Hydrofining catalyst, its preparation and application thereof

Patent metadata

Field	Value
Publication number	US-11439989-B2
Application number	US-201917044817-A
Country	US
Kind code	B2
Filing date	Apr 9, 2019
Priority date	Apr 10, 2018
Publication date	Sep 13, 2022
Grant date	Sep 13, 2022

Abstract

Disclosed is a hydrofining catalyst comprising: an inorganic refractory component comprising a first hydrodesulfurization catalytically active component in a mixture with at least one oxide selected from the group consisting of alumina, silica, magnesia, calcium oxide, zirconia and titania; a second hydrodesulfurization catalytically active component; and an organic component comprising a carboxylic acid and optionally an alcohol. The hydrofining catalyst of the present application shows improved performance in the hydrofining of distillate oils. Also disclosed are a hydrofining catalyst system comprising the hydrofining catalyst, a method for preparing the catalyst and catalyst system, and a process for the hydrofining of distillate oils using the catalyst or catalyst system.

First claim

The invention claimed is:

1. A hydrofining catalyst comprising:
an inorganic refractory component comprising a first hydrodesulfurization catalytically active component comprising a first metal element in a mixture with at least one oxide selected from the group consisting of alumina, silica, magnesia, calcium oxide, zirconia, and titania;
a second hydrodesulfurization catalytically active component comprising a second metal element and is supported on the inorganic refractory component; and
an organic component supported on the inorganic refractory component and comprising a carboxylic acid and optionally an alcohol,
wherein the first metal element is selected from the group consisting of Group VIII metal elements and Group VIB metal elements, and the second metal element is a combination of at least a Group VIII metal element and at least a Group VIB metal element; and
wherein the Group VIII metal element is selected from the group consisting of iron, cobalt, and nickel, and the Group VIB metal element is selected from the group consisting of chromium, molybdenum, and tungsten.

2. The hydrofining catalyst according to claim 1 , wherein the Group VIII metal element present in
the first hydrodesulfurization catalytically active component accounts for about 60-90% of a total amount of the Group VIII metal element present in the hydrofining catalyst.

3. The hydrofining catalyst according to claim 2 , wherein in the hydrofining catalyst, a total content of the Group VIII metal element is 15-35 wt %, and a total content of the Group VIB metal element is 35-75 wt %, based on the dry weight of the catalyst and calculated as oxides, and
a percentage of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 5-40 wt %, based on the weight on a dry basis of the catalyst.

4. The hydrofining catalyst according to claim 1 , wherein the hydrofining catalyst has a specific surface area of 70-200 m 2 /g, a total pore volume of 0.15-0.6 mL/g, and an average pore size of 5-25 nm.

5. The hydrofining catalyst according to claim 1 , wherein:
when the organic component comprises the carboxylic acid without the alcohol, a ratio of the an amount by weight of the carboxylic acid to a weight on a dry basis of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 0.1-0.8:1; or
when the organic component comprises both the carboxylic acid and the alcohol, the ratio of the amount by weight of the carboxylic acid to the weight on a dry basis of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 0.002-0.1:1; and a ratio of a molar amount of the alcohol to the weight on a dry basis of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 0.005-0.03:1.

6. The hydrofining catalyst according to claim 5 , wherein the carboxylic acid is selected from the group consisting of C 1-18 monobasic saturated carboxylic acids, C 7-10 phenyl acids, citric acid, adipic acid, malonic acid, succinic acid, maleic acid, tartaric acid, and combinations thereof;
and the alcohol is selected from the group consisting of C 1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, trimethylolethane, and combinations thereof.

7. The hydrofining catalyst according to claim 6 , wherein the hydrofining catalyst further comprises phosphorus in an amount of 0.8-10 wt %, based on the dry weight of the catalyst and calculated as P 2 O 5 .

8. A method for preparing a hydrofining catalyst according to claim 1 , comprising the steps of:
(1) mixing a precursor of a first hydrodesulfurization catalytically active component with a precursor of at least one oxide selected from the group consisting of alumina, silica, magnesia, calcium oxide, zirconia and titania, and calcining to obtain an inorganic refractory component;
(2) mixing a precursor of a second hydrodesulfurization catalytically active component with an organic component and optionally a phosphorus-containing compound to obtain an impregnation solution, wherein the organic component comprises a carboxylic acid and optionally an alcohol; and
(3) mixing the inorganic refractory component with the impregnation solution, and shaping and drying the resulting mixture to obtain the hydrofining catalyst,
wherein the precursor of the first hydrodesulfurization catalytically active component comprises a precursor of a metal element selected from the group consisting of Group VIII metal elements and Group VIB metal elements, and the precursor of the second hydrodesulfurization catalytically active component comprises a precursor of a Group VIII metal element and a precursor of a Group VIB metal element, and
wherein the Group VIII metal element is selected from the group consisting of iron, cobalt, and nickel, and the Group VIB metal element is selected from the group consisting of chromium, molybdenum, and tungsten.

9. The method according to claim 8 ,
wherein the precursor of the Group VIII metal element present in the precursor of the first hydrodesulfurization catalytically active component accounts for 60-90% of the total amount of the precursor of the Group VIII metal element;
the precursors of the first and second hydrodesulfurization catalytically active components are in such amounts that, in the hydrofining catalyst, the total content of the Group VIII metal element is about 15-35 wt %, and the total content of the Group VIB metal element is about 35-75 wt %, based on the dry weight of the catalyst and calculated as oxides;
and the inorganic refractory component is in such an amount that the inorganic refractory component minus the first hydrodesulfurization catalytically active component is about 5-40 wt %, based on the dry weight of the hydrofining catalyst.

10. The method according to claim 8 , wherein:
when the organic component comprises the carboxylic acid and without the alcohol, the ratio of the weight of the carboxylic acid used in step (2) to the weight on a dry basis of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 0.1-0.8:1; or
when the organic component comprises both the carboxylic acid and the alcohol, the ratio of the weight of the carboxylic acid used in step (2) to the weight on a dry basis of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 0.002-0.1:1, and the ratio of the molar amount of the alcohol to the weight on a dry basis of the inorganic refractory component minus the first hydrodesulfurization catalytically active component is 0.005-0.03:1;
and wherein the carboxylic acid is selected from the group consisting of C 1-18 monobasic saturated carboxylic acids, C 7-10 phenyl acids, citric acid, adipic acid, malonic acid, succinic acid, maleic acid, tartaric acid, and combinations thereof;
and the alcohol is selected from the group consisting of C 1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, trimethylolethane, and combinations thereof.

11. The method according to claim 10 , wherein, in step (2), the phosphorus-containing compound is in such an amount that the phosphorus element is present in an amount of 0.8-10 wt %, based on the dry weight of the hydrofining catalyst and calculated as P 2 O 5 ;
wherein the phosphorus-containing compound is selected from the group consisting of phosphoric acid, hypophosphorous acid, ammonium phosphate, ammonium dihydrogen

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Chen Wenbin
• Zhang Le
• Long Xiangyun
• Nie Hong
• Li Mingfeng
• Li Dadong
• Liu Qinghe
• Ju Xueyan

Classifications

• B01J21/04

  Alumina · CPC title

• B01J23/882

  and cobalt · CPC title

• B01J23/888

  Tungsten · CPC title

• C10G45/08

  in combination with chromium, molybdenum, or tungsten metals, or compounds thereof · CPC title

• B01J21/066

  Zirconium or hafnium; Oxides or hydroxides thereof · CPC title