# US 9,518,232 B2 · Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oil

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- Number: US 9,518,232 B2
- Document ID: US9518232B2
- Status: Granted
- Kind: B2
- Application number: 12/865,921
- Filed: 2009-02-04
- Published: 2011-02-24
- Granted: 2016-12-13
- Earliest claimed: 2008-02-08
- Assignees: Jx Nippon Oil & Energy Corporation
- Applicants: Kazuaki Hayasaka
- Inventors: Kazuaki Hayasaka
- Web page: https://patentgrep.com/patent/US9518232B2

## CPC

- C10G 45/64: containing crystalline alumino-silicates, e.g. molecular sieves
- B01J 29/064: containing iron group metals, noble metals or copper
- B01J 29/068: Noble metals
- B01J 29/076: containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J 29/7284: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 29/7484: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 29/7884: {TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22}
- B01J 37/0009: {Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst}
- C01B 39/48: using at least one organic template directing agent
- B01J 29/7461: {MRE-type, e.g. ZSM-48}
- B01J 29/7492: {MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13}
- B01J 29/7861: {MRE-type, e.g. ZSM-48}
- B01J 29/7892: {MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13}
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/55: Cylinders or rings
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 2229/186: not in framework positions
- B01J 2229/20: to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
- B01J 2229/40: Special temperature treatment, i.e. other than just for template removal
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C10G 2300/1022: Fischer-Tropsch products
- C10G 2300/1085: Solid paraffins
- C10G 2400/10: Lubricating oil
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

A hydroisomerization catalyst of the present invention is obtained by calcining a catalyst composition containing an ion-exchanged molecular sieve or a calcined product thereof, and at least one metal selected from the group consisting of metals of Groups 8 to 10 in Periodic Table of the elements, molybdenum and tungsten, carried on the ion-exchanged molecular sieve or the calcined product thereof, wherein the ion-exchanged molecular sieve is obtained by ion-exchanging a molecular sieve, which includes nanocrystals having a pore structure of ten-membered rings or eight-membered rings and having a ratio of the pore volume to the external surface area ([pore volume]/[external surface area]) of 2.0×10−4 mL/m2 to 8.0×10−4 mL/m2 and contains an organic template, in a solution containing a cationic species.

## Claims

### Claim 1

A hydroisomerization catalyst, obtained by calcining a catalyst composition comprising a calcined and ion-exchanged molecular sieve and at least one metal selected from the group consisting of metals of Groups 8to 10in the Periodic Table of the elements, molybdenum, and tungsten, carried on the calcined and ion-exchanged molecular sieve, wherein
the calcined and ion-exchanged molecular sieve is obtained by ion-exchanging a molecular sieve comprising an organic template in a solution containing water as a main solvent and a cationic species to remove a part of the organic template and calcining the molecular sieve comprising an organic template to remove another part of the organic template, and
the molecular sieve comprising an organic template has a nanocrystal having a pore structure of ten-membered rings or eight-membered rings and has a ratio of the pore volume to the external surface area ([pore volume][external surface area]) of 2.0×104 mL/m2 to 8.0×10−4 mL/m2.

### Claim 2 (depends on 1)

The hydroisomerization catalyst according to claim 1, wherein the molecular sieve comprising an organic template is ZSM-22, ZSM-23, or ZSM-48 type zeolite.

### Claim 3 (depends on 1)

The hydroisomerization catalyst according to claim 1, wherein the calcined and ion-exchanged molecular sieve is obtained by ion-exchanging the molecular sieve comprising an organic template in the presence of ammonium ions or protons.

### Claim 4 (depends on 1)

The hydroisomerization catalyst according to claim 1, wherein the calcined and ion-exchanged molecular sieve is obtained by ion-exchanging the molecular sieve comprising an organic template by replacing the solution with a new one once or more.

### Claim 5 (depends on 1)

The hydroisomerization catalyst according to claim 1, wherein the catalyst composition comprises platinum and/or palladium carried on the calcined and ionexchanged molecular sieve.

### Claim 6 (depends on 1)

The hydroisomerization catalyst according to claim 1, obtained by calcining the catalyst composition in an atmosphere containing molecular oxygen, and thereafter, reducing the calcined composition in an atmosphere containing molecular hydrogen.

### Claim 7 (depends on 1)

The hydroisomerization catalyst according to claim 1, wherein the catalyst composition comprises 1 part by mass to 90 parts by mass of the calcined and ionexchanged molecular sieve and 99 parts by mass to 10 parts by mass of at least one porous oxide selected from the group consisting of alumina, silica, titania, boria, magnesia and zirconia.

### Claim 8 (depends on 1)

The hydroisomerization catalyst according to claim 1, wherein the catalyst composition comprises:
a carrier obtained by calcining a carrier composition comprising 1 part by mass to 90 parts by mass of the calcined and ion-exchanged molecular sieve and 99 parts by mass to 10 parts by mass of at least one porous oxide selected from the group consisting of alumina, silica, titania, boria, magnesia and zirconia; and
the metal carried on the carrier.

### Claim 9

A hydroisomerization catalyst, obtained by calcining a catalyst composition comprising a calcined and ion-exchanged molecular sieve and at least one metal selected from the group consisting of metals of Groups 8 to 10 in the Periodic Table of the elements, molybdenum, and tungsten, carried on the calcined and ion-exchanged molecular sieve, wherein
the calcined and ion-exchanged molecular sieve, is obtained by ion-exchanging a molecular sieve comprising an organic template in a solution containing water as a main component and a cationic species and calcining the molecular sieve comprising an organic template, and
the molecular sieve comprising an organic template has a nanocrystal having a pore structure of ten-membered rings or eight-membered rings and has a ratio of the pore volume to the external surface area ([pore volume]/[external surface area]) of 2.0×10−4 mL/m2 to 8.0×10−mL/m2.

### Claim 10 (depends on 1)

A method for dewaxing a hydrocarbon oil, comprising bringing the hydrocarbon oil containing normal paraffins having 10 or more carbon atoms into contact with the hydroisomerization catalyst according to claim 1 in the presence of hydrogen to convert a part of or the whole of the normal paraffins into isoparaffins.

### Claim 11 (depends on 10)

the method for dewaxing a hydrocarbon oil according to claim 10, wherein the hydrocarbon oil is at least one selected from the group consisting of slack wax, deoiled wax, paraffin wax, microcrystalline wax, petrolatum, and wax from Fischer-Tropsch synthesis.

### Claim 12 (depends on 1)

A method for manufacturing a lube-oil base oil, comprising a step of bringing a hydrocarbon oil containing normal paraffins having 10 or more carbon atoms into contact with the hydroisomerization catalyst according to claim 1, in the presence of hydrogen under the condition of a conversion of the normal paraffins of substantially 100% by mass, the conversion being defined by the formula (I) described below:
Conversion of normal paraffins (%) =[1−(total mass % of normal paraffins having Cn or more carbon atoms contained in a hydrocarbon oil after the contact)/(total mass % of normal paraffins having Cn or more carbon atoms contained in the hydrocarbon oil before the contact)]×100 (I)
wherein Cn denotes a minimum number of carbon atoms of normal paraffins having 10 or more carbon atoms contained in the hydrocarbon oil before the contact.