# US 11,439,989 B2 · Hydrofining catalyst, its preparation and application thereof

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,439,989 B2
- Document ID: US11439989B2
- Status: Granted
- Kind: B2
- Application number: 17/044,817
- Filed: 2019-04-09
- Published: 2021-04-01
- Granted: 2022-09-13
- Earliest claimed: 2018-04-10
- Assignees: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Applicants: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Inventors: Wenbin Chen; Le Zhang; Xiangyun Long; Hong Nie; Mingfeng Li; Dadong Li; Qinghe Liu; Xueyan Ju
- Web page: https://patentgrep.com/patent/US11439989B2

## CPC

- B01J 23/8885: {containing also molybdenum}
- B01J 21/04: Alumina
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 21/18: Carbon
- B01J 23/02: of the alkali- or alkaline earth metals or beryllium
- B01J 23/882: and cobalt
- B01J 23/883: and nickel
- B01J 23/888: Tungsten
- B01J 27/16: containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr}
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/651: {50-500 nm}
- B01J 35/66: Pore distribution
- B01J 35/69: bimodal
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0205: {in several steps}
- B01J 37/0213: {Preparation of the impregnating solution}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/024: {Multiple impregnation or coating}
- B01J 37/088: {Decomposition of a metal salt}
- B01J 37/20: Sulfiding
- C10G 45/08: in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
- C10G 2300/1074: Vacuum distillates
- 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

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.

## Claims

### Claim 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.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 2)

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.

### Claim 4 (depends on 1)

The hydrofining catalyst according to claim 1, wherein the hydrofining catalyst has a specific surface area of 70-200 m2/g, a total pore volume of 0.15-0.6 mL/g, and an average pore size of 5-25 nm.

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 5)

The hydrofining catalyst according to claim 5, wherein the carboxylic acid is selected from the group consisting of C1-18 monobasic saturated carboxylic acids, C7-10 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 C1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, trimethylolethane, and combinations thereof.

### Claim 7 (depends on 6)

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 P2O5.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 8)

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.

### Claim 10 (depends on 8)

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 C1-18 monobasic saturated carboxylic acids, C7-10 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 C1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, trimethylolethane, and combinations thereof.

### Claim 11 (depends on 10)

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 P2O5;
wherein the phosphorus-containing compound is selected from the group consisting of phosphoric acid, hypophosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, and combinations thereof.

### Claim 12 (depends on 8)

The method according to claim 8, wherein:
in step (1), the calcining conditions include: a calcining temperature of 300-900° C.; and a calcining time of 1-15 hours; and
in step (3), the drying conditions include: a drying temperature of 50-250° C.; a drying time of 2-10 h.

### Claim 13 (depends on 8)

The method according to claim 8, wherein the precursor of the alumina is selected from the group consisting of pseudo-boehmite, aluminum hydroxide powder, aluminum nitrate, aluminum carbonate, aluminum citrate, and combinations thereof; the precursor of the silica is selected from the group consisting of silica sol, white carbon black, silica and combinations thereof; the precursor of the magnesia is selected from the group consisting of magnesium hydroxide, magnesium nitrate, magnesium carbonate, magnesium acetate, magnesium oxide and combinations thereof; the precursor of the calcium oxide is selected from calcium hydroxide, calcium carbonate, calcium oxalate, calcium nitrate, calcium acetate, calcium oxide and combinations thereof; the precursor of the zirconia is selected from the group consisting of zirconium hydroxide, zirconium carbonate, zirconium nitrate, zirconium acetate, zirconium oxide and combinations thereof; the precursor of the titania is selected from the group consisting of titanium hydroxide, titanium nitrate, titanium acetate, titanium oxide and combinations thereof.

### Claim 14 (depends on 1)

A hydrofining catalyst system comprising a first catalyst and a second catalyst, wherein:
the first catalyst is a hydrofining catalyst according to claim 1;
the second catalyst comprises a second inorganic refractory component comprising alumina, a third hydrodesulfurization catalytically active component supported on the second inorganic refractory component, and an organic component supported on the second inorganic refractory component, wherein the organic component is selected from the group consisting of carboxylic acids and alcohols, and a pore size of the second catalyst is in the range of 2-100 nm;
wherein a volume ratio of the first catalyst to the second catalyst is from 1:1 to 1:8.

### Claim 15 (depends on 14)

The hydrofining catalyst system according to claim 14, wherein:
in the second catalyst, the third hydrodesulfurization catalytically active component comprises at least one Group VIII metal element and at least one Group VIB metal element;
and, in the second catalyst, a total content of the Group VIII metal element is 1-8 wt %, and a total content of the Group VIB metal element is 10-35 wt %, based on the dry weight of the second catalyst and calculated as oxides;
wherein, the Group VIII metal element is at least one selected from the group consisting of iron, cobalt, nickel, ruthenium, rhodium, and palladium, and the Group VIB metal element is at least one selected from the group consisting of chromium, molybdenum, and tungsten;
and the second inorganic refractory component is present in the second catalyst in an amount of 60-85 wt %, based on the dry weight of the second catalyst.

### Claim 16 (depends on 14)

The hydrofining catalyst system of claim 14, wherein:
the second catalyst has a specific surface area of 130-300 m2/g, a total pore volume of 0.2-0.7 mL/g, and an average pore size of 6-20 nm;
and, in the second catalyst, a molar ratio of the organic component to the Group VIII metal element contained in the second catalyst is 0.5-8;
the carboxylic acid in the second catalyst is selected from the group consisting of C1-18 monobasic saturated carboxylic acids, C7-10 phenyl acids, citric acid, adipic acid, malonic acid, succinic acid, maleic acid, tartaric acid, and combinations thereof;
and the alcohol in the second catalyst is selected from the group consisting of C1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, trimethylolethane, and combinations thereof.

### Claim 17 (depends on 1)

A method for preparing a hydrofining catalyst system comprising a first catalyst and a second catalyst, said method comprising:
(1) providing a hydrofining catalyst according to claim 1 as the first catalyst;
(2) preparing the second catalyst by the steps of:
(2a) mixing an alumina precursor with an extrusion aid and a peptizing agent, and subjecting the resulting mixture to shaping, drying and calcining sequentially to obtain a second inorganic refractory component;
(2b) mixing a precursor of a third hydrodesulfurization catalytically active component with an organic component selected from the group consisting of carboxylic acids and alcohols and optionally a phosphorus-containing compound to obtain a second impregnation solution;
(2c) mixing the second impregnation solution with the second inorganic refractory component and then drying to obtain the second catalyst; and
(3) loading the first catalyst and the second catalyst into a first catalyst bed and a second catalyst bed, respectively, in a volume ratio of 1:1 to 1:8, to obtain the hydrofining catalyst system;
wherein, in step (2), the precursor of the third hydrodesulfurization catalytically active component comprises a precursor of at least one Group VIII metal element and a precursor of at least one Group VIB metal element;
the precursor of the third hydrodesulfurization catalytically active component is in such an amount that, in the second catalyst, the total content of the Group VIII metal element is 1-8 wt %; the content of the Group VIB metal element is 10-35 wt %, based on the dry weight of the second catalyst and calculated as oxides;
in step (2), the second inorganic refractory component is in such an amount that the second inorganic refractory component is present in the second catalyst in an amount of 60-85 wt %, based on the dry weight of the second catalyst;
the Group VIII metal element is at least one selected from the group consisting of iron, cobalt, and nickel, and the Group VIB metal element is at least one selected from the group consisting of chromium, molybdenum, and tungsten.

### Claim 18 (depends on 17)

The method according to claim 17, wherein:
in step (2b), the molar ratio of the organic component to the Group VIII metal element used in the preparation of the second catalyst is 0.5-8;
the carboxylic acid used in step (2b) is selected from the group consisting of C1-18 monohydric saturated carboxylic acids, C7-10 phenyl acids, citric acid, adipic acid, malonic acid, succinic acid, maleic acid, tartaric acid, and combinations thereof;
the alcohol in step (2b) is selected from the group consisting of C1-18 monohydric saturated alcohols, ethylene glycol, polyethylene glycol, glycerol, polyglycerol, erythritol, pentaerythritol, xylitol, sorbitol, trimethylolethane and combinations thereof;
in step (2b), 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 second catalyst and calculated as P2O5;
and the phosphorus-containing compound in step (2b) is selected from the group consisting of phosphoric acid, hypophosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, and combinations thereof.

### Claim 19 (depends on 17)

The method according to claim 17, wherein:
in step (2a), the calcining conditions include: a calcining temperature of 400-1000° C.; and a calcining time of 1-15 hours; and
in step (2c), the drying conditions include: a drying temperature of 50-250° C.; a drying time of 2-10 h;
step (2a) is performed under such conditions that, in the resulting second inorganic refractory component, a volume of pores having a pore size in the range of 2-4 nm is 0-2% of the total pore volume, a volume of pores having a pore size in the range of 4-6 nm is 2-15% of the total pore volume, a volume of pores having a pore size in the range of 6-40 nm is 85-95% of the total pore volume.

### Claim 20 (depends on 1)

A process for the hydrofining of distillate oils, comprises the following steps:
subjecting a hydrofining catalyst according to claim 1 to sulfurization; and
contacting a distillate oil to be hydrodesulfurized with the sulfurized hydrofining catalyst under hydrodesulfurization conditions.

### Claim 21 (depends on 1)

The hydrofining catalyst according to claim 1, wherein the hydrofining catalyst has pores with pore sizes in the ranges of 2-40 nm and 100-300 nm, respectively, wherein a volume of pores having a pore size in the range of 2-40 nm is 60-95% of a total pore volume, and a volume of pores having a pore size in the range of 100-300 nm is 0.5-30% of the total pore volume, as determined after being calcined at 400° C. for 3 h,
and wherein in the hydrofining catalyst, a volume of pores having a pore size in the range of 2-4 nm is no more than 10% of the total pore volume.