Zeolitic granular material having a connected structure

Patent metadata

Field	Value
Publication number	US-2016289146-A1
Application number	US-201415037896-A
Country	US
Kind code	A1
Filing date	Nov 20, 2014
Priority date	Nov 20, 2013
Publication date	Oct 6, 2016
Grant date	—

Abstract

The present invention relates to a zeolitic granular material having a connected zeolitic structure across the entire volume thereof, having high mechanical resistance to crushing in the bed, and optimised material transfer in the macro-mesopores. The invention also relates to the method for preparing said zeolitic granular material, as well as to the use thereof as an adsorbent material in co-current or counter-current liquid phase separation methods, typically in a simulated mobile bed.

First claim

1 . A zeolitic granular material with a size of between 0.1 mm and 1 mm, limits inclusive, whose zeolite structure forms a connected assembly over the entire volume of said material, and which has a mechanical bulk crushing strength of greater than or equal to 1.0 MPa.

2 . The zeolitic granular material as claimed in claim 1 , comprising at least one zeolite selected from the group consisting of zeolites of FAU structure and zeolites of EMT, LTA and MFI structure.

3 . The zeolitic granular material as claimed in claim 1 , comprising at least one zeolite selected from the group consisting of zeolites LSX, MSX and X.

4 . The zeolitic granular material as claimed in claim 1 , comprising more than 94% by weight of zeolite(s), relative to the total weight of the zeolitic granular material.

5 . The zeolitic granular material as claimed in claim 1 , in which the pore distribution satisfies the inequalities 1), 2) and 3) below:

Vme

Vme
+
Vma

≤
0.1

,

1
)

0.4
≤

Vmi

Vma
+
Vme
+
Vmi

,

2
)

and

0.25
≤

Vma
+
Vme

Vg

≤
0.35

,

3
)

in which “Vma” represents the macropore volume, “Vme” represents the mesopore volume, “Vmi” represents the micropore volume and “Vg” represents the total volume of the granular material.

6 . A process for preparing a zeolitic granular material as claimed in claim 1 , comprising at least the steps of:
a) mixing crystals of at least one zeolite with a clay binder containing at least 80% , by weight of zeolitizable clay, and optionally a source of silica to form a mixture, b) placing the mixture in contact with an alkaline basic solution to form a suspension, c) bringing the suspension to a temperature between 80° C. and 600° C., in a closed and leaktight container, at a pressure at least equal to the autogenous pressure, to obtain zeolitic granular material, d) optionally, carrying out cationic exchange of the cations contained in the reaction medium of step c) by placing the reaction medium in contact with a solution of barium ions, or of barium ions and potassium ions, e) washing and drying of the zeolitic granular material thus obtained, and optionally at least one step of forming the zeolitic granular material to the desired size, and f) activating the zeolitic granular material obtained in step e) by heating to a temperature in general between 100° C. and 400° C.,

7 . The process as claimed in claim 6 , in which the clay binder used in step a) contains at least 80% by weight of clay or of mixture of clays from among kaolins, kaolinites, nacrites, dickites, halloysite and/or metakaolins and may also contain other mineral binders such as bentonite, attapulgite, sepiolite and the like.

8 . A co-current or counter-current liquid-phase separation process, comprising using at least one zeolitic granular material as claimed in claim 1 .

9 . A process for separating aromatic fractions comprising mixtures of isomers containing 8 carbon atoms, in which is used at least one zeolitic granular material as claimed in claim 1 .

10 . The process as claimed in claim 9 , wherein the process is a liquid-phase process for separating xylenes in a simulated mobile bed.

11 . The zeolitic granular material as claimed in claim 1 , having a size between 0.3 mm and 0.8 mm, limits inclusive.

12 . The zeolitic granular material as claimed in claim 1 , having a mechanical bulk crushing strength greater than or equal to 2.0 MPa.

13 . The zeolitic granular material as claimed in claim 1 , comprising zeolite X.

14 . The zeolitic granular material as claimed in claim 1 , comprising between 96% and 98% by weight of zeolite(s), limits inclusive, relative to the total weight of the zeolitic granular material.

15 . The zeolitic granular material as claimed in claim 5 , wherein

0.01
≤

Vme

Vme
+
Vma

≤

0.1
.

16 . The zeolitic granular material as claimed in claim 5 , wherein

0.01
≤

Vme

Vme
+
Vma

≤

0.06
.

17 . The zeolitic granular material as claimed in claim 5 , wherein

0.4
≤

Vmi

Vma
+
Vme
+
Vmi

≤

0.6
.

18 . The zeolitic granular material as claimed in claim 5 , wherein

0.45
≤

Vmi

Vma
+
Vme
+
Vmi

≤

0.55
.

Assignees

• Ceca Sa
• Ifp Energies Now

Inventors

• Laroche Catherine
• Bouvier Ludivine
• Leflaive Philibert
• Lutz Cécile
• Gay Anne-Sophie
• Moreau Florent

Classifications

• B01J20/28083

  being in the range 2-50 nm, i.e. mesopores · CPC title

• C10G2400/30

  Aromatics · CPC title

• C07C37/82

  by solid-liquid treatment; by chemisorption · CPC title

• B01J20/28004

  Sorbent size or size distribution, e.g. particle size · CPC title

• B01J20/2803

  Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products · CPC title