Hydrodesulfurization catalyst for diesel oil and hydrotreating method for diesel oil

Patent metadata

Field	Value
Publication number	US-9987622-B2
Application number	US-201414779479-A
Country	US
Kind code	B2
Filing date	Mar 3, 2014
Priority date	Mar 25, 2013
Publication date	Jun 5, 2018
Grant date	Jun 5, 2018

Abstract

A hydrodesulfurization catalyst supports one or more metals selected from elements in Group 6 of the Periodic table, one or more metals selected from elements in Group 9 or Group 10 of the same, phosphorus, and an organic acid on a composite oxide support having a specific content of both alumina and HY zeolite having a specific crystallite size. The catalyst includes 10% to 40% by mass of the Group 6 metal, 1% to 15% by mass of the Group 9 or Group 10 metal, and 1.5% to 8% by mass of phosphorus in terms of an oxide based on the catalyst. The catalyst includes 0.8% to 7% by mass of carbon derived from an organic acid and for 1 mole of the Group 9 or Group 10 element metal in terms of an element based on the catalyst, and includes 0.2 to 1.2 moles of the organic acid.

First claim

The invention claimed is:

1. A hydrodesulfurization catalyst for diesel oil which supports one or more metals selected from the group consisting of elements in Group 6 of the long periodic table, one or more metals selected from the group consisting of elements in Group 9 or 10 of the long periodic table, phosphorus, and an organic acid on a composite oxide support containing 80% by mass to 99.5% by mass of alumina, and 0.5% by mass to 20% by mass of HY zeolite, the catalyst comprising:
10% by mass to 40% by mass of one or more metals selected from the group consisting of elements in Group 6 in terms of an oxide based on the catalyst;
1% by mass to 15% by mass of one or more metals selected from the group consisting of elements in Group 9 or 10 in terms of an oxide based on the catalyst;
1.5% by mass to 8% by mass of phosphorus in terms of an oxide based on the catalyst;
0.8% by mass to 7% by mass of carbon derived from the organic acid in terms of an element based on the catalyst; and
0.2 moles to 1.2 moles of the organic acid per 1 mole of one or more metals selected from the group consisting of elements in Group 9 or 10 of the long periodic table,
wherein a specific surface area measured by a nitrogen adsorption method is from 110 m 2 /g to 300 m 2 /g,
a pore volume measured by a mercury penetration method is from 0.3 ml/g to 0.6 ml/g,
an average pore diameter measured by a mercury penetration method is from 6.5 nm to 14 nm, and
the HY zeolite has (a) a SiO 2 /Al 2 O 3 (molar ratio) of 3 to 10, (b) a crystal lattice constant of 2.435 nm to 2.465 nm, (c) a molar ratio of Al in the zeolite framework to total Al of 0.2 to 0.9, and (d) a crystallite diameter of 30 nm to 100 nm.

2. A hydrotreating method for diesel oil comprising:
subjecting a diesel oil fraction to a catalytic reaction under the presence of the hydrodesulfurization catalyst according to claim 1 .

3. A method for producing a hydrodesulfurization catalyst, wherein the method comprises impregnating a composite oxide support containing 80% by mass to 99.5% by mass of alumina, and 0.5% by mass to 20% by mass of HY zeolite with a solution containing one or more metals selected from the group consisting of elements in Group 6 of the long periodic table, one or more metals selected from the group consisting of elements in Group 9 or 10 of the long periodic table, phosphorus, and an organic acid, followed by drying at a temperature of 200° C. or lower,
wherein the hydrodesulfurization catalyst supports the one or more metals and wherein the hydrodesulfurization catalyst comprises:
10% by mass to 40% by mass of one or more metals selected from the group consisting of elements in Group 6 in terms of an oxide based on the catalyst;
1% by mass to 15% by mass of one or more metals selected from the group consisting of elements in Group 9 or 10 in terms of an oxide based on the catalyst;
1.5% by mass to 8% by mass of phosphorus in terms of an oxide based on the catalyst;
0.8% by mass to 7% by mass of carbon derived from the organic acid in terms of an element based on the catalyst; and
0.2 moles to 1.2 moles of the organic acid per 1 mole of one or more metals selected from the group consisting of elements in Group 9 or 10 of the long periodic table,
wherein a specific surface area measured by a nitrogen adsorption method is from 110 m 2 /g to 300 m 2 /g,
a pore volume measured by a mercury penetration method is from 0.3 ml/g to 0.6 ml/g,
an average pore diameter measured by a mercury penetration method is from 6.5 nm to 14 nm, and
wherein the HY zeolite has (a) a SiO 2 /Al 2 O 3 (molar ratio) of 3 to 10, (b) a crystal lattice constant of 2.435 nm to 2.465 nm, (c) a molar ratio of Al in the zeolite framework to total Al of 0.2 to 0.9, and (d) a crystallite diameter of 30 nm to 100 nm.

Assignees

• Cosmo Oil Co Ltd

Inventors

• Nakajima Nobumasa
• Hashimoto Minoru
• YOSHINARI Motoki
• Fujikawa Takashi

Classifications

• B01J2231/70

  Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues · CPC title

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title

• B01J31/34

  of chromium, molybdenum or tungsten · CPC title

• B01J2231/645

  of C=C or C-C triple bonds · CPC title

• B01J2229/186

  not in framework positions · CPC title