(12) international application published under … · *bea type structure, a lta type structure, a...
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(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 "
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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
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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.
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