# US 2013/0153467 A1 · Hydrodesulfurization catalyst for hydrocarbon oil, process of producing same and method for hydrorefining

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- Number: US 2013/0153467 A1
- Document ID: US20130153467A1
- Status: Published application
- Kind: A1
- Application number: 13/805,739
- Filed: 2011-06-21
- Published: 2013-06-20
- Earliest claimed: 2010-06-25
- Assignees: JGC Catalysts and Chemicals Ltd.; Jx Nippon Oil & Energy Corporation
- Inventors: Hiroyuki Seki; Masanori Yoshida; Shogo Tagawa; Tomoyasu Kagawa
- Web page: https://patentgrep.com/patent/US20130153467A1

## CPC

- B01J 27/051: Molybdenum
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 21/12: Silica and alumina
- B01J 23/882: and cobalt
- B01J 27/19: Molybdenum
- B01J 37/0045: {Drying a slurry, e.g. spray drying}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/20: Sulfiding
- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 2300/1059: Gasoil having a boiling range of about 330 - 427 °C
- C10G 2300/1074: Vacuum distillates
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- 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

## Abstract

A hydrodesulfurization catalyst is produced by pre-sulfurizing a hydrodesulfurization catalyst Y including a support containing silica, alumina and titania and at least one metal component supported thereon and selected from VIA and VIII groups of the periodic table (comprising at least Mo), in which the total area of the diffraction peak area indicating the crystal structure of anatase titania (101) planes and the diffraction peak area indicating the crystal structure of rutile titania (110) planes in the support, measured by X-ray diffraction analysis being ¼ or less of the alumina diffraction peak area assigned to γ-alumina (400) planes. The molybdenum is formed into molybdenum disulfide crystal disposed in layers on the support by the pre-sulfurization, and having an average length of longer than 3.5 nm and 7 nm or shorter in the plane direction and an average number of laminated layers of more than 1.0 and 1.9 or fewer.

## Claims

### Claim 1

A hydrodesulfurization catalyst for hydrocarbon oils, comprising a hydrodesulfurization catalyst Y comprising a support containing silica, alumina and titania and at least one type of metal component supported thereon and selected from VIA and VIII groups of the periodic table, the catalyst Y being pre-sulfurized,
the total area (titania diffraction peak area) of the diffraction peak area indicating the crystal structure of anatase titania (101) planes and the diffraction peak area indicating the crystal structure of rutile titania (110) planes in the support, measured by X-ray diffraction analysis being ¼ or less of the diffraction peak area (alumina diffraction peak area) indicating the aluminum crystal structure assigned to γ-alumina (400) planes,
the metal component comprising at least molybdenum,
the molybdenum being formed into molybdenum disulfide crystal and disposed in layers on the support by the pre-sulfurization and the molybdenum disulfide crystal layers having an average length of longer than 3.5 nm and 7 nm or shorter in the plane direction and an average number of laminated layers of more than 1.0 and 1.9 or fewer.

### Claim 2 (depends on 1)

A hydrodesulfurization catalyst according to claim 1, wherein the support contains silica in the form of SiO2 in an amount of 1 to 10 percent by mass, titania in the form of TiO2 in an amount of 3 to 40 percent by mass and alumina in the form of Al2O3 in an amount of 50 percent by mass or more.

### Claim 3 (depends on 1)

A hydrodesulfurization catalyst according to claim 1, wherein the content of the metal component is from 1 to 35 percent by mass on the hydrodesulfurization catalyst Y prior to the pre-sulfurization basis, and the content of the molybdenum is from 1 to 25 percent by mass in the form of MoO3 on the hydrodesulfurization catalyst Y prior to the pre-sulfurization basis.

### Claim 4 (depends on 1)

A hydrodesulfurization catalyst according to claim 1, wherein said pre-sulfurization is carried out by contacting the hydrodesulfurization catalyst Y with a mix oil of a hydrocarbon oil and a sulfating agent or hydrogen sulfide at a temperature of 200 to 400° C.

### Claim 5

A process of producing a hydrodesulfurization catalyst for hydrocarbon oil, comprising:
(1) a first step of mixing a basic aluminum salt aqueous solution and a mixed aqueous solution of a titanium mineral acid salt and an acidic aluminum salt in the presence of silicate ion so that the pH is from 6.5 to 9.5 to produce a hydrate;
(2) a second step of producing a support by washing, extruding, drying and calcining the hydrate in turn;
(3) a third step of contacting the support with an impregnating solution containing at least one type of metal component selected from VIA and VIII groups of the periodic table (provided that molybdenum is indispensably contained) and a chelating agent;
(4) a fourth step of drying the support with the metal supported thereon, produced by contacting the support with the impregnating solution to produce a hydrodesulfurization catalyst Y; and
(5) a fifth step of pre-sulfurizing the hydrodesulfurization catalyst Y,
the total area (titania diffraction peak area) of the diffraction peak area indicating the crystal structure of anatase titania (101) planes and the diffraction peak area indicating the crystal structure of rutile titania (110) planes in the support, measured by X-ray diffraction analysis being ¼ or less of the diffraction peak area (alumina diffraction peak area) indicating the aluminum crystal structure assigned to γ-alumina (400) planes,
the molybdenum being formed into molybdenum disulfide crystal and disposed in layers on the support by the pre-sulfurization, and the molybdenum disulfide crystal layers having an average length of longer than 3.5 nm and 7 nm or shorter in the plane direction and an average number of laminated layers of more than 1.0 and 1.9 or fewer,
the impregnating solution having a peak intensity in the range of 940 to 950 cm−1 2.5 times or more of the peak intensity in the range of 890 to 910 cm−1 in the Raman spectrum.

### Claim 6 (depends on 5)

A process of producing a hydrodesulfurization catalyst according to claim 5, wherein the pre-sulfurization of the fifth step is carried out by contacting the hydrodesulfurization catalyst Y with a mix oil of a hydrocarbon oil and a sulfating agent or hydrogen sulfide at a temperature of 200 to 400° C.

### Claim 7 (depends on 5)

A process of producing a hydrodesulfurization catalyst according to claim 5, wherein said impregnating solution further contains a phosphoric compound.

### Claim 8 (depends on 5)

A process of producing a hydrodesulfurization catalyst according to claim 5, wherein said chelating agent is citric acid or malic acid.

### Claim 9 (depends on 1)

A method for hydrorefining a hydrocarbon oil comprising hydrotreating a hydrocarbon oil under a hydrogen atmosphere using the hydrodesulfurization catalyst according to claim 1.

### Claim 10 (depends on 9)

A method for hydrorefining hydrocarbon oils according to claim 9, wherein said hydrocarbon oil is selected from the group consisting of straight-run gas oil, vacuum gas oil, light cycle oil, hydrocracked gas oil, and thermal-cracked gas oil.

### Claim 11 (depends on 9)

A method for hydrorefining hydrocarbon oils according to claim 9, wherein the oil produced from the hydrotreating of a hydrocarbon oil has a sulfur content of 10 ppm by mass or less and a nitrogen content of 3 ppm by mass or less.

### Claim 12 (depends on 9)

A method for hydrorefining hydrocarbon oils according to claim 9, wherein the reaction pressure is from 1 to 12 MPa, the liquid-space velocity is from 0.1 to 4.0 h−1, the hydrogen/oil ratio is from 80 to 500 NL/L and the reaction temperature is from 250 to 400° C.