Ethylene Oligomerization Processes
A process comprising A) continuously introducing into a reaction zone i) ethylene, ii) an iron salt, iii) a pyridine bisimine, iv) an organoaluminum compound, and v) an organic reaction medium, and B) forming an oligomer product in the reaction zone, the reaction zone having i) an iron of the iron salt concentration in a range of 5×10 −4 mmol/kg to 5×10 −3 mmol/kg, ii) an aluminum of the organoaluminum compound to iron of the iron salt molar ratio in a range of 300:1 to 800:1, ii) an ethylene partial pressure in a range of 750 psig to 1200 psig, iv) an ethylene to organic reaction medium mass ratio in a range of 0.8 to 4.5, v) a temperature in a range of 75° C. to 95° C., and optionally vi) a hydrogen partial pressure of at least 5 psi.
1 . A process comprising:
A) continuously introducing into a reaction zone
i) ethylene,
ii) an iron salt,
iii) a pyridine bisimine,
iv) an organoaluminum compound, and
v) an organic reaction medium, and
B) forming an oligomer product in the reaction zone, the reaction zone having
i) an iron of the iron salt concentration in a range of 5×10 −4 mmol/kg to 5×10 −3 mmol/kg,
ii) an aluminum of the organoaluminum compound to iron of the iron salt molar ratio in a range of 300:1 to 800:1,
ii) an ethylene partial pressure in a range of 750 psig to 1200 psig,
iv) an ethylene to organic reaction medium mass ratio in a range of 0.8 to 4.5,
v) a temperature in a range of 75° C. to 95° C.; and optionally
vi) a hydrogen partial pressure of at least 5 psi.
2 . The process of claim 1 , wherein the organic reaction medium comprises one or more C 8 to C 18 aliphatic hydrocarbons.
3 . The process of claim 1 , wherein the organic reaction medium comprises one or more C 8 to C 16 olefinic aliphatic hydrocarbons.
4 . The process of claim 2 , wherein the organic reaction medium is substantially devoid of a halogenated compound.
5 . The process of claim 1 , wherein the reaction zone has an aluminum of the organoaluminum compound concentration in the range of 0.75 mmol Al/kg to 2.6 mmol Al/kg, an aluminum of the organoaluminum compound to iron of the iron salt molar ratio in the range of 300:1 to 500:1, an ethylene partial pressure in the range of 750 to 1000 psi, and a temperature in the range of 80° C. to 90° C.; wherein the oligomer product formed in the reaction zone has a Schultz-Flory K value in the range of 0.4 to 0.9 and wherein the organic reaction medium consists essentially of one or more of C 8 to C 16 olefinic aliphatic hydrocarbons.
6 . The process of claim 5 , wherein the organic reaction medium is selected from the group consisting of 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
7 . The process of claim 1 , wherein the pyridine bisimine comprises
i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different,
ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or
iii) an [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.
8 . The process of claim 7 , wherein
1) one, two, or three of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
2) one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen is a tertiary carbon atom group; none, one, or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
3) two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group; none, or one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
4) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group(s); and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
5) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are a quaternary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, or
6) all four of the substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are fluorine.
9 . The process of claim 6 , wherein the pyridine bisimine is selected from the group consisting of 2,6-bis[(phenylimine) methyl]pyridine, 2,6-bis[(2-methylphenylimine)methyl]pyridine, 2,6-bis [(2-ethylphenylimine)methyl]pyridine, 2,6-bis [(2-isopropylphenylimine)methyl]pyridine, 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine, and 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine and combinations thereof.
10 . A process comprising:
A) continuously introducing into a reaction zone
i) ethylene,
ii) a pyridine bisimine iron salt complex,
iii) an organoaluminum compound, and
iv) an organic reaction medium; and
B) forming an oligomer product in the reaction zone, the reaction zone having
i) an iron of the pyridine bisimine iron salt complex concentration in a range of 5×10 −4 mmol/kg to 5×10 −3 mmol/kg,
ii) an aluminum of the organoaluminum compound to iron of the pyridine bisimine iron salt complex molar ratio in a range of 300:1 to 800:1,
iii) an ethylene partial pressure in a range of 750 psig to 1200 psig,
iv) an ethylene to organic reaction medium mass ratio of 0.8 to 4.5, and
v) an average temperature in a range of 75° C. to 95° C.; and optionally
vi) a hydrogen partial pressure of at least 5 psi.
11 . The process of claim 10 , wherein the organic reaction medium comprises one or more C 8 to C 18 aliphatic hydrocarbons.
12 . The process of claims 10 , wherein the organic reaction medium comprises one or more C 8 to C 16 olefinic aliphatic hydrocarbons.
13 . The process of claim 11 , wherein the organic reaction medium is substantially devoid of a halogenated compound.
14 . The process of claim 10 , wherein the reaction zone has an aluminum of the organoaluminum compound concentration in the range of 0.75 mmol Al/kg to 2.6 mmol Al/kg, an aluminum of the organo aluminum compound to iron of the pyridine bisimine iron salt complex molar ratio in the range of 300:1 to 500:1, an ethylene partial pressure in the range of 750 to 1000 psi, a temperature in the range of 80° C. to 90° C.; wherein the oligomer product formed in the reaction zone has a Schultz-Flory K value in the range of 0.4 to 0.9; and wherein the organic reaction medium consists essentially of one or more C 8 to C 16 olefinic aliphatic hydrocarbons.
15 . The process of claim 14 , wherein the organic reaction medium consists essentially of 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
16 . The process of claim 10 , wherein the pyridine bisimine or the pyridine bisimine of the pyridine bisimine iron salt complex comprises
i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different,
ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or
iii) an [(arylimine)hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine.
17 . The process of claim 16 , wherein
1) one, two, or three of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
2) one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen is a tertiary carbon atom group' none, one, or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
3) two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group; none, or one of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a halogen, a primary carbon atom group, or a secondary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
4) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen independently are a tertiary carbon atom group(s); and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen,
5) one or two of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are a quaternary carbon atom group; and the remainder of the aryl groups and/or substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are hydrogen, or
6) all four of the substituted aryl groups positions ortho to the carbon atom attached to the imine nitrogen are fluorine.
18 . The process of claim 15 , wherein the pyridine bisimine is selected from the group consisting of 2,6-bis[(phenylimine) methyl]pyridine, 2,6-bis[(2-methylphenylimine)methyl]pyridine, 2,6-bis [(2-ethylphenylimine)methyl]pyridine, 2,6-bis[(2-isopropylphenylimine)methyl]pyridine, 2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine, 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5 -dimethylphenylimine)methyl]pyridine, and 2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.
19 . A process comprising:
A) continuously introducing into a reaction zone
i) ethylene,
ii) an iron salt,
iii) a pyridine bisimine,
iv) an organoaluminum compound, and
v) an organic reaction medium comprising one or more C 8 to C 18 aliphatic hydrocarbons; and
B) forming an oligomer product in the reaction zone, the reaction zone having an average temperature in a range of 75° C. to 95° C.
20 . The process of claim 19 , wherein the organic reaction medium comprises one or more C 8 to C 16 olefinic aliphatic hydrocarbons.
21 . The process of claim 20 , wherein the organic reaction medium comprises 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
22 . The process of claim 19 , wherein the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or iii) a [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.
23 . A process comprising:
A) continuously introducing into a reaction zone
i) ethylene,
ii) an pyridine bisimine iron salt complex,
iii) an organoaluminum compound, and
iv) an organic reaction medium comprising one or more C 8 to C 18 aliphatic hydrocarbons; and
B) forming an oligomer product in the reaction zone, the reaction zone having an average temperature in a range of 75° C. to 95° C.
24 . The process of claims 23 , wherein the organic reaction medium comprises one or more C 8 to C 16 olefinic aliphatic hydrocarbons.
25 . The process of claim 23 , wherein the organic reaction medium comprises 1-decene, 1-dodecene, 1-tetradecene, or any combination thereof.
26 . The process of claim 23 wherein the pyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can be the same or different, ii) a bis[(substituted arylimine)hydrocarbyl]pyridine, wherein the substituted aryl groups can be the same or different, or iii) a [(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.