Modified crystalline aluminosilicate for dehydration of alcohols

Patent metadata

Field	Value
Publication number	US-10773250-B2
Application number	US-201916680709-A
Country	US
Kind code	B2
Filing date	Nov 12, 2019
Priority date	Sep 26, 2014
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

The present invention relates to a catalyst composition comprising a modified crystalline aluminosilicate of the Framework Type FER having Si/Al framework molar/ratio greater than 20 characterized in that in said modified crystalline aluminosilicate the ratio between the strong acid sites and the weak acid sites, S/W, is lower than 1.0 and having the extra framework aluminum (EFAL) content lowered to less than 10 wt % preferably 5 wt % even more preferably less than 2 wt % measured by 27Al MAS NMR. The present invention further relates to a process for producing olefins from alcohols in presence of said catalyst composition.

First claim

The invention claimed is:

1. A process for the preparation of a catalyst composition comprising the steps of:
(A) providing a crystalline aluminosilicate of the Framework Type FER having Si/Al framework molar ratio greater than 20, and
(B) treating said crystalline aluminosilicate to form a modified crystalline aluminosilicate with the following steps:
i. Not performing any steaming on said crystalline aluminosilicate and;
ii. treating the product obtained at step i.) with an organic acidic medium and/or an organic medium; and/or
iii. selectively poisoning strong acid sites of the product obtained at step i.) or ii.) by adding a solution comprising alkali salts or alkaline earth salts or silver, so that the weight percent of alkali or alkaline earth or silver on the catalyst composition is of at least 0.5% weight, measured by chemical analysis with the method ASTM UOP961-12;

wherein said modified crystalline aluminosilicate obtained with said treatment (B) comprises a modified crystalline aluminosilicate wherein
said modified crystalline aluminosilicate is of the Framework Type FER having Si/Al framework molar ratio greater than 20;
in said modified crystalline aluminosilicate the extra framework aluminum, EFAL, content is lower than 15 wt % measured by 27 Al MAS NMR;
in said modified crystalline aluminosilicate the ratio between the strong acid sites and the weak acid sites, S/W, is lower than 1.0; the ratio S/W being measured by temperature-programmed desorption of ammonia and being determined by the ratio of the peak area of ammonia desorbed above 340° C. to that desorbed below 340° C.

2. The process for the preparation of a catalyst composition according to claim 1 further characterized in that said organic acidic medium or an organic medium of step ii.)
comprises one or more —CO 2 H, —SO 3 H or —SO 4 H groups or salts thereof; or
comprises citric acid, formic acid, oxalic acid, tartaric acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, phthalic acid, isophthalic acid, fumaric acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, ethylene di amine tetracetic acid, or their corresponding salts being sodium salts or any mixture of thereof.

3. The process for the preparation of a catalyst composition according to claim 1 further characterized in that a calcination is performed before step ii.) said calcination being performed at a temperature lower than 600° C. and with a temperature increase of less than 10° C./min, for a period of at least 30 min and under a gas flow containing at most 1000 ppm volume of water measured at the inlet of calcination reactor.

4. The process for the preparation of a catalyst composition according to claim 1 wherein said modified crystalline aluminosilicate of the Framework Type FER has Si/Al framework molar ratio ranging from 25 to 50.

5. The process for the preparation of a catalyst composition according to claim 1 wherein said modified crystalline aluminosilicate of the Framework Type FER has a ratio between the strong acid sites and the weak acid sites, S/W, lower than 0.96.

6. The process for the preparation of a catalyst composition according to claim 1 wherein said modified crystalline aluminosilicate has a content in metals or cations thereof lower than 1000 wt ppm measured with the method ASTM UOP961-12, said metals belonging to columns 3 to 12 of the Periodic Table excluding silver.

7. The process for the preparation of a catalyst composition according to claim 1 wherein said modified crystalline aluminosilicate comprises the sequences —[—Al—O(H)—Si—]— and —[—Al—O(X)—Si—]— wherein X is alkali ions, alkaline earth ions or silver ions, the sequence —[—Al—O(X)—Si—]— representing less than 75% wt based on the total amount of sequences —[—Al—O(H)—Si—]— and —[—Al—O(X)—Si—]— in said modified crystalline aluminosilicate.

Assignees

• Total Res & Technology Feluy
• Ifp Energies Now

Inventors

• Nesterenko Nikolai
• Minoux Delphine
• Danilina Nadiya
• Dath Jean-Pierre
• Coupard Vincent
• Maury Sylvie

Classifications

• C07C2529/65

  of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 · CPC title

• B01J29/90

  Regeneration or reactivation · CPC title

• B01J29/74

  Noble metals · CPC title

• B01J37/0201

  Impregnation · CPC title

• B01J2229/186

  not in framework positions · CPC title