Process for isomerization of alpha olefins to internal olefins
View Patent ↗The present invention relates to embodiments for a process for the isomerization of at least one alpha olefin to an internal olefin via a multi-step process resulting in a mixture comprising alkene isomers and a low level of oligomers. According to the present invention an alkylaluminum compound is used in combination with the Group VIII transition metal salt for interaction with the latter, and thereby generating catalytically active species for the isomerization of 1-alkenes to internal alkenes, wherein this mixture is subsequently combined with an acid washed clay.
1. A process for the isomerization of 1-alkene to an internal alkene comprising:
a.) combining at least one 1-alkene in liquid phase at a temperature of from about 50° C. to about 200° C. with a catalyst, wherein the catalyst is formed by contacting (i) at least one Group VIII transition metal salt and (ii) at least one alkylaluminum compound thereby resulting in a first mixture; and
b.) combining the first mixture of step a) with at least one acid washed clay at a temperature of about 100° C. to about 300° C. to form a final mixture.
2. The process of claim 1 , wherein the at least one 1-alkene contains at least 4 carbon atoms.
3. The process of claim 2 , wherein the at least one 1-alkene contains about 5 to about 40 carbon atoms.
4. The process of claim 3 , wherein the at least one 1-alkene contains about 6 to about 30 carbon atoms.
5. The process of claim 4 , wherein the at least one 1-alkene contains about 10 to about 20 carbon atoms.
6. The process of claim 1 , wherein the at least one 1-alkene is 1-pentene, 3-methyl-1-butene, 2-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 2-methyl-1-octene, 2-ethyl-1-hexene, 5-methyl-1-heptene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 2-methyl-1-dodecene, 1-tetradecene, 2-methyl-1-tetradecene, 1-hexadecene, 2-methyl-1-hexadecene, 5-methyl-1-hexadecene, 1-octadecene, 2-methyl-1-octadecene, 1-eicosene, 2-methyl-1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene, vinylcyclohexane, 2-phenyl-1-butene or mixtures thereof.
7. The process according to claim 1 , wherein the at least one Group VIII transition metal is at least one of nickel, cobalt, iron, palladium, rhodium, platinum, ruthenium, osmium, iridium or mixtures thereof.
8. The process according to claim 7 , wherein the at least one Group VIII transition metal is at least one of nickel, cobalt, palladium or mixtures thereof.
9. The process according to claim 8 , wherein the at least one Group VIII transition metal is at least one of cobalt, palladium or mixtures thereof.
10. The process of claim 1 , wherein the at least one Group VIII transition metal salt comprises a halogen.
11. The process of claim 10 , wherein the halogen is chlorine.
12. The process of claim 1 , wherein the at least one Group VIII transition metal salt comprises a chelate-forming ligand.
13. The process of claim 12 , wherein the chelate-forming ligand is acetylacetonate.
14. The process according to claim 1 , wherein the at least one Group VIII transition metal salt includes at least one compound selected from Ni(II) chloride, Ni(II) acetylacetonate, Co(III) acetylacetonate, PdCl 2 , PtCl 2 (cyclooctadienyl) 2 , Ir(III) acetylacetonate or Rh(III) acetylacetonate.
15. The process according to claim 14 , wherein the at least one Group VIII transition metal salt includes at least one compound selected from Ni(II) chloride, Ni(II) acetylacetonate, Rh(III) acetylacetonate; Ir(III) acetylacetonate or Co(III) acetylacetonate.
16. The process according to claim 15 , wherein the at least one Group VIII transition metal salt includes at least one compound selected from Ni(II) acetylacetonate, Ir(III) acetylacetonate or Co(III) acetylacetonate.
17. The process according to claim 16 , wherein the at least one Group VIII transition metal salt is cobalt (III) acetylacetonate.
18. The process according to claim 1 , wherein if the at least one Group VIII transition metal salt includes cobalt and the at least one alkylaluminum compound includes a trialkylaluminum compound, the process is carried out having a substantial absence of alkoxyaluminum species.
19. The process according to claim 1 , wherein the at least one alkylaluminum compound comprises a compound having the general formula: AlR a X b , wherein R is an alkyl radical, X is a halogen radical, a is an integer from 1 to 3, b is 0, 1 or 2, and the sum (a+b) is 3.
20. The process of claim 19 , wherein the radical R represents alkyl of from 1 to about 40 carbon atoms.
21. The process of claim 20 , wherein the radical R represents alkyl of from 1 to about 10 carbon atoms.
22. The process of claim 21 , wherein the radical R represents alkyl of from 1 to about 6 carbon atoms.
23. The process of claim 19 , wherein the radical R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, and n-decyl.
24. The process of claim 23 , wherein the radical R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, n-pentyl, and n-hexyl.
25. The process of claim 19 , wherein a is 2 or 3.
26. The process of claim 25 , wherein a is 3.
27. The process of claim 19 , wherein b is 1 or 2.
28. The process of claim 19 , wherein X includes Cl or Br.
29. The process of claim 28 , wherein X includes Cl.
30. The process according to claim 19 , wherein the at least one alkylaluminum compound is a trialkylaluminum compound or an alkylaluminum halide.
31. The process according to claim 30 , wherein the trialkylaluminum compound is trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, diethylisobutylaluminum, trihexylaluminum, triheptylaluminum or trioctylaluminum.
32. The process according to claim 30 , wherein the alkylaluminum halide is diethylaluminumchloride (DEAC), ethylaluminumdichloride or isobutylaluminumdichloride.
33. The process of claim 1 , wherein the 1-alkene and Group VIII transition metal are in a molar ratio of from about 1:1 to about 10,000:1.
34. The process of claim 33 , wherein the molar ratio is from about 10:1 to about 5,000:1.
35. The process of claim 34 , wherein the molar ratio is from about 500:1 to about 4,000:1.
36. The process of claim 35 , wherein the molar ratio is from about 700:1 to about 2,000:1.
37. The process of claim 1 , wherein the Group VIII transition metal(s) and Al in the alkylaluminum compound(s) are in an atomic ratio of from about 2:1 to about 1:500.
38. The process of claim 37 , wherein the atomic ratio is from about 1:1 to about 1:300.
39. The process of claim 38 , wherein the atomic ratio is from about 1:2 to about 1:100.
40. The process according to claim 1 , wherein the temperature of step (a) ranges from about 80° C. to about 150° C.
41. The process according to claim 40 , wherein the temperature of step (a) ranges from about 80° C. to about 120° C.
42. The process according to claim 1 , wherein step (a) has a reaction time ranging from about 1 hour to about 12 hours.
43. The process according to claim 42 , wherein step (a) has a reaction time ranging from about 2 hours to about 6 hours.
44. The process according to claim 43 , wherein step (a) has a reaction time ranging from about 2 hours to about 4 hours.
45. The process according to claim 1 , wherein step (a) results in a degree of isomerization of about 90% or greater.
46. The process according to claim 1 , wherein the first mixture comprises up to about 5 wt-% of 1-alkene, about 50 wt-% to about 70 wt-% or more of 2-alkene and less than about 2 wt-% of oligomers.
47. The process according to claim 1 , wherein step (b) has a reaction time ranging from about 10 minutes to about 6 hours.
48. The process according to claim 47 , wherein the reaction time ranges from about 20 minutes to about 4 hours.
49. The process according to claim 48 , wherein the reaction time ranges from about 30 minutes to about 2 hours.
50. The process according to claim 1 , wherein the at least one acid washed clay is a calcined acid washed clay.
51. The process according to claim 50 , wherein the calcined acid washed clay is an acid activated Bentonite, Engelhard's product F 13 , F 22 , F 24 , F 20X or mixtures thereof.
52. The process according to claim 1 , wherein the at least one acid washed clay has a residual acidity ranging from about 1.0 to about 0.025 meq/g.
53. The process according to claim 52 , wherein the at least one acid washed clay has a residual acidity ranging from about 0.5 to about 0.1 meq/g.
54. The process according to claim 53 , wherein the at least one acid washed clay has a residual acidity ranging from about 0.4 to about 0.2 meq/g.
55. The process according to claim 1 , wherein the at least one acid washed clay is utilized in amounts ranging from about 0.25 wt-% to about 3.0 wt-% based on olefins.
56. The process according to claim 55 , wherein the at least one acid washed clay is utilized in amounts ranging from about 0.5 wt-% to about 2.0 wt-%.
57. The process according to claim 56 , wherein the at least one acid washed clay is utilized in amounts ranging from about 0.75 wt-% to about 1.0 wt-%.
58. The process according to claim 1 , wherein in step (b) the temperature ranges from about 120° C. to about 200° C.
59. The process according to claim 58 , wherein the temperature ranges from about 150° C. to about 175° C.
60. The process according to claim 1 , wherein the final mixture of step (b) comprises about 1-5 wt-% of alpha olefins, about 15-50 wt-% of C 2 alkenes, about 15-25 wt-% of C 3 alkenes, about 5-20 wt-% of C 4 alkenes, about 10-50 wt-% of C 5 and up alkenes and less than about 10 wt-% of dimers.
61. The process according to claim 60 , wherein the final mixture contains less than about 6 wt-% of dimers.
62. The process of claim 1 , wherein step (a) is carried out in the presence of solvent.
63. The process of claim 62 , wherein the solvent is selected from aliphatic, cycloaliphatic and aromatic hydrocarbons, halogenated aliphatic, cycloaliphatic and aromatic hydrocarbons, aliphatic ethers and mixtures thereof.
64. The process of claim 1 , wherein step (a) is carried out in the absence of solvent.
65. The process of claim 1 , wherein step (a) is carried out under substantially anhydrous conditions.
66. The process of claim 1 , wherein step (a) is carried out in the substantial absence of molecular oxygen.
67. The process of claim 1 , wherein the process is carried out batchwise.
68. The process of claim 1 , wherein the process is carried out in a semi-continuous fashion.
69. The process of claim 1 , wherein the process is carried out in a continuous fashion.
70. The process of claim 1 , wherein the catalyst is formed in situ.
71. The process of claim 1 , wherein the predominant isomerization product is 2-alkene.
72. The process of claim 1 , wherein at least one 1-alkene having from 6 to 30 carbon atoms is contacted, at a temperature from about 80 to about 150° C. and under substantially anhydrous conditions and in the substantial absence of molecular oxygen, with at least one Group VIII transition metal salt selected from chlorides and acetylacetonates of Ni, Co and Pd and with at least one alkylaluminum compound selected from trimethylaluminum, triethylaluminum and diethylaluminumchloride, the 1-alkene(s) and Group VIII transition metal(s) having a molar ratio of from about 100:1 to about 2,000:1, and the Group VIII transition metal(s) and Al in the alkylaluminum compound(s) having an atomic ratio of from about 1:2 to about 1:100, thereby forming internal olefin comprised of at least about 60 mole-% of 2-alkene(s), without concurrent formation of more than about 5% of oligomers.
73. A process for the isomerization of 1-alkene to an internal alkene comprising:
a.) combining at least one 1-alkene in liquid phase and at a temperature of from about 50° C. to about 200° C. with a catalyst, wherein the catalyst is formed by contacting (i) at least one Group VIII transition metal salt and (ii) at least one alkylaluminum compound thereby resulting in a first mixture; wherein the alkylaluminum compound contains at least one alkyl group directly bonded to an aluminum atom and
b.) combining the first mixture of step a) with at least one acid washed clay to form a final mixture.
74. A process for the isomerization of 1-alkene to an internal alkene comprising:
a.) combining at least one 1-alkene in liquid phase and at a temperature of from about 50° C. to about 200° C. with a catalyst, wherein the catalyst is formed by contacting (i) at least one Group VIII transition metal salt and (ii) at least one alkylaluminum compound thereby resulting in a first mixture; wherein the alkylaluminum compound contains at least one alkyl group directly bonded to an aluminum atom and wherein if the at least one Group VIII transition metal salt includes cobalt and the at least one alkylaluminum compound includes a trialkylaluminum compound, the process is carried out having a substantial absence of alkoxyaluminum species, and
b.) combining the first mixture of step a) with at least one acid washed clay to form a final mixture.
75. A process for the isomerization of 1-alkene to an internal alkene comprising:
a.) combining at least one 1-alkene in liquid phase and at a temperature of from about 50° C. to about 200° C. with a catalyst, wherein the catalyst is formed by contacting (i) at least one salt of a Group VIII transition metal selected from cobalt, iron, palladium, platinum, osmium, iridium, rhodium, ruthenium and mixtures thereof and (ii) at least one alkylaluminum compound thereby resulting in a first mixture; wherein the alkylaluminum compound contains at least one alkyl group directly bonded to an aluminum atom and wherein if the at least one Group VIII transition metal salt includes cobalt and the at least one alkylaluminum compound includes a trialkylaluminum compound, the process is carried out having a substantial absence of alkoxyaluminum species, and
b.) combining the first mixture of step a) with at least one acid washed clay to form a final mixture.