(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual PropertyOrganization

International Bureau(10) International Publication Number

(43) International Publication Date WO 2017/141132 Al24 August 2017 (24.08.2017) P O P C T

(51) International Patent Classification: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,B01J 29/08 (2006.01) B01J 29/06 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM,B01J 29/10' (2006.01) C01B 39/02 (2006.01) DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,B01J 29/12 (2006.01) C01B 39/20' (2006.01) HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KH, KN,B01J 29/14' (2006.01) C07C 2/66 (2006.01) KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA,B01J 35/00 (2006.01) C07C 15/02 (2006.01) MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG,B01J 35/10 (2006.01) B01J 35/02 (2006.01) NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS,

RU, RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY,(21) International Application Number: TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN,

PCT/IB20 17/050654 ZA, ZM, ZW.

(22) International Filing Date: (84) Designated States (unless otherwise indicated, for every7 February 2017 (07.02.2017) kind of regional protection available): ARIPO (BW, GH,

(25) Filing Language: English GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ,TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,

(26) Publication Language: English TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE,

(30) Priority Data: DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,

62/296,699 18 February 2016 (18.02.2016) US LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,

62/378,460 23 August 2016 (23.08.2016) US SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,GW, KM, ML, MR, NE, SN, TD, TG).

(71) Applicant: SABIC GLOBAL TECHNOLOGIES B.V.[NL/NL]; Plasticslaan 1, 4612 PX Bergen op Zoom (NL). Declarations under Rule 4.17 :

— as to applicant's entitlement to apply for and be granted a(72) Inventor: RAVON, Ugo; SABIC Research & Innovation

patent (Rule 4.1 7(H))Center at KAUST, P.O. Box 454-4700, Thuwal, 23955-6900 (SA). Published:

(81) Designated States (unless otherwise indicated, for every — with international search report (Art. 21(3))kind of national protection available): AE, AG, AL, AM,

(54) Title: HOLLOW ZEOLITE TYPE CATALYSTS WITH VARYING FRAMEWORK AND ZEOLITE TOPOLOGIES

FIG. 1C

(57) Abstract: Hollow zeolite particles are disclosed. The hollow zeolite particle can have a zeolite type framework peripheral shellthat defines and encloses an intra-particle hollow space within the interior of the shell, with the proviso that the peripheral shell doesnot have a MFI- type framework. Methods of making and using the hollow zeolite particle are also described.

HOLLOW ZEOLITE TYPE CATALYSTS WITH VARYING FRAMEWORK AND

ZEOLITE TOPOLOGIES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Patent

Application No. 62/296,699 filed February 18, 2016, and U.S. Provisional Patent Application

No. 62/378,460 filed August 23, 2016. The entire contents of each of the above-referenced

disclosures are specifically incorporated herein by reference without disclaimer.

BACKGROUND OF THE INVENTION

A. Field of the Invention

[0002] The invention generally concerns a non-MFI zeolite catalyst for chemical

applications (e.g., hydrocarbon reforming reactions such as dry or steam reforming of

methane). In particular, the invention concerns a catalyst that includes a hollow zeolite

particle having a zeolite framework type structure with a peripheral shell that defines and

encloses an intra-particle hollow space within the interior of the shell.

B. Description of Related Art

[0003] Zeolites belong to a broader material category known as "molecular sieves" and

are often referred as such. Zeolites have uniform, molecular-sized pores, and can be

separated based on their size, shape, and polarity. For example, zeolites may have pore sizes

ranging from about 0.3 nm to about 1 nm. The crystalline structure of zeolites can provide

good mechanical properties and good thermal and chemical stability. Zeolites are

microporous, possess regular pores and cavities, and have acidic behavior, which make them

useful as catalysts or support material in commercial chemical processes (e.g., fluid catalytic

cracking, alkylation, reforming, etc.). Many conventional zeolite catalysts include catalytic

material. These catalysts suffer from deactivation, stability, and leaching of the catalytic

material. By way of example, the catalytic material can be smaller than the pores of the

zeolite allowing the catalytic material to diffuse through the pore, which diminishes the

stability of the catalyst. Other problems associated with deactivation of zeolites containing

catalytic material include poor dispersion of the catalytic material on the surface of the

zeolite, and/or leaching of the catalytic material from the zeolite.

[0004] Several recent disclosures have focused on improving the activity and life of

reforming catalysts by using MFI-type zeolites that include catalytic material. The attempts

have focused on reducing the particle size of the catalytic metal, using promoters in the

catalyst matrix, or encapsulating the catalytic metal in a metal oxide by forming core@shell

type structures. (See, for example, Li et al., Chem. Commun. 2013, 49; Li, Ph.D. Thesis,

L'Universite Claude Bernard Lyon 1, HAL Id: tel-1 163661, June 2015, and Dai et al., J.

Materials of Chemistry A, 2015, 3, 16461-16468).

[0005] Other attempts to improve the stability and activity of non-MFI type zeolite

catalysts include making composite type materials that include the zeolite as a component of

the composite. These composite shells are aggregations of several zeolite particles with inter-

particle hollow spaces in the shell. By way of example, U.S. Patent No. 4,546,090 to Olson

et al. discloses composite material that includes a shell made from powdered zeolitic material

and matrix material {e.g., clay, a binder, or other inorganic materials). In another example,

Chinese Patent No. 1202966 C describes a zeolite crystallized around a fly ash hollow

microsphere (mullite) to produce a zeolite/mullite hollow composite having. In yet another

example, Japanese Patent Application Publication No. 2009-269788 describes a composite

hollow material that includes a drug/*BEA-type aggregate zeolite shell with inter-particle

aggregates.

[0006] Despite all of the currently available research on hollow zeolite catalysts, many of

the resulting non-MFI type zeolites are composite structures that can be inefficient to produce

on a commercial scale. Further, the composite materials can have adverse effects on pore

size, reactant and product diffusion into and out of the materials, can ultimately reduce

catalytic efficiency, or can contribute to deactivation of the catalyst.

SUMMARY OF THE INVENTION

[0007] A solution to the problems associated with the costs, deactivation, synthesis, and

degradation of non-MFI type zeolites has been discovered. In particular, the solution of the

present invention concerns a hollow zeolite particle having a zeolite type structure peripheral

shell that defines and encloses an intra-particle hollow space within the interior of the shell,

with the proviso that the peripheral shell does not have a MFI-type framework. The hollow

zeolite particle of the present invention can have a single type of zeolite framework structure

throughout the particle in that it is not a composite where two or more different materials

(e.g., different zeolites, inert/non-catalytic materials (e.g., binders, fly ash, drugs, etc.))

constitute the particle. The particle can be a pure non-MFI zeolite shell having the intra-

particle hollow space. The particles of the present invention can have: 1) any desired Si/Al

ratio ( 1 to ∞) ; 2) different framework and zeolite topologies; and/or 3) a shell with high

surface area on both internal and external surfaces. The high surface area allows more than

one type of reaction to occur on the same catalyst site. For example, a dehydrogenation of

hydrocarbon reaction can occur on the internal surface and a hydrocarbon alkylation reaction

can occur on the external surface of the hollow zeolite of the present invention. Furthermore,

the hollow zeolite particle of the present invention can be used to control dispersion of metal

or metal oxide deposition inside the pore, and the size of the active material (metal or metal

oxide) in the hollow surface and/or on the external surface of the zeolite particle. The

methods to make the hollow zeolite particle of the present invention provides an elegant

manner to achieve simultaneously, macroporous and/or mesoporous and/or microporous

channels that offer shape selectivity which could be interconnected to overcome mass transfer

limitations.

[0008] In a particular aspect of the present invention, there is disclosed a hollow zeolite

particle having a zeolite type structure peripheral shell that defines and encloses an intra-

particle hollow space within the interior of the shell, with the proviso that the peripheral shell

does not have a MFI-type structure. In particular, the hollow zeolite particle has a FAU X-

type or Y-type framework peripheral shell, preferably a FAU-X type framework structure,

more preferably a 13X-type structure peripheral shell as characterized by an X-ray diffraction

pattern shown in FIG. 5 . Another hollow zeolite particle can have a MWW type structure, a

*BEA type structure, a LTA type structure, a MOR type structure, an ITH type structure, a

CHA type structure, a *MRE type structure, a MER type structure, or a VFI type structure

peripheral shell. The hollow particle can have at least a second intra-particle hollow space

(e.g., 2, 3, 4, 5 hollow spaces) within the interior of the shell. The intra-particle hollow space

can have a diameter of 50% to 80% of the diameter of the particle. The hollow particle can

have a BET surface area of 140 cm /g to 600 cm /g and/or a diameter of 10 nanometers to

450 nanometers. The framework of hollow zeolite particle can include pores having a

diameter of 2 nanometers or less, preferably 0.1 nanometers to 0.5 nanometers. Catalytic

metal or oxides thereof can be included in the hollow zeolite particle. The catalytic metal or

oxide thereof can be positioned in the intra-particle hollow space, on the surface of the shell,

embedded in the shell or any combination thereof. Catalytic metal or metal oxides thereof

can include Column 1 (e .g., lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium

(Cs)) metal or oxides thereof or any alloy or combination thereof) , a Column 2 (e.g.,

magnesium (Mg), calcium (Ca), or barium (Ba)) metal, a transition (e.g., vanadium (V),

chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium

(Re), cobalt (Co), rhodium (Rh), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu),

silver (Ag), gold (Au), zinc (Zn)) metal, a post-transition (gallium (Ga), germanium (Ge), tin

(Sn), lead (Pb), antimony (Sb), bismuth (Bi)) metal, a lanthanide (lanthanum (La), ytterbium

(Yb)) metal, or any alloy or combination thereof.

[0009] In another aspect, a method to make the hollow zeolite particle described above

can include (a) obtaining a synthesis mixture of a protonated zeolite and a templating agent

and (b) heat treating the synthesis mixture to form a zeolite framework type structure

peripheral shell that defines and encloses an intra-particle hollow space within the interior of

the shell. Heat-treating in step (b) can remove aluminum ions from the protonated zeolite

framework. The templating agent can be a quaternary or a tertiary ammonium compound or

a salt thereof, preferably tetramethylammonium hydroxide. In a particular aspect, the

templating agent is metal free. Heat-treating the synthesis mixture can include (i) heating the

synthesis mixture to obtain a crystalline material, and (ii) calcining the crystalline material.

Heating in step (i) can include subjecting the solution to a temperature of 100 °C to 250 °C,

preferably 150 °C to 200 °C, for 1 to 3 days, preferably 1 to 5 days under static conditions.

Calcining the crystalline material in step (ii) can include subjecting the crystalline material to

a temperature of 350 °C to 550 °C, preferably 400 °C to 500 °C, for 3 to 10 hours, preferably

4 to 8 hours. Obtaining a protonated form of the zeolite can include subjecting the zeolite to

a cation exchange process to exchange cations with proton. The calcined catalyst can be

subjecting to reducing conditions to convert the metal oxide to the metal having a zero

valence. In some embodiments, the protonated zeolite can be impregnated with a metal

precursor.

[0010] Systems for producing a chemical product are also described. A system can

include (a) an inlet for a reactant feed; (b) a reaction zone (e.g., a continuous flow reactor

selected from a fixed-bed reactor, a fluidized reactor, or a moving bed reactor) that is

configured to be in fluid communication with the inlet, wherein the reaction zone includes the

hollow zeolite particle of the present invention; and (c) an outlet configured to be in fluid

communication with the reaction zone and configured to remove a product stream from the

reaction zone. The reaction zone can a continuous flow reactor selected from a fixed-bed

reactor, a fluidized reactor, or a moving bed reactor. A saturated hydrocarbon stream or a

hydrocarbon stream having a boiling point of 340 °C or more at atmospheric pressure or both

can be used as a reactant feed and/or the product stream can include alkylated hydrocarbons,

gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.

[0011] Methods of using the hollow zeolite particle described above in a chemical

reaction (e.g., fluid catalytic cracking reaction, a hydrocracking reaction, an alkylation of an

aromatic hydrocarbon reaction, etc.) are disclosed. The method can include contacting the

hollow zeolite particle of the present inventions with a reactant feed to catalyze a chemical

reaction; and producing a product feed. In some particular, instances the chemical reaction

can be an alkylation of an aromatic hydrocarbon reaction (e.g., alkylation of benzene with

ethylene to produce ethylbenzene, alkylation of benzene with propylene to produce

isopropylbenzene (cumene), etc.).

[0012] Also disclosed in the context of the present invention are thirty-seven

embodiments. In a first embodiment, a hollow zeolite particle is described. The hollow

zeolite particle of embodiment 1 can have a zeolite type framework peripheral shell that

defines and encloses an intra-particle hollow space within the interior of the shell, with the

proviso that the peripheral shell does not have a MFI-type framework. Embodiment 2 is the

hollow zeolite particle of embodiment 1, having a FAU X-type or Y-type structure peripheral

shell. Embodiment 3 is the hollow zeolite particle of embodiment 2, having a FAU X-type

structure peripheral shell. Embodiment 4 is the hollow zeolite particle of embodiment 3,

wherein the FAU X-type structure peripheral shell is a 13X-type structure peripheral shell.

Embodiment 5 is the hollow zeolite particle of embodiment 4, characterized by an X-ray

diffraction (XRD) pattern shown in FIG. 5 . Embodiment 6 is the hollow zeolite particle of

any one of embodiments 1 to 5, having a surface area of 140 cm /g to 600 cm /g.

Embodiment 7 is the hollow zeolite particle of any one of embodiments 1 to 6, including at

least a second intra-particle hollow space within the interior of the shell. Embodiment 8 is

the hollow zeolite particle of any one of embodiments 1 to 7, having a diameter of 10

nanometers to 450 nanometers. Embodiment 9 is the hollow zeolite particle of embodiment

8, wherein the intra-particle hollow space has a diameter of 50% to 80% of the diameter of

the particle. Embodiment 10 is the hollow zeolite particle of any one of embodiments 1 to 9,

wherein the zeolite framework type peripheral shell includes pores having a diameter of 2

nanometers or less, preferably 0.1 nanometers to 0.5 nanometers. Embodiment 11 is the

hollow zeolite particle of any one of embodiments 1 to 10, wherein the thickness of the

zeolite framework type peripheral shell is 5 nanometers to 20 nanometers. Embodiment 12 is

the hollow zeolite particle of any one of embodiments 1 to 11 that further includes a catalytic

metal or oxide thereof. Embodiments 13 is the hollow zeolite particle of embodiment 12,

wherein the catalytic metal or oxide thereof is positioned in the intra-particle hollow space,

on the surface of the shell, embedded in the shell or any combination thereof. Embodiment

14 is the hollow zeolite particle of any one of embodiments 12 to 13, wherein the catalytic

metal or metal oxide is a Column 1 metal, a Column 2 metal, a transition metal, a post-

transition metal, a lanthanide metal, or any alloy or combination thereof. Embodiment 15 is

the hollow zeolite particle of embodiment 14, wherein the Column 1 metal is lithium (Li),

sodium (Na), potassium (K), rubidium (Rb), cesium (Cs) or oxides thereof or any alloy or

combination thereof. Embodiment 15 is the hollow zeolite particle of embodiment 14,

wherein the Column 2 metal is magnesium (Mg), calcium (Ca), or barium (Ba) or oxides

thereof or any alloy or combination thereof. Embodiment 16 is the hollow zeolite particle of

embodiment 14, wherein the transition metal is vanadium (V), chromium (Cr), molybdenum

(Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh),

nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), or

oxides or any alloy or combination thereof. Embodiment 17 is the hollow zeolite particle of

embodiment 14, wherein the post transition metal is gallium (Ga), germanium (Ge), tin (Sn),

lead (Pb), antimony (Sb), bismuth (Bi), or oxides thereof, or any alloy or combination

thereof. Embodiment 18 is the hollow zeolite particle of embodiment 14, wherein the

lanthanide metal is lanthanum (La), ytterbium (Yb) or oxides thereof or any alloy or

combination thereof. Embodiment 19 is the hollow zeolite particle of any one of

embodiments 1 and 5 to 19, having a MWW type structure, a *BEA type structure, a LTA

type structure, a MOR type structure, an ITH type structure, a CHA type structure, a MRE

type structure, a MFE type structure, or a VFI type structure peripheral shell.

[0013] Embodiment 2 1 is a method of making the hollow zeolite particle of any one of

embodiments 1 to 20. The method of embodiment 2 1 includes (a) obtaining a synthesis

mixture of a protonated zeolite and a templating agent; and (b) heat treating the synthesis

mixture to form a zeolite framework type structure peripheral shell that defines and encloses

an intra-particle hollow space within the interior of the shell. Embodiment 22 is the method

of embodiment 21, wherein the templating agent is a quaternary or a tertiary ammonium

compound or a salt thereof, preferably tetramethylammonium hydroxide. Embodiment 23 is

the method of any one of embodiments 2 1 to 22, wherein the templating agent is metal free.

Embodiment 24 is the method of any one of embodiments 2 1 to 23, wherein heat-treating the

synthesis mixture includes (i) heating the synthesis mixture to obtain a crystalline material,

and (ii) calcining the crystalline material. Embodiment 25 is the method of embodiment 24,

wherein heating in step (i) includes subjecting the solution to a temperature of 100 °C to

250 °C, preferably 150 °C to 200 °C, for 1 to 3 days, preferably 1 to 5 days under static

conditions. Embodiment 26 is the method of any one of embodiments 20 to 25, wherein step

(ii) includes subjecting the crystalline material to a temperature of 350 °C to 550 °C,

preferably 400 °C to 500 °C, for 3 to 10 hours, preferably 4 to 8 hours. Embodiment 27 is the

method of embodiment 26 that further includes drying the crystalline material at 90 °C to

110 °C for 8 to 12 hours prior to step (b). Embodiment 28 is the method of any one of

embodiments 20 to 27, wherein step (a) includes subjecting the zeolite to a cation exchange

process to exchange cations with protons. Embodiment 29 is the method of embodiment 28,

wherein the cation is ammonium ion ( H4+) . Embodiment 30 is the method of any one of

embodiments 20 to 29, wherein heat-treating in step (b) removes aluminum ions from the

protonated zeolite. Embodiment 3 1 is the method of any one of embodiments 20 to 30,

wherein the protonated zeolite is impregnated with a metal precursor material.

[0014] Embodiment 32 is a method of using the hollow zeolite particle of any one of

embodiments 1 to 20 in a chemical reaction. The method of embodiment 32 includes (a)

contacting the hollow zeolite particle of any one of embodiments 1 to 20 with a reactant feed

to catalyze a chemical reaction; and (b) producing a product feed. Embodiment 33 is the

method of embodiment 32, wherein the chemical reaction is a fluid catalytic cracking

reaction, a hydrocracking reaction, or an alkylation reaction. In particular instances, the

alkylation reaction can be an alkylation of an aromatic hydrocarbon reaction such as

alkylation of benzene with ethylene to produce ethylbenzene or alkylation of benzene with

propylene to produce cumene.

[0015] Embodiment 34 is a system for producing a chemical product. The system of

embodiment 34 includes (a) an inlet for a reactant feed; (b) a reaction zone that is configured

to be in fluid communication with the inlet, wherein the reaction zone includes the hollow

zeolite particle of any one of embodiments 1 to 20; and (c) an outlet configured to be in fluid

communication with the reaction zone and configured to remove a product stream from the

reaction zone. Embodiment 35 is the system of embodiment 34, wherein the reaction zone is

a continuous flow reactor selected from a fixed-bed reactor, a fluidized reactor, or a moving

bed reactor. Embodiment 36 is the system of any one of embodiments 34 to 35, wherein the

reactant feed is a saturated hydrocarbon stream or a hydrocarbon stream having a boiling

point of 340 °C or more at atmospheric pressure or both. Embodiment 37 is the system of

any one of embodiments 34 to 36, wherein the product stream includes alkylated

hydrocarbons, gasoline, jet fuel, diesel, olefinic gases, or any combination thereof.

[0016] The following includes definitions of various terms and phrases used throughout

this specification.

[0017] The phrase "intra-particle hollow space" refers to a hollow space or void in within

the interior surface of a zeolite shell. FIG. 1A provides a non-limiting example of a particle

of the present invention that includes a single intra-particle hollow space. FIG. IB provides a

non-limiting example of a particle of the present invention that includes two intra-particle

hollow spaces.

[0018] The phrase "inter-particle space" refers to a space or void that is created when

multiple particles are contacted with one another and spaces or voids are created between the

outer surfaces of such particles. FIG. 1C provides a non-limiting example of a plurality of

particles of the present invention, each having a single intra-particle hollow space, that form

inter-particle spaces or voids between the outer surfaces of such particles.

[0019] The term "catalyst" refers to a single hollow zeolite particle or a plurality of

hollow zeolite particles positioned adjacent to each other in a catalytic bed and/or shaped into

a form that can catalyze a chemical reaction. FIGS. 1A-1C provide non-limiting examples of

catalysts of the present invention.

[0020] The term "nanostructure" refers to an object or material in which at least one

dimension of the object or material is equal to or less than 1000 nm (e.g., one dimension is 1

to 1000 nm in size). In a particular aspect, the nanostructure includes at least two dimensions

that are equal to or less than 1000 nm (e .g., a first dimension is 1 to 1000 nm in size and a

second dimension is 1 to 1000 nm in size). In another aspect, the nanostructure includes

three dimensions that are equal to or less than 1000 nm (e.g., a first dimension is 1 to 1000

nm in size, a second dimension is 1 to 1000 nm in size, and a third dimension is 1 to 1000 nm

in size). The shape of the nanostructure can be of a wire, a particle (e .g., having a

substantially spherical shape), a rod, a tetrapod, a hyper-branched structure, a tube, a cube, or

mixtures thereof. "Nanostructures" include particles having an average diameter size of 1 to

1000 nanometers. In a particular instance the nanostructure is a nanoparticle.

[0021] Particle size of the nanostructures or other particles can be measured using known

techniques. Non-limiting examples include transmission electron spectroscopy (TEM),

scanning electron microscopy (SEM), preferably TEM.

[0022] The term "about" or "approximately" are defined as being close to as understood

by one of ordinary skill in the art. In one non-limiting embodiment the terms are defined to

be within 10%, preferably within 5%, more preferably within 1%, and most preferably within

0.5%.

[0023] The term "substantially" and its variations are defined to include ranges within

10%, within 5%, within 1%, or within 0.5%.

[0024] The terms "inhibiting" or "reducing" or "preventing" or "avoiding" or any

variation of these terms, when used in the claims and/or the specification includes any

measurable decrease or complete inhibition to achieve a desired result.

[0025] The term "effective," as that term is used in the specification and/or claims, means

adequate to accomplish a desired, expected, or intended result.

[0026] The use of the words "a" or "an" when used in conjunction with any of the terms

"comprising," "including," "containing," or "having" in the claims, or the specification, may

mean "one," but it is also consistent with the meaning of "one or more," "at least one," and

"one or more than one."

[0027] The words "comprising" (and any form of comprising, such as "comprise" and

"comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and

any form of including, such as "includes" and "include") or "containing" (and any form of

containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude

additional, unrecited elements or method steps.

[0028] The hollow zeolite nanoparticle of the present invention can "comprise," "consist

essentially of," or "consist of particular ingredients, components, compositions, etc.

disclosed throughout the specification. With respect to the transitional phase "consisting

essentially of," in one non-limiting aspect, a basic and novel characteristic of the hollow

zeolite nanoparticle of the present invention are (1) a zeolite type framework peripheral shell

that defines and encloses an intra-particle hollow space within the interior of the shell, with

the proviso that the peripheral shell does not have a MFI-type framework and (2) their use in

catalyzing chemical reactions.

[0029] The terms "wt.%", "vol.%", or "mol.%" refers to a weight, volume, or molar

percentage of a component, respectively, based on the total weight, the total volume of

material, or total moles, that includes the component. A non-limiting example is 1 wt.% of

M means that a 100 gram sample of catalyst contains 0.01 grams of M in its metallic form.

[0030] Other objects, features and advantages of the present invention will become

apparent from the following figures, detailed description, and examples. It should be

understood, however, that the figures, detailed description, and examples, while indicating

specific embodiments of the invention, are given by way of illustration only and are not

meant to be limiting. Additionally, it is contemplated that changes and modifications within

the spirit and scope of the invention will become apparent to those skilled in the art from this

detailed description. In further embodiments, features from specific embodiments may be

combined with features from other embodiments. For example, features from one

embodiment may be combined with features from any of the other embodiments. In further

embodiments, additional features may be added to the specific embodiments described

herein.

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Advantages of the present invention may become apparent to those skilled in the

art with the benefit of the following detailed description and upon reference to the

accompanying drawings.

[0032] FIG. 1A is an illustration of an embodiment of cross-sectional view of a hollow

zeolite with an intra-particle hollow space within the interior of the shell.

[0033] FIG. IB is an illustration of an embodiment of a cross-sectional view of a hollow

zeolite with two intra-particle hollow spaces within the interior of the shell.

[0034] FIG. 1C is an illustration of an embodiment of a cross-sectional view of a

plurality of zeolite particles, each having an intra-particle hollow space, that form inter-

particle spaces between the outer surfaces of the particles.

[0035] FIG. 2A is an illustration of an embodiment of a cross-sectional view of a hollow

zeolite with a nanostructure contacting the inner surface of the intra-particle hollow space

within the interior of the shell.

[0036] FIG. 2B is an illustration of an embodiment of a cross-sectional view of a hollow

zeolite with a nanostructure not contacting the inner surface of the intra-particle hollow space

within the interior of the shell.

[0037] FIG. 2C is an illustration an embodiment of a cross-sectional view of a hollow

zeolite with a plurality of nanostmctures in the intra-particle hollow space within the interior

of the shell of the present invention.

[0038] FIG. 3 is an illustration of a method of making the hollow zeolite having an intra-

particle hollow space within the interior of the shell of the present invention.

[0039] FIG. 4 is an illustration of a method of making the hollow zeolite with a

nanostructure in the intra-particle hollow space within the interior of the shell of the present

invention.

[0040] FIG. 5 shows X-ray diffraction patterns of a comparative FAU 13X- type zeolite

particle (top) and a hollow FAU 13X type zeolite particle of the present invention (bottom).

[0041] FIG. 6 shows nitrogen isotherms of the comparative FAU 13X type zeolite

particle (top isotherms) and a hollow FAU 13X type zeolite particle of the present invention

(bottom isotherms).

[0042] While the invention is susceptible to various modifications and alternative forms,

specific embodiments thereof are shown by way of example in the drawings and may herein

be described in detail. The drawings may not be to scale.

DETAILED DESCRIPTION OF THE INVENTION

[0043] A discovery has been made that avoids problems associated with deactivation of

zeolite type catalysts that do not have MFI-type framework structure. The discovery is based

on the premise to create an intra-particle hollow (void) space within the interior portion of a

zeolite particle. The hollow zeolite particle can include a catalytic material. The catalytic

material and the zeolite type can be selected for a desired result (e.g., catalytic metals can be

included in the hollow to catalyze a given chemical reaction). The method of making the

hollow zeolite nanoparticle allows for creation of an intra-particle hollow space in the zeolite

particle and/or tuning of the thickness and/or acidity of the zeolite shell surrounding the intra-

particle hollow space.

[0044] These and other non-limiting aspects of the present invention are discussed in

further detail in the following sections.

A. Catalyst Structure and Materials

1. Hollow Zeolite Particle and Zeolite Material

[0045] The hollow zeolite structure of the present invention includes an intra-particle

hollow space within the interior surface of the zeolite particle shell. FIGS. 1A-1C are cross-

sectional illustrations of hollow zeolite particle 10 having an intra-particle hollow space

zeolite structure. The hollow zeolite particle 10 has a zeolite-type framework peripheral shell

12 and intra-particle hollow space 14. FIG. IB depicts the intra-particle hollow zeolite

particle 10 having two intra-particle hollow spaces. FIG. 1C depicts a catalyst that includes a

plurality of the hollow zeolite particles 10. The hollow zeolite particle 10 can have a surface

area of 140 cm /g to 600 cm /g, 150 cm /g to 500 cm /g, 200 cm /g to 400 cm /g, or 140

cm /g, 150 cm /g, 200 cm /g, 250 cm /g, 300 cm /g, 350 cm /g, 400 cm /g, 450 cm /g, 500

cm /g, 550 cm /g, 600 cm /g or any range or value there between and/or a diameter of 10

nanometers (nm) to 450 nm, 100 to 300 nm, 150 to 250 nm, or 10 nm, 50 nm, 100 nm, 150

nm, 200 nm, 250 nm, 300 nm, 400 nm, 450 nm or any range or value there between. A

volume space of the intra-particle hollow space 14 can be about 30 to 80%, 40 to 70%, or 50

to 60% of the zeolite particle volume or 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%,

7 5% , 80% or any value or range there between. The diameter of the intra-particle hollow

space can be 50 to 80%, or 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any range or value

there between of the diameter of the particle.

[0046] The zeolite shell 12 can be any porous zeolite or zeolite-like material devoid of

zeolite material having a MFI-type structure. The zeolite material can be a naturally

occurring zeolite, a synthetic zeolite, a zeolite that have other materials in the zeolite

framework (e.g., phosphorous), or combinations thereof. X-ray diffraction (XRD) analysis

and scanning electron microscopy (SEM) may be carried out to determine the properties of

zeolite materials, including their crystallinity, size and morphology. The network of such

zeolites is made up of Si0 4 and A104 tetrahedra, which are joined via shared oxygen bridges.

An overview of the known structures may be found, for example, in W. M . Meier, D . H .

Olson and Ch. Baerlocher, "Atlas of Zeolite Structure Types", Elsevier, 5th edition,

Amsterdam 2001. The zeolite material can have secondary building blocks of 4, 5, 6, 8, 18,

4-1, 4-2, 4-4, 5-1, 5-2, 5-3, 6-1, 6-1 (1:4), 6-2, 6-3, 6-6, 8-8, 1-4-1, 1-6-1, 2-6-2, or

combinations thereof. In a particular instance, a zeolite having secondary building units of 6-

6 or 6-2 or 6 or 4-2 or 1-4-1 or 4 is used. It should be understood that a zeolite having a

pentasil and/or 5-1 secondary building unit can possess different characteristics than a MFI

zeolite (for example, structure, porosity, pore volume, thermal stability and the like) and is

these zeolites are not considered a MFI framework type zeolite in the present invention.

Non-limiting examples of zeolites include ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI,

AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ATN, ATO, ATS,

ATT, ATV, AWO, AWW, *BEA, BIK, BOG, BPH, BRE, CAN, CAS, CFI, CGF, CGS,

CHA, CHI, -CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI,

ERI, ESV, EUO, *EWT, FAU, FER, GIS, GME, GOO, HEU, IFR, ISV, ITE, ITH, ITG,

JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, MAZ, MEI, MEL, MEP, MER,

MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAT, NES, NON, OFF, OSI,

PAR, PAU, PHI, RHO, RON, RSN, RTE, RTH, RUT, SAO, SAT, SBE, SBS, SBT, SFF,

SGT, SOD, STF, STI, STT, TER, THO, TON, TSC, VET, VFI, VNI, VSV, WIE, WEN,

YUG and ZON structures and mixed structures of two or more of the abovementioned

structures. In some embodiments, the zeolite includes phosphorous to form an AIPOx

structure. Non-limiting examples of AIPOx zeolites include AABW, AACO, AAEI, AAEL,

AAEN, AAET, AAFG, AAFI, AAFN, AAFO, AAFR, AAFS, AAFT, AAFX, AAFY,

AAHT, AANA, AAPC, AAPD, AAST, AATN, AATO, AATS, AATT, AATV, AAWO,

AAWW, ABEA, ABIK, ABOG, ABPH, ABRE, ACAN, ACAS, ACFI, ACGF, ACGS,

ACHA, ACHI, A-CLO, ACON, ACZP, ADAC, ADDR, ADFO, ADFT, ADOH, ADON,

AEAB, AEDI, AEMT, AEPI, AERI, AESV, AEUO, A*EWT, AFAU, AFER, AGIS, AGME,

AGOO, AHEU, AIFR, AISV, AITE, AITH, AITG, AJBW, AKFI, ALAU, ALEV, ALIO,

ALOS, ALOV, ALTA, ALTL, ALTN, AMAZ, AMEI, AMEL, AMEP, AMER, AMFS,

AMON, AMOR, AMSO, AMTF, AMTN, AMTT, AMTW, AMWW, ANAT, ANES,

ANON, AOFF, AOSI, APAR, APAU, APHI, ARHO, ARON, ARSN, ARTE, ARTH,

ARUT, ASAO, ASAT, ASBE, ASBS, ASBT, ASFF, ASGT, ASOD, ASTF, ASTI, ASTT,

ATER, ATHO, ATON, ATSC, AVET, AVFI, AVNI, AVSV, AWIE, AWEN, AYUG and

AZON structures and mixed structures of two or more of the abovementioned structures. In

particular embodiments, the zeolite is a porous zeolite in pure silica (Si/Al= ∞ ) form or with a

small amount of Al, for example, a FAU type structure (including X and Y structures), a

MWW type structure, a *BEA type structure, a LTA type structure, a MOR type structure, an

ITH type structure, a CHA type structure, a MER type structure, a MFE type structure, or a

VFI type structure zeolites. Zeolites may be obtained from a commercial manufacturer such

as Zeolyst (Valley Forge, Pennsylvania, U.S.A.). Shell 12 can include at least 90 wt.%, 9 1

wt.%, 92 wt.%, 93 wt.% 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.% or 99 wt.%, or 100

wt .% of zeolite material. The shell is porous and includes pores having a diameter of 2

nanometers or less, 0.1 nanometers to 0.5 nanometers, or 0.1 nm, 0.2 nm, 0.3 nm, 0.4 nm, 0.5

nm, 0.6 nm, 0.7 nm, 0.8 nm, 0.9 nm, 1 nm, 1.1 nm 1.2 nm, 1.3 nm, 1.4 nm, 1.5 nm, 1.6 nm,

1.7 nm, 1.8 nm, 1.9 nm, 2.0 nm or any value or range there between. Depending on the

application, the thickness of the shell can be tuned. The thickness can range from 5 to 20 nm,

or 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm 16 nm, 17 nm,

18 nm, 19 nm, 20 nm or any range or value there between. Shell 12 includes an inner surface

16 and outer surface 18. Inner surface 16 forms the outer surface of the intra-particle hollow

space 14. Inner surface 16 and outer surface 18 are made of the same zeolite material, or a

combination of zeolite materials.

[0047] A plurality of the hollow zeolite particles 10 can be used to together to form a

catalytic material 15. FIG. 1C depicts a plurality of hollow zeolite particles 10 in

combination with an inert surface 17. Inert surface 17 can be a holder (e.g., tray, tube, etc.)

or a material (e.g., binder, clays, polymeric material, etc.) that holds the hollow zeolite

particles in position so that they can be used in a reaction zone. When two or more hollow

zeolite particles 10 are positioned next to each other, inter-particle void 19 is formed. In

some instances, the inert surface imparts structural integrity to the hollow zeolite particle.

Since the zeolite is pure silicalite zeolite and/or substantially inert, the inter-particle void

spaces between the hollow zeolite particles 10 will have no activity or substantially no

activity.

2. Catalytic Material

[0048] The hollow zeolite particle can include catalytic material. The catalytic material

can be a metal nanostructure contained within the intra-particle hollow space that is present in

the zeolite. FIGS. A through 2C are cross-sectional illustrations of catalyst material 20

having an encapsulated metal nanostructure/hollow zeolite structure. The catalyst material 20

has a zeolite shell 12, a catalytic (e.g., metal, bimetallic or trimetallic) nanostructure 22 and

intra-particle hollow space 14. In some embodiments, a portion of the nanostructure 22 (e.g.,

M , M and M2 and/or M3) can be deposited on the surface of the zeolite (not shown). As

discussed in detail below, the intra-particle hollow space 14 can be formed by removal of a

portion of the zeolite core during the making of the catalyst material. As shown in FIG. 2A,

the catalytic nanostructure 22 contacts a portion of the inner wall of hollow space 14. As

shown in FIG. 2B, the catalytic nanostructure 22 does not contact the walls of the intra-

particle hollow space 14. As shown in FIG. 2C, multiple catalytic nanostructures 22 are in

the intra-particle hollow space 14 with some catalytic nanostructures touching the inner wall

of the intra-particle hollow space. In certain aspects, 1% to 99%, 10% to 80%, 20% to 70%,

30% to 60% , 4 0% to 50% or any range or value there between of the nanostructures fills the

intra-particle hollow space 14. A diameter of the catalytic nanostructure 14 can range from 1

nm to 100 nm, preferably 1 nm to 50 nm, or more preferably 1 nm to 5 nm or any value or

range there between. In some embodiments, 1 to 100 nm, preferably 1 to 30 nm, more

preferably 3 to 15 nm, most preferably < 10 nm with a size distribution having a standard

deviation of ± 20%>. The pore size of the resulting catalyst is the same or similar to the pore

size of the starting zeolite. Diameters of the catalytic nanostructure and pore size of the

catalyst can be determined using transmission electron microscopy (TEM) and Barrett-

Joyner-Halenda (BJH) methods known in the art.

[0049] Catalytic nanostructure(s) 22 can include one or more active (catalytic) metals to

promote a desired chemical reaction (e .g., hydrocarbon cracking, alkylation, isomerization,

etc.). In particular instances, the chemical reaction can be an alkylation reaction such as an

alkylation of an aromatic hydrocarbon reaction (e.g., alkylation of benzene with ethylene to

produce ethylbenzene or alkylation of benzene with propylene to produce cumene). The

nanostructure(s) 22 can include one or more catalytic metals or metal oxides from Column 1

metal, a Column 2 metal, a transition metal, a post-transition metal, a lanthanide metal, or any

alloy or combination thereof. Non-limiting examples of metals include lithium (Li), sodium

(Na), potassium (K), rubidium (Rb), cesium (Cs), lithium (Li), sodium (Na), potassium (K),

rubidium (Rb), cesium (Cs), vanadium (V), chromium (Cr), molybdenum (Mo), tungsten

(W), manganese (Mn), iron (Fe), ruthenium (Re), cobalt (Co), rhodium (Rh), nickel (Ni),

palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), gallium (Ga),

germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), lanthanum (La), ytterbium

(Yb). Many of the metals can be obtained from metal precursor compounds. For example,

the transition and post-transition metals can be obtained as a metal nitrate, a metal amine, a

metal chloride, a metal coordination complex, a metal sulfate, a metal phosphate hydrate,

metal complex, or any combination thereof. Examples of metal precursor compounds

include, nickel nitrate hexahydrate, nickel chloride, cobalt nitrate hexahydrate, cobalt

chloride hexahydrate, cobalt sulfate heptahydrate, cobalt phosphate hydrate, or ruthenium

chloride, diammonium hexachorouthenate, hexammineruthenium trichloride,

pentaammineruthenium dichloride, etc. These metals or metal compounds can be purchased

from any chemical supplier such as Sigma-Aldrich (St. Louis, Missouri, USA), Alfa-Aeaser

(Ward Hill, Massachusetts, USA), and Strem Chemicals (Newburyport, Massachusetts,

USA).

[0050] The amount of catalytic nanostructure depends, inter alia, on the use of the

catalysts in the desired chemical reaction. In some embodiments, the amount of catalytic

metal present in the particle(s) in the hollow ranges from 0.01 to 100 parts by weight of

catalyst per 100 parts by weight of catalyst, from 0.01 to 5 parts by weight of catalyst per 100

parts by weight of catalyst. M , M and M2 are each 1 to 20 weight % of the total weight of

the catalytic nanostructure. A molar amount of each metal {e.g., M , M and M2 or M , M2,

and M3) in the nanostructure 22 can range from 1 to 95 molar %, or 10 to 80 molar%, 50 to

70 molar% of the total moles of the catalytic nanostructure. An average particle size of the

catalytic nanoparticle, or oxides thereof, can be 1 to 100 nm, preferably 1 to 30 nm, more

preferably 0.7 to 10 nm, most preferably < 10 nm with a size distribution having a standard

deviation of ± 20%.

B. Preparation of the Hollow Zeolite Particle

[0051] The catalysts of the present invention can be prepared by processes known to those

having ordinary skill in the art as well as the process described in the Examples. FIG. 3 is a

schematic of an embodiment of a method to make the hollow shell zeolite material. In

method 30, step 1, the zeolite material 32 can be obtained either through a commercial source

{e.g., Sigma-Aldrich®, USA) or prepared using known methods for making zeolites and

calcined in air {e.g., 6 hours at 500 °C) to remove the cationic component {e.g., H4+) to

form the protonated (H+) form of the zeolite material 34. In step 2, the protonated (active)

zeolite material 34 can be contacted (suspended) with an aqueous solution of a templating

agent (e.g., a quaternary ammonium compound, tertiary ammonium compound, or

tetramethyl ammonium hydroxide) and the resulting suspension can be subjected to a

dissolution-recrystallization process to produce the zeolite composite material 36 having

hollow 14. The dissolution-recrystallization process under hydrothermal conditions can

include techniques of heating aqueous solutions of the aqueous templated zeolite suspension

at high vapor pressures. In a particular embodiment, the suspension can be heated to 100 °C

to 250 °C, preferably 150 °C to 200 °C, for 12 to 36 hours, preferably 18 to 30 hours under

autogenous pressure. Dissolution-recrystallization can be performed in a pressure vessel,

such as an autoclave, by a temperature-difference method, temperature-reduction method, or

a metastable-phase technique. Without wishing to be bound by theory, it is believed that

during the dissolution-recrystallization process, the hollow space is formed in the zeolite

framework through dissolution of some of the silicon core by the templating agent. The

removed silica species can recrystallize on the outer surface upon cooling. In step 3, the

resulting metal-zeolite composite material 36 can be heated in the presence of air (e.g.,

calcined) to remove the template and any organic residues to form hollow zeolite material 10.

Calcination conditions can include a temperature of 350 °C to 550 °C, preferably 400 °C to

500 °C and a time of 3 to 10 hours, preferably 4 to 8 hours.

C. Preparation Encapsulated Nanoparticle/Hollow Zeolite Material

[0052] The catalysts can be prepared by processes known to those having ordinary skill

in the art, for example the catalytic material (metal nanostructure) can be prepared by any one

of the methods comprising liquid-liquid blending, solid-solid blending, or liquid-solid

blending (e.g., any of precipitation, co-precipitation, impregnation, complexation, gelation,

crystallization, microemulsion, sol-gel, solvothermal, dissolution-recrystallization,

hydrothermal, sonochemical, or combinations thereof). The metal nanostructure can be

encapsulated in the hollow zeolite particle such that it is present in the intra-particle hollow

space. The method can also allow for control of the size the metal nanostructure. Without

wishing to be bound by theory it is believed that because the metal nanostructure size is

larger than the pore size of the zeolite, the metal nanostructure cannot diffuse out of the

zeolite so they remain inside the intra-particle hollow space of the zeolite created. Thus, the

particle cannot grow or sinter, and hence size is maintained (i.e., sintering is prevented).

Moreover, because the size of the metal nanostructure is reduced, the formation of coke can

be inhibited. Furthermore, the methods used to prepare the catalysts of the present invention

allow tuning of the size of metallic nanostructures as well as the type of metals that can be

used.

[0053] FIG. 4 is a schematic of an embodiment of a method to make the encapsulated

metal nanoparticle/hollow shell zeolite material. In method 40, step 1, the zeolite material 32

can be obtained either through a commercial source and heated as described above to obtain

the active zeolite material 34. In step 2, an aqueous solution of the M precursor material

(e.g., a nickel precursor), a M2 precursor material (e.g., ruthenium or cobalt precursors), and

optionally a M3 precursor material can be contacted with the zeolite material 34 to allow

impregnation of the zeolite material with the precursor materials 42. The amount of solution

of metal precursor material is the same or substantially the same as the pore volume of the

zeolite material. The impregnated zeolite material can be dried to obtain a catalytic

impregnated zeolite material 44. Drying conditions can include heating the impregnated

zeolite material from 30 °C to 100 °C, preferably 40 °C to 60 °C, for 4 to 24 hours. In step 3,

the impregnated zeolite material 44 can be contacted (suspended) with an aqueous solution of

a templating agent (e .g., a quaternary ammonium hydroxide compound) and the resulting

suspension is subjected to a dissolution-recrystallization process to produce the encapsulated

nanoparticle/zeolite composite material 46 having metal nanostructures 42 positioned in

hollow 14. In some embodiments, the zeolite is subjected to a vacuum prior to impregnation

(e.g., 100 to 300 °C for 6 h under 10 6 bar) to facilitate metal diffusion through the pores. The

dissolution-recrystallization process under hydrothermal conditions can include techniques of

heating aqueous solutions of the aqueous templated zeolite suspension at high vapor

pressures. In a particular embodiment, the suspension is heated to 100 °C to 250 °C,

preferably 150 °C to 200 °C, for 12 to 36 hours, preferably 18 to 30 hours under autogenous

pressure. Dissolution-recrystallization can be performed in a pressure vessel, such as an

autoclave, by a temperature-difference method, temperature-reduction method, or a

metastable-phase technique. Without wishing to be bound by theory, it is believed that

during the dissolution-recrystallization process, the hollow is formed in the zeolite framework

through dissolution of some of the silicon core by the templating agent. The removed silica

species can recrystallize on the outer surface upon cooling. During the hydrothermal process,

the metal precursors can form a catalytic (e.g., metallic, bimetallic, or trimetallic)

nanostructure in the intra-particle hollow space. Since the catalytic nanostructures are too

large to migrate through the microporous zeolite walls, they remain in the intra-particle

hollow space. In some instances, small nanostructures come together and form a larger

nanostructure or a single nanostructure in the intra-particle hollow space. In step 4, the

resulting metal-zeolite composite material 46 can be heated in the presence of air (e .g.,

calcined) to remove the template and any organic residues to form encapsulated catalytic

nanostructure/ hollow zeolite material 10. Calcination conditions can include a temperature

of 350 °C to 550 °C, preferably 400 °C to 500 °C and a time of 3 to 10 hours, preferably 4 to

8 hours. In step 5, the encapsulated catalytic nanostructure/ hollow zeolite material 42 can be

subjected to conditions sufficient to reduce the metals to their lowest valence and form

catalytic nanostructure 2 . Without wishing to be bound by theory, it is believed that treating

the metal nanostructure with hydrogen can generate larger metal particles from smaller metal

oxide particles in the hollow zeolite.

D. Use of Hollow Zeolite and/or Catalytic Nanostructure/Hollow Zeolite

[0054] Also disclosed is a method of producing a chemical product. The method includes

contacting a reactant feed of a hydrocarbon with any one of the hollow zeolites and/or

catalytic nanostructure/hollow zeolite catalyst materials 10 and 20 discussed above and/or

throughout this specification under sufficient conditions to produce a desired chemical

product. The reactant feed can be saturated hydrocarbon stream and/or a hydrocarbon stream

having a boiling point of 340 °C or more at atmospheric pressure. The product stream can

include alkylated hydrocarbons (e.g., ethylbenzene, cumene), gasoline, jet fuel, diesel,

olefinic gases, or any combination thereof. In particular instances, carbon formation or

coking and/or sintering can be reduced or inhibited occur when the catalyst 22 is subjected to

the reaction conditions. The method can further include isolating, separating and/or storing

the produced product mixture.

[0055] In a particularly preferred embodiment, a method for producing alkyl aromatic

hydrocarbons is described. The method can include contacting any one of the catalysts

described above or throughout the specification with an aromatic hydrocarbon and an olefin

in a reaction zone under reaction conditions sufficient to produce an alkyl aromatic

compound. Reaction conditions can include a temperature of about 150 °C to about 400 °C,

a pressure of about 5 bar to 70 bar and/or a gas hourly space velocity (GHSV) ranging from

about 1000 to about 100,000 h 1 . In preferred aspects, the catalyst can be contacted with

benzene and ethylene to produce ethylbenzene, or the catalyst can be contacted with benzene

and propylene to produce cumene.

[0056] The hollow zeolites of the present invention can be used in a system for

production of chemical products (e.g., ethylbenzene, cumene, etc.). The system can include

an inlet for a reactant feed, a reaction zone that is configured to be in fluid communication

with the inlet, and an outlet configured to be in fluid communication with the reaction zone

and configured to remove a product stream from the reaction zone. The reaction zone can

include the hollow zeolite particle of the present invention described above and in the

Example section. The reaction zone can be a continuous flow reactor selected from a fixed-

bed reactor, a fluidized reactor, or a moving bed reactor. In some embodiments, the system is

a fluid catalytic cracking system (FCC) or an alkylation reaction system (e.g., to produce

ethylbenzene from benzene and ethylene or to produce cumene from benzene and propylene).

EXAMPLES

[0057] The present invention will be described in greater detail by way of specific

examples. The following examples are offered for illustrative purposes only, and are not

intended to limit the invention in any manner. Those of skill in the art will readily recognize

a variety of noncritical parameters, which can be changed or modified to yield essentially the

same results.

Example 1(Synthesis of Hollow FAU 13X Type Zeolite Material)

[0058] 13X zeolite (Sigma-Aldrich®) was calcined at 500 °C under air to remove the

H4+ cation and produce the activated (protonated) zeolite. The activated 13X zeolite ( 1 g)

was dispersed with tetramethyl ammonium hydroxide (TMAOH, 12 mL, AZ® 326 MIF

developer, Microchemical, GmbH, Germany). The mixture was transferred into Teflon-lined

autoclave and heated at 100 °C under static conditions for 5 days. The material was

recovered by centrifugation and washed 3 times with water to remove the excess of template

and sodium hydroxide by-product. After drying the material at 100 °C under air for 10 h, the

zeolite was calcined 6 h at 500 °C under air to remove the tetramethyl ammonium material

trapped into the zeolite pore.

Example 2(Characterization of Hollow FAU 13X Type Zeolite Material)

[0059] X-ray diffraction (XRD): XRD patterns were collected with Empyrean X-ray

diffractometer from PANalytical (the Netherlands) using a nickel-filtered CuKa X-ray

source, a convergence mirror and a PIXcelld detector. The scanning rate was 0.01 degrees

over the range between 5 degrees and 80 degrees at 2 theta (Θ) . FIG. 5 shows XRD

diffraction patterns of the comparative FAU-13X type zeolite (top) and hollow FAU-13X

type zeolite of the present invention (bottom). From comparison of the two patterns it was

determined that the crystal structure remained intact and that the relative peak intensities of

the 2 patterns were different. The difference in peak intensities was attributed to a de-

alumination process that occurred during the synthesis of the hollow zeolite.

[0060] Isothermal Analysis: Nitrogen adsorption/desorption isotherms of comparative

calcined FAU-13X type zeolite and hollow FAU-13X type zeolite of the present invention

were collected at 77 K using a Micromeritics® ASAP 2010 instrument (Micromeritics®,

USA) were obtained. Before the measurement, approximately 100 mg of sample was

degassed under vacuum (10 6 bar) at 350 °C for 10 hours. FIG. 6 shows the N2 Isotherm of

the comparative calcined FAU-13X type zeolite (top curves) and hollow FAU-13X type

zeolite of the present invention (bottom curves). From comparison of the data, it was

determined that the surface area of the FAU-13X type zeolite of the present invention

decreased. This decrease was attributed to the de-alumination during the synthesis process.

Hysteresis of FAU-13X type zeolite of the present invention at about 0.48 to 0.5 P/P0 small

hysteresis was observed, which is in agreement with the formation of an intra-particle hollow

space in the zeolite.

CLAIMS

A hollow zeolite particle having a zeolite type framework peripheral shell that defines

and encloses an intra-particle hollow space within the interior of the shell, with the

proviso that the peripheral shell does not have a MFI-type framework.

The hollow zeolite particle of claim 1, having a FAU X-type or Y-type structure

peripheral shell.

The hollow zeolite particle of claim 2, having a FAU X-type structure peripheral

shell.

The hollow zeolite particle of claim 3, wherein the FAU X-type structure peripheral

shell is a 13X-type structure peripheral shell.

The hollow zeolite particle of claim 4, characterized by an X-ray diffraction (XRD)

pattern shown in FIG. 5 .

The hollow zeolite particle of any one of claims 1 to 5, having a surface area of 140

cm3/g to 600 cm3/g.

The hollow zeolite particle of any one of claims 1 to 6, comprising at least a second

intra-particle hollow space within the interior of the shell.

The hollow zeolite particle of any one of claims 1 to 7, having a diameter of 10

nanometers to 450 nanometers.

The hollow zeolite particle of claim 8, wherein the intra-particle hollow space has a

diameter of 50% to 80% of the diameter of the particle.

The hollow zeolite particle of any one of claims 1 to 9, wherein the zeolite framework

type peripheral shell comprises pores having a diameter of 2 nanometers or less,

preferably 0.1 nanometers to 0.5 nanometers.

The hollow zeolite particle of any one of claims 1 to 10, wherein the thickness of the

zeolite framework type peripheral shell is 5 nanometers to 20 nanometers.

The hollow zeolite particle of any one of claims 1 to 11, further comprising a catalytic

metal or oxide thereof.

13. The hollow zeolite particle of claim 12, wherein the catalytic metal or oxide thereof is

positioned in the intra-particle hollow space, on the surface of the shell, embedded in

the shell or any combination thereof.

14. The hollow zeolite particle of any one of claims 12 to 13, wherein the catalytic metal

or metal oxide is a Column 1 metal, a Column 2 metal, a transition metal, a post-

transition metal, a lanthanide metal, or any alloy or combination thereof.

15. A method of making the hollow zeolite particle of any one of claims 1 to 14, the

method comprising:

a) obtaining a synthesis mixture of a protonated zeolite and a templating agent; and

b) heat treating the synthesis mixture to form a zeolite framework type structure

peripheral shell that defines and encloses an intra-particle hollow space within

the interior of the shell.

16. The method of claim 15, wherein the templating agent is a quaternary or a tertiary

ammonium compound or a salt thereof, preferably tetramethylammonium hydroxide.

17. The method of any one of claims 15 to 16, wherein the templating agent is metal free.

18. The method of any one of claims 25 to 17, wherein heat treating the synthesis mixture

comprises:

(i) heating the synthesis mixture to obtain a crystalline material; and

(ii) calcining the crystalline material.

19. A method of using the hollow zeolite particle of any one of claims 1 to 14 in a

chemical reaction, the method comprising:

a) contacting the hollow zeolite particle of any one of claims 1 to 14 with a

reactant feed to catalyze a chemical reaction; and

b) producing a product feed.

20. The method of claim 19, wherein the chemical reaction is an alkylation reaction

comprising contacting the hollow zeolite particle of any one of claims 1 to 14 with an

aromatic hydrocarbon and an olefin in a reaction zone under reaction conditions

sufficient to produce the alkyl aromatic compound, preferably wherein (a) the alkyl

aromatic compound is ethylbenzene, the aromatic hydrocarbon is benzene, and the

olefin is ethylene or (b) the alkyl aromatic compound is cumene, the aromatic

hydrocarbon is benzene, and the olefin is propylene.

A . CLASSIFICATION O F SUBJECT MATTERINV. B01J29/08 B01J29/10 B01J29/12 B01J29/14 B01J35/00

B01J35/10 B01J29/06 C01B39/02 C01B39/20 C07C2/66C07C15/02 B01J35/02

According to International Patent Classification (IPC) or to both national classification and IPC

B . FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols)

B01J C01B C07C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal

C. DOCUMENTS CONSIDERED TO B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

VALTCHEV V ET AL: " Layer-by- 1ayer 1-18preparati on of zeol i t e coati ngs ofnanosi zed crystal s " ,MICROPOROUS AND MES0P0R0US MATERIALS,ELSEVI ER, AMSTERDAM, NL,vol . 43 , no. 1, 1 March 2001 (2001-03-01) ,pages 41-49 , XP004317682 ,ISSN : 1387-1811 , D0I :10. 1016/51387-1811 (00)00345-0abstractpar. 2 . " Experimental "

-/-

X| Further documents are listed in the continuation of Box C. See patent family annex.

* Special categories of cited documents :"T" later document published after the international filing date or priority

date and not in conflict with the application but cited to understand"A" document defining the general state of the art which is not considered the principle or theory underlying the invention

to be of particular relevance

"E" earlier application or patent but published o n or after the international "X" document of particular relevance; the claimed invention cannot befiling date considered novel or cannot be considered to involve an inventive

"L" documentwhich may throw doubts on priority claim(s) orwhich is step when the document is taken alonecited to establish the publication date of another citation or other "Y" document of particular relevance; the claimed invention cannot bespecial reason (as specified) considered to involve an inventive step when the document is

"O" document referring to an oral disclosure, use, exhibition or other combined with one o r more other such documents, such combinationmeans being obvious to a person skilled in the art

"P" document published prior to the international filing date but later thanthe priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

19 Apri l 2017 02/05/2017

Name and mailing address of the ISA/ Authorized officer

European Patent Office, P.B. 5818 Patentlaan 2NL - 2280 HV Rijswijk

Tel. (+31-70) 340-2040,Fax: (+31-70) 340-3016 Omegna, Anna

C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

ULI YANG ET AL: " LAYER-BY-LAYER ASSEMBLY 1-20OF NANOZEOLITE BASED ON POLYMERICMICROSPHERE: ZEOLITE COATED SPHERE AND

HOLLOW ZEOLITE SPHERE" ,JOURNAL OF MACROMOLECULAR SCI ENCE , PART A- PURE AND APPLI ED CHEMISTRY. ,vol . 39 , no. 6 , 28 May 2002 (2002-05-28) ,pages 509-526, XP055360096,US

ISSN : 1060-1325 , D0I : 10. 1081/MA-120004244abstractpar. " Introducti on"par. " Experimental "f i gure 8

WANG LEI ET AL: "A faci l e method for the 1-20fabri cati on of IM-5 hol l ow zeol i t e spherei n emul s i on system" ,MICROPOROUS AND MES0P0R0US MATERIALS,vol . 163 , 14 July 2012 (2012-07-14) , pages243-248, XP028936596,ISSN : 1387-1811 , D0I :10. 1016/J .MICR0MES0.2012 .06.032abstractpar. 1 . " Introducti on"par. 2 . " Experimental secti on"f i gures 4,5 , 10tabl e 1

J P 2009 269788 A (TOKYO INST TECH) 1-2019 November 2009 (2009-11-19)c i ted i n the appl i cati onthe whol e document

US 4 546 090 A (OLSON PAUL B [US] ET AL) 1-208 October 1985 (1985-10-08)c i ted i n the appl i cati oncol umn 2 , l i ne 35 - l i ne 47col umn 3 , l i ne 11 - l i ne 16col umn 6 , l i ne 2 1 - l i ne 25exampl e s

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C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

X YI HUANG ET AL: " I n Si t u Crystal l i zati on 1-20of Macroporous Monol i ths wi t h Hol l ow NaPZeol i t e Structure" ,CHEMISTRY OF MATERIALS,vol . 22 , no. 18,28 September 2010 (2010-09-28) , pages5271-5278, XP55365245 ,US

ISSN : 0897-4756, D0I : 10. 1021/cml01408nabstractpar. " Introducti on"par. " Experimental secti on"par. " Resul t s and di scussi on"f i gures 3 , 7 ,8,9

X JIAJUN ZHENG ET AL: "Synthesi s of Hol l ow 1-20Zeol i t e Composi t e Spheres by Usi ng[beta] -Zeol i t e Crystal as Templ ate" ,CHEMISTRY LETTERS,vol . 39 , no. 4 , 5 Apri l 2010 (2010-04-05) ,pages 330-331 , XP55365247 ,JAPANISSN : 0366-7022 , D0I : 10. 1246/cl .2010.330the whol e document

X DANNY VERB0EKEND ET AL: "Hi erarchi cal Y 1-20and USY Zeol i tes Desi gned byPost-Syntheti c Strategi es" ,ADVANCED FUNCTIONAL MATERIALS,vol . 22 , no. 5 , 7 March 2012 (2012-03-07) ,pages 916-928, XP055116922 ,ISSN : 1616-301X, D0I :10. 1002/adfm. 201102411abstractpar. 2 . 6 .par. 2 . 6 "Hi erarchi cal USY Zeol i tes"para 2 . 7 . "Strategi es for the Preparati onof Hi erarchi cal FAU"para 4 . " Experimental secti on"tabl e 3f i gure 11

A CHENGYI DAI ET AL: "Synthesi s of Hol l ow 1-20Nanocubes and Macroporous Monol i ths ofSi l i cal i te-1 by Al kal i ne Treatment" ,CHEMISTRY OF MATERIALS,vol . 25 , no. 21 ,12 November 2013 (2013-11-12) , pages4197-4205 , XP055360137 ,US

ISSN : 0897-4756, D0I : 10. 1021/cm401739eabstractpar. " Experimental secti on"f i gures

-/--

C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

WANG ET AL: "Hol l ow TS-1 crystal s formed 1-20v i a a d i ssol uti on-recrystal 1i zati onprocess " ,MICROPOROUS AND MESOPOROUS MATERIALS,ELSEVI ER, AMSTERDAM, NL,vol . 102 , no. 1-3 ,21 Apri l 2007 (2007-04-21) , pages 80-85 ,XP022042308,ISSN : 1387-1811 , D0I :10. 1016/J .MICROMESO. 2006. 12 .019abstractpar. 2 . " Experimental "f i gures

Patent document Publication Patent family Publicationcited in search report date member(s) date

JP 2009269788 19-11-2009 NONE

US 4546090 A 08-10-1985 NONE