Diene removal from an olefin feedstock

Abstract

The invention pertains to a process of removing dienes from an olefin feedstock. A preferred olefin feedstock is for the production of primary alcohol compositions by skeletal isomerization of the olefins followed by hydroformylation. In this preferred embodiment, the olefin feedstock may be purified before and/or after skeletal isomerization. The olefins in the feedstock preferably have a carbon chain length of about 8 to about 36 carbon atoms, preferably about 10 to about 20 carbon atoms, most preferably about 12 to about 18 carbon atoms.

1. A method for purifying an olefin stream comprising:
 providing an olefin feedstock wherein said olefins have an average molecular chain length of from about 10 to about 20 carbon atoms, said olefin feedstock comprising a quantity of dienes;  
 contacting said olefin feedstock with a hydrogenation catalyst that is sensitive to diene poisoning in the presence of a gas feed comprising an inert gas, said gas feed also comprising from about 2 to about 6 vol. % hydrogen, at a feedstock flow rate of about 1 LHSV or less under conditions effective to convert a majority of said dienes to olefins.  
 
     
     
       2. The method of  claim 1  wherein said hydrogenation catalyst comprises a fixed bed. 
     
     
       3. The method of  claim 1  wherein said hydrogenation catalyst comprises palladium. 
     
     
       4. The method of  claim 1  wherein said hydrogenation catalyst comprises palladium. 
     
     
       5. The method of  claim 1  wherein said hydrogenation catalyst comprises about 0.2 wt. % palladium on a support. 
     
     
       6. The method of  claim 2  wherein said hydrogenation catalyst comprises about 0.2 wt. % palladium on a support. 
     
     
       7. The method of  claim 1  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       8. The method of  claim 2  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       9. The method of  claim 3  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       10. The method of  claim 4  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       11. The method of  claim 5  wherein said support comprises alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       12. The method of  claim 6  wherein said support comprises alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       13. The method of  claim 1  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       14. The method of  claim 2  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       15. The method of  claim 3 , wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       16. A method for purifying an olefin stream comprising:
 providing an olefin feedstock wherein said olefins have an average molecular chain length of from about 8 to about 36 carbon atoms, said olefin feedstock comprising a quantity of dienes;  
 contacting said olefin feedstock and a gas feed comprising an inert gas with a hydrogenation catalyst that is sensitive to diene poisoning under conditions effective to produce a purified olefin stream comprising a paraffin content of about 1 wt.% or less, said conditions comprising a quantity of hydrogen in said gas feed of from about 2 to about 6 vol. % and a flow rate of said olefin feedstock, said quantity and said flow rate being sufficiently low to convert a majority of said dienes to olefins.  
 
     
     
       17. The method of  claim 16  wherein said average molecular chain length is about 10 carbon atoms or more. 
     
     
       18. The method of  claim 16  wherein said hydrogenation catalyst comprises a fixed bed. 
     
     
       19. The method of  claim 17  wherein said hydrogenation catalyst comprises a fixed bed. 
     
     
       20. The method of  claim 16  wherein said hydrogenation catalyst comprises palladium. 
     
     
       21. The method of  claim 17  wherein said hydrogenation catalyst comprises palladium. 
     
     
       22. The method of  claim 18  wherein said hydrogenation catalyst comprises palladium. 
     
     
       23. The method of  claim 19  wherein said hydrogenation catalyst comprises palladium. 
     
     
       24. The method of  claim 16  wherein said hydrogenation catalyst comprises about 0.2 wt. % palladium on a support. 
     
     
       25. The method of  claim 17  wherein said hydrogenation catalyst comprises about 0.2 wt. % palladium on a support. 
     
     
       26. The method of  claim 16  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       27. The method of  claim 19  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about 2 to about 5 m 2 /g. 
     
     
       28. The method of  claim 16  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       29. The method of  claim 17  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       30. The method of  claim 18  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       31. The method of  claim 19  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       32. The method of  claim 20  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       33. The method of  claim 21  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       34. The method of  claim 22  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       35. The method of  claim 23  wherein said feedstock flow rate is about 1 LHSV or less. 
     
     
       36. The method of  claim 16  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       37. The method of  claim 17  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       38. The method of  claim 18  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       39. The method of  claim 19  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       40. The method of  claim 20  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       41. The method of  claim 21  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       42. The method of  claim 22  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       43. The method of  claim 23  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       44. The method of  claim 16  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       45. The method of  claim 17  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       46. The method of  claim 18  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       47. The method of  claim 19  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       48. The method of  claim 20  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       49. The method of  claim 21  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       50. The method of  claim 22  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       51. The method of  claim 23  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less. 
     
     
       52. A method for purifying an olefin stream comprising:
 providing an olefin feedstock wherein said olefins have an average molecular chain length of from about 10 to about 20 carbon atoms and an average number of branches per molecular chain of at least 0.7, said olefin feedstock comprising a quantity of dienes;  
 contacting said olefin feedstock with a fixed bed hydrogenation catalyst in the presence of a gas feed comprising an inert gas, said gas feed also comprising from about 2 to about 6 vol. % hydrogen, said hydrogenation catalyst comprising from about 0.05 wt. % to about 0.2 wt. % palladium on alumina, said alumina having a surface area of about 15 m 2 /g or less, wherein said olefin feedstock has a flow rate through said fixed bed of about 1 LHSV or less under conditions effective to convert a majority of said dienes to olefins.  
 
     
     
       53. The method of  claim 52  wherein said alumina has a surface area of about 2 to about 5 m 2 /g. 
     
     
       54. The method of  claim 52  wherein said hydrogenation catalyst comprises about 0.2 wt. % palladium. 
     
     
       55. The method of  claim 53  wherein said hydrogenation catalyst comprises about 0.2 wt. % palladium. 
     
     
       56. The method of  claim 52  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       57. The method of  claim 53  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       58. The method of  claim 54  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       59. The method of  claim 55  wherein said feedstock flow rate is about 0.5 LHSV or less. 
     
     
       60. The method of  claim 52  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       61. The method of  claim 53  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       62. The method of  claim 54  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       63. The method of  claim 55  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       64. The method of  claim 56  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       65. The method of  claim 57  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       66. The method of  claim 58  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       67. The method of  claim 59  wherein said method produces a purified olefin stream comprising about 40% of said quantity of dienes or less and a paraffin content of about 1 wt. % or less. 
     
     
       68. A method for purifying an olefin stream comprising:
   providing an olefin feedstock wherein said olefins have an average molecular chain length of from about  8  to about  36  carbon atoms, said olefin feedstock comprising a quantity of dienes;        contacting said olefin feedstock with a hydrogenation catalyst that is sensitive to diene poisoning in the presence of a gas feed comprising an inert gas, said gas feed also comprising from about  2  to about  6  vol.  %  hydrogen at a feedstock flow rate and under conditions effective to convert a majority of said dienes to olefins.     
     
     
       69. The method of  claim 68  wherein said hydrogenation catalyst comprises a fixed bed. 
     
     
       70. The method of  claim 69  wherein said hydrogenation catalyst comprises palladium. 
     
     
       71. The method of  claim 68  wherein said hydrogenation catalyst comprises palladium. 
     
     
       72. The method of  claim 69  wherein said hydrogenation catalyst comprises about  0 . 2  wt. %  palladium on a support.   
     
     
       73. The method of  claim 68  wherein said hydrogenation catalyst comprises about  0 . 2  wt. %  palladium on a support.   
     
     
       74. The method of  claim 69  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about  2  to about  5  m 2   /g.   
     
     
       75. The method of  claim 70  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about  2  to about  5  m 2   /g.   
     
     
       76. The method of  claim 71  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about  2  to about  5  m 2   /g.   
     
     
       77. The method of  claim 72  wherein said hydrogenation catalyst comprises a support comprising alumina having a surface area of from about  2  to about  5  m 2   /g.   
     
     
       78. The method of  claim 68  wherein said support comprises alumina having a surface area of from about  2  to about  5  m 2   /g.   
     
     
       79. The method of  claim 69  wherein said feedstock flow rate is about  0 . 5  LHSV or less. 
     
     
       80. The method of  claim 70  wherein said feedstock flow rate is about  0 . 5  LHSV or less. 
     
     
       81. The method of  claim 71  wherein said feedstock flow rate is about  0 . 5  LHSV or less. 
     
     
       82. The method of  claim 72  wherein said feedstock flow rate is about  0 . 5  LHSV or less. 
     
     
       83. The method of  claim 69  wherein said average molecular chain length is about  10  carbon atoms or more. 
     
     
       84. The method of  claim 70  wherein said average molecular chain length is about  10  carbon atoms or more. 
     
     
       85. The method of  claim 69  wherein said feedstock flow rate is about  1  LHSV or less. 
     
     
       86. The method of  claim 69  wherein said method produces a purified olefin stream comprising about  40 %  of said quantity of dienes or less.   
     
     
       87. The method of  claim 68  wherein said method produces a purified olefin stream comprising about  40 %  of said quantity of dienes or less.