IP Library Granted Patent US 9,586,879
Granted Patent B2
US 9,586,879 · App. 14/774,792 · Granted Mar 7, 2017

Process for the selective production of propanols by hydrogenation of glycerol

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Quick Facts
Patent No.
US 9,586,879
App. No.
14/774,792
Granted
Mar 7, 2017
Kind
B2
Abstract

The present invention discloses a process for the selective hydrogenation of glycerol in the liquid phase to produce 1- and 2-propanols in high yields as the major organic products. The process comprises subjecting a glycerol stream having at least 30% by weight water to a combination of low pressure and high temperature hydrogenation conditions in the presence of a promoted or un-promoted skeletal copper catalyst.

Claims (27)

1. A catalytic process for the hydrogenation of glycerol comprising

a) obtaining a glycerol-containing stream having a water content of at least 30% by weight of the total glycerol containing stream;

b) subjecting the glycerol-containing stream to hydrogenation in the liquid phase in a reactor in the presence of a skeletal copper catalyst at a reaction temperature of greater than 250° C., and a reaction pressure of less than 100 bar; and

c) wherein a combined weight % yield of 1-propanol and 2-probanol of at least 15% based on the total weight of glycerol feed is obtained as a major product.

2. The catalytic process of claim 1 wherein the skeletal copper catalyst is promoted with at least one transition metal other than copper selected from the group consisting of Groups 4, 6, 7, 8, 9, 10 and 12 of the Periodic Table of Elements, and combinations thereof.

3. The catalytic process of claim 2 wherein the skeletal copper catalyst is promoted with a transition metal selected from the group consisting of nickel, cobalt, molybdenum, zinc, chromium, zirconium and combinations thereof.

4. The catalytic process of claim 1 wherein the reaction pressure is less than 60 bar.

5. The catalytic process of claim 4 wherein the reaction pressure ranges from about 10 bar to about 50 bar.

6. The catalytic process of claim 1 wherein the water content of the glycerol is at least 50% by weight based on the total weight of the glycerol feed.

7. The catalytic process of claim 1 wherein a glycerol conversion of at least 80% is obtained.

8. The catalytic process of claim 1 wherein the reactor is a fixed bed reactor.

9. The catalytic process of claim 8 wherein the reactor is operated in a continuous manner.

10. A process for the selective production of 1-propanol and 2-propanol from glycerol in which a feed comprising:

contacting a glycerol containing feed as a liquid in a reactor with a hydrogen-containing gas;

subjecting the feed to hydrogenation in the presence of a skeletal copper catalyst at a reaction temperature of greater than 250° C., and a reaction pressure of less than 100 bar, wherein the water content of the glycerol feed is at least 30% by weight of the total feed; and

recovering 1- and 2-propanol as the major product.

11. The process of claim 10 wherein the skeletal copper catalyst is promoted with at least one transition metal other than copper selected from the group consisting of Groups 4, 6, 7, 8, 9, 10 and 12 of the Periodic Table of Elements, and combinations thereof.

12. The process of claim 11 wherein the skeletal copper catalyst is promoted with a transition metal selected from the group consisting of nickel, cobalt, molybdenum, zinc, chromium, zirconium and combinations thereof.

13. The process of claim 10 wherein the reaction temperature is from about 260° C. to about 320° C.

14. The process of claim 13 wherein the reaction temperature is from about 270° C. to about 310° C.

15. The process of claim 10 wherein the reaction pressure is less than 60 bar.

16. The process of claim 15 wherein the reaction pressure ranges from about 10 bar to about 50 bar.

17. The process of claim 10 wherein the water content of the glycerol is at least 50% by weight based on the total weight of the glycerol feed.

18. The catalytic process of claim 10 wherein a glycerol conversion of at least 80% is obtained.

19. The catalytic process of claim 10 wherein a combined weight % yield of 1-propanol and 2-propanol recovered is at least 15% based on the total weight of glycerol feed.

20. The catalytic process of claim 10 wherein the reactor is a fixed bed reactor.

21. The catalytic process of claim 20 wherein the reactor is operated in a continuous manner.

Assignments (7)
NOTES SECURITY INTEREST Recorded Jan 29, 2026
From: W. R. GRACE & CO.-CONN.; ADVANCED REFINING TECHNOLOGIES LLC
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 074532/0229 →
SECURITY AGREEMENT (NOTES) Recorded Aug 19, 2025
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 072520/0653 →
SECURITY INTEREST Recorded Feb 17, 2023
From: W.R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 062792/0510 →
TERM LOAN SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: JPMORGAN CHASE BANK, N.A.
Reel/Frame 057594/0104 →
NOTES SECURITY AGREEMENT Recorded Sep 23, 2021
From: W. R. GRACE & CO.-CONN.
To: WILMINGTON TRUST, NATIONAL ASSOCIATION
Reel/Frame 057594/0156 →
RELEASE OF SECURITY INTEREST Recorded Sep 23, 2021
From: GOLDMAN SACHS BANK USA
To: W. R. GRACE & CO.-CONN.
Reel/Frame 057594/0026 →
SECURITY INTEREST Recorded Apr 3, 2018
From: W. R. GRACE & CO.-CONN.
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 045828/0683 →