# US 11,998,899 B2 · Bifunctional catalyst for deep desulfurization and gasoline quality improvement and preparation method therefor

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

- Number: US 11,998,899 B2
- Document ID: US11998899B2
- Status: Granted
- Kind: B2
- Application number: 17/390,820
- Filed: 2021-07-30
- Published: 2021-11-18
- Granted: 2024-06-04
- Earliest claimed: 2019-02-01
- Assignees: China University of Petroleum-Beijing
- Applicants: China University of Petroleum-Beijing
- Inventors: Liang Zhao; Jinsen Gao; Butian Xia; Lixia Dong; Jingye Chen; Yuhao Zhang; Chunming Xu
- Web page: https://patentgrep.com/patent/US11998899B2

## CPC

- B01J 29/405: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 21/04: Alumina
- B01J 23/10: of rare earths
- B01J 23/883: and nickel
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/70: of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 37/0201: {Impregnation}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/082: {Decomposition and pyrolysis}
- C10G 45/12: containing crystalline alumino-silicates, e.g. molecular sieves
- B01J 2229/18: to introduce other elements into or onto the molecular sieve itself
- B01J 2229/20: to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
- B01J 2235/10: Infrared [IR]
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C10G 2300/104: Light gasoline having a boiling range of about 20 - 100 °C
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/4006: Temperature
- C10G 2300/4012: Pressure
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- C10G 2300/70: Catalyst aspects
- C10G 2400/02: Gasoline
- 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

Provided are a bifunctional catalyst for deep desulfurization and gasoline quality improvement and a preparation method therefore and a use thereof. The bifunctional catalyst includes a modified catalyst and a loaded active metal, where the modified catalyst carrier is a γ-Al2O3 modified with a rare earth element, or the modified catalyst carrier is a composite carrier prepared by mixing and calcinating γ-Al2O3 and an acid molecular sieve through a binder, and then modifying with the rare earth element. The bifunctional catalyst for deep desulfurization and gasoline quality improvement can achieve deep desulfurization of high-sulfur fluid catalytic cracking gasoline, and ensure no significant loss of octane number under relatively mild conditions.

## Claims

### Claim 1

A hydrodesulfurization catalyst comprising a modified catalyst carrier and a loaded active metal,
wherein
the modified catalyst carrier is a composite carrier prepared by mixing and calcinating γ-Al2O3 and an acid molecular sieve through a binder, and then modifying with the rare earth element;
the binder is amino trimethylene phosphonic acid (ATMP) or polyvinylpyrrolidone (PVP), and a mass ratio of the binder to a sum of the γ-Al2O3 and the acid molecular sieve is (1.5-3): 1;
the active metal is selected from more than two elements of VIB Group and VIII Group in a Periodic Table of Elements; and
the hydrodesulfurization catalyst is prepared by an impregnation method, wherein a molar ratio of an organic complexing agent in an impregnation solution to the VIII Group element is (0.3-2): 1.

### Claim 2 (depends on 1)

The hydrodesulfurization catalyst according to claim 1, wherein a content of the rare earth element in the hydrodesulfurization catalyst is 0.5-5 wt % based on a weight of an oxide of the rare earth element with respect to a weight of the hydrodesulfurization catalyst.

### Claim 3 (depends on 1)

The hydrodesulfurization catalyst according to claim 1, wherein the rare earth element is selected from at least one of La, Ce, Pr, and Y.

### Claim 4 (depends on 2)

The hydrodesulfurization catalyst according to claim 2, wherein the rare earth element is selected from at least one of La, Ce, Pr, and Y.

### Claim 5 (depends on 1)

The hydrodesulfurization catalyst according to claim 1, wherein the hydrodesulfurization catalyst is obtained by loading the active metal on the modified catalyst carrier using the impregnation method, and then aging and drying.

### Claim 6 (depends on 2)

The hydrodesulfurization catalyst according to claim 2, wherein the hydrodesulfurization catalyst is obtained by loading the active metal on the modified catalyst carrier using the impregnation method, and then aging and drying.

### Claim 7 (depends on 3)

The hydrodesulfurization catalyst according to claim 3, wherein the hydrodesulfurization catalyst is obtained by loading the active metal on the modified catalyst carrier using the impregnation method, and then aging and drying.

### Claim 8 (depends on 4)

The hydrodesulfurization catalyst according to claim 4, wherein the hydrodesulfurization catalyst is obtained by loading the active metal on the modified catalyst carrier using the impregnation method, and then aging and drying.

### Claim 9 (depends on 1)

The hydrodesulfurization catalyst according to claim 1, wherein a mass ratio of γ-Al2O3 to the acid molecular sieve is (9-1): 1; and/or, the acidic molecule sieve is selected from one or more of ZSM-5, MCM-41, SAPO-34, and Bata molecular sieve.

### Claim 10 (depends on 1)

A preparation method of the hydrodesulfurization catalyst according to claim 1, characterized by comprising steps of:
loading a rare earth element on γ-Al2O3 by an impregnation method, then aging, drying, and calcinating to obtain a modified catalyst carrier; or mixing and calcinating γ-Al2O3 and an acid molecular sieve through a binder to prepare a composite carrier, and then loading the rare earth element on the composite carrier by the impregnation method, and then aging, drying, calcining to obtain the modified catalyst carrier;
loading an active metal on the modified catalyst carrier by the impregnation method, and then aging, drying, and calcinating to obtain the hydrodesulfurization catalyst.

### Claim 11 (depends on 10)

The preparation method according to claim 10, wherein the modified catalyst carrier is obtained by loading an impregnation solution containing a rare earth compound on γ-Al2O3 or the composite carrier by an equal volume impregnation method, then aging at room temperature for 6-12 h, drying at 100-160° C. for 4-8 h, and calcining at 500-700° C. for 4-8 h; a calcination atmosphere is nitrogen, argon, or helium.

### Claim 12 (depends on 10)

The preparation method according to claim 10, wherein the active metal is loaded on the modified catalyst carrier by an equal volume impregnation method, and an impregnation solution used contains an organic complexing agent, and the organic complexing agent is selected from at least one of citric acid, tartaric acid, and ethylenediaminetetraacetic acid.

### Claim 13 (depends on 1)

A method for hydrodesulfurization of gasoline comprises contacting the gasoline with the hydrodesulfurization catalyst according to claim 1.