Co-feeding ethylene with allyl alcohol in hydroformylation to make 1,4-butanediol and n-propanol

Patent metadata

Field	Value
Publication number	US-11370737-B2
Application number	US-202117480265-A
Country	US
Kind code	B2
Filing date	Sep 21, 2021
Priority date	Sep 25, 2020
Publication date	Jun 28, 2022
Grant date	Jun 28, 2022

Abstract

A process of co-feeding gaseous ethylene with liquid allyl alcohol in the presence of a catalyst to produce 1,4-butanediol and n-propanol may include: introducing a gaseous mixture of ethylene, carbon monoxide and hydrogen into a reactor in the presence of a hydroformylation catalyst in a solvent; introducing liquid allyl alcohol (AA) into the reactor; and carrying out hydroformylation reaction at a temperature between 50 and 100° C. to obtain hydroformylation products.

First claim

What is claimed is:

1. A method comprising the steps of:
a) introducing a gaseous mixture of ethylene, carbon monoxide and hydrogen into a reactor in the presence of a hydroformylation catalyst in a solvent;
b) introducing liquid allyl alcohol (AA) into the reactor; and
c) carrying out hydroformylation reaction at a temperature between 50 and 100° C. to obtain hydroformylation products, wherein the hydroformylation products include 4-hydroxybutyraldehyde, 3-hydroyx-2-methylpropionaldehyde, propionaldehyde or a combination thereof.

2. The method of claim 1 , wherein the molar ratio of ethylene to allyl alcohol ranges from 1:3 to 1:7.

3. The method of claim 1 , wherein the molar ratio of ethylene to allyl alcohol ranges from 1:4 to 1:5.

4. The method of claim 1 , wherein the amount of allyl alcohol ranges between 10 and 25 wt. % concentration in the solvent, calculated by

weight
⁢

⁢
of
⁢

⁢
AA

weight
⁢

⁢
of
⁢

⁢
the
⁢

⁢
solvent

+
AA

×

⁢
100
⁢

%
.

5. The method of claim 1 , wherein molar ratio of ethylene:carbon monoxide:hydrogen is (0.18-0.35):(2.7-4.1):(5-7).

6. The method of claim 1 , wherein the molar ratio of ethylene:carbon monoxide:hydrogen is about 1:13:22.

7. The method of claim 1 , wherein in step c) the hydroformylation reaction is carried out at a moderate pressure in the range of from about 137.9 kPa to about 1378.95 kPa.

8. The method of claim 1 , wherein in step c) the hydroformylation reaction is carried out at a moderate pressure in the range of from about 689.48 kPa to about 1034.21 kPa.

9. The method of claim 1 , wherein in step c) the hydroformylation reaction is carried out at a moderate pressure in the range of from about 896.32 kPa to about 965.27 kPa.

10. The method of claim 1 , wherein the hydroformylation catalyst is a mixture of rhodium and a ligand selected from the group consisting of trans-1,2-bis(3,5-trimethylphenylphosphinomethyl) cyclobutane (Ligand A), 1,4-bis(diphenylphosphinobutane) (DPPB), triphenylphosphine (TPP), bidentate biphosphate, and combinations thereof.

11. The method of claim 10 , wherein the molar ratio of rhodium to Ligand A ranges from 1:1 to 1:5.

12. The method of claim 10 , wherein the molar ratio of rhodium to Ligand A is about 1:2.

13. The method of claim 10 , wherein the hydroformylation catalyst is a mixture of rhodium, Ligand A, DPPB and TPP.

14. The method of claim 13 , wherein the molar ratio of rhodium:Ligand A:DPPB:TPP is about 1:2:0.1:2.

15. The method of claim 10 , wherein the rhodium is present in an amount of 50 to 500 ppm.

16. The method of claim 1 , wherein in step c) the temperature is between 50 and 80° C.

17. The method of claim 1 , further comprising the step of: separating the products from the solvent and the catalyst by water extraction.

18. The method of claim 17 , wherein a water-to-feed ratio ranges from 1:5 to 2:1.

19. The method of claim 1 , further comprising the step of:
(d) treating the hydroformylation products include 4 -hydroxybutyraldehyde, 3-hydroxy-2-methylpropionaldehyde, and propionaldehyde with a Ni hydrogenation catalyst to produce a hydrogenation product, wherein the hydrogenation product includes, 1,4-butanediol, 2-methyl-1,3-propanediol, propanol or a combination thereof.

20. The method of claim 19 , wherein the hydroformylation catalyst is a mixture of rhodium and a ligand selected from the group consisting of trans-1,2-bis(3,5-trimethylphenylphosphinomethyl) cyclobutane (Ligand A), 1,4-bis(diphenylphosphinobutane) (DPPB), triphenylphosphine (TPP), bidentate biphosphate, and combinations thereof.

Assignees

• Lyondell Chemical Tech Lp

Inventors

• White Daniel F
• Mandimutsira Beaven S
• Alvarez Roberto

Classifications

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• B01J2531/822

  Rhodium · CPC title

• C07C29/141

  with hydrogen or hydrogen-containing gases · CPC title

• B01J31/2414 Primary

  comprising aliphatic or saturated rings · CPC title

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title