Catalytic composition and process using it for the alkylation of aromatic hydrocarbons with alcohols, or mixtures of alcohols and olefins

Patent metadata

Field	Value
Publication number	US-10329216-B2
Application number	US-201415026924-A
Country	US
Kind code	B2
Filing date	Oct 14, 2014
Priority date	Oct 15, 2013
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

The invention relates to a new catalytic composition for the alkylation of aromatic compounds with alcohols, or mixtures of alcohols and corresponding olefins, wherein said composition comprises a zeolite of the MTW type and is characterized in that it contains one or more alkaline metals in a total quantity which is less than or equal to 0.02% by weight. The use of said catalyst in the alkylation of aromatic compounds with alcohols, in particular benzene with isopropanol or ethanol, allows the formation, as by-product, of the aldehyde or ketone corresponding to the alcohol used, to be minimized: the formation of reaction by-products of said aldehydes or ketones having a boiling point very close to that of polyalkylation products, is therefore significantly reduced. This provides a considerable advantage in the subsequent transalkylation step for the recovery of said polyalkylates by transformation into the corresponding monoalkylates.

First claim

The invention claimed is:

1. A process for the alkylation of an aromatic hydrocarbon with an aliphatic alcohol having 1-8 carbon atoms, or with a mixture of the aliphatic alcohol having 1-8 carbon atoms and a corresponding olefin, which comprises effecting said alkylation in the presence of a catalytic composition comprising:
a zeolite of the MTW type,
5 to 40 ppm of sodium ions, and
5 to 80 ppm of potassium ions,
wherein:
the SiO 2 /Al 2 O 3 molar ratio in said zeolite is 20-95, and
the total amount of alkaline metals, including sodium ions and potassium ions, in the catalytic composition is lower than or equal to 0.015% by weight with respect to the total weight of the catalytic composition.

2. The process according to claim 1 , wherein the zeolite is ZSM-12.

3. The process according to claim 1 , wherein said catalytic composition further comprises a binder.

4. The process according to claim 1 , wherein said catalytic composition comprises said MTW zeolite in acid form wherein the cationic sites present in its structure are occupied by Na + and K + ions and the remaining cationic sites are occupied by H + ions.

5. The process according to claim 4 , wherein the zeolite is a ZSM-12 zeolite, having, in its calcined and anhydrous form, a molar composition of the oxides corresponding to the following formula:
1.0±0.4 M 2 O.Al 2 O 3 .20-500 SiO 2 .zH 2 O,

wherein z ranges from 0 to 60, M is H + and Na + and K + ions, in a total amount lower than 0.015% by weight with respect to the total weight of the catalytic composition.

6. The process according to claim 3 , wherein said catalytic composition is in the form of a pellet having a diameter ranging from 1.5 to 5 mm and a length ranging from 1 to 50 mm, with a hardness higher than or equal to 8 kg.

7. The process according to claim 3 , wherein said catalytic composition has an extrazeolitic porosity not lower than 0.4 ml/g, wherein said extrazeolitic porosity is for at least 30% characterized by pores having a diameter greater than 100 Å.

8. The process according to claim 1 , wherein the aromatic hydrocarbon is benzene or toluene.

9. The process according to claim 1 , wherein the aliphatic alcohol is ethanol or iso-propanol.

10. The process according to claim 1 , carried out in gas phase, mixed phase or liquid phase.

11. The process according to claim 10 , carried out under reaction conditions corresponding to a complete gas phase of the reagents.

12. The process according to claim 1 , carried out under trickle-flow conditions.

13. The process according to claim 1 , wherein the aromatic hydrocarbon is benzene, the aliphatic alcohol is isopropanol, the alkylation product is cumene and said process further comprises:
oxidizing the cumene thus obtained to cumyl-hydroperoxide;
treating the cumyl-hydroperoxide with acids to obtain a mixture of phenol and acetone;
hydrogenating the acetone to isopropanol which is recycled to the alkylation.

14. The process according to claim 1 , wherein the process comprises the alkylation of the aromatic hydrocarbon with the aliphatic alcohol having 1-8 carbon atoms, and not with the mixture of the aliphatic alcohol having 1-8 carbon atoms and the corresponding olefin.

15. The process according to claim 1 , wherein the process comprises the alkylation of the aromatic hydrocarbon with the mixture of the aliphatic alcohol having 1-8 carbon atoms and the corresponding olefin.

16. The process according to claim 1 , wherein the catalytic composition comprises 5 to 30 ppm of said sodium ions and 5 to 30 ppm of said potassium ions.

17. The process according to claim 1 , wherein the aliphatic alcohol having 1-8 carbon atoms is selected from ethyl alcohol, iso-propyl alcohol, n-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, and t-butyl alcohol.

Assignees

• Versalis Spa

Inventors

• Bencini Elena
• Fois Giovanni Antonio
• Buzzoni Roberto

Classifications

• C07C2/864 Primary

  the non-hydrocarbon is an alcohol · CPC title

• C07C15/085

  Isopropylbenzene · CPC title

• C07C2523/02

  of the alkali- or alkaline earth metals or beryllium · CPC title

• B01J35/026

  Operations & Transport · mapped topic

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title