Ga2O3/La2O3-gamma Al2O3 catalysts for CO2-mediated oxidative dehydrogenation of propane to propylene

Patent metadata

Field	Value
Publication number	US-12508574-B2
Application number	US-202318461883-A
Country	US
Kind code	B2
Filing date	Sep 6, 2023
Priority date	Sep 6, 2023
Publication date	Dec 30, 2025
Grant date	Dec 30, 2025

Abstract

A method for producing propylene (C 3 H 8 ) via oxidative dehydrogenation (ODH) of propane includes introducing a propane-containing feed gas stream into a reactor containing an alumina-supported Ga 2 O 3 /La 2 O 3 catalyst comprising Ga 2 O 3 particles at least partially disposed on surfaces of a matrix comprising rough and irregular-sized La 2 O 3 and alumina particles; passing the propane-containing feed gas stream through the reactor in contact with the alumina supported Ga 2 O 3 /La 2 O 3 catalyst at a temperature of 500 to 600° C. to convert at least a portion of the propane to propylene (C 3 H 6 ) and produce a propylene-containing gas stream leaving the reactor; and separating the propylene from the propylene-containing gas stream. The method has a propane conversion of up to 95% based on an initial weight of the propane in the propane-containing feed gas stream, and a propylene yield of up to 60% based on the propane conversion.

First claim

The invention claimed is:

1 . A method for producing propylene (C 3 H 8 ) via oxidative dehydrogenation (ODH) of propane, comprising:
introducing a propane-containing feed gas stream into a reactor containing an alumina supported Ga 2 O 3 /La 2 O 3 catalyst comprising Ga 2 O 3 particles at least partially disposed on surfaces of a matrix comprising rough and irregular sized La 2 O 3 and alumina particles; passing the propane-containing feed gas stream through the reactor in contact with the alumina supported Ga 2 O 3 /La 2 O 3 catalyst at a temperature of 500 to 600° C. to convert at least a portion of the propane to propylene (C 3 H 6 ) and produce a propylene-containing gas stream leaving the reactor; and separating the propylene from the propylene-containing gas stream; wherein the method has a propane conversion of up to 95% based on an initial weight of the propane in the propane-containing feed gas stream; and wherein the method has a propylene yield of up to 60% based on the propane conversion, wherein the reactor is a fixed-bed reactor in the form of a cylindrical reactor comprising: a top portion; a cylindrical body portion; a bottom portion; a housing having an open top and open bottom supportably maintained with the cylindrical body portion; wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst is supportably retained within the housing permitting fluid flow therethrough; at least one propeller agitator is disposed in the bottom portion of the reactor; wherein the bottom portion is cone shaped or pyramidal; and wherein a plurality of recirculation tubes fluidly connects the bottom portion of the cylindrical reactor with the cylindrical body portion of the cylindrical reactor.

2 . The method of claim 1 , wherein the C 3 H 8 is present in the propane-containing feed gas stream at a concentration of 20 to 99 vol. % based on a total volume of the propane-containing feed gas stream.

3 . The method of claim 1 , wherein the propane-containing feed gas stream further comprises carbon dioxide (CO 2 ), and wherein a volume ratio of C 3 H 8 to CO 2 present in the propane-containing feed gas stream is in a range of 1:1 to 1:4.

4 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst is at least one of a gamma-alumina supported Ga 2 O 3 /La 2 O 3 catalyst (Ga 2 O 3 /La 2 O 3 -γ-Al 2 O 3 ), an alpha-alumina supported Ga 2 O 3 /La 2 O 3 catalyst (Ga 2 O 3 /La 2 O 3 -α-Al 2 O 3 ), and a delta-alumina supported Ga 2 O 3 /La 2 O 3 catalyst (Ga 2 O 3 /La 2 O 3 -δ-Al 2 O 3 ).

5 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst is Ga 2 O 3 /La 2 O 3 -γ-Al 2 O 3 catalyst having a mesoporous structure, and wherein the Ga 2 O 3 particles of the Ga 2 O 3 /La 2 O 3 -γ-Al 2 O 3 catalyst form a layer disposed on surfaces of the matrix comprising rough and irregular sized La 2 O 3 and γ-Al 2 O 3 particles.

6 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst comprises particles having a micropore area in a range of 2 to 20 square meter per gram (m 2 /g).

7 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst comprises particles having a specific surface area in a range of 30 to 150 square meter per gram (m 2 /g).

8 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst comprises particles having a total pore volume in a range of 0.1 to 0.3 cubic centimeter per gram (cm 3 /g).

9 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst comprises particles having an average pore diameter in a range of 5 to 15 nanometers (nm).

10 . The method of claim 1 , wherein the alumina supported Ga 2 O 3 /La 2 O 3 catalyst has an ammonia temperature-programmed desorption (NH 3 -TPD) of 0.35 to 0.5 millimoles per gram (mmol/g).

11 . The method of claim 1 , wherein the propylene-containing gas stream leaving the reactor further comprises ethylene, methane, ethane, propane, carbon monoxide, and carbon dioxide.

12 . The method of claim 1 , wherein the method further comprises preparing the Ga 2 O 3 /La 2 O 3 -γ-Al 2 O 3 catalyst by:
mixing an aluminum salt and a lanthanum salt in water to form a first mixture;
adjusting a pH of the first mixture to 8.5 by adding an ammonium salt;
heating the first mixture after adjusting the pH to precipitate a precursor composite from the first mixture;
separating the precursor composite from the first mixture and calcining the precursor composite at a temperature of about 500° C. to form a La 2 O 3 -γ-Al 2 O 3 support;
wherein the La 2 O 3 -γ-Al 2 O 3 support comprises rough and irregular sized La 2 O 3 and γ-Al 2 O 3 particles, and wherein the γ-Al 2 O 3 particles have a particle size in a range of 1 to 150 micrometers (μm);
mixing a gallium salt and the La 2 O 3 -γ-Al 2 O 3 support in water to form a second mixture; and
drying the second mixture and calcining the second mixture at a temperature of about 500° C. to deposit Ga 2 O 3 particles on surfaces of the La 2 O 3 -γ—Al 2 O 3 support thereby generating the Ga 2 O 3 /La 2 O 3 -γ—Al 2 O 3 ;
wherein the Ga 2 O 3 particles present in the Ga 2 O 3 /La 2 O 3 -γ-Al 2 O 3 are in the form of a layer having an average thickness of 50 to 1000 nm.

13 . The method of claim 12 , wherein a molar ratio of the La 2 O 3 to the γ-Al 2 O 3 present in the La 2 O 3 -γ-Al 2 O 3 support is in a range of 1:1 to 1:3.

14 . The method of claim 12 , wherein a weight ratio of the gallium salt to the La 2 O 3 -γ-Al 2 O 3 support is in a range of 1:5 to 1:15.

15 . The method of claim 12 , wherein the aluminum salt comprises aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum acetate, aluminum carbonate, aluminum phosphate, and/or a hydrate thereof.

16 . The method of claim 12 , wherein the lanthanum salt comprises lanthanum sulfate, lanthanum nitrate, lanthanum chloride, lanthanum acetate, lanthanum carbonate, lanthanum phosphate, and/or a hydrate thereof.

17 . The method of claim 12 , wherein the gallium salt comprises gallium sulfate, gallium nitrate, gallium chloride, gallium acetate, gallium carbonate, gallium phosphate, and/or a hydrate thereof.

18 . The method of claim 12 , wherein the ammonium salt comprises ammonium carbonate, ammonium hydrogen carbonate, ammonium acetate, ammonium hydroxide, and/or a hydrate thereof.

Assignees

• Univ King Fahd Pet & Minerals

Inventors

• Hossain Mohammad Mozahar
• Balogun Majid Lasisi
• Ba-Shammakh Mohammed S
• Ahmed Shakeel
• Khan Wasim Ullah

Classifications

• B01J35/647

  2-50 nm · CPC title

• B01J35/633

  less than 0.5 ml/g · CPC title

• B01J35/615

  100-500 m2/g · CPC title

• B01J35/613

  10-100 m2/g · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title