# US 9,040,449 B2 · Platinum-free monometallic and bimetallic nanoparticles as ring-opening catalysts

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- Number: US 9,040,449 B2
- Document ID: US9040449B2
- Status: Granted
- Kind: B2
- Application number: 13/748,370
- Filed: 2013-01-23
- Published: 2013-09-26
- Granted: 2015-05-26
- Earliest claimed: 2012-03-22
- Assignees: The Governors of the University of Alberta
- Applicants: Governors of the University of Alberta
- Inventors: Natalia Semagina; Xing Yin; Jing Shen; Kavithaa Loganathan
- Web page: https://patentgrep.com/patent/US9040449B2

## CPC

- B01J 23/468: {Iridium}
- B01J 21/04: Alumina
- B01J 23/462: {Ruthenium}
- B01J 23/464: {Rhodium}
- B01J 23/64: with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 23/6567: {Rhenium}
- B01J 23/892: {Nickel and noble metals}
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/397: {Egg shell like}
- B01J 35/45: Nanoparticles
- B01J 35/53: with a core-shell structure
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/0211: {using a colloidal suspension}
- B01J 37/18: with gases containing free hydrogen
- C10G 45/60: characterised by the catalyst used
- C10G 45/62: containing platinum group metals or compounds thereof
- B01J 23/44: Palladium
- B01J 35/23: in a colloidal state
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- Y10S 977/773: Nanoparticle, i.e. structure having three dimensions of 100 nm or less
- Y10S 977/81: Of specified metal or metal alloy composition
- Y10S 977/892: Liquid phase deposition
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Nanoparticle catalyst compositions and methods for preparation of same are described. The nanoparticle catalysts are platinum-free and are useful in effecting selective ring-opening reactions, for example in upgrading heavy oil. The catalyst may be of monometallic composition, or may comprise an alloyed or core-shell bimetallic composition. The nanoparticles are of controlled size and shape.

## Claims

### Claim 1

A bi-metallic nanoparticle ring-opening catalyst composition comprising:
a plurality of monodispersed bimetallic nanoparticles, each of the monodispersed nanoparticles having a size between 1-5 nm in diameter, and each of the monodispersed bimetallic nanoparticles comprising:
a primary non-platinum transition metal having ring-opening catalytic activity; and
a secondary transition metal.

### Claim 2 (depends on 1)

The ring-opening catalyst composition as in claim 1, further comprising a capping agent.

### Claim 3 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the primary non-platinum transition metal has suitable activity and selectivity in catalyzing single-cleavage ring-opening reactions.

### Claim 4 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the primary non-platinum transition metal is a metal selected from the group consisting of: palladium, ruthenium, rhodium, iridium, and rhenium.

### Claim 5 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the primary non-platinum transition metal is iridium.

### Claim 6 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the secondary transition metal is a catalytically active transition metal.

### Claim 7 (depends on 6)

The bimetallic nanoparticle ring-opening catalyst as in claim 6, wherein the secondary transition metal has ring-opening catalytic activity.

### Claim 8 (depends on 6)

The bimetallic nanoparticle ring-opening catalyst as in claim 6, wherein the secondary transition metal is a hydrodesulfurization catalyst.

### Claim 9 (depends on 6)

The bimetallic nanoparticle ring-opening catalyst as in claim 6, wherein the secondary transition metal is a hydrogenation catalyst.

### Claim 10 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the secondary transition metal is a readily available, catalytically inactive transition metal.

### Claim 11 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the secondary transition metal is a metal selected from the group consisting of: palladium, nickel, ruthenium, rhenium, and rhodium.

### Claim 12 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the secondary transition metal is palladium.

### Claim 13 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the secondary transition metal is nickel.

### Claim 14 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the nanoparticle is an alloy of the primary and secondary metal.

### Claim 15 (depends on 14)

The bimetallic nanoparticle ring-opening catalyst as in claim 14, wherein the primary non-platinum transition metal is iridium and the secondary metal is palladium.

### Claim 16 (depends on 14)

The bimetallic nanoparticle ring-opening catalyst as in claim 14, wherein the primary non-platinum transition metal is selected from the group consisting of: iridium, palladium, ruthenium, rhodium, and rhenium; and wherein the secondary metal is a different metal than the primary metal, and is selected from the group consisting of: palladium, ruthenium, rhenium, and rhodium.

### Claim 17 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the nanoparticle comprises a core-shell structure, and wherein the secondary metal comprises the nanoparticle core and the primary non-platinum transition metal comprises the nanoparticle shell.

### Claim 18 (depends on 17)

The bimetallic nanoparticle ring-opening catalyst as in claim 17, wherein the primary non-platinum transition metal is iridium and the secondary metal is palladium.

### Claim 19 (depends on 17)

The bimetallic nanoparticle ring-opening catalyst as in claim 17, wherein the primary non-platinum transition metal is iridium and the secondary metal is nickel.

### Claim 20 (depends on 17)

The bimetallic nanoparticle ring-opening catalyst as in claim 17, wherein the primary non-platinum transition metal is selected from the group consisting of: iridium, palladium, ruthenium, rhodium, and rhenium; and wherein the secondary metal is a different metal than the primary metal, and is selected from the group consisting of: palladium, nickel, ruthenium, rhenium, and rhodium.

### Claim 21 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, wherein the nanoparticle comprises a stabilizing agent.

### Claim 22 (depends on 21)

The bimetallic nanoparticle ring-opening catalyst as in claim 21, wherein the stabilizing agent is polyvinylpyrrolidone.

### Claim 23 (depends on 1)

The bimetallic nanoparticle ring-opening catalyst as in claim 1, further comprising a support loaded with the nanoparticles.

### Claim 24 (depends on 23)

The bimetallic nanoparticle ring-opening catalyst as in claim 23, wherein the support is gamma-alumina.

### Claim 25 (depends on 23)

The bimetallic nanoparticle ring-opening catalyst as in claim 23, wherein the support is gamma-alumina having a minimum pore size of at least 5 nm.

### Claim 26

A monometallic ring-opening catalyst composition comprising:
a plurality of monodispersed nanoparticles, each of the monodispersed nanoparticles having a size between 1-5 nm in diameter, each of the monodispersed nanoparticles comprising a primary non-platinum transition metal having ring-opening catalytic activity; and
a support having a minimum pore size of at least 5 nm.

### Claim 27 (depends on 26)

The monometallic ring-opening catalyst composition as in claim 26, further comprising a stabilizing agent.

### Claim 28 (depends on 27)

The monometallic ring-opening catalyst composition as in claim 27, wherein the stabilizing agent is polyvinylpyrrolidone.

### Claim 29 (depends on 26)

The monometallic ring-opening catalyst composition as in claim 26, wherein the support is gamma-alumina.

### Claim 30 (depends on 26)

The monometallic ring-opening catalyst composition as in claim 26, wherein the primary non-platinum transition metal is selected from the group consisting of: palladium, ruthenium, rhodium, iridium, and rhenium.

### Claim 31 (depends on 26)

The monometallic ring-opening catalyst composition as in claim 26, wherein the primary non-platinum transition metal is iridium.

### Claim 32

A method for forming a platinum-free nanoparticle ring-opening catalyst, the method comprising the steps of:
providing a primary metal precursor and a stabilizing polymer, the primary metal precursor comprising a primary metal having ring-opening catalytic activity;
refluxing the primary metal precursor with the stabilizing polymer to create a colloidal dispersion of a polymer-stabilized primary metal nanoparticle;
adding acetone to the colloidal dispersion to precipitate polymer-stabilized nanoparticles therefrom;
depositing the precipitated nanoparticles onto a support, the support having a minimum pore size of at least 5 nm;
calcining the deposited nanoparticles to remove the stabilizing polymer from the nanoparticles; and
reducing the deposited nanoparticles in a hydrogen-rich environment.

### Claim 33 (depends on 32)

The method as in claim 32, wherein the primary metal is palladium, ruthenium, rhodium, iridium, or rhenium.

### Claim 34 (depends on 32)

The method as in claim 32, wherein the primary metal is iridium.

### Claim 35 (depends on 32)

The method as in claim 32, wherein the stabilizing polymer is polyvinylpyrrolidone.

### Claim 36 (depends on 32)

The method as in claim 32, wherein the support comprises gamma-alumina.

### Claim 37 (depends on 32)

The method as in claim 32, further comprising the step of oven drying the support prior to the step of depositing the precipitated nanoparticles.

### Claim 38 (depends on 37)

The method as in claim 37, wherein the nanoparticles are deposited onto the support by wet impregnation.

### Claim 39

A method for forming a platinum-free nanoparticle ring-opening catalyst, the method comprising the steps of:
providing a secondary metal precursor and a stabilizing polymer;
refluxing the primary metal precursor with the stabilizing polymer to create a colloidal dispersion of a polymer-stabilized secondary metal nanoparticle;
providing a reduced primary metal precursor, the primary metal precursor comprising a primary metal having ring-opening catalytic activity;
reducing and hydrogenating the polymer-stabilized secondary metal nanoparticles;
combining the hydrogenated polymer-stabilized secondary metal nanoparticle with the reduced primary metal precursor in a hydrogen-rich environment to generate polymer-stabilized nanoparticles having a primary metal shell deposited over a secondary metal core;
adding acetone to precipitate the polymer-stabilized nanoparticles;
depositing the polymer-stabilized nanoparticles onto a support having a minimum of at least 5 nm;
calcining the deposited nanoparticles to remove the polymer from the nanoparticles; and
reducing the nanoparticles in a hydrogen-rich environment.

### Claim 40 (depends on 39)

The method as in claim 39, wherein the primary metal is palladium, ruthenium, rhodium, iridium, or rhenium.

### Claim 41 (depends on 39)

The method as in claim 39, wherein the primary metal is iridium.

### Claim 42 (depends on 39)

The method as in claim 39, wherein the secondary metal precursor comprises a secondary metal having catalytic activity.

### Claim 43 (depends on 39)

The method as in claim 39, wherein the secondary metal precursor comprises iridium, palladium, ruthenium, rhenium, rhodium, or nickel.

### Claim 44 (depends on 39)

The method as in claim 39, wherein the primary metal precursor comprises iridium and the secondary metal precursor comprises palladium.

### Claim 45 (depends on 39)

The method as in claim 39, wherein the primary metal precursor comprises iridium and the secondary metal precursor comprises nickel.

### Claim 46 (depends on 39)

The method as in claim 39, wherein the primary metal precursor and the secondary metal precursor are the same.

### Claim 47 (depends on 32)

The method as in claim 32, wherein the stabilizing polymer is polyvinylpyrrolidone.

### Claim 48 (depends on 32)

The method as in claim 32, wherein the support comprises gamma-alumina.

### Claim 49 (depends on 32)

The method as in claim 32, further comprising the step of oven drying the support prior to the step of depositing the precipitated nanoparticles.

### Claim 50 (depends on 37)

The method as in claim 37, wherein the nanoparticles are deposited onto the support by wet impregnation.

### Claim 51

A method for forming a platinum-free nanoparticle ring-opening catalyst, the method comprising the steps of:
refluxing a mixture of a primary metal precursor with a secondary metal precursor and a stabilizing polymer to generate a colloidal dispersion of alloyed nanoparticles, the primary metal precursor comprising a metal having ring-opening catalytic activity;
adding acetone to the colloidal dispersion to precipitate the alloyed nanoparticles therefrom;
depositing the polymer-stabilized bimetallic nanoparticles onto a support having a minimum pore size of at least 5 nm;
calcining the deposited nanoparticles to remove the polymer from the nanoparticles; and
reducing the deposited nanoparticles in a hydrogen-rich environment.

### Claim 52 (depends on 51)

The method as in claim 51, wherein the primary metal is palladium, ruthenium, rhodium, iridium, or rhenium.

### Claim 53 (depends on 51)

The method as in claim 51, wherein the primary metal is iridium.

### Claim 54 (depends on 51)

The method as in claim 51, wherein the secondary metal precursor comprises a secondary metal having catalytic activity.

### Claim 55 (depends on 54)

The method as in claim 54, wherein the secondary metal precursor comprises iridium, palladium, ruthenium, rhenium, or rhodium.

### Claim 56 (depends on 51)

The method as in claim 51, wherein the primary metal precursor comprises iridium and the secondary metal precursor comprises palladium.

### Claim 57 (depends on 51)

The method as in claim 51, wherein the stabilizing polymer is polyvinylpyrrolidone.

### Claim 58 (depends on 51)

The method as in claim 51, wherein the support comprises gamma-alumina.

### Claim 59 (depends on 51)

The method as in claim 51, further comprising the step of oven drying the support prior to the step of depositing the precipitated nanoparticles.

### Claim 60 (depends on 59)

The method as in claim 59, wherein the nanoparticles are deposited onto the support by wet impregnation.

### Claim 61 (depends on 1)

A method for effecting selective cleavage of a naphthenic ring, the method comprising the steps of:
preparing a bimetallic nanoparticle catalyst according to claim 1, including:
refluxing a mixture of a primary metal precursor with a secondary metal precursor and a stabilizing polymer to generate a colloidal dispersion of alloyed nanoparticles, the primary metal precursor comprising a metal having ring-opening catalytic activity;
adding acetone to the colloidal dispersion to precipitate the alloyed nanoparticles therefrom;
depositing the polymer-stabilized bimetallic nanoparticles onto a support having a minimum pore size of at least 5 nm;
calcining the deposited nanoparticles to remove the polymer from the nanoparticles;
reducing the deposited nanoparticles in a hydrogen-rich environment; and
reacting a composition containing naphthenic ring-containing compounds with hydrogen at a temperature greater than 300° C. in the presence of the bimetallic nanoparticle.

### Claim 62 (depends on 61)

The method as in claim 61, further comprising the step of separating the bimetallic nanoparticle from the reaction products.

### Claim 63 (depends on 61)

The method as in claim 61, wherein the composition containing naphthenic ring-containing compounds is a heavy oil fraction.