Process for the production of alkenols and use thereof for the production of 1,3-butadiene

Patent metadata

Field	Value
Publication number	US-9862664-B2
Application number	US-201515303640-A
Country	US
Kind code	B2
Filing date	May 15, 2015
Priority date	May 16, 2014
Publication date	Jan 9, 2018
Grant date	Jan 9, 2018

Abstract

Process for the production of alkenols comprising the dehydration of at least one diol in the presence of at least one catalyst based on cerium oxide, wherein said catalyst based on cerium oxide is obtained by precipitation, in the presence of at least one base, of at least one compound containing cerium. Preferably, said diol may be a butanediol, more preferably 1,3-butanediol, still more preferably bio-1,3-butanediol derived from biosynthetic processes. Said alkenols may advantageously be used for the production of 1,3-butadiene, in particular of bio-1,3-butadiene.

First claim

The invention claimed is:

1. Process for the production of alkenols comprising:
dehydrating 1,3-butanediol in the presence of at least one catalyst based on cerium oxide in at least one diluent at a process temperature ranging from 300° C. to 430° C. to produce alkenols;
wherein said catalyst based on cerium oxide is obtained by precipitation, in the presence of at least one base, of at least one compound containing cerium;
wherein said catalyst based on cerium oxide is pre-treated at a temperature the same as said process temperature before said dehydrating;
said dehydrating being carried out in said at least one diluent selected from: inert gas; or from a compound having a boiling point greater than or equal to 50° C. and a melting temperature of less than or equal to 40° C. as follows:
in the case in which the diluent is selected from said inert gas, at a molar ratio between diol and diluent of at least 0.5;
in the case in which the diluent is selected from said compound having a boiling point greater than or equal to 50° C. and a melting temperature of less than or equal to 40° C., at a molar ratio between diol and diluent ranging from 0.4 to 100.

2. Process for the production of alkenols according to claim 1 , wherein said catalyst based on cerium oxide is obtained by a process comprising:
preparing a solution including at least one compound containing cerium;
adding to said solution at least one base in a time ranging from 1 minute to 16 hours to obtain a reaction mixture;
allowing said reaction mixture to react at a temperature ranging from 15° C. to 100° C., for a time ranging from 1 minute to 120 hours, to obtain a precipitate;
recovering the precipitate and subjecting it to drying and, optionally, to calcination.

3. Process for the production of alkenols according to claim 1 , wherein said catalyst based on cerium oxide is obtained by a process comprising:
preparing a solution including at least one base;
adding to said solution at least one compound containing cerium in a time ranging from 1 minute to 16 hours, to obtain a reaction mixture;
allowing said reaction mixture to react at a temperature ranging from 15° C. to 100° C., for a time ranging from 1 minute to 120 hours, to obtain a precipitate;
recovering the precipitate and subjecting it to drying and, optionally, to calcination.

4. Process for the production of alkenols according to claim 2 , wherein said solution including at least one compound containing cerium or said solution including at least one base, is an aqueous solution comprising from 5% by weight to 70% by weight, relative to the total weight of said aqueous solution, of at least one compound containing cerium or of at least one base.

5. Process for the production of alkenols according to claim 2 , wherein said solution including at least one compound containing cerium or said solution including at least one base is a water-alcohol solution comprising from 5% by weight to 95% by weight, relative to the total weight of said water-alcohol solution, of at least one alcohol selected from ethanol, 2-methoxyethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, or mixtures thereof.

6. Process for the production of alkenols according to claim 1 , wherein said cerium containing compound is selected from: soluble cerium salts; or cerium alkoxides.

7. Process for the production of alkenols according to claim 2 , wherein, in the case in which said solution containing at least one compound containing cerium mainly comprises cerium(III), at least one oxidising agent is added to said solution.

8. Process for the production of alkenols according to claim 2 , wherein, in the case in which said solution containing at least one compound containing cerium mainly comprises cerium(III), the recovered precipitate, before being subjected to drying and, optionally, calcination, is treated with at least one oxidising agent.

9. Process for the production of alkenols according to claim 1 , wherein said base is selected from: hydroxides of alkali metals or alkaline earth metals; secondary or tertiary amines; quaternary ammonium salts; ammonium hydroxide (NH 4 OH), urea.

10. Process for the production of alkenols according to claim 9 , wherein said base is selected from aqueous solutions of: ammonium hydroxide (NH 4 OH), triethylamine, tetrapropylammonium hydroxide.

11. Process for the production of alkenols according to claim 1 , wherein said catalyst based on cerium oxide has a specific surface area ranging from 0.5 m 2 /g to 250 m 2 /g.

12. Process for the production of alkenols according to claim 1 , wherein said catalyst based on cerium oxide is used in the form of an extrudate, optionally containing conventional binders.

13. Process for the production of alkenols according to claim 1 , wherein said diol is bio-1,3-butanediol derived from the fermentation of sugars.

14. Process for the production of alkenols according to claim 1 , wherein said diol is bio-1,3-butanediol derived from the fermentation of sugars derived from guayule or thistle, including discards, residues or waste arising from said guayule and/or thistle or the processing thereof.

15. Process for the production of alkenols according to claim 1 , wherein said process for the production of alkenols is carried out at a pressure ranging from 0.05 bara to 50 bara.

16. Process for the production of alkenols according to claim 1 , wherein said process for the production of alkenols is carried out using a “Weight Hourly Space Velocity” (WHSV), which is a ratio between the weight of the diol fed in one hour and the weight of catalyst based on cerium oxide, said ratio being measured in h −1 , ranging from 0.5 h −1 to 20 h −1 .

17. Process for the production of 1,3-butadiene comprising bringing at least one of the alkenols obtained with the process of claim 1 , into contact with at least one catalyst, under suitable conditions for the dehydration of said at least one alkenol.

18. Process for the production of 1,3-butadiene according to claim 17 , wherein said catalyst is selected from solid acid catalysts.

19. Process for the production of alkenols comprising:
providing a catalyst based on cerium oxide by a process including:
providing at least one cerium containing compound;
providing a first addition of at least one base;
wherein said at least one cerium containing compound and said at least one base are mixed to form a reaction mixture at a pH of at least 9.0;
allowing said reaction mixture to react until decreasing to a pH of about 4.0;
providing a second addition of said base such that said reaction mixture reaches a pH of 9.0;
allowing said reaction mixture to react until a precipitate is formed and recovered to form said catalyst based on cerium oxide; and

dehydrating 1,3-butanediol in a presence of said catalyst based on cerium oxide and a diluent at a process temperature ranging from 300° C. to 430° C. to produce alkenols, said diluent being selected from: inert gas, or from a compound having a boiling point greater than or equal to 50° C. and a melting temperature of less than or equal to 40° C.;
said dehydrating being carried out as follows:
in the case in which the diluent is selected from said inert gas, at a molar ratio between diol and diluent of at least 0.5;
in the case in which the diluent is selected from said compound having a boiling point greater than or equal to 50° C. and a melting temperature of less than or equal to 40° C., at a molar ratio between diol and diluent ranging from 0.4 to 100.

Assignees

• Versalis Spa

Inventors

• Cesana Alberto
• Ramello Stefano
• Spano′ Guido

Classifications

• C07C2521/12

  Silica and alumina · CPC title

• C07C1/24

  by elimination of water · CPC title

• B01J21/12

  Silica and alumina · CPC title

• B01J23/10 Primary

  of rare earths · CPC title

• B01J37/0036

  Grinding · CPC title