Porous aluminum hydrate

Patent metadata

Field	Value
Publication number	US-11897783-B2
Application number	US-201816772621-A
Country	US
Kind code	B2
Filing date	Dec 18, 2018
Priority date	Dec 22, 2017
Publication date	Feb 13, 2024
Grant date	Feb 13, 2024

Abstract

The present invention relates to a porous aluminum hydrate, to a process for preparing same and to the use of same as intermediate in the preparation of an alumina or of a mixed oxide based on aluminum, on cerium and on zirconium. The invention also relates to the alumina obtained from the aluminum hydrate.

First claim

The invention claimed is:

1. An aluminum hydrate identified by X-ray diffraction as including boehmite, which may optionally comprise at least one additional element selected from lanthanum, praseodymium or a mixture of the two elements, characterized in that, after having been calcined in air at a temperature of 900° C. for 2 h, it has:
a pore volume in the domain of the pores having a size of less than or equal to 20 nm (denoted by VP 20nm -N 2 ) such that VP 20nm -N 2 :
is greater than or equal to 30%×VPT-N 2 ;
is less than or equal to 60%×VPT-N 2 ; and

a pore volume in the domain of the pores having a size of between 40 and 100 nm (denoted by VP 40-100nm -N 2 ) such that VP 40-100nm -N 2 is greater than or equal to 20%×VPT-N 2 ;
VPT-N 2 denoting the total pore volume of the aluminum hydrate after calcination in air at 900° C. for 2 hours and being between 0.65 and 1.15 mL/g;
the pore volumes being determined by the nitrogen porosimetry technique.

2. The aluminum hydrate as claimed in claim 1 , characterized in that it is identifiable by X-ray diffraction in the form of a mixture of a boehmite and of an amorphous phase.

3. The aluminum hydrate as claimed in claim 1 , characterized by a percentage of crystalline phase which is less than or equal to 60%.

4. The aluminum hydrate as claimed in claim 1 , characterized in that the boehmite has a mean size of the crystallites of at most 6.0 nm.

5. The aluminum hydrate as claimed in claim 1 , characterized in that, after having been calcined in air at 900° C. for 2h, it has a (BET) specific surface area of at least 130 m 2 /g.

6. The aluminum hydrate as claimed in claim 1 , characterized in that, after having first been calcined in air at 940° C. for 2h, then calcined in air at 1100° C. for 3h, it has a (BET) specific surface area of at least 80 m 2 /g.

7. The aluminum hydrate as claimed in claim 1 , characterized in that it comprises an additional element selected from the group formed by lanthanum, praseodymium or a mixture of the two elements and in that, after having first been calcined in air at 940° C. for 2h, then calcined in air at 1200° C. for 5h, it has a (BET) specific surface area of at least 45 m 2 /g.

8. The aluminum hydrate of claim 1 , further comprising residual sulfate, the content of residual sulfate being less than or equal to 0.50% by weight.

9. The aluminum hydrate of claim 1 , further comprising residual sodium, the content of residual sodium being less than or equal to 0.15% by weight.

10. The aluminum hydrate as claimed in claim 1 , characterized in that the proportion of the additional element or the total proportion of the additional elements is by weight between 0% and 15%.

11. A process for preparing the aluminum hydrate as claimed in claim 1 , the process comprising the following steps:
(a) introducing the following into a stirred tank containing an aqueous nitric acid solution:
an aqueous solution (A) comprising aluminum sulfate, optionally the additional element(s) in nitrate form, and nitric acid;
an aqueous sodium aluminate solution (B);

the aqueous solution (A) being introduced continuously throughout step (a) and the flow rate of introduction of the solution (B) being regulated so that the mean pH of the reaction mixture is equal to a target value of between 4.0 and 6.0;
(b) when the entire aqueous solution (A) has been introduced, continuing the introduction of the aqueous solution (B) until a target pH of between 8.0 and 10.5 is reached;
(c) filtering the reaction mixture to recover the solid and washing said solid with water;
(d) drying the solid resulting from step (c) to form the aluminum hydrate of claim 1 .

12. The process as claimed in claim 11 , wherein the aluminum hydrate powder obtained at the end of step (d) is ground and/or screened.

13. A process for preparing alumina, the process consisting of calcining the aluminum hydrate as claimed in claim 1 .

14. A process for preparing a mixed oxide comprising aluminum, cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum, the process consisting of calcining, in air, a solid precipitate obtained from a dispersion of the aluminum hydrate as claimed in claim 1 and an aqueous solution comprising the salts of the elements cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum.

15. A process for preparing a mixed oxide comprising aluminum, cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum, the process comprising:
(i-a) adding a basic aqueous solution to a dispersion formed from the aluminum hydrate as claimed in claim 1 and an aqueous solution S comprising the salts of cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum, to precipitate a solid; or
(i-b) adding an aqueous solution S comprising the salts of cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum to a dispersion formed from the aluminum hydrate as claimed in claim 1 and a basic aqueous solution to precipitate a solid; or
(i-c) adding to a basic aqueous solution a dispersion formed from the aluminum hydrate as claimed in claim 1 and an aqueous solution S comprising the salts of cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum to precipitate a solid;
(ii) optionally washing the solid obtained at the end of step (i);
(iii) calcining the solid obtained at the end of step (i) or (ii) in air at a temperature of between 700° C. and 1200° C. to obtain the mixed oxide.

16. The process as claimed in claim 15 , comprising an additional step between steps (ii) and (iii) during which the solid is subjected to heating at a temperature of between 70° C. and 150° C.

17. The process as claimed in claim 14 , wherein the mixed oxide comprises hafnium.

18. The process as claimed in claim 17 , for which the proportion of hafnium is less than or equal to 2.0%, expressed as oxide equivalent relative to the total weight of the mixed oxide.

19. A dispersion of the aluminum hydrate as claimed in claim 1 in an aqueous solution comprising the salts of cerium, zirconium, lanthanum and optionally at least one rare-earth metal (REM) other than cerium and lanthanum.

20. A dispersion of the aluminum hydrate as claimed in claim 1 in a basic aqueous solution.

Assignees

• Rhodia Operations

Inventors

• Hernandez Julien
• Larcher Olivier

Classifications

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/30

  characterised by their physical properties · CPC title

• C01F7/441 Primary

  by calcination · CPC title

• C01F7/34 Primary

  Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts · CPC title