WO2020076745A1 - Porous zeolite-containing particles with a hierarchical pore structure - Google Patents

Porous zeolite-containing particles with a hierarchical pore structure Download PDF

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Publication number
WO2020076745A1
WO2020076745A1 PCT/US2019/055087 US2019055087W WO2020076745A1 WO 2020076745 A1 WO2020076745 A1 WO 2020076745A1 US 2019055087 W US2019055087 W US 2019055087W WO 2020076745 A1 WO2020076745 A1 WO 2020076745A1
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batch
porous zeolite
zeolite
particles
ceramic
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PCT/US2019/055087
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French (fr)
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Samuel Morse KOCH
Michael Francis
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Saint-Gobain Ceramics & Plastics, Inc.
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Publication of WO2020076745A1 publication Critical patent/WO2020076745A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B01J35/40—
    • B01J35/51—
    • B01J35/60—
    • B01J35/647—
    • B01J35/651—
    • B01J35/66—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
    • B01J35/50—

Definitions

  • each of the plurality of porous zeolite-containing particles comprises mesopores ranging about 2 to 50 nanometers in diameters and
  • FIG. 3 includes a flow chart illustrating other embodiments of a process for forming a batch of porous zeolite-containing ceramic particles with a hierarchical structure
  • FIG. 5 includes a schematic diagram of an embodiment of a porous zeolite- containing ceramic particle showing a core region and a layered region with multiple layered sections of the particle;
  • Dense, spherical zeolite-containing particles may be prepared by spray fluidization. However, such particles are prepared using a continuous spray fluidization forming process. Producing zeolite-containing particles having the various desired qualities noted above, such as, a particular porosity and with a narrow size distribution using a continuous spray fluidization forming process requires a complex manufacturing process that may include intermediate and/or post-process mechanical screening operations (i.e., cutting, grinding or filtering) to reduce and normalize the average particle size of oversized fractions of the zeolite-containing ceramic particles. These fractions may then be recycled back to the continuous process or otherwise recycled or be potentially considered as a lost material.
  • intermediate and/or post-process mechanical screening operations i.e., cutting, grinding or filtering
  • the coating fluid includes a slurry mix of zeolite and alumina.
  • the coating fluid includes a slurry mix of zeolite and suitable ceramic materials such as alumina, zirconia, titania, silica, hafnia or a combination thereof.
  • the coating fluid includes a slurry mix of zeolite and other ceramic materials.
  • the coating fluid includes a slurry mix of no greater than 90% of ceramic material, such as, no greater than 80% of ceramic material, no greater than 70% of ceramic material, no greater than 60% of ceramic material, no greater than 50% of ceramic material, no greater than 40% of ceramic material, no greater than 30% of ceramic material, no greater than 20% of ceramic material, or no greater than 10% of ceramic material.
  • the coating fluid includes a slurry mix of at least 20% of ceramic material and up to 80% of zeolite.
  • the coating fluid includes no greater than 90% of ceramic materials, and at least 10% of zeolite.
  • the coating fluid includes no greater than 80% of ceramic materials, and at least 20% of zeolite.
  • the initial particle size distribution span IPDS of the initial batch of ceramic particles is equal to (M90 -Idio)/Id 5 o, where H90 is equal to a dgo, a cumulative 90% pass particle size distribution measurement of the initial batch of ceramic particles; Id l0 is equal to a dio, a cumulative 10% pass particle size distribution measurement of the initial batch of ceramic particles; and Idso is equal to a dso, a cumulative 50% pass particle size distribution measurement of the initial batch of ceramic particles.
  • H90 is equal to a dgo
  • Id l0 is equal to a dio
  • Idso is equal to a dso, a cumulative 50% pass particle size distribution measurement of the initial batch of ceramic particles.
  • particle size distribution measurements can be determined by a particle size analyzer, for example, a Malvern Mastersizer 2000 or a
  • the first coating material composition may include a particular concentration of a material or particular concentrations of multiple materials as measured in volume percent for a total volume of the first coating fluid.
  • the layered region may have a porosity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the layered region may have a porosity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the layered region 420 may have an average porosity of at least about 0.6 cc/g and not greater than about 1.9 cc/g, such as, at least about 0.9 cc/g and not greater than about 1.7 cc/g, or at least about 0.9 cc/g and not greater than about 1.5 cc/g.
  • the core region 510 may be different than the second layered section 524. According to still other embodiments, the core region 510 may have different composition than the second layered section 524. According to particular embodiments, the core region 510 and the second layered section 524 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the core region 510 may have a different microstructure than the second layered section 524. According to yet other embodiments, the core region 510 may have a different particle density than the second layered section 524, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the core region 510 may have a different porosity than the second layered section 524.
  • the second layered section 524 may be defined as having an inner surface 524 A and an outer surface 524B.
  • the inner surface 524 A of the second layered section 524 is defined as the surface closest to the first layered section 522.
  • the outer surface 524B of the second layered section 524 is defined as the surface farthest from the first layered section 522.
  • a third layer section 526 may include overlapping layers surrounding the second layered section 524.
  • the layered region may have a porosity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the layered region may have a porosity of any value within a range between any of the minimum and maximum values noted above.
  • the third layer section 526 may make up a particular volume percentage of the total volume of the porous zeolite-containing ceramic particle 500.
  • the third layer section 526 may make up at least about 50 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, at least about 55 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 75 vol of the total volume of the porous zeolite-containing ceramic particle 500, at least about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 85 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 90 vol%
  • the third layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
  • At least 20 samples are used to determine a statistically reliable value of Idio, Idso , 90, Pdio, and Pdso,

Abstract

A method of forming porous zeolite-containing ceramic particles with a hierarchical structure includes using a spray fluidization forming process conducted in a batch mode including one or more batch spray fluidization forming cycles. In each of the forming cycles, an initial batch of ceramic particles are coated with a slurry mix of zeolite and ceramic materials to form a processed batch of porous zeolite-containing ceramic particles. The processed batch of porous zeolite-containing ceramic particles can be used as an initial batch in the next forming cycle. The porous zeolite-containing ceramic particles formed by the spray fluidization forming process may include mesopore and macropore structures in a layered region overlying a core region of each particle.

Description

POROUS ZEOLITE-CONTAINING PARTICLES WITH A HIERARCHICAL PORE
STRUCTURE
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 62/744,712 filed Oct. 12, 2018.
FIELD OF THE DISCLOSURE
[0002] The present disclosure relates to porous zeolite particles with a hierarchical pore structure and a method of forming a plurality of porous zeolite particles with a hierarchical pore structure. In particular, the disclosure relates to the use of a spray fluidization forming process in batch mode for forming porous zeolite particles.
BACKGROUND
[0003] Zeolites may be used in a wide variety of applications and in particular are suited to serve, for example, in the catalytic field as a catalyst carrier or component of a catalyst carrier.
[0004] For some particular industrial applications, zeolites are formed into shaped bodies suitable for the given reactor configurations. One issue arising in formed zeolite bodies used in heterogeneous catalytic reactions is mass transfer limitation. Since zeolite particles typically have very fine pores (from about 0.5-0.8 nanometer in diameter), mass transfer within a formed body can also be diffusion limited, in such instances, which reduces the activity of a zeolite-catalyzed chemical reaction.
[0005] In addition, an increase in the porosity of the zeolite particles may alter other properties, such as, the crush strength of the catalyst carrier or the component of the catalyst carrier. Conversely, high crush strength may require lower porosity, which then reduces surface area and water absorption of the catalyst carrier or component of the catalyst carrier.
[0006] Therefore, balancing of these properties in the porous zeolite particles, particularly when the particles are used in the catalytic field, is integral to the performance of the component. Once a balance of the necessary properties in the porous zeolite particles is achieved, uniform production of the particles is required in order to guarantee uniform performance of the component. Porous zeolite particles used as catalyst carriers or as components of catalyst carriers should therefore have a uniform degree of porosity, be of a uniform average particle size and have a uniform shape.
SUMMARY [0007] Accordingly, the industry continues to demand improved porous zeolite particles having various desired qualities, such as, a particular porous structure with improved diffusivity and improved methods for uniformly forming these porous zeolite particles.
[0008] Porous zeolite particles used in the catalytic field ideally possess, for example, a combination of a minimum surface area on which a catalytic component may be deposited, high water absorption and high crush strength. Achieving a minimum surface area and high water absorption may be, at least partially, accomplished through incorporating a minimum amount of porosity in the zeolite particles used as the catalyst carrier or as the component of the catalyst carrier.
[0009] There is a need for improving mass transfer within a formed zeolite body especially for catalytic applications. One prominent area of such catalytic applications is in the conversion of biomass to bulk commodity chemicals. The present disclosure addresses these issues by providing hierarchically structured porous zeolite-containing particles. The hierarchically structured porous zeolite-containing particles include both mesopores and macropores interconnected and spanning within the zeolite particle bodies. The hierarchical pore structures within the zeolite-containing particles effectively facilitate diffusion of reactants within the zeolite bodies and to the catalytically active zeolite surface. In addition, a uniform distribution of the particle sizes can improve attrition resistance of the catalyst.
[0010] According to one aspect of the invention described herein, a method of forming a plurality of porous zeolite-containing particles includes one or more batch spray fluidization forming cycles. In some embodiments, a first cycle of the one or more batch spray fluidization forming cycles includes: coating a first initial batch of ceramic particles with a first slurry mix of porous zeolite-containing ceramic droplets using spray fluidization techniques to form a first processed batch of porous zeolite-containing particles. The ceramic particles in the first initial batch have a first initial median particle diameter size. In some embodiments, the porous zeolite-containing particles in the first processed batch have a first median particle diameter size that is at least about 10% greater than the first initial median particle diameter size. In some embodiments, at the completion of the batch spray fluidization forming cycles, the plurality of porous zeolite-containing particles have a median particle diameter size of at least about 100 microns and not greater than about 4500 microns and have a hierarchical pore structure. [0011] In some embodiments, the first cycle further includes providing the first initial batch of ceramic particles that includes selecting a particle diameter range and a
predetermined amount of the first initial batch of ceramic particles, and loading the first initial batch of ceramic particles into a spray fluidizer.
[0012] In some embodiments, a second cycle of the one or more batch spray fluidization forming cycles includes: providing a second initial batch of porous zeolite- containing ceramics particles using the first processed batch; and coating the second initial batch of porous zeolite-containing ceramics particles with a second slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a second processed batch of porous zeolite-containing particles. In some embodiments, the porous zeolite-containing particles in the second processed batch have a second median particle diameter size that is at least about 10% greater than the first median particle diameter size.
[0013] In some embodiments, the method of claim 3, wherein a third cycle of the one or more batch spray fluidization forming cycles includes: providing a third initial batch of porous zeolite-containing ceramics particles using the second processed batch; and coating the third initial batch of porous zeolite-containing ceramics particles with a third slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a third processed batch of porous zeolite-containing particles. In some embodiments, the porous zeolite-containing particles in the third processed batch have a third median particle diameter size that is at least about 10% greater than the second median particle diameter size.
[0014] In some embodiments, a fourth cycle of the one or more batch spray fluidization forming cycles includes: providing a fourth initial batch of porous zeolite- containing ceramics particles using the third processed batch; and coating the fourth initial batch of porous zeolite-containing ceramics particles with a fourth slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a fourth processed batch of porous zeolite-containing particles. In some embodiments, the porous zeolite-containing particles in the fourth processed batch have a fourth median particle diameter size that is at least about 10% greater than the third median particle diameter size.
[0015] In some embodiments, each of the plurality of porous zeolite-containing particles comprises mesopores ranging about 2 to 50 nanometers in diameters and
macropores ranging about 50 to 1000 nanometers in diameters. [0016] In some embodiments, each of the plurality of porous zeolite-containing particles has mesopores substantially ranging about 4 to 10 nanometers in diameters and macropores substantially ranging about 60 to 200 nanometers in diameters.
[0017] In some embodiments, the mesopores and micropores are interconnected.
[0018] In some embodiments, the first initial batch of ceramic particles include alumina, zirconia, titania, silica or a combination thereof.
[0019] In some embodiments, the first slurry mix of porous zeolite-containing ceramic droplets includes at least 20% of ceramic materials, and no greater than 80% of zeolite.
[0020] In some embodiments, the first slurry mix of porous zeolite-containing ceramic droplets includes no greater than 90% of ceramic materials, and at least 10% of zeolite.
[0021] In some embodiments, the first slurry mix of porous zeolite-containing ceramic droplets includes no greater than 70% of ceramic materials, and at least 30% of zeolite.
[0022] In some emhodiments, the first slurry mix of porous zeolite-containing ceramic droplets includes at least 20% and no greater than 50% of ceramic materials, and at least 50 % and no greater than 80% of zeolite.
[0023] In some embodiments, the first slurry mix of porous zeolite-containing ceramic droplets includes a first slip of zeolite and a second slip of ceramic materials, wherein the first slip of zeolite is introduced into a spray fluidizer via a first inlet and a second slip of ceramic materials is introduced into the spray fluidizer via a second inlet.
[0024] In some embodiments, a composition of the first slurry mix is substantially the same as a composition of the second slurry mix.
[0025] In some embodiments, a mass of the first processed batch of porous zeolite- containing particles is about 2 to 5 times of a mass of the first initial batch.
[0026] In some embodiments, a mass of the second processed batch of porous zeolite- containing particles is about 2 to 5 times of a mass of the second initial batch.
[0027] In some embodiments, a mass of the third processed batch of porous zeolite- containing particles is about 2 to 5 times of a mass of the third initial batch.
[0028] In some embodiments, a mass of the fourth processed batch of porous zeolite- containing particles is about 2 to 5 times of a mass of the fourth initial batch. [0029] In some embodiments, a mass of a processed batch of porous zeolite- containing particles is about 4 times of a mass of the initial batch in the same forming cycle.
[0030] In some embodiments, a mass of the first slurry mix is about 5 to 15 times of a mass of the first initial batch.
[0031] In some embodiments, a mass of the second slurry mix is about 5 to 15 times of a mass of the second initial batch.
[0032] In some embodiments, a mass of the third slurry mix is about 5 to 15 times of a mass of the third initial batch.
[0033] In some embodiments, a mass of the fourth slurry mix is about 5 to 15 times of a mass of the fourth initial batch.
[0034] In some embodiments, a mass of the slurry mix is about 6 to 12 times of a mass of the initial batch in the same forming cycle.
[0035] In some embodiments, the plurality of porous zeolite-containing particles are substantially spherical with a sphericity of at least about 85% and up to about 97%.
[0036] In some embodiments, the plurality of porous zeolite-containing particles are substantially spherical with a sphericity of at least about 90% and up to about 97%.
[0037] In some embodiments, the plurality of porous zeolite-containing particles are substantially spherical with a sphericity of at least about 95% and up to about 97%.
[0038] In some embodiments, each of the plurality of porous zeolite-containing particles includes a core region and a layered region overlaying the core region,
[0039] In some embodiments, the core region has a core region composition, and the layered region has a layered region composition different than the core region composition.
[0040] In some embodiments, the layered region comprises mesopores substantially ranging about 4 to 10 nanometers in diameters and macropores substantially ranging about 60 to 200 nanometers in diameters, and the mesopores and macropores are interconnected.
[0041] In some embodiments, the spray fluidization techniques include repeatedly dispensing finely dispersed droplets of a slurry mix of porous zeolite-containing ceramics onto air borne ceramic particles to form a processed batch of porous zeolite-containing particles.
[0042] In some embodiments, a method of forming a plurality of porous zeolite- containing particles further includes sintering the fourth processed batch of porous zeolite- containing particles at a temperature of at least about 350 °C and not greater than about 1400 °C.
[0043] In some embodiments, a method of forming a plurality of porous zeolite- containing particles further includes sintering a final processed batch of porous zeolite- containing particles at a temperature of at least about 350 °C and not greater than about 1400 °C.
[0044] In some embodiments, a method of forming a plurality of porous zeolite- containing particles further includes sintering a final processed batch of porous zeolite- containing particles at a temperature of at least about 600 °C.
[0045] In some embodiments, the first initial batch of ceramic particles has an initial particle diameter size distribution span IPDS equal to (Idpo-Idi o)/Idso, where H90 is equal to a cumulative 90% pass particle size distribution measurement of the first initial batch of ceramic particles; Idio is equal to a cumulative 10% pass particle size distribution
measurement of the first initial batch of ceramic particles; and Id5o is equal to a cumulative 50% pass particle size distribution measurement of the first initial batch of ceramic particles. And the first processed batch of porous zeolite-containing particles has a processed particle diameter size distribution span PPDS equal to (Pdgo-PdioyPdso, where Pd9o is equal to a cumulative 90% pass particle size distribution measurement of the first processed batch of porous zeolite-containing particles; Pdio is equal to a cumulative 10% pass particle size distribution measurement of the first processed batch of porous zeolite-containing particles; and Pd5o is equal to a cumulative 50% pass particle size distribution measurement of the first processed batch of porous zeolite-containing particles. The first batch spray fluidization forming cycle has a ratio IPDS/ PPDS of at least about 0.90. In some embodiments, the first batch spray fluidization forming cycle has a ratio IPDS/ PPDS of at least about 1.0.
[0046] In some embodiments, the second initial batch of porous zeolite-containing ceramics particles has an initial particle diameter size distribution span IPDS equal to (M90- Idio)/Id5o, where W90 is equal to a cumulative 90% pass particle size distribution measurement of the second initial batch of porous zeolite-containing ceramics particles; Idio is equal to a cumulative 10% pass particle size distribution measurement of the second initial batch of porous zeolite-containing ceramics particles; and Idso is equal to a cumulative 50% pass particle size distribution measurement of the second initial batch of porous zeolite-containing ceramics particles. And the second processed batch of porous zeolite-containing particles has a processed particle diameter size distribution span PPDS equal to (Pd9o-Pdio)/Pdso, where Pd9o is equal to a cumulative 90% pass particle size distribution measurement of the second processed batch of porous zeolite-containing particles; Pdio is equal to a cumulative 10% pass particle size distribution measurement of the second processed batch of porous zeolite- containing particles; and Pd5o is equal to a cumulative 50% pass particle size distribution measurement of the second processed batch of porous zeolite-containing particles. The second batch spray fluidization forming cycle has a ratio IPDS/ PPDS of at least about 0.90. In some embodiments, the second batch spray fluidization forming cycle has a ratio IPDS/ PPDS of at least about 1.0.
[0047] In some embodiments, a batch spray fluidization forming cycle has a ratio
IPDS/ PPDS of at least about 1.1.
[0048] In some embodiments, the fourth processed batch of porous zeolite-containing ceramics particles has a processed particle diameter size distribution span PPDS equal to (Pd9o-Pdlo)/Pd5o, where Pd90 is equal to a cumulative 90% pass particle size distribution measurement of the fourth processed batch of porous zeolite-containing particles; Pdio is equal to a cumulative 10% pass particle size distribution measurement of the fourth processed batch of porous zeolite-containing particles; and Pd;o is equal to a cumulative 50% pass particle size distribution measurement of the fourth processed batch of porous zeolite- containing particles. PPDS of the fourth processed batch of porous zeolite-containing particles is less than 0.2.
[0049] In some embodiments, PPDS of a processed batch of porous zeolite- containing particles is less than 0.4.
[0050] In some embodiments, PPDS of a processed batch of porous zeolite- containing particles is less than 0.12.
[0051] In some embodiments, each of the plurality of porous zeolite-containing particles includes micropores having a diameter ranging about 0.5 to 0.8 nanometers.
[0052] In some embodiments, the spray fluidization techniques comprise more than one batch forming cycles, each of the cycles after the first cycle including repeatedly dispensing finely dispersed droplets of a respective slurry mix of porous zeolite-containing ceramics onto air borne processed batch of porous zeolite-containing particles from a previous cycle. [0053] In some embodiments, a respective composition of the respective slurry mix is adjusted for each of the forming cycles.
[0054] According to another aspect of the invention described herein, a porous zeolite-containing particle with a hierarchical pore structure includes: a core region and; a layered region overlaying the core region, the layered region having a microstructure including interconnected mesopores and macropores. Diameters of the mesopores range from about 2 to 50 nanometers, and diameters of the macropores range from about 50 to 1000 nanometers. A porosity of the porous zeolite-containing particle is at least about 0.3 cm3/g and not greater than about 2.00 cm3/g. A median diameter of the porous zeolite-containing particle is at least about 100 microns and not greater than about 4500 microns. And the core region has a core region composition, and the layered region has a layered region
composition different than the core region composition.
[0055] In some embodiments, the porosity of the porous zeolite-containing particle is at least about 0.5 cm3/g and not greater than about 1.5 cm3/g.
[0056] In some embodiments, the core region includes a monolithic structure.
[0057] In some embodiments, the core region composition comprises alumina, zirconia, titania, silica or a combination thereof.
[0058] In some embodiments, the layered region composition comprises at least 20 % of alumina, zirconia, titania, silica or a combination thereof, and no greater than 80 % of zeolite.
[0059] In some embodiments, the layered region composition comprises no greater than 90 % of alumina, zirconia, titania, silica or a combination thereof, and at least 10 % of zeolite.
[0060] In some embodiments, the layered region composition comprises no greater than 70 % of alumina, zirconia, titania, silica or a combination thereof, and at least 30 % of zeolite.
[0061] In some embodiments, the layered region composition comprises at least 20 % and no greater than 50 % of alumina, zirconia, titania, silica or a combination thereof, and at least 50 % and no greater than 80 % of zeolite.
[0062] In some embodiments, the porous zeolite-containing particle is substantially spherical. [0063] In some embodiments, the porous zeolite-containing particle comprises micropores having a diameter ranging from about 0.5 to 0.8 nanometers.
[0064] Note that the various embodiments described above can be combined with any other embodiments described herein. The features and advantages described in the specification are not all inclusive and, in particular, many additional features and advantages will be apparent to one of ordinary skill in the art in view of the drawings, specification, and claims. Moreover, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0065] The present disclosure may be better understood, and its numerous features and advantages made apparent to those skilled in the art by referencing the accompanying drawings. The accompanying drawings, however, merely illustrate pertinent features of the present disclosure and are therefore not to be considered limiting, for the description may admit to other effective features.
[0066] FIG. 1 includes a flow chart illustrating an embodiment of a process for forming a batch of porous zeolite-containing ceramic particles with a hierarchical structure;
[0067] FIGS. 2A and 2B include graph representations illustrating an initial particle size distribution span for a batch of initial ceramic particles and a processed particle size distribution span for a batch of porous zeolite-containing ceramic particles;
[0068] FIG. 3 includes a flow chart illustrating other embodiments of a process for forming a batch of porous zeolite-containing ceramic particles with a hierarchical structure;
[0069] FIG. 4 includes a schematic diagram of an embodiment of a porous zeolite- containing ceramic particle showing a core region and a layered region of the particle;
[0070] FIG. 5 includes a schematic diagram of an embodiment of a porous zeolite- containing ceramic particle showing a core region and a layered region with multiple layered sections of the particle;
[0071] FIG. 6 shows detailed experimental parameters and properties of the materials used for each cycle of a four cycle spray fluidization process.
[0072] FIG. 7 shows properties of a finished product of the fourth processed batch of porous zeolite-containing particles with a hierarchical pore structure in a four cycle spray fluidization process. [0073] FIG. 8 shows an exemplary pore size distribution plot for a finished product from a fourth processed batch of porous zeolite-containing particles with a hierarchical pore structure.
[0074] The use of the same reference symbols in different drawings indicates similar or identical items. In accordance with common practice, the various features illustrated in the drawings may not be drawn to scale. Accordingly, the dimensions of the various features may be arbitrarily expanded or reduced for clarity. In addition, some of the drawings may not depict all of the components of a given system, method or device.
DETAILED DESCRIPTION
[0075] Numerous details are described herein in order to provide a thorough understanding of the example embodiments illustrated in the accompanying drawings.
However, some embodiments may be practiced without many of the specific details, and the scope of the claims is only limited by those features and aspects specifically recited in the claims. Furthermore, well-known processes, components, and materials have not been described in exhaustive detail so as not to unnecessarily obscure pertinent aspects of the embodiments described herein.
[0076] A plurality of porous zeolite-containing particles with a hierarchical pore structure and a method of forming a plurality of porous zeolite-containing particles having a hierarchical pore structure are described herein. Embodiments described herein relate to the production of porous zeolite-containing ceramic particles by a spray fluidization forming process. In particular, a batch spray fluidization forming process is described for the production of a batch of spherical porous particles having a narrow size distribution. It has been found that by employing a batch spray fluidization forming process, spherical particles having a narrow size distribution can be produced efficiently and economically. Further, by using an iterative growth process and a divided scheme that may include multiple batch production cycles, large particle sizes up to 4500 microns can be produced while maintaining the narrow size distribution. Also, by using an iterative growth process and a divided scheme that may include multiple batch production cycles, porous particles can be formed with distinct layered regions having distinct compositions.
[0077] Dense, spherical zeolite-containing particles may be prepared by spray fluidization. However, such particles are prepared using a continuous spray fluidization forming process. Producing zeolite-containing particles having the various desired qualities noted above, such as, a particular porosity and with a narrow size distribution using a continuous spray fluidization forming process requires a complex manufacturing process that may include intermediate and/or post-process mechanical screening operations (i.e., cutting, grinding or filtering) to reduce and normalize the average particle size of oversized fractions of the zeolite-containing ceramic particles. These fractions may then be recycled back to the continuous process or otherwise recycled or be potentially considered as a lost material.
Such continuous operations may therefore require excessive expense and may only be practical in certain large production situations.
[0078] According to particular embodiments described herein, a plurality of porous zeolite-containing ceramic particles may be formed using a spray fluidization forming process operating in a batch mode. Forming a plurality of porous zeolite-containing particles using such a process essentially uniformly increases the average particle size of a batch of ceramic particles while maintaining a relatively narrow particle size distribution and a uniform shape with an average sphericity between 0.8 and 0.97 of all particles in the batch of porous zeolite-containing particles.
[0079] According to particular embodiments, a spray fluidization forming process operating in a batch mode may be defined as any spray fluidization forming process where a first finite number of ceramic particles (i.e., an initial batch) begins the spray fluidization forming process essentially in the same process step and are formed into a second finite number of porous zeolite-containing ceramic particles (i.e., a processed batch) that all end the spray fluidization forming process essentially in the same process step. According to still other embodiments, a spray fluidization forming process operating in a batch mode may be further defined as being non-cyclic or non-continuous, meaning that the zeolite-containing ceramic particles are not continuously removed and re-introduced into the spray fluidization forming process at different times than other ceramic particles in the same batch.
[0080] According to yet other embodiments, a spray fluidization forming process operating in a batch mode may include at least a first batch spray fluidization forming cycle. For purposes of illustration, FIG. 1 includes a flow chart showing a batch spray fluidization forming cycle to form a batch of porous zeolite-containing ceramic particles with a hierarchical structure according to embodiments described herein. As illustrated in FIG. 1, a batch spray fluidization forming cycle 100 for forming a plurality of porous zeolite- containing ceramic particles may include a step 110 of providing an initial batch of ceramic particles and a step 120 of coating the initial batch of ceramic particles with a slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a processed batch of porous zeolite-containing ceramic particles. It will be appreciated that, as used herein, the term batch refers to a finite number of particles that may undergo a forming process cycle as described herein.
[0081] According to particular embodiments, the initial batch of ceramic particles provided in step 110 may each include a core region composition. According to yet other embodiments, the core region composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the core region composition may include a ceramic material. According to still other embodiments, the core region of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafhia or a combination thereof. According to still other embodiments, the core region composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[0082] According to still other embodiments, the initial batch of ceramic particles may include monolithic seed particles. According to yet other embodiments, the initial batch of ceramic particles may include monolithic seed particles with a layered region overlying a surface of the seed particles. It will be appreciated that, depending of the cycle of the spray fluidization forming process, the initial batch of ceramic particles may include previously unprocessed particles or particles that have undergone a previous forming process cycle.
[0083] According to still other embodiments, the initial batch of ceramic particles provided in step 110 may have a particular average or median particle size (Idso) measured as the longest dimension or diameter of the particle. For example, the initial batch of ceramic particles may have an Idso of at least about 50 microns, such as, at least about 100 microns, at least about 200 microns, at least about 300 microns, at least about 400 microns, at least about 500 microns, at least about 600 microns, at least about 700 microns, at least about 800 microns, at least about 900 microns, at least about 1000 microns, at least about 1100 microns, at least about 1200 microns, at least about 1300 microns, at least about 1400 microns or even at least about 1490 microns. According to still other embodiments, the initial batch of ceramic particles may have an Idso of not greater than about 1500 microns, such as, not greater than about 1400 microns, not greater than about 1300 microns, not greater than about 1200 microns, not greater than about 1 100 microns, not greater than about 1000 microns, not greater than about 900 microns, not greater than about 800 microns, not greater than about 700 microns, not greater than about 600 microns, not greater than about 500 microns, not greater than about 400 microns, not greater than about 300 microns, not greater than about 200 microns, or even not greater than about 150 microns. It will be appreciated that the initial batch of ceramic particles may have an Id50 of any value between any of the minimum and maximum values noted above. It will be farther appreciated that the initial batch of ceramic particles may have an Idso of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the initial batch of ceramic particles may have an Idso of at least about 50 microns and no greater than about 4500 microns, such as, at least about 100 microns and no greater than about 3000 microns, at least about 200 microns and no greater than about 1500 microns. In some embodiments, the initial batch of ceramic particles may have an Idso of at least about 50 microns and no greater than about 200 microns.
[0084] According to other embodiments, the processed batch of porous zeolite- containing particles formed from the initial batch of ceramic particles in step 120 may include any desired ceramic material, in addition to zeolite, suitable for forming porous zeolite- containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, haihia or a combination thereof. According to still other embodiments, the processed batch of porous zeolite-containing ceramic particles in step 120 may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
According to still other embodiments, the processed batch of porous zeolite-containing ceramic particles may include monolithic seed particles with a layered region overlying a surface of the seed particles.
[0085] According to still other embodiments, the processed batch of porous zeolite- containing ceramic particles formed from the initial batch of ceramic particles in step 120 may have a particular average or median particle size (Pdso) measured as the longest dimension or diameter of the particle. For example, the processed batch of porous zeolite- containing ceramic particles may have a Pdso of at least about 200 microns, such as, at least about 300 microns, at least about 400 microns, at least about 500 microns, at least about 600 microns, at least about 700 microns, at least about 800 microns, at least about 900 microns, at least about 1000 microns, at least about 1100 microns, at least about 1200 microns, at least about 1300 microns, at least about 1400 microns, at least about 1500 microns, at least about 1600 microns, at least about 1700 microns, at least about 1800 microns, at least about 1900 microns, or even at least about 1950 microns. According to still other embodiments, the processed batch of porous zeolite-containing ceramic particles may have a Pdso of not greater than about 4500 microns, such as, not greater than about 4400 microns, not greater than about 4300 microns, not greater than about 4200 microns, not greater than about 4100 microns, not greater than about 4000 microns, not greater than about 3900 microns, not greater than about 3800 microns, not greater than about 3700 microns, not greater than about 3600 microns, not greater than about 3500 microns, not greater than about 3400 microns, not greater than about 3300 microns, not greater than about 3200 microns, not greater than about 3100 microns, not greater than about 3000 microns, not greater than about 2900 microns, not greater than about 2800 microns, not greater than about 2700 microns, not greater than about 2600 microns, not greater than about 2500 microns, not greater than about 2400 microns, not greater than about 2300 microns, not greater than about 2200 microns, not greater than about 2100 microns, not greater than about 2000 microns not greater than about 1900 microns, not greater than about 1800 microns, not greater than about 1700 microns, not greater than about 1600 microns, not greater than about 1500 microns, not greater than about 1400 microns, not greater than about 1300 microns, not greater than about 1200 microns, not greater than about 1100 microns, not greater than about 1000 microns, not greater than about 900 microns, not greater than about 800 microns, not greater than about 700 microns, not greater than about 600 microns, not greater than about 500 microns, not greater than about 400 microns, not greater than about 300 microns, not greater than about 200 microns, or even not greater than about 150 microns. It will be appreciated that the processed batch of porous zeolite-containing ceramic particles may have a Pdso of any value between any of the minimum and maximum values noted above. It will be further appreciated that the processed batch of porous zeolite-containing ceramic particles may have a Pdso of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the processed batch of porous zeolite-containing ceramic particles may have a Pdso of at least about 50 microns and no greater than about 4500 microns, such as, at least about 100 microns and no greater than 3000 microns, at least about 200 microns and no greater than about 1500 microns. In some embodiments, the processed batch of porous zeolite-containing ceramic particles may have a Pdso of at least about 150 microns and no greater than about 400 microns.
[0086] It will be appreciated that as used herein, and in particular as used in reference to step 120 of cycle 100, a first batch spray fluidization forming cycle may include, generally, any particle forming or growing process where initial or seed particles are fluidized in a stream of heated gas and introduced into a solid material that has been atomized in a liquid. The atomized material collides with the initial or seed particles and, as the liquid evaporates, the solid material is deposited on the outer surface of the initial or seed particles forming a layer or coating that increases the general size or shape of the seed particles. As the particles repeatedly circulate in and out of the atomized material, multiple layers of the solid material are formed or deposited on the initial or seed particles.
[0087] According to particular embodiments, spray fluidization may be described as repeatedly dispensing finely dispersed droplets of a coating fluid onto air borne ceramic particles to form the processed batch of porous zeolite-containing ceramic particles. It may be further appreciated that a spray fluidization forming process as described herein may not include any form of or additional mechanism for manually altering, for example, reducing the size of particles during the spray fluidization forming process.
[0088] According to still other embodiments, a first batch spray fluidization forming cycle may be described as repeatedly dispensing finely dispersed droplets of a first coating fluid onto air borne ceramic particles to form the processed batch of porous zeolite- containing ceramic particle.
[0089] Accordingly to still other embodiments, the coating fluid includes a slurry mix of zeolite and alumina. In some embodiments, the coating fluid includes a slurry mix of zeolite and suitable ceramic materials such as alumina, zirconia, titania, silica, hafnia or a combination thereof. In some embodiments, the coating fluid includes a slurry mix of zeolite and other ceramic materials. In some embodiments, the coating fluid includes a slurry mix of up to 90% of zeolite, such as, up to 80% of zeolite, up to 70% of zeolite, up to 60% of zeolite, up to 50% of zeolite, up to 40% of zeolite, up to 30% of zeolite, up to 20% of zeolite, or up to 10% of zeolite. In some embodiments, the coating fluid includes a slurry mix of at least 10% of zeolite, such as, at least 20% of zeolite, at least 30% of zeolite, at least 40% of zeolite, at least 50% of zeolite, at least 60% of zeolite, at least 70% of zeolite, at least 80% of zeolite, or at least 90% of zeolite. In some embodiments, the coating fluid includes a slurry mix of at least 10% of ceramic material, such as, at least 20% of ceramic material, at least 30% of ceramic material, at least 40% of ceramic material, at least 50% of ceramic material, at least 60% of ceramic material, at least 70% of ceramic material, at least 80% of ceramic material, or at least 90% of ceramic material. In some embodiments, the coating fluid includes a slurry mix of no greater than 90% of ceramic material, such as, no greater than 80% of ceramic material, no greater than 70% of ceramic material, no greater than 60% of ceramic material, no greater than 50% of ceramic material, no greater than 40% of ceramic material, no greater than 30% of ceramic material, no greater than 20% of ceramic material, or no greater than 10% of ceramic material. In some embodiments, the coating fluid includes a slurry mix of at least 20% of ceramic material and up to 80% of zeolite. In some embodiments, the coating fluid includes no greater than 90% of ceramic materials, and at least 10% of zeolite. In some embodiments, the coating fluid includes no greater than 80% of ceramic materials, and at least 20% of zeolite. In some embodiments, the coating fluid includes no greater than 70% of ceramic materials, and at least 30% of zeolite. In some embodiments, the coating fluid includes no greater than 60% of ceramic materials, and at least 40% of zeolite. In some embodiments, the coating fluid includes at least 20% and no greater than 50% of ceramic materials, and at least 50% and no greater than 80% of zeolite. In some embodiments, the coating fluid includes at least 30% and no greater than 60% of ceramic materials, and at least 40% and no greater than 70% of zeolite. It will be further appreciated that the weight percentage of zeolite and/or ceramic materials in the coating fluid may have any value within a range between any of the minimum and maximum values noted above.
[0090] In some embodiments, the spray fluidization forming cycle 100 takes place in a spray fluidizer. In some embodiments, the coating fluid is provided by introducing, during step 120, a slip of zeolite through a first inlet into the spray fluidizer, and a slip of ceramic materials through a second inlet into the spray fluidizer, in substantially the same process step or at the same time. In some embodiments, the first inlet and the second inlet are distinct and separate.
[0091] In some embodiments, the coating fluid is provided by first mixing a slip of zeolite and a slip of ceramic materials to form a slurry of zeolite and ceramic materials, before the mixed slurry of zeolite and ceramic materials is introduced, during step 120, into the fluidizer.
[0092] Referring back to FIG. 1, according to certain embodiments described herein, the initial batch of ceramic particles provided during step 110 may be described as having an initial particle size (measured as the longest dimension or diameter of the particle) distribution span IPDS and the processed batch of porous zeolite-containing ceramic particles formed during step 120 may be described as having a processed particle size (measured as the longest dimension or diameter of the particle) distribution span PPDS. For purposes of illustration, FIGS. 2 A and 2B include a graph representation of the initial particle size distribution for an initial batch of ceramic particles and the processed particle size distribution for a processed batch of porous zeolite-containing ceramic particles, respectively. As shown in FIG. 2A, the initial particle size distribution span IPDS of the initial batch of ceramic particles is equal to (M90 -Idio)/Id5o, where H90 is equal to a dgo, a cumulative 90% pass particle size distribution measurement of the initial batch of ceramic particles; Idl0 is equal to a dio, a cumulative 10% pass particle size distribution measurement of the initial batch of ceramic particles; and Idso is equal to a dso, a cumulative 50% pass particle size distribution measurement of the initial batch of ceramic particles. As shown in FIG. 2B, the processed particle size distribution span PPDS of the processed batch of porous zeolite- containing ceramic particles is equal to (Pdgo-Pdio)/Pd5o, where Pdgo is equal to a d9o particle size distribution measurement of the processed batch of porous zeolite-containing ceramic particles; Pdl0 is equal to a dio particle size distribution measurement of the processed batch of porous zeolite-containing ceramic particles; and Pdso is equal to a dso particle size distribution measurement of the processed batch of porous zeolite-containing ceramic particles.
[0093] In some embodiments, particle size distribution measurements can be determined by a particle size analyzer, for example, a Malvern Mastersizer 2000 or a
CAMSIZER® . Particle size distribution measurements especially for a processed batch of particles described herein were determined using a Retsch Technology’s CAMSIZER® (for example, the model 8524). The CAMSIZER® measured the two-dimensional projection of the microsphere cross-sections through optical imaging. The projection was converted to a circle of equivalent diameter. The sample was fed to the instrument with a 75 mm width feeder, using the guidance sheet in the top of the sample chamber, with maximum obscuration set at 1.0%. The measurements were done with both the Basic and Zoom CCD cameras. An image rate of 1 :l is used. All particles in a representative sample of a batch were included in the calculation; no particles were ignored because of size or shape limits. A measurement typically will image several thousand to several million particles. Calculations were done using the instrument’s statistical functions included in CAMSIZER® software version 5.1.27.312. An“xFe_min” particle model was used, with the shape settings for “spherical particles.” Statistics were calculated on a volume basis.
[0094] According to a certain embodiment described herein, the cycle 100 of forming a plurality of porous zeolite-containing ceramic particles may include maintaining a particular ratio IPDS/PPDS for the forming of the initial batch of ceramic particles into the processed batch of porous zeolite-containing ceramic particles. For example, the method of forming the initial batch of ceramic particles into the processed batch of porous zeolite- containing ceramic particles may have a ratio IPDS/PPDS of at least about 0.90, such as, at least about 1.00, at least about 1.10, at least about 1.20, at least about 1.30, at least about 1.40, at least about 1.50, at least about 1.60, at least about 1.70, at least about 1.80, at least about 1.90, at least about 2.00, at least about 2.50, at least about 3.00, at least about 3.50, at least about 4.00 or even at least about 4.50. According to still other embodiments, the method of forming the initial batch of ceramic particles into the processed batch of porous zeolite-containing ceramic particles may have a ratio IPDS/PPDS of not greater than about 10.00, such as, not greater than about 9.00, not greater than about 8.00, not greater than about 7.00, not greater than about 6.00, not greater than about 5.00, not greater than about 4.50 or even not greater than about 4.00. It will be appreciated that the method of forming the initial batch of ceramic particles into the processed batch of porous zeolite-containing ceramic particles may have a ratio IPDS/PPDS of any value between any of the minimum and maximum values noted above. It will be further appreciated that the method of forming the initial batch of ceramic particles into the processed batch of porous zeolite-containing ceramic particles may have a ratio IPDS/PPDS of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the method of forming the initial batch of ceramic particles into the processed batch of porous zeolite- containing ceramic particles may have a ratio IPDS/PPDS of at least about 0.90 and not greater than about 4.50. In some embodiments, the method of forming the initial batch of ceramic particles into the processed batch of porous zeolite-containing ceramic particles may have a ratio IPDS/PPDS of at least about 1.0 and not greater than about 2.0.
[0095] According to another particular embodiment, the initial batch of ceramic particles may have a particular initial particle size distribution span IPDS. As noted herein, the initial particle size distribution span is equal to (M90 -Idio)/Idso, where W90 is equal to a d9o particle size distribution measurement of the initial batch of ceramic particles; Idio is equal to a dio particle size distribution measurement of the initial batch of ceramic particles; and 50 is equal to a dso particle size distribution measurement of the initial batch of ceramic particles. For example, the initial batch of ceramic particles may have an IPDS of not greater than about 2.00, such as, not greater than about 1.90, not greater than about 1.80, not greater than about 1.70, not greater than about 1.60, not greater than about 1.50, not greater than about 1.40, not greater than about 1.30, not greater than about 1.20, not greater than about 1.10, not greater than about 1.00, not greater than about 0.90, not greater than about 0.80, not greater than about 0.70, not greater than about 0.60, not greater than about 0.50, not greater than about 0.40, not greater than about 0.30, not greater than about 0.20, not greater than about 0.10, not greater than about 0.05 or even substantially no initial particle size distribution span where IPDS is equal to zero. According to another particular embodiment, the initial batch of ceramic particles may have an IPDS of at least about 0.01, such as, at least about 0.05, at least about 0.10, at least about 0.20, at least about 0.30, at least about 0.40, at least about 0.50, at least about 0.60 or even at least about 0.70. It will be appreciated that the initial batch of ceramic particles may have an IPDS of any value between any of the minimum and maximum values noted above. It will be further appreciated that the initial batch of ceramic particles may have an IPDS of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the initial batch of ceramic particles may have an IPDS of at least about 0.1 and not greater than about 1.2, such as at least about 0.3 and not greater than about 1.0.
[0096] According to yet other embodiments, the processed batch of porous zeolite- containing ceramic particles may have a particular processed particle size distribution span PPDS. As noted herein, the processed particle size distribution span is equal to (Pdgo- Pdio)/Pd5o, where Pd$io is equal to a d9o particle size distribution measurement of the processed batch of porous zeolite-containing ceramic particles; Pdio is equal to a dio particle size distribution measurement of the processed batch of porous zeolite-containing ceramic particles; and Pdso is equal to a d50 particle size distribution measurement of the processed batch of porous zeolite-containing ceramic particles. For example, the processed batch of porous zeolite-containing ceramic particles may have a PPDS of not greater than about 2.00, such as, not greater than about 1.90, not greater than about 1.80, not greater than about 1.70, not greater than about 1.60, not greater than about 1.50, not greater than about 1.40, not greater than about 1.30, not greater than about 1.20, not greater than about 1.10, not greater than about 1.00, not greater than about 0.90, not greater than about 0.80, not greater than about 0.70, not greater than about 0.60, not greater than about 0.50, not greater than about 0.40, not greater than about 0.30, not greater than about 0.20, not greater than about 0.10, not greater than about 0.05 or even substantially no processed particle size distribution span where PPDS is equal to zero. According to another particular embodiment, the processed batch of porous zeolite-containing ceramic particles may have a PPDS of at least about 0.01, such as, at least about 0.05, at least about 0.10, at least about 0.20, at least about 0.30, at least about 0.40, at least about 0.50, at least about 0.60 or even at least about 0.70. It will be appreciated that the processed batch of porous zeolite-containing ceramic particles may have a PPDS of any value between any of the minimum and maximum values noted above. It will be further appreciated that the processed batch of porous zeolite-containing ceramic particles may have a PPDS of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the processed batch of porous zeolite-containing ceramic particles may have a PPDS of at least about 0.05 and no greater than about 0.7, such as at least about 0.08 and no greater than about 0.5, or at least about 0.1 and no greater than about 0.2.
[0097] According to yet other embodiments, the average or median particle size of the processed batch of porous zeolite-containing ceramic particles (Pdso) may be greater than the average particle size of the initial batch of ceramic particles (Idso). According to still other embodiments, the average particle size of the processed batch of porous zeolite- containing ceramic particles (Pdso) may be a particular percentage greater than the average particle size of the initial batch of ceramic particles (Idso). For example, the average particle size of the processed batch of porous zeolite-containing ceramic particles (Pdso) may be at least about 10% greater than the average particle size of the initial batch of ceramic particles (Idso), such as, at least about 20% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 30% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 40% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 50% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 60% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 70% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 80% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 90% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 100% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 120% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 140% greater than the average particle size of the initial batch of ceramic particles (Id50), at least about 160% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 180% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 200% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 220% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about 240% greater than the average particle size of the initial batch of ceramic particles (Id50), at least about 260% greater than the average particle size of the initial batch of ceramic particles (Idso), at least about or even at least about 280% greater than the average particle size of the initial batch of ceramic particles (Idso). According to still other embodiments, the average particle size of the processed batch of porous zeolite-containing ceramic particles (Pdso) may be not greater than about 300% greater than the average particle size of the initial batch of ceramic particles (Idso), such as, not greater than about 280% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 260% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 240% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 220% greater than the average particle size of the initial batch of ceramic particles (Id50), not greater than about 200% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 180% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 160% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 140% greater than the average particle size of the initial batch of ceramic particles (Id50), not greater than about 120% greater than the average particle size of the initial batch of ceramic particles (W50), not greater than about 100% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 90% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 80% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 70% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 60% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 50% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 40% greater than the average particle size of the initial batch of ceramic particles (Idso), not greater than about 30% greater than the average particle size of the initial batch of ceramic particles (Idso) or even not greater than about 20% greater than the average particle size of the initial batch of ceramic particles (Idso). It will be appreciated that the processed batch of porous zeolite-containing ceramic particles may have a Pdso of any percentage greater than the average particle size of the initial batch of ceramic particles (Idso) between any of the minimum and maximum values noted above. It will be further appreciated that the processed batch of porous zeolite-containing ceramic particles may have a Pdso of any percentage greater than the average particle size of the initial batch of ceramic particles (Idso) within a range between any of the minimum and maximum values noted above. In some embodiments, the average particle size of the processed batch of porous zeolite-containing ceramic particles (Pdso) may be at least about 10% greater than and not greater than about 400% greater than the average particle size of the initial batch of ceramic particles (Idso), such as, at least about 20% greater than and not greater than about 100% greater than the average particle size of the initial batch of ceramic particles (Idso), or at least about 40% greater than and not greater than about 60% greater than the average particle size of the initial batch of ceramic particles (Idso).
[0098] According to yet other embodiments, the initial batch of ceramic particles may have a particular average sphericity. The average sphericity can be determined with any suitable sphericity measurement instruments. For example, the initial particles may have an average sphericity of at least about 0.80, such as, at least about 0.82, at least about 0.85, at least about 0.87, at least about 0.90, at least about 0.92 or even at least about 0.94. According to still other embodiments, the initial batch of ceramic particles may have an average sphericity of not greater than about 0.99, such as, not greater than about 0.97, not greater than about 0.95, not greater than about 0.93, not greater than about 0.90, not greater than about 0.88, not greater than about 0.85, not greater than about 0.83 or even not greater than about 0.81. It will be appreciated that the initial batch of ceramic particles may have a sphericity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the initial batch of ceramic particles may have a sphericity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the initial particles may have an average sphericity of at least about 0.90 and not greater than about 0.98, such as at least about 0.92 and not greater than about 0.97, or at least about 0.94 and not greater than about 0.96. The sphericity as described herein was measured using CAMSIZER® Shape Analysis.
[0099] According to yet other embodiments, the processed batch of porous zeolite- containing ceramic particles may have a particular average sphericity. The average sphericity can be determined with any suitable sphericity measurement instruments. For example, the processed batch of porous zeolite-containing ceramic particles may have an average sphericity of at least about 0.80, such as, at least about 0.82, at least about 0.85, at least about 0.87, at least about 0.9, at least about 0.92 or even at least about 0.94. According to still other embodiments, the processed batch of porous zeolite-containing ceramic particles may have an average sphericity of not greater than about 0.99, such as, not greater than about 0.97, not greater than about 0.95, not greater than about 0.93, not greater than about 0.90, not greater than about 0.88, not greater than about 0.85, not greater than about 0.83 or even not greater than about 0.81. It will be appreciated that the processed batch of porous zeolite-containing ceramic particles may have a sphericity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the processed batch of porous zeolite-containing ceramic particles may have a sphericity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the processed batch of porous zeolite-containing ceramic particles may have an average sphericity of at least about 0.90 and not greater than about 0.98, such as at least about 0.92 and not greater than about 0.97, or at least about 0.94 and not greater than about 0.96. The sphericity as described herein was measured using CAMSIZER® Shape Analysis.
[00100] According to still other embodiments, the processed batch of porous zeolite- containing ceramic particles may have a particular porosity. Porosity can be determined using any suitable porosity, pore volume and pore size distribution measurement instruments. For example, the processed batch of porous zeolite-containing ceramic particles may have an average porosity of at least about 0.01 cc/g, such as, at least about 0.05 cc/g, at least about 0.10 cc/g, at least about 0.25 cc/g, at least about 0.50 cc/g, at least about 0.75 cc/g, at least about 1.00 cc/g, at least about 1.10 cc/g, at least about 1.20 cc/g, at least about 1.30 cc/g, at least about 1.40 cc/g, at least about 1.50 cc/g or even at least about 1.55 cc/g. According to still other embodiments, the processed batch of porous zeolite-containing ceramic particles may have an average porosity of not greater than about 1.60 cc/g, such as, not greater than about 1.55 cc/g, not greater than about 1.50 cc/g, not greater than about 1.45 cc/g, not greater than about 1.40 cc/g, not greater than about 1.35 cc/g, not greater than about 1.30 cc/g, not greater than about 1.25 cc/g, not greater than about 1.20 cc/g, not greater than about 1.15 cc/g, not greater than about 1.10 cc/g, not greater than about 1.05 cc/g, not greater than about 1.00 cc/g, not greater than about 0.95 cc/g, not greater than about 0.90 cc/g or even not greater than about 0.85 cc/g. It will be further appreciated that the processed batch of porous zeolite-containing ceramic particles may have a porosity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the processed batch of porous zeolite-containing ceramic particles may have an average porosity of at least about 0.5 cc/g and not greater than about 1.8 cc/g, such as, at least about 0.8 cc/g and not greater than about 1.6 cc/g, or at least about 0.9 cc/g and not greater than about 1.5 cc/g. It will also be appreciated that porosity may be referred to as pore volume or pore size distribution. Porosity, pore volume or pore size distribution as described herein was determined by mercury intrusion using pressures from 25 to 60,000 psi, using a Micrometries Autopore 9500 model (130° contact angle, mercury with a surface tension of 0.480 N/m, and no correction for mercury compression).
[00101] According to yet other embodiments, the number of ceramic particles that make- up the processed batch of porous zeolite-containing ceramic particles may be equal to a particular percentage of the number of ceramic particles that make up the initial batch of ceramic particles. For example, the number of ceramic particles in the processed batch may be equal to at least about 80% of the number of ceramic particles in the initial batch, such as, at least about 85% of the number of ceramic particles in the initial batch, at least about 90% of the number of ceramic particles in the initial batch, at least about 91% of the number of ceramic particles in the initial batch, at least about 92% of the number of ceramic particles in the initial batch, at least about 93% of the number of ceramic particles in the initial batch, at least about 94% of the number of ceramic particles in the initial batch, at least about 95% of the number of ceramic particles in the initial batch, at least about 96% of the number of ceramic particles in the initial batch, at least about 97% of the number of ceramic particles in the initial batch, at least about 98% of the number of ceramic particles in the initial batch or even at least about 99% of the number of ceramic particles in the initial batch. According to yet another particular embodiment, the number of ceramic particles in the processed batch may be equal to the number of ceramic particles in the initial batch. It will be appreciated that the number of ceramic particles in the processed batch may be equal to any percentage of the number of ceramic particles in the initial batch between any of the minimum and maximum values noted above. It will be further appreciated that the number of ceramic particles in the processed batch may be equal to any percentage of the number of ceramic particles in the initial batch between any of the minimum and maximum values noted above.
[00102] According to still other embodiments, a batch spray fluidization forming cycle of a spray fluidization forming process operating in a batch made may include initiating spray fluidization of the entire initial batch of ceramic particles, spray fluidizing the entire initial batch of ceramic particles to form the entire processed batch of porous zeolite-containing ceramic particles, and terminating the spray fluidization of the entire processed batch.
[00103] According to still other embodiments, a spray fluidization forming process operating in a batch mode or a batch spray fluidization forming cycle of a spray fluidization forming process operating in a batch mode may include conducting spray fluidization on the initial batch of ceramic particles for a predetermined period of time where all ceramic particles in the initial batch begin the forming process essentially in the same process step and finish the forming process essentially in the same process step. For example, the spray fluidization forming process may last at least about 10 minutes, such as, at least about 30 minutes, at least about 60 minutes, at least about 90 minutes, at least about 120 minutes, at least about 240 minutes, at least about 360 minutes, at least about 480 minutes or even at least about 600 minutes. According to still other embodiments, the spray fluidization forming process may last not greater than about 720 minutes, such as, not greater than about 600 minutes, not greater than about 480 minutes, not greater than about 360 minutes, not greater than about 240 minutes, not greater than about 120 minutes, not greater than about 90 minutes, not greater than about 60 minutes or even not greater than about 30 minutes. It will be appreciated that the spray fluidization forming process may last any number of minutes between any of the minimum and maximum values noted above. It will be further appreciated that the spray fluidization forming process may last any number of minutes within a range between any of the minimum and maximum values noted above. In some embodiments, the spray fluidization forming process may last at least about 60 minutes and not greater than about 300 minutes, such as, at least about 120 minutes and not greater than about 180 minutes.
[00104] Again referring back to FIG. 1, according to particular embodiments, the step 120 of coating the initial batch of ceramic particles with a slurry mix of porous zeolite- containing ceramic droplets using the spray fluidization techniques to form a processed batch of porous zeolite-containing ceramic particles may further include sintering the porous zeolite-containing ceramic particles after the spray fluidization forming process is complete. Sintering the processed batch of porous zeolite-containing ceramic particles may occur at a particular temperature. For example, the processed batch of porous zeolite-containing ceramic particle may be sintered at a temperature of at least about 350 °C, such as, at least about 375 °C, at least about 400 °C, at least about 425 °C, at least about 450 °C, at least about 475 °C, at least about 500 °C, at least about 525 °C, at least about 550 °C, at least about 575 °C, at least about 600 °C, at least about 625 °C, at least about 650 °C, at least about 675 °C, at least about 700 °C, at least about 725 °C, at least about 750 °C, at least about 775 °C, at least about 800 °C, at least about 825 °C, at least about 850 °C, at least about 875 °C, at least about 900 °C, at least about 925 °C, at least about 950 °C, at least about 975 °C, at least about 1000 °C, at least about 1100 °C, at least about 1200 °C or even at least about 1300 °C. According to still other embodiments, the processed batch of porous zeolite-containing ceramic particle may be sintered at a temperature of not greater than about 1400 °C, such as, not greater than about 1300 °C, not greater than about 1200 °C, not greater than about 1100 °C, not greater than about 1000 °C, not greater than about 975 °C, not greater than about 950 °C, not greater than about 925 °C, not greater than about 900 °C, not greater than about 875 °C, not greater than about 850 °C, not greater than about 825 °C, not greater than about 800 °C, not greater than about 775 °C, not greater than about 750 °C, not greater than about 725 °C, not greater than about 700 °C, not greater than about 675 °C, not greater than about 650 °C, not greater than about 625 °C, not greater than about 600 °C, not greater than about 575 °C, not greater than about 550 °C, not greater than about 525 °C, not greater than about 500 °C, not greater than about 475 °C, not greater than about 450 °C, not greater than about 425 °C, not greater than about 400 °C or even not greater than about 375 °C. It will he appreciated that the processed batch of porous zeolite-containing ceramic particles may be sintered at any temperature between any of the minimum and maximum values noted above. It will be further appreciated that the spray fluidization forming process may last any number of minutes within a range between any of the minimum and maximum values noted above. In some embodiments, the processed batch of porous zeolite-containing ceramic particle may be sintered at a temperature of at least about 350 °C and not greater than about 1400 °C, such as, at least about 500 °C and not greater than about 700 °C.
[00105] Referring to still other embodiments, a plurality of porous zeolite-containing ceramic particles formed by a spray fluidization forming process operating in a batch mode according to embodiments described herein may have a particular average porosity. For example, a plurality of porous zeolite-containing ceramic particles may have an average porosity of at least about 0.01 cc/g, such as, at least about 0.05 cc/g, at least about 0.10 cc/g, at least about 0.25 cc/g, at least about 0.50 cc/g, at least about 0.75 cc/g, at least about 1.00 cc/g, at least about 1.10 cc/g, at least about 1.20 cc/g, at least about 1.30 cc/g, at least about 1.40 cc/g, at least about 1.50 cc/g or even at least about 1.55 cc/g. According to still other embodiments, a plurality of porous zeolite-containing ceramic particles may have an average porosity of not greater than about 1.60 cc/g, such as, not greater than about 1.55 cc/g, not greater than about 1.50 cc/g, not greater than about 1.45 cc/g, not greater than about 1.40 cc/g, not greater than about 1.35 cc/g, not greater than about 1.30 cc/g, not greater than about 1.25 cc/g, not greater than about 1.20 cc/g, not greater than about 1.15 cc/g, not greater than about 1.10 cc/g, not greater than about 1.05 cc/g, not greater than about 1.00 cc/g, not greater than about 0.95 cc/g, not greater than about 0.90 cc/g or even not greater than about 0.85 cc/g. It will be appreciated that a plurality of porous zeolite-containing ceramic particles may have an average porosity of any value between any of the minimu and maximum values noted above. It will be further appreciated that a plurality of porous zeolite-containing ceramic particles may have an average porosity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, a plurality of porous zeolite-containing ceramic particles may have an average porosity of at least about 0.5 cc/g and not greater than about 1.8 cc/g, such as, at least about 0.8 cc/g and not greater than about 1.6 cc/g, or at least about 0.9 cc/g and not greater than about 1.5 cc/g. [00106] According to still other embodiments, a plurality of porous zeolite-containing ceramic particles formed by a spray fluidization forming process operating in a batch mode according to embodiments described herein may have a particular average particle size measured as the longest dimension or diameter of the particle. For example, a plurality of porous zeolite-containing ceramic particles may have an average particle size of at least about 100 microns, such as, at least about 200 microns, at least about 300 microns, at least about 400 microns, at least about 500 microns, at least about 600 microns, at least about 700 microns, at least about 800 microns, at least about 900 microns, at least about 1000 microns, at least about 1100 microns, at least about 1200 microns, at least about 1300 microns, at least about 1400 microns or even at least about 1490 microns. According to still other
embodiments, a plurality of porous zeolite-containing ceramic particles may have an average particle size of not greater than about 4500 microns, such as, not greater than about 4400 microns, not greater than about 4300 microns, not greater than about 4200 microns, not greater than about 4100 microns, not greater than about 4000 microns, not greater than about 3900 microns, not greater than about 3800 microns, not greater than about 3700 microns, not greater than about 3600 microns, not greater than about 3500 microns, not greater than about 3400 microns, not greater than about 3300 microns, not greater than about 3200 microns, not greater than about 3100 microns, not greater than about 3000 microns, not greater than about 2900 microns, not greater than about 2800 microns, not greater than about 2700 microns, not greater than about 2600 microns, not greater than about 2500 microns, not greater than about 2400 microns, not greater than about 2300 microns, not greater than about 2200 microns, not greater than about 2100 microns, not greater than about 2000 microns not greater than about 1900 microns, not greater than about 1800 microns, not greater than about 1700 microns, not greater than about 1600 microns, not greater than about 1500 microns, not greater than about 1400 microns, not greater than about 1300 microns, not greater than about 1200 microns, not greater than about 1100 microns, not greater than about 1000 microns, not greater than about 900 microns, not greater than about 800 microns, not greater than about 700 microns, not greater than about 600 microns, not greater than about 500 microns, not greater than about 400 microns, not greater than about 300 microns, not greater than about 200 microns, or even not greater than about 150 microns. It will be appreciated that the plurality of porous zeolite- containing ceramic particles may have an average particle size of any value between any of the minimum and maximum values noted above. It will be further appreciated that the plurality of porous zeolite-containing ceramic particles may have an average particle size of any value within a range between any of the minimum and maximum values noted above. In some embodiments, a plurality of porous zeolite-containing ceramic particles may have an average particle size of at least about 50 microns and no greater than about 4500 microns, such as, at least about 100 microns and no greater than about 3000 microns, at least about 200 microns and no greater than about 1500 microns. In some embodiments, a plurality of porous zeolite-containing ceramic particles may have an average particle size of at least about 150 microns and no greater than about 400 microns.
[00107] According to yet other embodiments, a plurality of porous zeolite-containing ceramic particles formed by a spray fluidization forming process operating in a batch mode according to embodiments described herein may have a particular average sphericity. For example a plurality of porous zeolite-containing ceramic particles may have an average sphericity of at least about 0.80, such as, at least about 0.82, at least about 0.85, at least about 0.87, at least about 0.90, at least about 0.92 or even at least about 0.94. According to still other embodiments, a plurality of porous zeolite-containing ceramic particles may have an average sphericity of not greater than about 0.99, such as, not greater than about 0.97, not greater than about 0.95, not greater than about 0.93, not greater than about 0.90, not greater than about 0.88, not greater than about 0.85, not greater than about 0.83 or even not greater than about 0.81. It will be appreciated that the plurality of porous zeolite-containing ceramic particles may have a sphericity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the plurality of porous zeolite- containing ceramic particles may have a sphericity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, a plurality of porous zeolite-containing ceramic particles may have an average sphericity of at least about 0.90 and not greater than about 0.98, such as at least about 0.92 and not greater than about 0.97, or at least about 0.94 and not greater than about 0.96.
[00108] According to still other particular embodiments, a spray fluidization forming process operating in a batch mode may include multiple batch spray fluidization forming cycles as described herein with reference to the cycle 100 and illustrated in FIG. 1. As further described herein with reference to the cycle 100 and illustrated in FIG. 1, each batch spray fluidization forming cycle may include a step 110 of providing an initial batch of ceramic particles and a step 120 of coating the initial batch of ceramic particles with a slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a processed batch of porous zeolite-containing ceramic particles. It will be appreciated that the processed batch of porous zeolite-containing ceramic particles from any cycle may be used to form the initial batch of ceramic particles for the subsequent cycle. For example, the processed batch of porous zeolite-containing ceramic particles formed during a first batch spray fluidization forming cycle 100 may then be used as the initial batch in a second batch spray fluidization forming cycle 100. It will also be appreciated that all description, characteristics and embodiments described herein, such as the coating fluid composition, with regard to cycle 100 as illustrated in FIG. 1 may be applied to any cycle of a multi-cycle spray fluidization forming process operating in a batch mode for forming a plurality of porous zeolite-containing ceramic particle as described herein.
[00109] According to still other particular embodiments, a spray fluidization forming process operating in a batch mode may include a particular number of batch spray fluidization forming cycles. For example, a spray fluidization forming process operating in a batch mode may include at least 2 batch spray fluidization forming cycles, such as, at least 3 batch spray fluidization forming cycles, at least 4 batch spray fluidization forming cycles, at least 5 batch spray fluidization forming cycles, at least 6 batch spray fluidization forming cycles, at least 7 batch spray fluidization forming cycles, at least 8 batch spray fluidization forming cycles, at least 9 batch spray fluidization forming cycles or even at least 10 batch spray fluidization forming cycles. According to other embodiments, a spray fluidization forming process operating in a batch mode may include not greater than 15 batch spray fluidization forming cycles, such as, not greater than 10 batch spray fluidization forming cycles, not greater than 9 batch spray fluidization forming cycles, not greater than 8 batch spray fluidization forming cycles, not greater than 7 batch spray fluidization forming cycles, not greater than 6 batch spray fluidization forming cycles, not greater than 5 batch spray fluidization forming cycles, not greater than 4 batch spray fluidization forming cycles or even not greater than 3 batch spray fluidization forming cycles. It will be appreciated that a spray fluidization forming process operating in a batch mode may include any number of cycles between any of the minimum and maximum values noted above. It will be further appreciated that a spray fluidization forming process operating in a batch mode may include any number of cycles within a range between any of the minimum and maximum values noted above. [00110] For purposes of illustration, FIG 3 includes a flow chart showing an embodiment of a spray fluidization forming process operating in a batch mode for forming a plurality of porous zeolite-containing ceramic particles with a hierarchical structure where the spray fluidization forming process includes three batch spray fluidization forming cycles. As illustrated in FIG. 3, a process 300 for forming porous zeolite-containing ceramic particles may include, as the first batch spray fluidization forming cycle, a step 310 of providing a first initial batch of ceramic particles and a step 320 of coating the first initial batch of ceramic particles with a first slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a first processed batch of porous zeolite-containing ceramic particles. Next, the process 300 may include, as the second batch spray fluidization forming cycle, a step 330 of providing the first processed batch as a second initial batch of ceramic particles and a step 340 of coating the second initial batch of ceramic particles with a second slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a second processed batch of porous zeolite-containing ceramic particles. Finally, the process 300 may include, as the third batch spray fluidization forming cycle, a step 350 of providing the second processed batch as a third initial batch of ceramic particles and a step 360 of coating the third initial batch of ceramic particles with a third slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a third processed batch of porous zeolite-containing ceramic particles. It will be appreciated that the third processed batch may be referred to as a final processed batch.
[00111] According to certain embodiments, referring to the first batch spray fluidization forming cycle of process 300, the particles of the first initial batch of ceramic particles may include a core region composition. According to yet other embodiments, the core region composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the core region composition may include a ceramic material. According to still other
embodiments, the core region of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the core region of each ceramic particle may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00112] According to still other embodiments, the first batch spray fluidization forming cycle of process 300 (i.e., steps 310-320) may include repeatedly dispensing finely dispersed droplets of a first coating fluid onto air borne ceramic particles from the first initial batch of ceramic particles to form the first processed batch of porous zeolite-containing ceramic particles.
[00113] According to yet other embodiments, the first coating fluid may include a particular first coating material composition. According to yet other embodiments, the first coating material composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the first coating material composition may include zeolite and a ceramic material. In some embodiments, the first coating fluid includes a slurry mix of up to 80% of zeolite. In some embodiments, the first coating fluid includes a slurry mix of at least 20% of ceramic material. In some embodiments, the first coating fluid includes a slurry mix of at least 20% of ceramic material and up to 80% of zeolite. In some embodiments, the first coating fluid includes no greater than 90% of ceramic materials, and at least 10% of zeolite. In some embodiments, the first coating fluid includes no greater than 80% of ceramic materials, and at least 20% of zeolite. In some embodiments, the first coating fluid includes no greater than 70% of ceramic materials, and at least 30% of zeolite. In some embodiments, the first coating fluid includes no greater than 60% of ceramic materials, and at least 40% of zeolite. In some embodiments, the first coating fluid includes at least 20% and no greater than 50% of ceramic materials, and at least 50% and no greater than 80% of zeolite. In some embodiments, the first coating fluid includes at least 30% and no greater than 60% of ceramic materials, and at least 40% and no greater than 70% of zeolite. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof According to still other embodiments, the first coating material composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof [00114] According to still other embodiments, the first coating material composition may be different than the core region composition. It will be appreciated that when the first coating material composition is referred to as being different than the core region composition, the first coating material composition differs from the core region composition in materials and/or relative concentrations of materials.
[00115] According to still other embodiments, the first coating material composition may include a particular concentration of a material or particular concentrations of multiple materials as measured in volume percent for a total volume of the first coating fluid.
[00116] According to still other embodiments, the concentration of the particular material or the concentrations of the multiple materials in the first coating material composition may be held constant throughout the duration of the first batch spray fluidization forming cycle. Holding the concentration of the particular material or the concentrations of the multiple materials in the first coating material composition constant throughout the duration of the first batch spray fluidization forming cycle forms a first layered section that has a constant or generally homogeneous first layered section composition throughout the thickness of the first layered section.
[00117] According to still other embodiments, the concentration of the particular material or the concentrations of the multiple materials in the first coating material composition may be changed continuously for a portion of or throughout the duration of the first batch spray fluidization forming cycle. Continuously changing the concentration of the particular material or the concentrations of the multiple materials in the first coating material composition for a portion of or throughout the duration of the first batch spray fluidization forming cycle forms a first layered section that has non-homogenous or a continuously changing composition throughout the thickness of the first layered section.
[00118] According to still other embodiments, the second batch spray fluidization forming cycle of process 300 (i.e., steps 330-340) may include repeatedly dispensing finely dispersed droplets of a second coating fluid onto air borne ceramic particles from the first processed batch of porous zeolite-containing ceramic particles to form the second processed batch of porous zeolite-containing ceramic particles.
[00119] According to yet other embodiments, the second coating fluid may include a particular second coating material composition. According to yet other embodiments, the second coating material composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the second coating material composition may include zeolite and a ceramic material. In some embodiments, the second coating fluid includes a slurry mix of up to 80% of zeolite. In some embodiments, the second coating fluid includes a slurry mix of at least 20% of ceramic material. In some embodiments, the second coating fluid includes a slurry mix of at least 20% of ceramic material and up to 80% of zeolite. In some embodiments, the second coating fluid includes no greater than 90% of ceramic materials, and at least 10% of zeolite. In some embodiments, the second coating fluid includes no greater than 80% of ceramic materials, and at least 20% of zeolite. In some embodiments, the second coating fluid includes no greater than 70% of ceramic materials, and at least 30% of zeolite. In some embodiments, the second coating fluid includes no greater than 60% of ceramic materials, and at least 40% of zeolite. In some embodiments, the second coating fluid includes at least 20% and no greater than 50% of ceramic materials, and at least 50% and no greater than 80% of zeolite.
In some embodiments, the second coating fluid includes at least 30% and no greater than 60% of ceramic materials, and at least 40% and no greater than 70% of zeolite. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the second coating material composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00120] According to certain embodiments, the second coating material composition may be the same as the first coating material composition. It will be appreciated that when the second coating material composition is referred to as being the same as the first coating material composition, the second coating material composition includes the same materials at the same relative concentrations as the first coating material composition.
[00121] According to still other embodiments, the second coating material composition may be different than the core region composition. It will be appreciated that when the second coating material composition is referred to as being different than the core region composition, the second coating material composition differs from the core region composition in materials and/or relative concentrations of materials. [00122] According to still other embodiments, the second coating material composition may be different than the first coating material composition. It will be appreciated that when the second coating material composition is referred to as being different than the first coating material composition, the second coating material composition differs from the first coating material composition (not including fluidization liquid) in materials and/or relative concentrations of materials.
[00123] According to still other embodiments, the second coating material composition may include a particular concentration of a material or particular concentrations of multiple materials as measured in volume percent for a total volume of the second coating fluid.
[00124] According to still other embodiments, the concentration of the particular material or the concentrations of the multiple materials in the second coating material composition may be held constant throughout the duration of the second batch spray fluidization forming cycle. Holding the concentration of the particular material or the concentrations of the multiple materials in the second coating material composition constant throughout the duration of the second batch spray fluidization forming cycle forms a second layered section that has a constant or generally homogeneous second layered section composition throughout the thickness of the second layered section.
[00125] According to still other embodiments, the concentration of the particular material or the concentrations of the multiple materials in the second coating material composition may be changed continuously for a portion of or throughout the duration of the second batch spray fluidization forming cycle. Continuously changing the concentration of the particular material or the concentrations of the multiple materials in the second coating material composition for a portion of or throughout the duration of the second batch spray fluidization forming cycle forms a second layered section that has non-homogenous or a continuously changing composition throughout the thickness of the second layered section.
[00126] According to still other embodiments, the third batch spray fluidization forming cycle of process 300 (i.e., steps 350-360) may include repeatedly dispensing finely dispersed droplets of a third coating fluid onto air borne ceramic particles from the second processed batch of porous zeolite-containing ceramic particles to form the third processed batch of porous zeolite-containing ceramic particles.
[00127] According to yet other embodiments, the third coating fluid may include a particular third coating material composition. According to yet other embodiments, the third coating material composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the third coating material composition may include zeolite and a ceramic material. In some embodiments, the third coating fluid includes a slurry mix of up to 80% of zeolite. In some embodiments, the third coating fluid includes a slurry mix of at least 20% of ceramic material. In some embodiments, the third coating fluid includes a slurry mix of at least 20% of ceramic material and up to 80% of zeolite. In some embodiments, the third coating fluid includes no greater than 90% of ceramic materials, and at least 10% of zeolite. In some embodiments, the third coating fluid includes no greater than 80% of ceramic materials, and at least 20% of zeolite. In some embodiments, the third coating fluid includes no greater than 70% of ceramic materials, and at least 30% of zeolite. In some embodiments, the third coating fluid includes no greater than 60% of ceramic materials, and at least 40% of zeolite.
In some embodiments, the third coating fluid includes at least 20% and no greater than 50% of ceramic materials, and at least 50% and no greater than 80% of zeolite. In some embodiments, the third coating fluid includes at least 30% and no greater than 60% of ceramic materials, and at least 40% and no greater than 70% of zeolite. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafhia or a combination thereof. According to still other embodiments, the third coating material composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00128] According to certain embodiments, the third coating material composition may be the same as the first coating material composition. It will be appreciated that when the third coating material composition is referred to as being the same as the first coating material composition, the third coating material composition includes the same materials at the same relative concentrations as the first coating material composition.
[00129] According to certain embodiments, the third coating material composition may be the same as the second coating material composition. It will be appreciated that when the third coating material composition is referred to as being the same as the second coating material composition, the third coating material composition includes the same materials at the same relative concentrations as the second coating material composition. [00130] According to still other embodiments, the third coating material composition may be different than the core region composition. It will be appreciated that when the third coating material composition is referred to as being different than the core region composition, the third coating material composition differs from the core region composition in materials and/or relative concentrations of materials.
[00131] According to still other embodiments, the third coating material composition may be different than the first coating material composition. It will be appreciated that when the third coating material composition is referred to as being different than the first coating material composition, the third coating material composition differs from the first coating material composition in materials and/or relative concentrations of materials.
[00132] According to still other embodiments, the third coating material composition may be different than the second coating material composition. It will be appreciated that when the third coating material composition is referred to as being different than the first coating material composition, the third coating material composition differs from the second coating material composition in materials and/or relative concentrations of materials.
[00133] According to still other embodiments, the third coating material composition may include a particular concentration of a material or particular concentrations of multiple materials as measured in volume percent for a total volume of the third coating fluid.
[00134] According to still other embodiments, the concentration of the particular material or the concentrations of the multiple materials in the third coating material composition may be held constant throughout the duration of the third batch spray fluidization forming cycle. Holding the concentration of the particular material or the concentrations of the multiple materials in the third coating material composition constant throughout the duration of the third batch spray fluidization forming cycle forms a third layered section that has a constant or generally homogeneous third layered section composition throughout the thickness of the third layered section.
[00135] According to still other embodiments, the concentration of the particular material or the concentrations of the multiple materials in the third coating material composition may be changed continuously for a portion of or throughout the duration of the third batch spray fluidization forming cycle. Continuously changing the concentration of the particular material or the concentrations of the multiple materials in the third coating material composition for a portion of or throughout the duration of the third batch spray fluidization forming cycle forms a third layered section that has non-homogenous or a continuously changing composition throughout the thickness of the third layered section.
[00136] As noted according to certain embodiments herein a spray fluidization forming process operating in a batch mode may include any necessary number of batch spray fluidization forming cycles. It will be appreciated that any batch spray fluidization forming cycle may be carried out in accordance with the processes described herein in reference to the first batch spray fluidization forming cycle, the second batch spray fluidization forming cycle or the third batch spray fluidization forming cycle. In some embodiments, however, the maximum number of batch spray fluidization forming cycles can be limited by the characteristics, such as size, of the final particles, the limitation, such as space, of the spray fluidization equipment, and/or the duration, such as maximum time allowed, of the fluidization forming cycles. In some embodiments, the hours needed to form a processed batch in a forming cycle is longer than the hours needed in the previous forming cycle. For example, for a particle volume to grow the same 2 to 5 times than the initial particle volume for a particular batch, more materials and more time are needed compared with a previous batch forming cycle. In some embodiments, the hours needed to form a processed batch in a forming cycle is shorter than the hours needed in the previous forming cycle. In some embodiments, the hours needed to form a processed batch in a forming cycle is the same as the hours needed in the previous forming cycle.
[00137] Referring now to the plurality of porous zeolite-containing ceramic particles formed according to embodiments described herein, a plurality of porous zeolite-containing ceramic particles may each be described as including a particular cross-section having a core region and a layered region overlying the core region. By way of illustration, FIG. 4 shows a cross-sectional schematic diagram of an embodiment of a porous zeolite-containing ceramic particle formed according to embodiments described herein. As shown in FIG. 4, a porous zeolite-containing ceramic particle 400 may include a core region 410 and a layered region 420 overlying the core region 410.
[00138] It will be appreciated that, according to certain embodiments, the core region 410 may be referred to as a seed or initial particle. According to still other embodiments, the core region 410 may be monolithic. According to still other embodiments, the core region 410 may include a core region composition. According to yet other embodiments, the core region composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the core region composition may include a ceramic material. According to still other embodiments, the core region of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafhia or a combination thereof. According to still other embodiments, the core region composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00139] According to yet other embodiments, the layered region 420 may be referred to as an outer region or shell region overlying the core region 410. According to still other embodiments, the layered region 420 may include overlapping layers surrounding the core region 410, e.g. multiple layers.
[00140] According to still other embodiments, the layered region 420 may include a layered region composition. According to yet other embodiments, the layered region composition may include a particular material or a combination of particular materials.
According to still other embodiments, the material or materials included in the layered region composition may include zeolite and a ceramic material. According to still other
embodiments, the layered region of each ceramic particle may consist essentially of zeolite and a ceramic material. In some embodiments, the layered region includes up to 90% of zeolite, such as, up to 80% of zeolite, up to 70% of zeolite, up to 60% of zeolite, up to 50% of zeolite, up to 40% of zeolite, up to 30% of zeolite, up to 20% of zeolite, or up to 10% of zeolite. In some embodiments, the layered region includes at least 10% of zeolite, such as, at least 20% of zeolite, at least 30% of zeolite, at least 40% of zeolite, at least 50% of zeolite, at least 60% of zeolite, at least 70% of zeolite, at least 80% of zeolite, or at least 90% of zeolite. In some embodiments, the layered region includes at least 10% of ceramic material, such as, at least 20% of ceramic material, at least 30% of ceramic material, at least 40% of ceramic material, at least 50% of ceramic material, at least 60% of ceramic material, at least 70% of ceramic material, at least 80% of ceramic material, or at least 90% of ceramic material. In some embodiments, the layered region includes no greater than 90% of ceramic material, such as, no greater than 80% of ceramic material, no greater than 70% of ceramic material, no greater than 60% of ceramic material, no greater than 50% of ceramic material, no greater than 40% of ceramic material, no greater than 30% of ceramic material, no greater than 20% of ceramic material, or no greater than 10% of ceramic material. In some embodiments, the layered region includes at least 20% of ceramic material and up to 80% of zeolite. In some embodiments, the layered region includes no greater than 90% of ceramic material, and at least 10% of zeolite. In some embodiments, the layered region includes no greater than 80% of ceramic material, and at least 20% of zeolite. In some embodiments, the layered region includes no greater than 70% of ceramic material, and at least 30% of zeolite. In some embodiments, the layered region includes no greater than 60% of ceramic material, and at least 40% of zeolite. In some embodiments, the layered region includes at least 20% and no greater than 50% of ceramic material, and at least 50% and no greater than 80% of zeolite. In some embodiments, the layered region includes at least 30% and no greater than 60% of ceramic material, and at least 40% and no greater than 70% of zeolite. It will be further appreciated that the weight percentage of zeolite and/or ceramic material in the layered region may have any value within a range between any of the minimum and maximum values noted above. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the layered region composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00141] According to still other embodiments, the layered region 420 may have a particular porosity. For example, the layered region 420 may have an average porosity of at least about 0.01 cc/g, such as, at least about 0.05 cc/g, at least about 0.10 cc/g, at least about 0.25 cc/g, at least about 0.50 cc/g, at least about 0.75 cc/g, at least about 1.00 cc/g, at least about 1.10 cc/g, at least about 1.20 cc/g, at least about 1.30 cc/g, at least about 1.40 cc/g, at least about 1.50 cc/g or even at least about 1.55 cc/g. According to still other embodiments, the layered region 420 may have an average porosity of not greater than about 1.60 cc/g, such as, not greater than about 1.55 cc/g, not greater than about 1.50 cc/g, not greater than about 1.45 cc/g, not greater than about 1.40 cc/g, not greater than about 1.35 cc/g, not greater than about 1.30 cc/g, not greater than about 1.25 cc/g, not greater than about 1.20 cc/g, not greater than about 1.15 cc/g, not greater than about 1.10 cc/g, not greater than about 1.05 cc/g, not greater than about 1.00 cc/g, not greater than about 0.95 cc/g, not greater than about 0.90 cc/g or even not greater than about 0.85 cc/g. It will be appreciated that the layered region may have a porosity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the layered region may have a porosity of any value within a range between any of the minimum and maximum values noted above. In some embodiments, the layered region 420 may have an average porosity of at least about 0.6 cc/g and not greater than about 1.9 cc/g, such as, at least about 0.9 cc/g and not greater than about 1.7 cc/g, or at least about 0.9 cc/g and not greater than about 1.5 cc/g.
[00142] According to other embodiments, the layered region 420 may make up a particular volume percentage of the total volume of the porous zeolite-containing ceramic particle 400. For example, the layered region 420 may make up at least about 50 vol% of the total volume of the porous zeolite-containing ceramic particle 400, such as, at least about 55 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 75 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 85 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 90 vol% of the total volume of the porous zeolite- containing ceramic particle 400, at least about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 400 or even at least about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 400. According to still other embodiments, the layered region may make up not greater than about 99.5 vol% of the total volume of the porous zeolite-containing ceramic particle 400, such as, not greater than about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 85 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 80 vol% of the total volume of the porous zeolite- containing ceramic particle 400, not greater than about 75 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 400, not greater than about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 400 or even not greater than about 55 vol% of the total volume of the porous zeolite-containing ceramic particle 400. It will be appreciated that the layered region 420 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 400 between any of the minimum and maximum values noted above. It will be further appreciated that the layered region 420 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 400 within a range between any of the minimum and maximum values noted above. In some embodiments, the layered region 420 may make up at least about 30 vol% and not greater than about 85 vol% of the total volume of the porous zeolite-containing ceramic particle 400, such as, at least about 50 vol% and not greater than about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 400, at least about 50 vol% and not greater than about 67 vol% of the total volume of the porous zeolite-containing ceramic particle 400.
[00143] According to certain embodiments, the core region 410 may be different than the layered region 420. According to still other embodiments, the core region 410 may have a different composition than the layered region 420. According to particular embodiments, the core region 410 and the layered region 420 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the core region 410 may have a different microstructure than the layered region 420. According to yet other embodiments, the core region 410 may have a different particle density than the layered region 420, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the core region 410 may have a different porosity than the layered region 420.
[00144] According to yet another particular embodiment, the core region 410 may include a first alumina phase and the layered region may include a second alumina phase. According to still other embodiments, the first alumina phase and the second alumina phase may be the same. According to still other embodiments, the first alumina phase and the second alumina phase may be distinct. According to yet other embodiments, the first alumina phase may be an alpha alumina and the second alumina phase may be a non-alpha alumina phase, for example, gamma or kappa alumina. [00145] According to still other embodiments, the layered region composition may be different than the core region composition. It will be appreciated that when the layered region composition is referred to as being different than the core region composition, the layered region composition differs from the core region composition in materials and/or relative concentrations of materials.
[00146] Referring to yet other embodiments of the plurality of porous zeolite- containing ceramic particles formed according to embodiments described herein, a plurality of porous zeolite-containing ceramic particles may each be described as including a particular cross-section having a core region and a layered region overlying the core region where the layered region includes multiple distinct layered sections. By way of illustration, FIG. 5 shows a cross-sectional a schematic diagram of an embodiment of a porous zeolite-containing ceramic particle formed according to embodiments described herein having a layered region having distinct layered sections. As shown in FIG. 5, a porous zeolite-containing ceramic particle 500 may include a core region 510 and a layered region 520 overlying the core region 510. The layered region 520 may further include distinct layered sections 522, 524 and 526.
[00147] It will be appreciated that the core region 510 and the layered region 520 may include any of the characteristics described in reference to corresponding components shown in FIG. 4 (i.e., core region 410 and layered region 420), for example, both homogeneous layered sections and/or varying layered sections in FIG. 5 can include any of the
characteristics described in the layered region 420.
[00148] It will be appreciated that, according to certain embodiments, the core region 510 may be referred to as a seed or initial particle. According to still other embodiments, the core region 510 may be monolithic. According to still other embodiments, the core region 510 may include a core region composition. According to yet other embodiments, the core region composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the core region composition may include a ceramic material. According to still other embodiments, the core region of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the core region composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00149] According to still other embodiments, a first layered section 522 may include overlapping layers surrounding the core region 510.
[00150] According to still other embodiments, the first layered section 522 may have a particular porosity. For example, the first layered section 522 may have an average porosity of at least about 0.01 cc/g, such as, at least about 0.05 cc/g, at least about 0.10 cc/g, at least about 0.25 cc/g, at least about 0.50 cc/g, at least about 0.75 cc/g, at least about 1.00 cc/g, at least about 1.10 cc/g, at least about 1.20 cc/g, at least about 1.30 cc/g, at least about 1.40 cc/g, at least about 1.50 cc/g or even at least about 1.55 cc/g. According to still other
embodiments, the first layered section 522 may have an average porosity of not greater than about 1.60 cc/g, such as, not greater than about 1.55 cc/g, not greater than about 1.50 cc/g, not greater than about 1.45 cc/g, not greater than about 1.40 cc/g, not greater than about 1.35 cc/g, not greater than about 1.30 cc/g, not greater than about 1.25 cc/g, not greater than about 1.20 cc/g, not greater than about 1.15 cc/g, not greater than about 1.10 cc/g, not greater than about 1.05 cc/g, not greater than about 1.00 cc/g, not greater than about 0.95 cc/g, not greater than about 0.90 cc/g or even not greater than about 0.85 cc/g. It will be appreciated that the layered region may have a porosity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the layered region may have a porosity of any value within a range between any of the minimum and maximum values noted above.
[00151] According to other embodiments, the first layered section 522 may make up a particular volume percentage of the total volume of the porous zeolite-containing ceramic particle 500. For example, the first layered section 522 may make up at least about 50 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, at least about 55 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 75 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 80 vol% of the total volume of the porous zeolite- containing ceramic particle 500, at least about 85 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 500 or even at least about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 500. According to still other embodiments, the layered region may make up not greater than about 99.5 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, not greater than about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 85 vol% of the total volume of the porous zeolite- containing ceramic particle 500, not greater than about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 75 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500 or even not greater than about 55 vol% of the total volume of the porous zeolite- containing ceramic particle 500. It will be appreciated that the first layered section 522 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 500 between any of the minimum and maximum values noted above. It will be further appreciated that the first layered section 522 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 500 within a range between any of the minimum and maximum values noted above.
[00152] According to certain embodiments, the core region 510 may be different than the first layered section 522. According to still other embodiments, the core region 510 may have different composition than the first layered section 522. According to particular embodiments, the core region 510 and the first layered section 522 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the core region 510 may have a different microstructure than the first layered section 522. According to yet other embodiments, the core region 510 may have a different particle density than the first layered section 522, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the core region 510 may have a different porosity than the first layered section 522.
[00153] According to certain embodiments, the first layered section 522 may include a first layered section composition. According to yet other embodiments, the first layered section composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the first layered section composition may include zeolite and a ceramic material. According to still other embodiments, the first layered section of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. In some embodiments, the first layered section includes up to 80% of zeolite. In some embodiments, the first layered section includes at least 20% of ceramic material. In some embodiments, the first layered section includes at least 20% of ceramic material and up to 80% of zeolite. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite- containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafhia or a combination thereof. According to still other embodiments, the first layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00154] According to yet other embodiments, the first layered section 522 may be defined as having an inner surface 522A and an outer surface 522B. The inner surface 522A of the first layered section 522 is defined as the surface closest to the core region 510. The outer surface 522B of the first layered section 522 is defined as the surface farthest from the core region 510.
[00155] According to certain embodiments, first layered section 522 may have a homogeneous first layered section composition throughout a thickness of the first layered section 522 from the inner surface 522A to the outer surface 522B of the first layered section 522. It will be appreciated that as described herein, a homogeneous first layered section composition is defined as having less than a 1 percent variation in the concentrations of any material or materials within the first layered section composition throughout a thickness of the first layered section 522 from the inner surface 522A to the outer surface 522B of the first layered section 522. [00156] It will also be appreciated that the concentration of a particular material within a formed porous zeolite-containing ceramic particle or catalyst carrier or within a particular portion of a formed porous zeolite-containing ceramic particle or catalyst carrier as described herein refers to the elemental composition of that material. The elemental composition is determined on mounted and polished samples using a Scanning Electron Microscope, for example, a Hitachi S-4300 Field Emission Scanning Electron Microscope with an Oxford Instruments EDS X-Max 150 detector and the Oxford Aztec software (version 3.1). A representative sample of the material was first mounted in a two-part epoxy resin, such as Struers Epofix. Once the epoxy had completely cured, the specimen was ground and polished. For example, the specimen can be mounted on a Struers Tegramin-30
grinder/polisher. The specimen was then ground and polished using a multi-step process with increasingly fine pads and abrasives. A typical sequence would be an MD-Piano 80 grinding disk at 300 rpm for nominally 1.5 minutes (till the specimen is exposed from the epoxy), an MP-Piano 220 at 300 rpm for 1.5 minutes, an MD-Piano 1200 at 300 rpm for 2 minutes, an MD-Largo polishing disk with DiaPro Allegro/Largo diamond abrasive at 150 rpm for 5 minutes, and finally an MD-Dur pad with DiaPro Dur at 150 rpm for 4 minutes. All of this was done with deionized water as the lubricant. After polishing, the polished surface of the sample was carbon-coated using, for example, a SPI Carbon Coater. The sample was placed on the stage of the coater 5.5 cm from the carbon fiber. A new carbon fiber was cut and secured into the coating head. The chamber was closed and evacuated. The coater was run at 3 volts for 20 seconds to clean the fiber surface. It was then run at 7 volts in pulse mode until the fiber stops glowing. The sample was then ready to be placed on an appropriate microscope mount and inserted into the microscope. The specimen was first examined in the SEM using the Backscatter mode. Typical conditions are a working distance of 15 mm, 15 kV acceleration voltage, and magnifications from x25 to x200. The specimen was examined to find spheres that have been appropriately sectioned so as to show their entire cross-section. Once appropriate sites were found, further examination was conducted with the Aztec software. In the Aztec software, the detector was first cooled to operating conditions using the“Control of the EDS detector EDS1” function. Once the detector was cool,“Point & ID” is selected, as well as the“Guided” mode. The“Linescan” option was selected and an electron image of the area of interest was obtained. One may look at the elemental composition in either Line Scan (one dimensional) or Mapping (two dimensional) mode. While in the Linescan mode, select the“Acquire Line Data” window. Using the line drawing tools, select the appropriate section for the scan (such as a diagonal across the middle of the sphere). Click“Start” to begin acquiring data. The software will automatically identify the chemical elements it finds. One can also manually select elements for inclusion or exclusion. For the two-dimensional mapping, select“Map” from the options, and then the“Acquire Map Data” window. You can either map the entire visible image or a selected region. As with the line scan, the software will automatically identify the chemical elements it finds or one can also manually select elements for inclusion or exclusion.
[00157] According to still other embodiments, first layered section 522 may have a varying first layered section composition throughout a thickness of the first layered section 522 from the inner surface 522A to the outer surface 522B of the first layered section 522. According to still other embodiments, first layered section 522 may have a varying first layered section composition described as a gradual concentration gradient composition throughout a portion or a the entire thickness of the first layered section 522 from the inner surface 522A to the outer surface 522B of the first layered section 522. It will be appreciated that as described herein, a gradual concentration gradient may be a continual change from a first concentration of a particular material in the first layered section composition as measured at the inner surface 522A of the first layered section 522 to a second concentration of the same particular material in the first layered section composition as measured at the outer surface 522B of the first layered section 522. According to certain embodiments, the particular material may be zeolite and a ceramic material within the first layered section composition. According to yet other embodiments, the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the first layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00158] According to still other embodiments, the gradual concentration gradient may be an increasing continual change where the first concentration of a particular material as measured at the inner surface 522A of the first layered section 522 is less than the second concentration of the same particular material as measured at the outer surface 522B of the first layered section 522. According to yet other embodiments, the gradual concentration gradient may be a decreasing continual change where the first concentration of a particular material as measured at the inner surface 522A of the first layered section 522 is greater than the second concentration of the same particular material as measured at the outer surface 522B of the first layered section 522. In some examples, the concentration of a particular material changes linearly or proportionally as the distance from a surface of a layered section changes.
[00159] According to still other embodiments, a second layered section 524 may include overlapping layers surrounding the first layered section 522.
[00160] According to still other embodiments, the second layered section 524 may have a particular porosity. For example, the second layered section 524 may have an average porosity of at least about 0.01 cc/g, such as, at least about 0.05 cc/g, at least about 0.10 cc/g, at least about 0.25 cc/g, at least about 0.50 cc/g, at least about 0.75 cc/g, at least about 1.00 cc/g, at least about 1.10 cc/g, at least about 1.20 cc/g, at least about 1.30 cc/g, at least about 1.40 cc/g, at least about 1.50 cc/g or even at least about 1.55 cc/g. According to still other embodiments, the second layered section 524 may have an average porosity of not greater than about 1.60 cc/g, such as, not greater than about 1.55 cc/g, not greater than about 1.50 cc/g, not greater than about 1.45 cc/g, not greater than about 1.40 cc/g, not greater than about 1.35 cc/g, not greater than about 1.30 cc/g, not greater than about 1.25 cc/g, not greater than about 1.20 cc/g, not greater than about 1.15 cc/g, not greater than about 1.10 cc/g, not greater than about 1.05 cc/g, not greater than about 1.00 cc/g, not greater than about 0.95 cc/g, not greater than about 0.90 cc/g or even not greater than about 0.85 cc/g. It will be appreciated that the layered region may have a porosity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the layered region may have a porosity of any value within a range between any of the minimum and maximum values noted above.
[00161] According to other embodiments, the second layered section 524 may make up a particular volume percentage of the total volume of the porous zeolite-containing ceramic particle 500. For example, the second layered section 524 may make up at least about 50 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, at least about 55 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 75 vol% of the total volume of the porous zeolite- containing ceramic particle 500, at least about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 85 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 500 or even at least about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 500. According to still other embodiments, the layered region may make up not greater than about 99.5 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, not greater than about 99 vol % of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 85 vol% of the total volume of the porous zeolite- containing ceramic particle 500, not greater than about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 75 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500 or even not greater than about 55 vol% of the total volume of the porous zeolite- containing ceramic particle 500. It will be appreciated that the second layered section 524 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 500 between any of the minimum and maximum values noted above. It will be further appreciated that the second layered section 524 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 500 within a range between any of the minimum and maximum values noted above.
[00162] According to certain embodiments, the first layered section 522 may be the same as the second layered section 524. According to still other embodiments, the first layered section 522 may have the same composition as the second layered section 524.
According to particular embodiments, the first layered section 522 and the second layered section 524 may be formed of the same material and/or the same relative concentration of materials. According to yet other embodiments, the first layered section 522 may have the same microstructure as the second layered section 524. According to yet other embodiments, the first layered section 522 may have the same particle density as the second layered section 524, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the first layered section 522 may have the same porosity as the second layered section 524.
[00163] According to certain embodiments, the core region 510 may be different than the second layered section 524. According to still other embodiments, the core region 510 may have different composition than the second layered section 524. According to particular embodiments, the core region 510 and the second layered section 524 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the core region 510 may have a different microstructure than the second layered section 524. According to yet other embodiments, the core region 510 may have a different particle density than the second layered section 524, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the core region 510 may have a different porosity than the second layered section 524.
[00164] According to certain embodiments, the first layered section 522 may be different than the second layered section 524. According to still other embodiments, the first layered section 522 may have different composition than the second layered section 524. According to particular embodiments, the first layered section 522 and the second layered section 524 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the first layered section 522 may have a different microstructure than the second layered section 524. According to yet other embodiments, the first layered section 522 may have a different particle density than the second layered section 524, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the first layered section 522 may have a different porosity than the second layered section 524.
[00165] According to certain embodiments, the second layered section 524 may include a second layered section composition. According to yet other embodiments, the second layered section composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the second layered section composition may include zeolite and a ceramic material.
According to still other embodiments, the first layered section of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. In some embodiments, the second layered section includes up to 80% of zeolite. In some
embodiments, the second layered section includes at least 20% of ceramic material. In some embodiments, the second layered section includes at least 20% of ceramic material and up to 80% of zeolite. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the second layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00166J According to yet other embodiments, the second layered section 524 may be defined as having an inner surface 524 A and an outer surface 524B. The inner surface 524 A of the second layered section 524 is defined as the surface closest to the first layered section 522. The outer surface 524B of the second layered section 524 is defined as the surface farthest from the first layered section 522.
[00167] According to certain embodiments, second layered section 524 may have a homogeneous second layered section composition throughout a thickness of the second layered section 524 from the inner surface 524A to the outer surface 524B of the second layered section 524. It will be appreciated that as described herein, a homogeneous first layered section composition is defined as having less than a 1 percent variation in the concentrations of any material or materials within the first layered section composition throughout a thickness of the first layered section 524 from the inner surface 524A to the outer surface 524B of the first layered section 524.
[00168] According to still other embodiments, second layered section 524 may have a varying second layered section composition throughout a thickness of the second layered section 524 from the inner surface 524A to the outer surface 524B of the second layered section 524. According to still other embodiments, second layered section 524 may have a varying second layered section composition described as a gradual concentration gradient composition throughout a portion or a the entire thickness of the second layered section 524 from the inner surface 524A to the outer surface 524B of the second layered section 524. It will be appreciated that as described herein, a gradual concentration gradient may be a continual change from a first concentration of a particular material in the second layered section composition as measured at the inner surface 524A of the second layered section 524 to a second concentration of the same particular material in the second layered section composition as measured at the outer surface 524B of the second layered section 524.
According to certain embodiments, the particular material may be zeolite and a ceramic material within the second layered section composition. According to yet other
embodiments, the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafhia or a combination thereof. According to still other embodiments, the second layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00169] According to still other embodiments, the gradual concentration gradient may be an increasing continual change where the first concentration of a particular material as measured at the inner surface 524A of the second layered section 524 is less than the second concentration of the same particular material as measured at the outer surface 524B of the second layered section 524. According to yet other embodiments, the gradual concentration gradient may be a decreasing continual change where the first concentration of a particular material as measured at the inner surface 524A of the second layered section 524 is greater than the second concentration of the same particular material as measured at the outer surface 524B of the second layered section 524. In some examples, the concentration of a particular material changes linearly or proportionally as the distance from a surface of a layered section changes.
[00170] According to still other embodiments, a third layer section 526 may include overlapping layers surrounding the second layered section 524.
[00171] According to still other embodiments, the third layer section 526 may have a particular porosity. For example, the third layer section 526 may have an average porosity of at least about 0.01 cc/g, such as, at least about 0.05 cc/g, at least about 0.10 cc/g, at least about 0.25 cc/g, at least about 0.50 cc/g, at least about 0.75 cc/g, at least about 1.00 cc/g, at least about 1.10 cc/g, at least about 1.20 cc/g, at least about 1.30 cc/g, at least about 1.40 cc/g, at least about 1.50 cc/g or even at least about 1.55 cc/g. According to still other
embodiments, the third layer section 526 may have an average porosity of not greater than about 1.60 cc/g, such as, not greater than about 1.55 cc/g, not greater than about 1.50 cc/g, not greater than about 1.45 cc/g, not greater than about 1.40 cc/g, not greater than about 1.35 cc/g, not greater than about 1.30 cc/g, not greater than about 1.25 cc/g, not greater than about 1.20 cc/g, not greater than about 1.15 cc/g, not greater than about 1.10 cc/g, not greater than about 1.05 cc/g, not greater than about 1.00 cc/g, not greater than about 0.95 cc/g, not greater than about 0.90 cc/g or even not greater than about 0.85 cc/g. It will be appreciated that the layered region may have a porosity of any value between any of the minimum and maximum values noted above. It will be further appreciated that the layered region may have a porosity of any value within a range between any of the minimum and maximum values noted above.
[00172] According to other embodiments, the third layer section 526 may make up a particular volume percentage of the total volume of the porous zeolite-containing ceramic particle 500. For example, the third layer section 526 may make up at least about 50 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, at least about 55 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 75 vol of the total volume of the porous zeolite-containing ceramic particle 500, at least about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 85 vol% of the total volume of the porous zeolite- containing ceramic particle 500, at least about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 500, at least about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 500 or even at least about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 500. According to still other embodiments, the layered region may make up not greater than about 99.5 vol% of the total volume of the porous zeolite-containing ceramic particle 500, such as, not greater than about 99 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 95 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 90 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 85 vol% of the total volume of the porous zeolite- containing ceramic particle 500, not greater than about 80 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 75 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 70 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 65 vol% of the total volume of the porous zeolite-containing ceramic particle 500, not greater than about 60 vol% of the total volume of the porous zeolite-containing ceramic particle 500 or even not greater than about 55 vol% of the total volume of the porous zeolite- containing ceramic particle 500. It will be appreciated that the third layer section 526 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 500 between any of the minimum and maximum values noted above. It will be further appreciated that the third layer section 526 may make up any volume percentage of the total volume of the porous zeolite-containing ceramic particle 500 within a range between any of the minimum and maximum values noted above.
[00173] According to certain embodiments, the first layered section 522 may be the same as the third layered section 526. According to still other embodiments, the first layered section 522 may have the same composition as the third layered section 526. According to particular embodiments, the first layered section 522 and the third layered section 526 may be formed of the same material and/or the same relative concentration of materials. According to yet other embodiments, the first layered section 522 may have the same microstructure as the third layered section 526. According to yet other embodiments, the first layered section 522 may have the same particle density as the third layered section 526, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the first layered section 522 may have the same porosity as the third layered section 526.
[00174] According to certain embodiments, the second layered section 524 may be the same as the third layered section 526. According to still other embodiments, the second layered section 524 may have the same composition as the third layered section 526.
According to particular embodiments, the second layered section 524 and the third layered section 526 may be formed of the same material and/or the same relative concentration of materials. According to yet other embodiments, the second layered section 524 may have the same microstructure as the third layered section 526. According to yet other embodiments, the second layered section 524 may have the same particle density as the third layered section 526, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the second layered section 524 may have the same porosity as the third layered section 526.
[00175] According to certain embodiments, the core region 510 may be different than the third layered section 526. According to still other embodiments, the core region 510 may have different composition than the third layered section 526. According to particular embodiments, the core region 510 and the third layered section 526 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the core region 510 may have a different microstructure than the third layered section 526. According to yet other embodiments, the core region 510 may have a different particle density than the third layered section 526, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the core region 510 may have a different porosity than the third layered section 526.
[00176] According to certain embodiments, the first layered section 522 may be different than the third layered section 526. According to still other embodiments, the first layered section 522 may have different composition than the third layered section 526.
According to particular embodiments, the first layered section 522 and the third layered section 526 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the first layered section 522 may have a different microstructure than the third layered section 526. According to yet other embodiments, the first layered section 522 may have a different particle density than the third layered section 526, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the first layered section 522 may have a different porosity than the third layered section 526.
[00177] According to certain embodiments, the second layered section 524 may be different than the third layered section 526. According to still other embodiments, the second layered section 524 may have different composition than the third layered section 526.
According to particular embodiments, the second layered section 524 and the third layered section 526 may be formed of different materials and/or different relative concentration of materials. According to yet other embodiments, the second layered section 524 may have a different microstructure than the third layered section 526. According to yet other embodiments, the second layered section 524 may have a different particle density than the third layered section 526, where the particle density is the particle mass divided by the particle volume including intraparticle porosity. According to yet other embodiments, the second layered section 524 may have a different porosity than the third layered section 526.
[00178] According to certain embodiments, the third layer section 526 may include a third layered section composition. According to yet other embodiments, the third layered section composition may include a particular material or a combination of particular materials. According to still other embodiments, the material or materials included in the third layered section composition may include zeolite and a ceramic material. According to still other embodiments, the third layered section of each zeolite-containing ceramic particle may consist essentially of zeolite and a ceramic material. In some embodiments, the third layered section includes up to 80% of zeolite. In some embodiments, the third layered section includes at least 20% of ceramic material. In some embodiments, the third layered section includes at least 20% of ceramic material and up to 80% of zeolite. It will be appreciated that the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafnia or a combination thereof. According to still other embodiments, the third layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00179] According to yet other embodiments, the third layer section 526 may be defined as having an inner surface 526A and an outer surface 526B. The inner surface 526A of the third layer section 526 is defined as the surface closest to the second layered section 524. The outer surface 526B of the third layer section 526 is defined as the surface farthest from the second layered section 524.
[00180] According to certain embodiments, third layer section 526 may have a homogeneous third layered section composition throughout a thickness of the third layer section 526 from the inner surface 526A to the outer surface 526B of the third layer section 526. It will be appreciated that as described herein, a homogeneous first layered section composition is defined as having less than a 1 percent variation in the concentrations of any material or materials within the first layered section composition throughout a thickness of the first layered section 526 from the inner surface 526A to the outer surface 526B of the first layered section 526.
[00181] According to still other embodiments, third layer section 526 may have a varying third layered section composition throughout a thickness of the third layer section 526 from the inner surface 526A to the outer surface 526B of the third layer section 526. According to still other embodiments, third layer section 526 may have a varying third layered section composition described as a gradual concentration gradient composition throughout a portion or a the entire thickness of the third layer section 526 from the inner surface 526A to the outer surface 526B of the third layer section 526. It will be appreciated that as described herein, a gradual concentration gradient may be a continual change from a first concentration of a particular material in the third layered section composition as measured at the inner surface 526A of the third layer section 526 to a second concentration of the same particular material in the third layered section composition as measured at the outer surface 526B of the third layer section 526. According to certain embodiments, the particular material may be zeolite and a ceramic material within the third layered section composition. According to yet other embodiments, the ceramic material may be any desired ceramic material suitable for forming porous zeolite-containing ceramic particles, such as, for example, alumina, zirconia, titania, silica, hafhia or a combination thereof. According to still other embodiments, the third layered section composition may include, in addition to zeolite, any one of lanthanum (La), zinc (Zn), nickel (Ni), cobalt (Co), niobium (Nb), tungsten (W), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), bismuth (Bi) or combinations thereof.
[00182] According to still other embodiments, the gradual concentration gradient may be an increasing continual change where the first concentration of a particular material as measured at the inner surface 526A of the third layer section 526 is less than the second concentration of the same particular material as measured at the outer surface 526B of the third layer section 526. According to yet other embodiments, the gradual concentration gradient may be a decreasing continual change where the first concentration of a particular material as measured at the inner surface 526A of the third layer section 526 is greater than the second concentration of the same particular material as measured at the outer surface 526B of the third layer section 526. In some examples, the concentration of a particular material changes linearly or proportionally as the distance from a surface of a layered section changes.
[00183] In some embodiments, the layered region of the formed processed and/or final product of porous zeolite-containing particles by spray fluidization includes macropores and mesopores. In some embodiments, the macropores and mesopores are interconnected, i.e., the macropores and mesopores are connected to one another. In some embodiments, the macropores and mesopores span across the layered region.
[00184] In some embodiments, the core region of the formed processed and/or final product of porous zeolite-containing particles by spray fluidization does not include macropores and mesopores.
[00185] In some embodiments, most of the macropores have a width or diameter of about 120 nm and most of the mesopores have a width or diameter of about 8 nm.
Furthermore, most of the macropores concentrate in a diameter range of about 60 nm-200 nm and most of the mesopores concentrate in a diameter range of about 4 nm-10 nm. In some embodiments, raw zeolite materials generally contain micropores less than 2 nm, and those micropores are ordinarily preserved in the processed and/or finished product. In some embodiments, raw zeolite materials generally contain mesopores about 2 nm to 50 nm, and those mesopores are ordinarily preserved in the processed and/or finished product. The macropores in the finished product are formed in the spray fluidization process described herein.
[00186] In some embodiments, depending on the spray fluidization process parameters, properties of materials used, and/or number of batches for the process, the mesopore and macropore size or diameter ranges can be slighted shifted and different from the above embodiments. For example, in some embodiments, the concentration of ranges for macropores on a pore size distribution curve can be between 60 nm to 130 nm, for example, the concentration for macropores on a pore size distribution curve can be 60 nm, the concentration for macropores on a pore size distribution curve can be 70 nm, the
concentration for macropores on a pore size distribution curve can be 80 nm, the
concentration for macropores on a pore size distribution curve can be 90 nm, the
concentration for macropores on a pore size distribution curve can be 100 nm, the concentration for macropores on a pore size distribution curve can be 110 nm, the concentration for macropores on a pore size distribution curve can be 120 nm, the concentration for macropores on a pore size distribution curve can be 130 nm. In some embodiments, the concentration of ranges for macropores on a pore size distribution curve can be between 50 nm to 250 nm. In some embodiments, the concentration of ranges for mesopores on a pore size distribution curve can be between 4 nm to 8 nm, for example, the concentration for mesopores on a pore size distribution curve can be 4 nm, the concentration for mesopores on a pore size distribution curve can be 5 nm, the concentration for mesopores on a pore size distribution curve can be 6 nm, the concentration for mesopores on a pore size distribution curve can be 7 nm, the concentration for mesopores on a pore size distribution curve can be 8 nm. In some embodiments, the concentration of ranges for mesopores on a pore size distribution curve can be between 2 nm to 20 nm.
[00187] In some embodiment, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the processed batch of porous zeolite-containing ceramic particles and final product of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the first processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the second processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the third processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the fourth processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in each of the processed batch of porous zeolite-containing ceramic particles if more than one batch cycles are involved in the spray fluidization process. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the final batch of the processed batch of porous zeolite-containing ceramic particles if more than one batch cycles are involved in the spray fluidization process.
[00188] In some embodiments, depending on the spray fluidization process parameters, properties of materials used, and/or number of batches for the process, the hierarchical porous structures including interconnected macropores and mesopores spanning in the layered region of the porous zeolite-containing ceramic particles are substantially similar between different layered sections around the core region. In some embodiments, depending on the spray fluidization process parameters, properties of materials used, and/or number of batches for the process, the hierarchical porous structures including interconnected macropores and mesopores spanning in the layered region of the porous zeolite-containing ceramic particles are substantially different between different layered sections around the core region. The similar or different layered structures with particular diffusivities, chemical properties and/or mechanical properties are designed for different catalytic applications.
[00189] According to still another particular embodiment, the porous zeolite- containing ceramic particles described herein may be formed as a catalyst carrier or a component of a catalyst carrier. It will be appreciated that where the porous zeolite- containing ceramic particles described herein are formed as a catalyst carrier or a component of a catalyst carrier, the catalyst carrier may be described as having any of the characteristics described herein with reference to a porous zeolite-containing ceramic particle or a batch of porous zeolite-containing ceramic particles.
[00190] Many different aspects and embodiments are possible. After reading this specification, those skilled in the art will appreciate that these aspects and embodiments are only illustrative and do not limit the scope of the present invention. Embodiments may be in accordance with any one or more of the items as disclosed herein.
EXAMPLE:
[00191] Example 1 : A four cycle spray fluidization process according to an embodiment described herein was used to form an example batch of zeolite-containing particles with a hierarchical structure that were then formed into a catalyst carrier.
[00192] FIG. 6 shows detailed experimental parameters and properties of the materials used for each cycle of a four cycle spray fluidization process in table 600. In cycle 1 of the process, seed particles of a Boehmite (alumina) material, e.g., Saint-Gobain NorPro spray- dried Boehmite greenware, were used to form a first initial batch of ceramic particles, which had a mass of 900 grams. As measured by a particle size analyzer, e.g., a Malvern
Mastersizer 2000 (Scirocco 2000 cell, used to measure dry particles), this first initial batch of ceramic particles had a particle size distribution including an Idl0 = 69 pm, an Id5o = 106 pm, and an M90 = 160 pm. The initial particle size distribution span IPDS was equal to 0.87. The first initial batch of ceramic particles was loaded into a lab scale fluid-bed spray coater, e.g., Freund-Vector VFC3 spray-fluidizer. These particles were fluidized with an airflow of 35 Standard Cubic Feet per Minute (SCFM) (at the beginning of the run) and a temperature of nominally 100°C. This airflow was gradually increased over the course of the run to 40 SCFM.
[00193] A zeolite slurry (e.g., Johnson Matthey ZSM-5 slurry) and milled boehmite (e.g., UOP Versal250) with their respective properties shown in Table A, are blended in proportions to form a slip (or slurry) such that the zeolite content is 60% of the solids, and the boehmite content is 40% of the solids. Each of the zeolite slurry and milled boehmite may contain deionized water, and concentrated nitric acid.
[00194] Table A. Properties of the respective zeolite slurry and milled Boehmite of the slip used to spray onto the fluidized bed of seed particles.
Figure imgf000063_0001
[00195] In Table A, particle size measurements were made on a Malvern Mastersizer 2000 (Hydro 2000S cell, used to measure slurries); viscosity was measured with a Zahn cup (Boekel #3, 44cc); solids were measured on a Mettler Toledo HB43 Halogen moisture balance; and pH was measured on a Fisher Scientific Accumet AB15 basic.
[00196] The zeolite and Boehmite slip was sprayed onto this fluidized bed of particles. The slip had a pH of 4.95, a solids content of 22.0%, and was milled to a median particle size D50 of 0.94 p . The slip was atomized through a two-fluid nozzle, with an atomization air pressure of 35 psi. A mass of 6510 grams of slip was applied to the bed of particles over the course of 148 minutes to form a first processed batch of porous zeolite-containing particles. In some embodiments, the first cycle process run was terminated after the mass of 6510 grams of slip was sprayed, and the first processed batch of porous zeolite-containing particles was discharged from the fluidizer container. The first processed batch of porous zeolite- containing particles had a mass of 2094 grams and a particle size distribution, measured by the CAMSIZER®, including a Pdio = 111 pm, a Pd5o = 128 pm and a Pdgo = 159 pm. The processed particle size distribution span PPDS was equal to 0.38. The ratio IPDS/PPDS for the first cycle of the forming process was equal to 2.3. The first processed batch of porous zeolite-containing particles had a sphericity of 94.2%, and a tapped bulk density of 1.0 g/cm3. Tapped bulk density can be measured by placing a known mass of particles in a graduated cylinder, placing the cylinder on the platform of a Quantachrome® Autotap Model DAT-5- 110-60 or equivalent, and tapping 1000 times. After tapping is completed, the volume of particles is determined, and the tapped bulk density is equal to the mass of particles (in grams) divided by the volume of the tapped particles (in cm3).
[00197] In cycle 2 of the process, 900 grams of the first processed batch of porous zeolite-containing particles (i.e., the product of cycle 1) were used to form a second initial batch of zeolite-containing particles. The second initial batch of zeolite-containing particles had a particle size distribution, measured by the CAMSIZER®, including an Idio = 11 1 pm, an Id so = 128 pm and an Idyo = 159 pm, and the initial particle size distribution span IPDS was equal to 0.38. These second initial batch of zeolite-containing particles were fluidized with a starting airflow of 55 SCFM, increasing to 57 SCFM by the end of the run, and a temperature of nominally l00°C. A slip of zeolite and Boehmite slurry mix with a similar composition as the first cycle was sprayed onto the bed of seeds through the two-fluid nozzle, with an atomization air pressure of 35 psi. A mass of 6013 grams of slip was applied to the second initial batch of zeolite-containing particles over the course of 88 minutes to form the second processed batch of porous zeolite-containing particles. The second cycle process run was terminated after the mass of 6013 grams of slip was sprayed, and the second processed batch of porous zeolite-containing particles was discharged from the fluidizer container. The second processed batch of zeolite-containing particles had a mass of 1926 grams and a particle size distribution, measured by the CAMSIZER®, including a Pdio = 164 pm, a Pd5o = 179 pm and a Pd9o = 199 pm. The processed particle size distribution span PPDS was equal to 0.20. The ratio IPDS/PPDS for the second cycle of the forming process was equal to 1.92. The second processed batch of porous zeolite-containing particles had a sphericity of 94.5%, and a tapped bulk density of 0.82 g/cm3.
[00198] In cycle 3 of the process, 900 grams of the second processed batch of porous zeolite-containing particles (i.e., the product of cycle 2) were used to form a third initial batch of zeolite-containing particles. The third initial batch of zeolite-containing particles had a particle size distribution, measured by the CAMSIZER®, including an Idl0 = 164 pm, an Idso = 179 pm and an H90 = 199 pm, and the initial particle size distribution span IPDS was equal to 0.20. These third initial batch of zeolite-containing particles were fluidized with a starting airflow of 63 SCFM, increasing to 65 SCFM by the end of the run, and a temperature of nominally l00°C. A slip of zeolite and Boehmite slurry mix with a similar composition as the first cycle was sprayed onto the bed of seeds through the two-fluid nozzle, with an atomization air pressure of 35 psi. A mass of 7217 grams of slip was applied to the third initial batch of zeolite-containing particles over the course of 104 minutes to form the third processed batch of porous zeolite-containing particles. The third cycle process run was terminated after the mass of 7217 grams of slip was sprayed, and the third processed batch of porous zeolite-containing particles was discharged from the fluidizer container. The third processed batch of zeolite-containing particles had a mass of 2257 grams and a particle size distribution, measured by the CAMSIZER®, including a Pdio = 234 pm, a Pdso = 251 pm and a Pdgo = 269 pm. The processed particle size distribution span PPDS was equal to 0.14. The ratio IPDS/PPDS for the third cycle of the forming process was equal to 1.40. The third processed batch of porous zeolite-containing particles had a sphericity of 94.9%, and a tapped bulk density of 0.75 g/cm3.
[00199] In cycle 4 of the process, 900 grams of the third processed batch of porous zeolite-containing particles (i.e., the product of cycle 3) were used to form a fourth initial batch of zeolite-containing particles. The fourth initial batch of zeolite-containing particles had a particle size distribution, measured by the CAMSIZER®, including an Idio = 234 pm, an Idso = 251 pm and an W90 = 269 pm, and the initial particle size distribution span IPDS was equal to 0.14. These fourth initial batch of zeolite-containing particles were fluidized with a starting airflow of 69 SCFM, increasing to 71 SCFM by the end of the run, and a temperature of nominally l00°C. A slip of zeolite and Boehmite slurry mix with a similar composition as the first cycle was sprayed onto the bed of seeds through the two-fluid nozzle, with an atomization air pressure of 35 psi. A mass of 10,241 grams of slip was applied to the fourth initial batch of zeolite-containing particles over the course of 138 minutes to form the fourth processed batch of porous zeolite-containing particles. The fourth cycle process run was terminated after the mass of 10,241 grams of slip was sprayed, and the fourth processed batch of porous zeolite-containing particles was discharged from the fluidizer container. The fourth processed batch of zeolite-containing particles had a mass of 2859 grams and a particle size distribution, measured by the CAMSIZER®, including a Pdio = 354 pm, a Pdso = 376 pm and a Pd9o = 398 pm. The processed particle size distribution span PPDS was equal to 0.12. The ratio IPDS/PPDS for the fourth cycle of the forming process was equal to 1.19.
The fourth processed batch of porous zeolite-containing particles had a sphericity of 95.7%, and a tapped bulk density of 0.73 g/cm3.
[00200] The fourth processed batch of porous zeolite-containing particles from cycle 4 was fired in a rotary calciner or box furnace, to 600°C for 6 hours, forming an alpha alumina (as determined by powder x-ray diffraction) catalyst carrier with a nitrogen BET surface area of 351 m2/gram, a mercury intrusion volume of 0.52 cm3 /gram. The box furnace was a Lindberg/Blue M Model BF51731B. FIG. 7 shows properties of the finished product of the fourth processed batch of porous zeolite-containing particles with a hierarchical pore structure in table 700. The catalyst carriers had a particle size distribution that includes a Dio = 350 pm, a D50 = 371 pm, a D90 = 393 pm. Further, the catalyst carriers had a distribution span of 0.12, and a CAMSIZER® Shape Analysis Sphericity of 96.4%.
[00201] FIG. 8 shows an exemplary pore size distribution curve 802 for the finished product of the fourth processed batch of porous zeolite-containing particles with a hierarchical pore structure in chart 800. The chart 800 was generated from data characterized by mercury porosimetry, a technique used to characterize macropores and mesopores.
Macropores generally have a width or diameter of about 50 nm to 1000 nm. Mesopores generally have a width or diameter of 2 nm to 50 nm. The X axis of the chart 800 represents “Pore Diameter” in nanometers (nm) in logarithmic scale. Raw zeolite materials, for example, ZSM-5, generally contain micropores below 2 nm, and generally about 0.5 nm-0.8 nm. And those pre-existing micropores are ordinarily preserved in the processed and/or finished product. In this example, pores with a width or diameter below 2 nm are not shown on the chart because mercury porosimetry cannot measure micropores having a diameter of less than 2 nm. The micropores, however, can be characterized by a suitable method, for example, nitrogen adsorption method. The Y axis represents“Logarithmic Differential Intrusion Volume” or“Differential Pore Volume” in cm3/g in terms of dV/dlogD, where dlogD is the incremental logarithmic diameters of the pores measured, and dV is the corresponding incremental mercury-intrusion volume.
[00202] The pore size distribution curve 802 has two peaks, a first peak at about 8 nm and a second peak at about 120 nm. The peak value on the pore size distribution curve 802 represents a pore diameter value that appears most or relatively often as the mode. This data indicates that, most of the macropores have a diameter of about 120 nm and most of the mesopores have a diameter of about 8 nm. Furthermore, most of the macropores concentrate in a diameter range of about 60 nm-200 nm and most of the mesopores concentrate in a diameter range of about 4 nm-lO nm. Raw zeolite materials, for example, ZSM-5, generally contain mesopores about 2 nm to 50 nm, and those mesopores are ordinarily preserved in the finished product. In contrast, the macropores in the finished product are formed in the spray fluidization process described herein.
[00203] In some examples, optionally, the first processed batch of porous zeolite- containing particles from cycle 1 were further selected to eliminate unevenly sized particles, e.g. certain relatively small sized particles, to form a second initial batch of zeolite-containing particles. In some examples, optionally, the second processed batch of porous zeolite- containing particles from cycle 2 were further selected to eliminate unevenly sized particles, e.g. certain relatively small sized particles, to form a third initial batch of zeolite-containing particles. In some examples, optionally, the third processed batch of porous zeolite- containing particles from cycle 3 were further selected to eliminate unevenly sized particles, e.g. certain relatively small sized particles, to form a fourth initial batch of zeolite-containing particles.
[00204] In some examples, depending on the spray fluidization process parameters, properties of materials used, and/or number of batches for the process, the mesopore and macropore size or diameter ranges can be slighted shifted and different from the above embodiments. For example, in some embodiments, the peak for macropores on a pore size distribution curve can be between 60 nm to 130 nm, for example, the peak for macropores on a pore size distribution curve can be 60 nm, the peak for macropores on a pore size distribution curve can be 70 nm, the peak for macropores on a pore size distribution curve can be 80 nm, the peak for macropores on a pore size distribution curve can be 90 nm, the peak for macropores on a pore size distribution curve can be 100 nm, the peak for macropores on a pore size distribution curve can be 110 nm, the peak for macropores on a pore size distribution curve can be 120 nm, the peak for macropores on a pore size distribution curve can be 130 nm. In some embodiments, the peak for macropores on a pore size distribution curve can be between 50 nm to 250 nm. In some embodiments, the peak for mesopores on a pore size distribution curve can be between 4 nm to 8 nm, for example, the peak for mesopores on a pore size distribution curve can be 4 nm, the peak for mesopores on a pore size distribution curve can be 5 nm, the peak for mesopores on a pore size distribution curve can be 6 nm, the peak for mesopores on a pore size distribution curve can be 7 nm, the peak for mesopores on a pore size distribution curve can be 8 nm. In some embodiments, the peak for mesopores on a pore size distribution curve can be between 2 nm to 20 nm.
[00205] Based on the above example, one could understand that the layered region of the formed porous zeolite-containing particles by spray fluidization includes macropores and mesopores and/or the core region of the formed porous zeolite-containing particles by spray fluidization does not include macropores and mesopores.
[00206] In some examples, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the processed batch of porous zeolite-containing ceramic particles and final product of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the first processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the second processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the third processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the fourth processed batch of porous zeolite-containing ceramic particles. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in each of the processed batch of porous zeolite-containing ceramic particles if more than one batch cycles are involved in the spray fluidization process. In some embodiments, similar pore size distributions as illustrated in the embodiments herein for macropores and mesopores in the porous zeolite-containing ceramic particles are achieved in the final batch of the processed batch of porous zeolite-containing ceramic particles if more than one batch cycles are involved in the spray fluidization process.
[00207] In some examples, depending on the spray fluidization process parameters, properties of materials used, and/or number of batches for the process, the hierarchical porous structures including interconnected macropores and mesopores spanning in the layered region of the porous zeolite-containing ceramic particles are substantially similar between different layered sections around the core region. In some embodiments, depending on the spray fluidization process parameters, properties of materials used, and/or number of batches for the process, the hierarchical porous structures including interconnected macropores and mesopores spanning in the layered region of the porous zeolite-containing ceramic particles are substantially different between different layered sections around the core region. The similar or different layered structures with particular diffusivities, chemical properties and/or mechanical properties are designed for different catalytic applications.
[00208] In the foregoing, it will be appreciated that the sphericity of the porous zeolite- containing ceramic particles or catalyst carriers shown in the illustrations of the figures is not necessarily indicative of the actual sphericity of these particles or catalyst carriers. It will be further appreciated that the sphericity of the porous zeolite-containing ceramic particles or catalyst carriers shown in the illustrations of the figures may be any sphericity described in reference to embodiments described herein, for example, the sphericity of the porous zeolite- containing ceramic particles or catalyst carriers shown in the illustrations of the figures may be within a range of at least about 0.80 and not greater than about 0.99.
[00209] In the foregoing, reference to specific embodiments and the connections of certain components is illustrative. It will be appreciated that reference to components as being coupled or connected is intended to disclose either direct connection between said components or indirect connection through one or more intervening components as will be appreciated to carry out the methods as discussed herein. As such, the above-disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments, which fall within the true scope of the present invention. Thus, to the maximum extent allowed by law, the scope of the present invention is to be determined by the broadest permissible
interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description. The embodiments were chosen and described in order to best explain principles of operation and practical applications, to thereby enable others skilled in the art.
[00210] For purposes of this application, at least 20 samples (for example, at least 20 particles) are used to determine a statistically reliable value of Idio, Idso , 90, Pdio, and Pdso,
Pd9o.
[00211] As used herein, the terms“comprises,”“comprising,”“includes,”“including,” “has,”“having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such process, method, article, or apparatus.
[00212] As used herein, and unless expressly stated to the contrary,“or” refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
[00213] Also, the use of“a” or“an” are employed to describe elements and
components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
[00214] It will be understood that, although the terms“first,”“second,” etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another.
[00215] The Abstract of the Disclosure is provided to comply with Patent Law and is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, various features may be grouped together or described in a single embodiment for the purpose of streamlining the disclosure. This disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter may be directed to less than all features of any of the disclosed embodiments. Thus, the following claims are incorporated into the Detailed Description, with each claim standing on its own as defining separately claimed subject matter.

Claims

WHAT IS CLAIMED IS:
1. A method of forming a plurality of porous zeolite-containing particles, the method comprising one or more batch spray fluidization forming cycles,
wherein a first cycle of the one or more batch spray fluidization forming cycles includes:
coating a first initial batch of ceramic particles with a first slurry mix of porous zeolite-containing ceramic droplets using spray fluidization techniques to form a first processed batch of porous zeolite-containing particles,
wherein the ceramic particles in the first initial batch have a first initial median particle diameter size,
wherein the porous zeolite-containing particles in the first processed batch have a first median particle diameter size that is at least about 10% greater than the first initial median particle diameter size,
wherein, at the completion of the batch spray fluidization forming cycles, the plurality of porous zeolite-containing particles have a median particle diameter size of at ieast about 100 microns and not greater than about 4500 microns and have a hierarchical pore structure
2. The method of claim 1, wherein the first cycle further includes providing the first initial batch of ceramic particles comprising:
sel ecting a particle diameter range and a predetermined amount of the first initial batch of ceramic particles, and loading the first initial batch of ceramic particles into a spray fluidizer.
3. The method of claim 1, wherein a second cycle of the one or more batch spray fluidization forming cycles includes:
providing a second initial batch of porous zeolite-containing ceramics particles using the first processed batch; and
coating the second initial batch of porous zeolite-containing ceramics particles with a second slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a second processed batch of porous zeolite-containing particles, wherein the porous zeolite-containing particles in the second processed batch have a second median particle diameter size that is at least about 10% greater than the first median particle diameter size.
4. The method of claim 3, wherein a third cycle of the one or more batch spray fluidization forming cycles includes:
providing a third initial batch of porous zeolite-containing ceramics particles using the second processed batch; and
coating the third initial batch of porous zeolite-containing ceramics particles with a third slurry mix of porous zeolite-containing ceramic drop lets using the spray fluidization techniques to form a third processed batch of porous zeolite-containing particles
wherein the porous zeolite-containing particles in the third processed batch have a third median particle diameter size that is at least about 10% greater than the second median particle diameter size.
5. The method of claim 4, wherein a fourth cycle of the one or more batch spray fluidization forming cycles includes:
providing a fourth initial batch of porous zeolite-containing ceramics particles using the third processed batch; and
coating the fourth initial batch of porous zeolite-containing ceramics particles with a fourth slurry mix of porous zeolite-containing ceramic droplets using the spray fluidization techniques to form a fourth processed batch of porous zeolite-containing particles
wherein the porous zeolite-containing particles in the fourth processed batch have a fourth median particle diameter size that is at least about 10% greater than the third median particle diameter size.
6. The method of claim 1, wherein each of the plurality of porous zeolite-containing particles comprises mesopores ranging about 2 to 50 nanometers in diameters and
macropores ranging about 50 to 1000 nanometers in diameters.
7. The method of claim 1 , wherein each of the plurality of porous zeolite-containing particles has mesopores substantially ranging about 4 to 10 nanometers in diameters and macropores substantially ranging about 60 to 200 nanometers in diameters,
8. The method of claim 6, '.'herein the mesopores and micropores are interconnected.
9. The method of claim 1 , wherein the first initial batch of ceramic particles comprise alumina, zirconia, titania, silica or a combination thereof.
10. The method of claim 1, wherein the first slurry mix of porous zeolite-containing ceramic droplets comprises at least 20% of ceramic materials, and no greater tha 80% of zeolite.
11. The method of claim 1, wherein the first slurry mix of porous zeolite-containing ceramic droplets comprises no greater than 90% of ceramic materials, and at least 10% of zeolite.
12 The method of claim 1 , wherein the first slurry mix of porous zeolite-containing ceramic droplets comprises no greater than 70% of ceramic materials, and at least 30% of zeolite.
13. The method of claim 1, wherein the first slurry mix of porous zeolite-containing ceramic droplets comprises at least 20% and no greater than 50% of ceramic materials, and at least 50% and no greater than 80% of zeolite.
14. The method of claim 1, wherein the first slurry mix of porous zeolite-containing ceramic droplets includes a first slip of zeolite and a second slip of ceramic materials, wherein the first slip of zeolite is introduced into a spray fluidizer via a first inlet and a second slip of ceramic materials is introduced into the spray fluidizer via a second inlet
15. The method of claim 3, wherein a composition of the first slurry mix is substantially the same as a composition of the second slurry mix.
16. The method of claim 1, wherein a mass of the first processed batch of porous zeolite-containing particles is about 2 to 5 times of a mass of the first initial batch.
17. The method of claim 1, wherein a mass of the first slurry mix is about 5 to 15 times of a mass of the first initial batch.
18. The method of claim 1, wherein the plurality of porous zeolite-containing particles are substantially spherical with a sphericity of at least about 85% and up to about 97%.
19. The method of claim i, wherein each of the plurality of porous zeolite-containing particles comprises a core region and a layered region overlaying the core region,
wherein the core region has a core region composition, and the layered region has a layered region composition different than the core region composition.
20. The method of claim 19, wherein the layered region comprises mesopores substantially ranging about 4 to 10 nanometers in diameters and macropores substantially ranging about 60 to 200 nanometers in diameters, and the mesopores and macropores are interconnected.
21. The method of claim 1, wherein the spray fluidization techniques comprise repeatedly dispensing finely dispersed droplets of a slurry mix of porous zeolite-containing ceramics onto air borne ceramic particles to form a processed batch of porous zeolite- containing particles.
22. The method of claim 5, further comprising sintering the fourth processed batch of porous zeolite-containing particles at a temperature of at least about 350 °C and not greater than about 1400 °C.
23. The method of claim 1, wherein the first initial batch of ceramic particles has an initial particle diameter size distribution span IPDS equal to (Td¾i~Idio)/id5o, where Moo is equal to a cumulative 90% pass particle size distribution measurement of the first initial batch of ceramic particles, Idio is equal to a cumulative 10% pass particle size distribution measurement of the first initial batch of ceramic particles and Idso is equal to a cumulative 50% pass particle size distribution measurement of the first initial batch of ceramic particles, and the first processed batch of porous zeolite-containing particles has a processed particle diameter size distribution span PPDS equal to (Pd9o-Pdio)/Pdso, where Pd o is equal to a cumulative 90% pass particle size distribution measurement of the first processed batch of porous zeolite-containing particles, Pdio is equal to a cumulative 10% pass particle size distribution measurement of the first processed batch of porous zeolite-containing particles and Pdso is equal to a cumulative 50% pass particle size distribution measurement of the first processed batch of porous zeolite-containing particles; and
wherein the first batch spray fluidization forming cycle has a ratio IPDS/ PPDS of at least about 0.90.
24. The method of claim 3, wherein the second initial batch of porous zeolite- containing ceramics particles has an initial particle diameter size distribution span IPDS equal to (Id9o-Idio)/Id5o, where M90 is equal to a cumulative 90% pass particle size distribution measurement of the second initial batch of porous zeolite-containing ceramics particles, Id 10 is equal to a cumulative 10% pass particle size distribution measurement of the second initial batch of porous zeolite-containing ceramics particles and Idso is equal to a cumulative 50% pass particle size distribution measurement of the second initial batch of porous zeolite- containing ceramics particles, and the second processed batch of porous zeolite-containing particles has a processed particle diameter size distribution span PPDS equal to (Pd9o~ Pdio)/Pdso, where I 90 is equal to a cumulative 90% pass particle size distribution
measurement of the second processed batch of porous zeolite-containing particles, Pdio is equal to a cumulative 10% pass particle size distribution measurement of the second processed batch of porous zeolite-containing particles and Pdso is equal to a cumulative 50% pass particle size distribution measurement of the second processed batch of porous zeolite- containing particles; and
wherein the second batch spray fluidization forming cycle has a ratio IPDS/ PPDS of at least about 0.90.
25. The method of claim 5, wherein the fourth processed batch of porous zeolite- containing ceramics particles has a processed particle diameter size distribution span PPDS equal to (Pd^-Pdnj dso, where Pd<>o is equal to a cumulative 90% pass particle size distribution measurement of the fourth processed batch of porous zeolite-containing particles, Pdio is equal to a cumulative 10% pass particle size distribution measurement of the fourth processed batch of porous zeolite-containing particles and Pdso is equal to a cumulative 50% pass particle size distribution measurement of the fourth processed batch of porous zeolite- containing particles; and
wherein PPDS of the fourth processed batch of porous zeolite-containing particles is less than 0.2.
26. The method of claim 1, wherein each of the plurality of porous zeolite-containing particles comprises micropores having a diameter ranging about 0.5 to 0.8 nanometers.
27. The method of claim 1, wherein the spray fluidization techniques comprise more than one batch forming cycles, each of the cycles after the first cycle including repeatedly dispensing finely dispersed droplets of a respective slurry mix of porous zeolite-containing ceram ics onto air borne processed batch of porous zeolite-containing particles from a previous cycle.
28. The method of claim 27, wherein a respective composition of the respective slurry mix is adj usted for each of the forming cycles.
29. A porous zeolite-containing particle with a hierarchical pore structure
comprising:
a core region and;
a layered region overlaying the core region, the layered region having a mierostmcture including interconnected mesopores and macropores,
wherein:
diameters of the mesopores range from about 2 to 50 nanometers, and diameters of tire macropores range from about 50 to 1000 nanometers,
a porosity of the porous zeolite-containing particle is at least about 0.3 cm3/g and not greater than about 2.00 cnrVg; a median diameter of the porous zeolite-containing particle is at least about 100 microns and not greater than about 4500 microns, and
the core region has a core region composition, and the layered region has a layered region composition different than the core region composition.
30. The porous zeolite-containing particle of claim 29, wherein the porosity of the porous zeolite-containing particle is at least about 0.5 cm3/g and not greater than about 1 5 cm3/g.
31. The porous zeolite-containing particle of claim 29, wherein the core region includes a monolithic structure.
32. The porous zeolite-containing particle of claim 29, wherein the core region composition comprises alumina, zirconia, titania, silica or a combination thereof.
33. The porous zeolite-containing particle of claim 29, wherein the layered region composition comprises at least 20 % of alumina, zirconia, titania, silica or a combination thereof, and no greater than 80 % of zeolite
34. The porous zeolite-containing particle of claim 29, wherein the layered region composition comprises no greater than 90 % of alumina, zirconia, titania, silica or a combination thereof, and at least 10 % of zeolite.
35. The porous zeolite-containing particle of claim 29, wherein the layered region composition comprises no greater than 70 % of alumina, zirconia, titania, silica or a combination thereof, and at least 30 % of zeolite.
36. The porous zeolite-containing particle of claim 29, wherein the layered region composition comprises at least 20 % and no greater than 50 % of alumina, zirconia, titania, silica or a combination thereof, and at least 50 % and no greater than 80 % of zeolite.
37. The porous zeolite-containing particle of claim 29, wherein the porous zeolite- containing particle is substantially spherical
38. The porous zeolite-containing particle of claim 29, wherein the porous zeolite- containing particle comprises micropores having a diameter ranging from about 0.5 to 0.8 nanometers.
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