. The synthesis mixture was placed in a shot bottle and heated in a synthesis furnace preheated to 100 °C for 5 days.

[0140] After this solvothermal treatment, the colloidal zeolite suspension was poured into a 60 ml Falcon tube, dried at 140 °C for 1 hour, and then slowly dried at 60 °C for 5 days to form a solid zeolite body. The zeolite body was calcined at 550 °C, washed in distilled water, cation exchanged, dried at 60 °C, and calcined at 550 °C.

[0141] The zeolite beta body material had a BET surface area of 973 m 2 / g. This is very high. The calculated micropore volume was 0.20 cm 3 / g according to t-plot analysis. The mesopore volume was 0.339 cm 3 / g. From the NL-DFT pore size distribution curve, mesopore sizes in the range from 2 to 16 nm are revealed. The body was robust and did not generate dust when shaken strongly.

[0142] Example 6 of the present invention: Preparation of a zeolite body of zeolite A 0.15 g of NaOH (97+%, ACS reagent, pellets), from Across Organics, was dissolved with strong stirring in 10.4 g of tetramethylammonium hydroxide (25 wt.% in H₂O), from Sigma-Aldrich, and 4 g of distilled water to form Aqueous Solution 1.

[0143] Solution 1 was divided into Solution A (8.55 g) and Solution B (6 g). 0.85 g of aluminum isopropoxide (≥98%), from Sigma-Aldrich, was dissolved in Solution A with strong magnetic stirring. 3.83 g of LUDOX® AS-40 colloidal silica (40 wt.% suspension in H₂O), from Sigma-Aldrich, was added to Solution B to form a clear solution.

[0144] Subsequently, Solution A was added dropwise to Solution B with strong magnetic stirring. The synthesis mixture was gently allowed to stand in a shot bottle at room temperature for 7 days and then heat-treated in a preheated synthesis furnace at 90 °C for 24 hours.

[0145] After this solvothermal treatment, the colloidal zeolite suspension was poured into a 60 ml Falcon tube and dried at 140 °C for 1 hour and then slowly dried at 60 °C over 5 days to form a solid zeolite body. The zeolite body was calcined at 550 °C, washed in distilled water, cation-exchanged, dried at 60 °C, and calcined at 550 °C.

[0146] The zeolite A body had a BET surface area of 483 m 2 / g. The calculated micropore volume was 0.12 cm 3 / g according to t-plot analysis. The mesopore volume was 0.18 cm 3 / g. From the NL-DFT pore size distribution curve, mesopore sizes in the range from 2 to 15 nm were revealed.

[0147] The zeolite body was robust even under strong shaking and did not generate dust.

Claims

1. (a) forming a zeolite reaction mixture, said reaction mixture comprising: (i) zeolite microcrystals having a submicron particle size; and (ii) water; and forming a step; (b) removing water from the zeolite reaction mixture to form a partially dried zeolite mass; (c) extruding and / or cutting / breaking the partially dried zeolite mass to form a partially dried zeolite body; (d) passing the partially dried zeolite body through at least one further processing step selected from any combination of spheronization, drying, and classification; (e) heating the partially dried zeolite body to a temperature greater than 400 °C to form a fired zeolite body; (f) contacting the fired zeolite body with water to form a washed and fired zeolite body; (g) contacting the washed and fired zeolite body with an ammonium ion exchange solution to exchange sodium ions in the zeolite with ammonium ions to form a cation-exchanged zeolite body; (h) heating the cation-exchanged zeolite body to a temperature greater than about 200 °C to form a zeolite body; A method for producing a zeolite body, comprising:

2. (i) (a) two or more zeolite precursor materials; and (b) water; contacting together to form a dilute reaction mixture, said dilute reaction mixture comprising: (a) zeolite microcrystals of submicron size; and (b) water; The method according to claim 1, which is carried out by comprising:

3. The method according to claim 2, wherein the zeolite precursor material and water are maintained at a temperature of less than about 100 °C.

4. The method according to any one of claims 1 to 3, wherein step (b) is carried out by drying the reaction mixture at a temperature of less than 100 °C.

5. The method according to any one of claims 1 to 4, wherein at least a part of step (b) is carried out in a wiped film evaporator.

6. The method according to any one of claims 1 to 5, wherein an adsorbent binder powder is incorporated into the partially dried zeolite mass during either step (b) or (c).

7. The method according to claim 6, wherein the adsorbent binder powder comprises silica, alumina, aluminosilicates, clays, and any combination thereof.

8. The method according to any one of claims 1 to 7, wherein the zeolite powder is incorporated into the partially dried zeolite mass.

9. The zeolite microcrystals are: (i) ZSM-5; (ii) Zeolite A; (iii) Zeolite beta (aluminosilicate beta and Sn-beta); (iv) Titanium silicate-1; (v) Faujasite (type X and Y); (vi) Chabazite (SSZ-13, Cu-SSZ-13, Fe-SSZ-13, and SAPO-34); (vii) Ferrierite; (viii) Sodarite; (ix) Mordenite; (x) ZSM-11; (xi) ZSM-22; (xii) ZSM-23; (xiii) Zeolite L; (xiv) MCM-22; and (xv) any combination thereof, The method according to any one of claims 1 to 8, selected from.

10. The method according to any one of claims 1 to 9, wherein step (c) is carried out by using an extruder and step (d) includes using a spheronizer.

11. The partially dried zeolite mass has a viscosity between 3.0×10 ５ mPa·s and 3.0×10 ６ mPa·s at 10 s －１ and 25 °C, according to any one of claims 1 to 10.

12. The method according to claim 6, wherein the level of the adsorbent binder powder is a zeolite body of less than about 15 wt%.

13. The method according to any one of claims 1 to 12, wherein non-zeolite catalyst species containing metal ions and metal-based nanoparticles are incorporated into the zeolite body.

14. A method of using a zeolite body produced according to the method of any one of claims 1 to 13 in the catalytic treatment of hydrocarbons or alcohols.

15. A zeolite body produced according to the method of any one of claims 1 to 13, at least one zeolite body comprises zeolite greater than 85%; At least one zeolite body has an envelope density between 0.6 g / cm ３ and 1.4 g / cm ３ ; at least one zeolite body has a macropore porosity of less than 15% as measured by mercury porosimetry.

16. d between 100 microns and 3000 microns ５０ At least one zeolite body according to claim 15, which is in the form of granules having a particle size

17. 0.5 g / cm ３ At least one zeolite body according to claim 15 or 16, having a bulk density greater than

Images