Process for producing dienes

Patent metadata

Field	Value
Publication number	US-11851385-B2
Application number	US-202017787754-A
Country	US
Kind code	B2
Filing date	Dec 18, 2020
Priority date	Dec 20, 2019
Publication date	Dec 26, 2023
Grant date	Dec 26, 2023

Abstract

A process for producing a diene, preferably a conjugated diene, more preferably 1,3-butadiene, includes the steps of dehydrating at least one alkenol in the presence of at least one catalytic material having at least one acid catalyst based on silica (SiO2) and alumina (Al2O3), preferably a silica-alumina (SiO2—Al2O3), the catalyst having an alumina content (Al2O3) lower than or equal to 12% by weight, preferably between 0.1% by weight and 10% by weight, with respect to the catalyst total weight. The alumina content is referred to the catalyst total weight without binder, and a pore modal diameter between 9 nm and 170 nm, preferably between 10 nm and 150 nm, still more preferably between 12 nm and 120 nm.Preferably, the alkenol is obtainable directly from biosynthetic processes, or catalytic dehydration processes of at least one diol, preferably a butanediol, more preferably 1,3-butanediol, still more preferably bio-1,3-butanediol, deriving from biosynthetic processes.

First claim

The invention claimed is:

1. A process for producing a diene, comprising dehydrating at least one alkenol in the presence of at least one catalytic material comprising at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ), said catalyst having an alumina content (Al 2 O 3 ) lower than or equal to 12% by weight, with respect to the catalyst total weight, said alumina content being referred to the catalyst total weight without binder, and a pore modal diameter between 9 nm and 170 nm.

2. The process according to claim 1 , wherein said alkenol is selected from 3-buten-2-ol (methyl vinyl carbinol), 3-buten-1-ol (allyl carbinol), 2-buten-1-ol (crotyl alcohol), or mixtures thereof.

3. The process according to claim 1 , wherein said alkenol is directly obtained from biosynthetic processes.

4. The process according to claim 1 , wherein said alkenol derives from the catalytic dehydration of at least one diol.

5. The process according to claim 4 , wherein said diol is bio-1,3-butanediol deriving from the fermentation of sugars deriving from biomass, including scraps, residues, waste deriving from said biomass or from the processing thereof.

6. The process according to claim 1 , wherein said acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ) is obtained by incipient wetness impregnation wherein the volume of a solution comprising at least one alumina precursor selected from aluminium alkoxides (such as tri-sec-aluminium butoxide), soluble aluminium salts (such as aluminium sulphate), aluminates (such as sodium aluminate), in a suitable concentration, is equal to or slightly lower than the pore volume of a solid support (for example, silica).

7. The process according to claim 1 , wherein said catalytic material comprising at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ) is obtained by a process comprising:
preparing an aqueous solution or an aqueous suspension of alumina (Al 2 O 3 ) or of at least one precursor thereof selected from aluminium alkoxides, soluble aluminium salts, and aluminates;
adding to said aqueous solution or aqueous suspension of alumina (Al 2 O 3 ) or of at least one precursor thereof, an aqueous solution or an aqueous suspension of silica (SiO 2 ) or of at least one precursor thereof selected from silicic acids and alkali metal silicates;
recovering a solid by precipitation or gelation, and optionally subjecting said solid to at least one of:
ion exchange with at least one compound capable of exchanging ions with the surface of said solid that is selected from aqueous solutions of salts containing ammonium ions;
binding with at least one silica precursor (SiO 2 ) selected from colloidal silicas, silica alkoxides; or at least one alumina precursor (Al 2 O 3 ) selected from boehmite and pseudoboehmite;
forming by extrusion, spherulization, tableting, or granulation;

optionally subjecting said solid to thermal treatment and/or calcination before or after one aforesaid ion exchange, binding, or forming.

8. The process according to claim 7 , wherein said catalytic material comprising at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ), obtained after binding and/or forming, has a pore modal diameter between 9 nm and 170 nm.

9. The process according to claim 1 , wherein said acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ) has a specific surface area between 40 m 2 /g and 800 m 2 /g.

10. The process according to claim 1 , wherein said catalytic material comprises at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ) and at least one binder selected from alumina (Al 2 O 3 ), silica (SiO 2 ), zirconium oxide, titanium oxide.

11. The process according to claim 10 , wherein said catalytic material comprising at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ) and at least one binder selected from alumina (Al 2 O 3 ) or silica (SiO 2 ), and/or subjected to forming, has a specific surface area between 25 m 2 /g and 700 m 2 /g.

12. The process according to claim 1 , wherein said process for producing a diene is carried out with a diluent selected from: inert gases such as nitrogen (N 2 ), argon (Ar); or from compounds having a boiling temperature higher than or equal to 50° C. and a melting temperature lower than or equal to 40° C., that are, preferably, in the liquid state at ambient temperature (25° C.) and at ambient pressure (1 atm), such as water, tetrahydrofuran, cyclohexane, benzene; preferably nitrogen (N 2 ), water, more preferably water.

13. The process according to claim 1 , wherein said process for producing a diene is carried out:
in case the diluent is selected from inert gases, at a molar ratio of diluent to alkenol/s greater than 0.3:
in case the diluent is selected from compounds having a boiling temperature higher than or equal to 50° C. and a melting temperature lower than or equal to 40° C., that are preferably, in the liquid state at ambient temperature (25° C.) and at ambient pressure (1 atm), at a molar ratio of diluent to alkenol/s between 0.01 and 100.

14. The process according to claim 1 , wherein said process for producing a diene is carried out:
at a temperature between 150° C. and 500° C.; and/or
at a pressure between 0.05 bara and 50 bara (bara=absolute bars); and/or
operating at a contact time (τ), calculated as the ratio of the catalytic material loaded to feeding volumetric rate, between 0.01 seconds and 10 seconds.

15. The process according to claim 1 , wherein said catalytic material comprising at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ), is pre-treated at the temperature to which said process for producing a diene is carried out, that is at a temperature between 150° C. and 500° C., in the presence of at least one diluent.

16. The process according to claim 4 , wherein the at least one diol is a butanediol.

17. The process according to claim 16 , wherein the butanediol is 1,3-butanediol or bio-1,3-butanediol derived from sugar fermentation.

18. The process according to claim 17 , wherein the bio-1,3-butanediol is bio-1,3-butanediol derived from the fermentation of guayule, including scraps, residues, waste derived from said guayule or from the processing thereof.

19. The process according to claim 1 , wherein said catalytic material comprising at least one acid catalyst based on silica (SiO 2 ) and alumina (Al 2 O 3 ) is obtained by a process comprising:
preparing an aqueous solution or an aqueous suspension of alumina (Al 2 O 3 ) or of at least one precursor thereof selected from tri-sec-aluminium butoxide, aluminium sulphate, and sodium aluminate;
adding to said aqueous solution or aqueous suspension of alumina (Al 2 O 3 ) or of at least one precursor thereof, an aqueous solution or an aqueous suspension of silica (SiO 2 ) or of at least one precursor thereof selected from orthosilicic acid and sodium silicate;
recovering the solid obtained by precipitation or gelation, and optionally subjecting said solid to at least one of:
ion exchange with at least one compound capable of exchanging ions with the surface of the obtained solid that is selected from aqueous solutions containing ammonium acetate, ammonium nitrate, or ammonium sulphate;
binding with at least one silica precursor (SiO 2 ) selected from Ludox® TMA″-Sigma-Aldrich, tetraethyl-orthosilicate; or of at least one alumina precursor (Al 2 O 3 ) selected from boehmite and VersalTM V-250-UOP; and
forming by extrusion, spherulization, tableting, or granulation;

Assignees

• Versalis Spa

Inventors

• Cerasoli Talisa
• Ramello Stefano
• Pastori Monica Vittoria

Classifications

• C07C1/24 Primary

  by elimination of water · CPC title

• C07C2521/04

  Alumina · CPC title

• C07C2521/08

  Silica · CPC title