Type II hydrotreating catalyst for hydrocarbon oil and method for hydrotreating hydrocarbon oil
Hydrotreating catalyst material and/or hydrotreating catalyst particles are provided having at least two hydrotreating metal components and a chelating agent carried on a support. The support comprises an inorganic oxide binder and a post-framework modified ultra-stable Y-type (USY) zeolite in which a portion of aluminum atoms constituting a zeolite framework thereof is substituted with zirconium atoms and/or titanium atoms and/or hafnium atoms. The hydrotreating metal components form a metal complex via the chelating agent, and are carried on said support as chelating complex type II active sites.
1 . A hydrotreating catalyst for hydrotreating middle distillates having a nominal boiling range of about 160-400° C., the hydrotreating catalyst comprising:
one or more hydrotreating metal components and a chelating agent carried on a support, said support comprising an inorganic oxide binder and a post-framework modified ultra-stable Y (USY) zeolite in which a portion of aluminum atoms constituting a zeolite framework thereof is substituted with zirconium atoms and/or titanium atoms and/or hafnium atoms,
wherein the one or more hydrotreating metal components form a metal complex via the chelating agent, and are carried on said support as chelating complex type II active sites,
wherein carbon including carbon content from the chelating agent is present in an amount of at least about 2 weight % of a total mass of said hydrotreating catalyst,
wherein mass loss of the hydrotreating catalyst resulting from heat treatment for 2 hours at 570° C. in atmospheric conditions is greater than about 10 weight % of the total mass of said hydrotreating catalyst prior to the heat treatment; and
wherein the hydrotreating catalyst is sulfided and wherein an amount of nitric oxide adsorption after sulfiding is more than about 10.0 milliliters per gram.
2 . The hydrotreating catalyst as in claim 1 , wherein the one or more hydrotreating metal components comprise sulfides of Mo, W, Co or Ni.
3 . The hydrotreating catalyst of claim 2 , wherein the hydrotreating catalyst comprises at least two hydrotreating metal components including about 0.01-30 weight % of MoS 2 and 0.01-15 weight % of one or more additional hydrotreating metal component, based on the total mass of hydrotreating catalyst.
4 . The hydrotreating catalyst of claim 1 , wherein the post-framework modified USY zeolite comprise two or more of titanium, zirconium and/or hafnium substituting aluminum atoms constituting a zeolite framework of the USY zeolite.
5 . The hydrotreating catalyst of claim 1 , wherein the post-framework modified USY zeolite comprise titanium and zirconium substituting aluminum atoms constituting a zeolite framework of the USY zeolite.
6 . The hydrotreating catalyst of claim 5 , wherein the post-framework modified USY zeolite is substituted with about 0.1-5.0 weight % zirconium atoms, and about 0.1-5.0 weight % titanium atoms, calculated on an oxide basis.
7 . The hydrotreating catalyst of claim 1 , wherein the post-framework modified USY zeolite comprises about 0.01-30 weight % of the total mass of said hydrotreating catalyst.
8 . The hydrotreating catalyst of claim 1 , wherein the one or more hydrotreating metal components comprises about 0.01-40 weight % of the total mass of said hydrotreating catalyst.
9 . The hydrotreating catalyst of claim 1 , wherein the chelating agent is selected from the group consisting of citric acid, maleic acid and ethylenediaminotetraacetic acid (EDTA).
10 . The hydrotreating catalyst of claim 1 , wherein the chelating agent comprises citric acid.
11 . The hydrotreating catalyst of claim 1 , wherein the chelating agent comprises an organic compound having a pKa in a range of about 1-20.
12 . The hydrotreating catalyst of claim 1 , having a specific surface area in a range of about 100-400 m 2 /g; an average pore diameter in a range of about 7.0-15.0 nm; and a pore volume of less than 600 nm diameter pores in a range of about 0.4-1.0 ml/g.
13 . The hydrotreating catalyst of claim 1 , wherein the post-framework modified USY zeolite in the hydrotreating catalyst has: unit cell dimensions (UD) in a range of about 2.425-2.450 nm; a specific surface area in a range of about 600-900 m 2 /g; a pore volume of about 0.3-0.75 ml/g; and wherein the post-framework modified USY zeolite includes SiO 2 and Al 2 O 3 at a molar ratio SiO 2 /Al 2 O 3 in a range of about 5-100.
14 . The hydrotreating catalyst of claim 1 ,
wherein the post-framework modified USY zeolite comprise titanium and zirconium substituting aluminum atoms constituting a zeolite framework of the USY zeolite, wherein the post-framework modified USY zeolite is substituted with about 0.1-5.0 weight % zirconium atoms, and about 0.1-5.0 weight % titanium atoms, calculated on an oxide basis, and wherein the post-framework modified USY zeolite comprises about 0.01-30 weight % of the total mass of said hydrotreating catalyst; and
wherein the one or more hydrotreating metal components comprise 20-30 weight % MoS 2 and 5-10 weight % an additional hydrotreating metal component comprising Co, Ni, oxides of Co, oxides of Ni, sulfides of Co or sulfides of Ni, of the total mass of said hydrotreating catalyst.
15 . A method for hydrotreating hydrocarbon oil, comprising: hydrotreating hydrocarbon oil with the hydrotreating catalyst according to claim 1 .
16 . The method for hydrotreating hydrocarbon oil according to claim 15 , wherein the hydrotreating comprises loading a flow reactor with the hydrotreating catalyst, wherein the flow reactor is selected from the group consisting of a stirred tank, an ebullient bed reactor, a baffled slurry tank, a fixed bed reactor, a rotating tubular reactor and a slurry-bed reactor.
17 . The method for hydrotreating hydrocarbon oil according to claim 15 , further comprising: filling a hydrotreating apparatus which is a flow reactor with the hydrotreating catalyst; and treating a hydrocarbon oil comprising middle distillates in the presence of hydrogen at a reactor temperature in a range of from about 270-430° C.; a hydrogen partial pressure in a range of from about 30-120 barg; a hydrogen gas feed rate of up to about 1000 standard liters per liter of hydrocarbon feed; and a liquid hourly space velocity, on a fresh feed volumetric rate relative to the volume of the hydrotreating catalyst, in a range of from about 0.1-10.0 h −1 .
18 . The method for hydrotreating hydrocarbon oil according to claim 15 , wherein the hydrocarbon oil comprises one or more of a) straight run middle distillates; b) one or more middle distillate fractions from hydroprocessing zones consisting of hydroprocessing of vacuum gas oil, deasphalted oil (DAO) obtained from a solvent deasphalting process or demetallized oil, coker gas oil obtained from a coker process, cycle oil obtained from a fluid catalytic cracking (FCC) process and gas oil obtained from a visbreaking process; c) light cycle oil obtained from a FCC process; d) light coker gas oil obtained from a coker process; e) light visbreaking gas oil obtained from a visbreaking process; f) plastic pyrolysis oils and g) bio-mass derived oils.