Amorphous mesoporous alumina with an optimized pore distribution, and process for its preparation

Patent metadata

Field	Value
Publication number	US-10131547-B2
Application number	US-201515318047-A
Country	US
Kind code	B2
Filing date	Jun 9, 2015
Priority date	Jun 13, 2014
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

An amorphous mesoporous alumina with a median mesopore diameter by volume of 16 nm or more, a mesopore volume of 0.5 mL/g or more, and a total pore volume of more than 0.75 mL/g. A process for preparing said alumina, comprising:
a) precipitating a basic precursor and an acidic precursor, at least one of which comprises aluminum, at a pH of 8.5 to 10.5, a temperature of 20° C. to 90° C. and for 2 minutes to 30 minutes, with a state of advance of 5% to 13%; b) heating the suspension; c) a second precipitating by adding another basic precursor and acidic precursor, at least one of which comprises aluminum, at a pH of 8.5 to 10.5, a temperature of 40° C. to 90° C. and for 2 to 50 minutes, with a state of advance of 87% to 95%; d) filtration; e) drying; f) shaping; g) heat treatment.

First claim

The invention claimed is:

1. A process for preparing an amorphous mesoporous alumina, said process comprising at least the following steps:
a) a first step for precipitating, in an aqueous reaction medium to form a suspension, at least one basic precursor selected from the group consisting of sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from the group consisting of aluminium sulphate, aluminium chloride, aluminium nitrate, sulphuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminium, the relative flow rate of the acidic and basic precursors being selected so as to obtain a pH of the reaction medium in the range of 8.5 to 10.5 and the flow rate of the acidic and basic precursor or precursors containing aluminium being adjusted in order to obtain a state of advance for the first step in the range of 5% to 13%, the state of advance being defined as the proportion of alumina formed, in Al 2 O 3 equivalents, during said first step for precipitating with respect to the total quantity of alumina formed at the end of step c) of the process, said first step being operated at a temperature in the range of 20° C. to 90° C. and for a period in the range of 2 minutes to 30 minutes;
b) a step for heating the suspension to a temperature in the range of 40° C. to 90° C. for a period in the range of 7 minutes to 45 minutes;
c) a second step for precipitating the suspension obtained at the end of the heating step b), to obtain a second suspension, by adding to the suspension obtained at the end of the heating step b), at least one basic precursor selected from the group consisting of sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from the group consisting of aluminium sulphate, aluminium chloride, aluminium nitrate, sulphuric acid, hydrochloric acid and nitric acid, in which at least one of the basic or acidic precursors comprises aluminium, the relative flow rate of the acidic and basic precursors being selected so as to obtain a pH of the reaction medium in the range of 8.5 to 10.5 and the flow rate of the acidic and basic precursors containing aluminium being adjusted in order to obtain a state of advance for the second step in the range of 87% to 95%, the state of advance being defined as the proportion of alumina formed, in Al 2 O 3 equivalents, during said second step for precipitating with respect to the total quantity of alumina formed at the end of step c) of the process, said second step being operated at a temperature in the range of 40° C. to 90° C. and for a period in the range of 2 minutes to 50 minutes;
d) a step for filtering the second suspension obtained at the end of the second precipitation step c) to obtain an alumina gel;
e) a step for drying said alumina gel to obtain a powder;
f) a step for shaping the powder to obtain a green material; and
g) a step for heat treating the green material at a temperature in the range of 500° C. to 1000° C., in the presence of a stream of air containing up to 60% by volume of water.

2. The process according to claim 1 , in which the state of advance in step a) is in the range of 6% to 12%.

3. The process according to claim 1 , in which the state of advance in step a) is in the range of 7% to 11%.

4. The process according to claim 1 , in which the basic precursor in one or both of steps a) and c) is sodium aluminate.

5. The process according to claim 1 , in which the acidic precursor in one or both of steps a) and c) is aluminium sulphate.

6. The process according to claim 1 , in which in the first step for precipitating, the aqueous reaction medium is water and said first step is operated with stirring, in the absence of an organic additive.

7. The process according to claim 1 , in which the basic precursor in both of steps a) and c) is sodium aluminate.

8. The process according to claim 1 , in which the acidic precursor in both of steps a) and c) is aluminium sulphate.

9. The process according to claim 1 , in which the basic precursor in both of steps a) and c) is sodium aluminate and the acidic precursor in both of steps a) and c) is aluminium sulphate.

10. An amorphous mesoporous alumina having a median mesopore diameter, by volume determined by mercury intrusion porosimetry, of 16 nm or more, a mesopore volume, as measured by mercury intrusion porosimetry, between 0.70 mL/g and 0.90 mL/g, and a total pore volume, measured by mercury porosimetry, of more than 0.75 mL/g, wherein the volume of macropores in the mesoporous alumina is less than 10% of the total pore volume.

11. The amorphous mesoporous alumina according to claim 10 , in which the volume of macropores in the mesoporous alumina is less than 5% of the total pore volume.

12. The amorphous mesoporous alumina according to claim 10 , having no micropores.

13. The amorphous mesoporous alumina according to claim 10 , having a median mesopore diameter, by volume determined by mercury intrusion porosimetry, of more than 18 nm.

14. The amorphous mesoporous alumina according to claim 13 , having a median mesopore diameter, by volume determined by mercury intrusion porosimetry, of more than 20 nm.

Assignees

• Ifp Energies Now

Inventors

• Boualleg Malika
• Bouvry Celine

Classifications

• C04B35/111

  Fine ceramics · CPC title

• B01J20/08

  comprising aluminium oxide or hydroxide; comprising bauxite · CPC title

• C04B35/64

  Burning or sintering processes (C04B33/32 takes precedence {; powder metallurgy B22F}) · CPC title

• C01P2006/14

  Pore volume · CPC title

• C04B2235/6588

  Water vapor containing atmospheres · CPC title