Method for the production of aldehydes
View Patent ↗Aldehydes are produced by unmodified rhodium catalyzed hydroformylation process in a homogeneous organic phase using a solution of unmodified rhodium catalyst and an organic acid in a total amount, calculated as acid equivalent, of from greater than 3 moles to 3000 moles of acid per mole of rhodium. The organic acid is selected from: saturated aliphatic monocarboxylic acids having from 5 to 13 carbon atoms in the molecule; saturated aliphatic dicarboxylic acids having from 5 to 13 carbon atoms in the molecule; sulphonic acids having from 1 to 12 carbon atoms in the molecule; and combinations thereof. Use of the process can lead to either a significant increase in conversion without reducing selectivity for the desired aldehyde or a reduction in the specific use of rhodium.
1. An improved process for preparing aldehydes in a homogeneous organic phase in the presence of at least one rhodium compound and in the absence of complex-forming organophosphorus compounds in this reaction zone by:
a. introduction of an organic solution containing at least one rhodium compound in dissolved form into a reaction zone; and
b. reaction of olefinically unsaturated compounds with carbon monoxide and hydrogen,
wherein the improvement comprises:
addition of at least one organic acid in a total amount, calculated as acid equivalent, of from greater than 3 mol to 3000 mol per mole of rhodium to the rhodium-containing organic solution and subsequent feeding of this solution to the reaction zone, said organic acid being selected from among:
saturated aliphatic monocarboxylic acids having from 5 to 13 carbon atoms in the molecule;
saturated aliphatic dicarboxylic acids having from 5 to 13 carbon atoms in the molecule;
sulphonic acids having from 1 to 12 carbon atoms in the molecule; and combinations thereof.
2. The improved process according to claim 1 , wherein the organic acid is a saturated aliphatic monocarboxylic acid selected from the group consisting of:
(a) n-valeric acid;
(b) 2-methylbutyric acid;
(c) 2-ethylhexanoic acid;
(d) isononanoic acid prepared by hydroformylation of diisobutylene and subsequent oxidation of the hydroformylation product;
(e) isotridecanoic acid prepared by hydroformylation of tetrapropylene and subsequent oxidation of the hydroformylation product; and
(f) combinations of any of (a)-(e).
3. The improved process according to claim 1 , wherein the organic acid is adipic acid.
4. The improved process according to claim 1 , wherein the organic acid is a sulphonic acid, selected from the group consisting of:
(a) aliphatic;
(b) cycloaliphatic;
(c) aromatic;
(d) araliphatic sulphonic acids; and
(e) combinations of any of (a)-(d).
5. The improved process according to claim 1 , wherein the organic acid is selected from the group consisting of:
(a) methanesulphonic acid,
(b) para-toluenesulphonic acid,
(c) benzenesulphonic acid;
(d) benzenedisulphonic acid; and
(e) combinations of any of (a)-(d).
6. The improved process according to claim 1 , wherein the solvent in the organic solution containing at least one rhodium compound in dissolved form is selected from the group consisting of 2-ethylhexanol; isononanol based on 3,5,5-trimethylhexanol and combinations thereof.
7. The improved process according to claim 1 , wherein the concentration of rhodium in the reaction zone is from 1 to 100 ppm, based on the homogeneous reaction mixture.
8. The improved process according to claim 1 , wherein the concentration of rhodium in the reaction zone is from 2 to 30 ppm based on the homogeneous reaction mixture.
9. The improved process according to claim 1 , wherein the olefinically unsaturated compounds contain from 2 to 12 carbon atoms in the molecule.
10. The improved process according to claim 1 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperatures of from 20 to 180° C., and a pressure of from 0.1 to 70 MPa.
11. The improved process according to claim 1 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperature of from 50 to 150° C. and a pressure of from 0.1 to 60 MPa.
12. The improved process according to claim 1 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperature of from 100 to 150° C., and a pressure of from 0.1 to 30 MPa.
13. The improved process according to claim 1 , wherein the organic solution containing at least one rhodium compound in dissolved form consists essentially of from 50 moles to 2000 moles of acid, in a total amount calculated as acid equivalent, per mole of rhodium.
14. The improved process according to claim 13 , wherein the organic acid is a saturated aliphatic monocarboxylic acid selected from the group consisting of:
(a) n-valeric acid;
(b) 2-methylbutyric acid;
(c) 2-ethylhexanoic acid;
(d) isononanoic acid prepared by hydroformylation of diisobutylene and subsequent oxidation of the hydroformylation product; (e) isotridecanoic acid prepared by hydroformylation of tetrapropylene and subsequent oxidation of the hydroformylation product; and
(e) combinations of any of (a)-(d).
15. The improved process according to claim 13 , wherein the organic acid is adipic acid.
16. The improved process according to claim 13 , wherein the organic acid is a sulphonic acid, selected from the group consisting of:
(a) aliphatic,
(b) cycloaliphatic,
(c) aromatic;
(d) araliphatic sulphonic acids; and
(e) combinations of any of (a)-(d).
17. Process according to claim 13 , wherein the organic acid is a sulphonic acid, selected from the group consisting of:
(a) methanesulphonic acid,
(b) para-toluenesulphonic acid,
(c) benzenesulphonic acid;
(d) benzenedisulphonic acid; and
(e) combinations of any of (a)-(d).
18. The improved process according to claim 13 , wherein the concentration of rhodium in the reaction zone is from 1 to 100 ppm, based on the homogeneous reaction mixture.
19. The improved process according to claim 13 , wherein the concentration of rhodium in the reaction zone is from 2 to 30 ppm based on the homogeneous reaction mixture.
20. The improved process according to claim 13 , wherein the olefinically unsaturated compounds contain from 2 to 12 carbon atoms in the molecule.
21. The improved process according to claim 13 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperatures of from 20 to 180° C., and a pressure of from 0.1 to 70 MPa.
22. The improved process according to claim 13 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperature of from 50 to 150° C. and a pressure of from 0.1 to 60 MPa.
23. The improved process according to claim 13 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperature of from 100 to 150° C., and a pressure of from 0.1 to 30 MPa.
24. The improved process according to claim 13 , wherein the organic solution containing at least one rhodium compound in dissolved form consists essentially of from 100 moles to 1000 moles organic acid in a total amount calculated as acid equivalent per mole of rhodium.
25. The improved process according to claim 24 , wherein the organic acid is a saturated aliphatic monocarboxylic acid selected from the group consisting of:
(a) n-valeric acid;
(b) 2-methylbutyric acid;
(c) 2-ethylhexanoic acid;
(d) isononanoic acid prepared by hydroformylation of diisobutylene and subsequent oxidation of the hydroformylation product;
(e) isotridecanoic acid prepared by hydroformylation of tetrapropylene and subsequent oxidation of the hydroformylation product; and
(f) combinations of any of (a)-(e).
26. The improved process according to claim 24 , wherein the organic acid is adipic acid.
27. The improved process according to claim 24 , wherein the organic acid is a sulphonic acid, selected from the group consisting of:
(a) aliphatic,
(b) cycloaliphatic,
(c) aromatic;
(d) araliphatic sulphonic acids; and
(e) combinations of any of (a)-(d).
28. The improved process according to claim 24 , wherein the organic acid is selected from the group consisting of:
(a) methanesulphonic acid,
(b) para-toluenesulphonic acid,
(c) benzenesulphonic acid;
(d) benzenedisulphonic acid; and
(e) combinations of any of (a)-(d).
29. The improved process according to claim 24 , wherein the concentration of rhodium in the reaction zone is from 1 to 100 ppm, based on the homogeneous reaction mixture.
30. The improved process according to claim 24 , wherein the concentration of rhodium in the reaction zone is from 2 to 30 ppm based on the homogeneous reaction mixture.
31. The improved process according to claim 24 , wherein the olefinically unsaturated compounds contain from 2 to 12 carbon atoms in the molecule.
32. The improved process according to claim 24 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperatures of from 20 to 180° C., and a pressure of from 0.1 to 70 MPa.
33. The improved process according to claim 24 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperature of from 50 to 150° C. and a pressure of from 0.1 to 60 MPa.
34. The improved process according to claim 24 , wherein the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a temperature of from 100 to 150° C., and a pressure of from 0.1 to 30 MPa.
35. An improved process for preparing aldehydes in a homogeneous organic phase in the presence of at least one rhodium compound and in the absence of complex-forming organophosphorus compounds in this reaction zone by:
a. introduction of an organic solution containing at least one rhodium compound in dissolved form into a reaction zone; and
b. reaction of olefinically unsaturated compounds with carbon monoxide and hydrogen,
wherein the improvement comprises:
addition of at least one organic acid in a total amount, calculated as acid equivalent, of from greater than 3 mol to 3000 mol per mole of rhodium to the rhodium-containing organic solution and subsequent feeding of this solution to the reaction zone, said organic acid being selected from the group consisting of:
(a) n-valeric acid;
(b) 2-methylbutyric acid;
(c) 2-ethylhexanoic acid;
(d) isononanoic acid prepared by hydroformylation of diisobutylene and subsequent oxidation of the hydroformylation product;
(e) isotridecanoic acid prepared by hydroformylation of tetrapropylene and subsequent oxidation of the hydroformylation product;
(f) methanesulphonic acid,
(g) para-toluenesulphonic acid,
(h) benzenesulphonic acid;
(i) benzenedisulphonic acid;
(j) adipic acid and
(k) combinations of any of (a)-(j).
36. The improved process according to claim 35 , wherein the rhodium content of the rhodium-containing organic solution fed to the reaction zone is from 1000 to 10 000 ppm.
37. The improved process according to claim 35 , wherein the rhodium content of the rhodium-containing organic solution fed to the reaction zone is from 100 to 10 000 ppm.
38. The improved process according to claim 37 , wherein the solvent in the organic solution containing at least one rhodium compound in dissolved form is selected from the group consisting of 2-ethylhexanol; isononanol based on 3,5,5-trimethylhexanol or combinations thereof.
39. The improved process according to claim 38 , characterized in that the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a rhodium content of from 1 to 100 ppm, based on the homogeneous reaction mixture.
40. The improved process according to claim 38 , characterized in that the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a rhodium content of from 2 to 30 ppm, based on the homogeneous reaction mixture.
41. The improved process according to claim 35 , characterized in that the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a rhodium content of from 1 to 100 ppm, based on the homogeneous reaction mixture.
42. The improved process according to claim 35 , characterized in that the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone is carried out at a rhodium content of from 2 to 30 ppm, based on the homogeneous reaction mixture.
43. An improved process for preparing aldehydes in a homogeneous organic phase in the presence of at least one rhodium compound and in the absence of complex-forming organophosphorus compounds in this reaction zone by:
a. introduction of an organic solution containing at least one rhodium compound in dissolved form into a reaction zone; and
b. reaction of olefinically unsaturated compounds with carbon monoxide and hydrogen,
wherein the improvement comprises:
addition of at least one organic acid in a total amount, calculated as acid equivalent, of from greater than 3 mol to 3000 mol per mole of rhodium to the rhodium-containing organic solution and subsequent feeding of this solution to the reaction zone, said organic acid being selected from the group consisting of:
(a) n-valeric acid;
(b) 2-methylbutyric acid;
(c) 2-ethylhexanoic acid;
(d) isononanoic acid prepared by hydroformylation of diisobutylene and subsequent oxidation of the hydroformylation product;
(e) isotridecanoic acid prepared by hydroformylation of tetrapropylene and subsequent oxidation of the hydroformylation product;
(f) methanesulphonic acid,
(g) para-toluenesulphonic acid,
(h) benzenesulphonic acid;
(i) benzenedisulphonic acid;
(j) adipic acid and
(k) combinations of any of (a)-(j);
the rhodium content of the rhodium-containing organic solution fed to the reaction zone being from 1000 to 10 000 ppm; the solvent in the organic solution containing at least one rhodium compound in dissolved form being selected from the group consisting of 2-ethylhexanol; isononanol based on 3,5,5-trimethylhexanol and combinations thereof; the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone being carried out at a rhodium content of from 2 to 30 ppm, based on the homogeneous reaction mixture; the reaction of the olefinically unsaturated compounds with carbon monoxide and hydrogen in the reaction zone being carried out at a temperature of from 100 to 150° C., and a pressure of from 0.1 to 30 MPa.