Process and catalyst for preparing 1,4-butanediol

Patent metadata

Field	Value
Publication number	US-11260375-B2
Application number	US-201716338015-A
Country	US
Kind code	B2
Filing date	Sep 27, 2017
Priority date	Sep 30, 2016
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

The present invention relates to a process for preparing 1,4-butanediol (BDO) by hydrogenating 2-butyne-1,4-diol (BYD) or 4-hydroxybutanal (4-HBA) in the presence of a catalyst of the Raney type having a porous foam structure, wherein the macroscopic pores have sizes in the range of 100 to 5000 μm, and a bulk density of up to 0.8 kg/L.

First claim

The invention claimed is:

1. A process for preparing 1,4-butanediol by hydrogenating 2-butyne-1,4-diol or 4-hydroxybutanal, said method comprising contacting an aqueous solution comprising 2-butyne-1,4-diol or 4-hydroxybutanal with hydrogen and an activated nickel catalyst, wherein said activated nickel catalyst comprises:
a) a porous foam structure;
b) macroscopic pores in the range of 100 to 5000 μm;
c) a bulk density of not more than 0.8 kg/L.

2. The process of claim 1 , wherein the hydrogenation of 4-hydroxybutanal is carried out at a hydrogen pressure in the range of 10 to 110 bar.

3. The process of claim 2 , wherein the hydrogenation is carried out in a temperature range of 50 to 200° C.

4. The process of claim 1 , wherein the hydrogenation of 2-butyne-1,4-diol is carried out at a hydrogen pressure in the range of 50 to 350 bar and a temperature range of 50 to 150° C.

5. The process of claim 1 , wherein said process is carried out in a fixed bed reactor.

6. The process of claim 5 , wherein the fixed bed reactor is operated adiabatically, with a temperature at the reactor inlet in the range of 80 to 100° C. and a temperature at the reactor outlet in the range of 110 to 150° C.

7. The process of claim 6 , wherein the activated nickel catalyst has an aluminum content of not more than 15% by weight.

8. The process of claim 7 , wherein the activated nickel catalyst comprises macroscopic pores with sizes in the range of 200 to 2500 μm.

9. The process of claim 5 , wherein the process is carried out continuously in a trickle bed reactor, liquid-filled reactor, or a bubble column.

10. The method of claim 5 , wherein the fixed bed reactor is operated in a “once through” mode, in which the reactants are introduced into the reactor and the product mixture is removed after the reaction.

11. The process of claim 1 , wherein the activated nickel catalyst comprises 0 to 10% by weight of at least one of the elements selected from the group consisting of: molybdenum, iron, and chromium.

12. The process of claim 11 , wherein the hydrogenation is carried out continuously.

13. The process of claim 12 , wherein the activated nickel catalyst has an aluminum content of not more than 15% by weight.

14. The process of claim 13 , wherein the activated nickel catalyst has a porous foam structure, wherein the macroscopic pores have sizes in the range of 200 to 2500 μm.

15. The process of claim 1 , wherein the hydrogenation is carried out batchwise in a stirred tank reactor using a two temperature reaction regime, wherein:
a) the temperature in the stirred tank at the start of the reaction is maintained in the range of 90 to 105° C. so that 2-butyne-1,4-diol is reacted with hydrogen to give 2-butene-1,4-diol;
b) after uptake of hydrogen stoichiometrically equivalent to the amount of 2-butyne-1,4-diol used, the first reaction stage is concluded and the temperature in the stirred tank is then increased to 130 to 135° C. and maintained in that range until completion of the hydrogenation to give 1,4-butanediol.

16. The process of claim 15 , wherein the catalyst is arranged in a holding device close to the stirrer shaft such that a flow of the reaction mixture through the catalyst bed is generated by the stirrer.

17. The process of claim 15 , wherein the hydrogenation of butyne-1,4-diol is carried out at a hydrogen pressure in the range of 50 to 350 bar.

18. The process of claim 17 , wherein the activated nickel catalyst has an aluminum content of not more than 15% by weight.

19. The process of claim 15 , wherein the activated nickel catalyst comprises macroscopic pores with sizes in the range of 200 to 2500 μm.

20. The process of claim 15 , wherein the activated nickel catalyst comprises 0 to 10% by weight of at least one of the elements selected from the group consisting of: molybdenum, iron, and chromium.

Assignees

• Evonik Operations Gmbh

Inventors

• Berweiler Monika
• Göttlinger Markus
• Roos Meike
• Schwarz Matthias
• Poss René

Classifications

• B01J23/745

  Iron · CPC title

• B01J23/28

  Molybdenum · CPC title

• B01J23/26

  Chromium · CPC title

• B01J25/02 Primary

  Raney nickel · CPC title

• B01J37/0217

  Pretreatment of the substrate before coating · CPC title