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Systems and methods to produced branched aliphatic alcohols are described. Systems may include a dehydrogenation-isomerization unit, an olefin dimerization unit, an olefin isomerization unit, a hydroformylation unit, a dehydrogenation unit, a hydrogenation unit and/or combinations thereof. Methods f

Systems and methods to produced branched aliphatic alcohols are described. Systems may include a dehydrogenation-isomerization unit, an olefin dimerization unit, an olefin isomerization unit, a hydroformylation unit, a dehydrogenation unit, a hydrogenation unit and/or combinations thereof. Methods for producing branched aliphatic alcohols may include isomerization of olefins in a process stream. The isomerized olefins may be hydroformylated to produce aliphatic alcohols. After hydroformylation of the aliphatic alcohols, unreacted components from the hydroformylation process may be separated from the aliphatic alcohols products. The unreacted components from the hydroformylation process may be recycled back into the main process stream or sent to other processing units. Addition of multiple streams to the units may be performed to control reaction conditions in the units.

대표청구항 ▼

What is claimed is: 1. A method for the production of alphatic alcohols, comprising: introducing a Fischer-Tropsch hydrocarbon stream comprising olefins and paraffins, said Fischer-Tropsch hydrocarbon stream containing from 5 to 80 percent olefins having an average carbon number of from 10 to 17, i

What is claimed is: 1. A method for the production of alphatic alcohols, comprising: introducing a Fischer-Tropsch hydrocarbon stream comprising olefins and paraffins, said Fischer-Tropsch hydrocarbon stream containing from 5 to 80 percent olefins having an average carbon number of from 10 to 17, into a dehydrogenation-isomerization unit, wherein the dehydrogenation-isomerization unit is configured to dehydrogenate at least a portion of the paraffins in the Fischer-Tropsch hydrocarbon stream to olefins, and wherein the dehydrogenation-isomerization unit is further configured to isomerize at least a portion of linear olefins to branched olefins in the presence of a dehydrogenation-isomerization catalyst comprising a hydrogen form of a zeolite having a ferrierite isotypic framework structure, and wherein the residence time is such that the conversion of paraffins to olefins is below 40 mole percent, and wherein at least a portion of the unreacted components of the Fischer-Tropsch hydrocarbon stream and at least a portion of the products of the dehydrogenation and isomerization reactions form a second hydrocarbon stream, the second hydrocarbon stream comprising olefins and paraffins, and wherein at least a portion of the olefins in the second hydrocarbon stream is branched olefins; and introducing at least a portion of the second hydrocarbon stream into a hydroformylation unit, wherein the hydroformylation unit is configured to hydroformylate at least a portion of the olefins in the second hydrocarbon stream to produce aliphatic alcohols having an average carbon number of from 11 to 18, and wherein at least a portion of the produced aliphatic alcohols comprises a branched alkyl group. 2. The method of claim 1, wherein the dehydrogenation-isomerization unit is operated at a temperature range from about 300�� C. to about 500�� C. 3. The method of claim 1, wherein the dehydrogenation-isomerization unit is configured to operate at a pressure range from about 0.10 atmosphere to about 15 atmospheres. 4. The method of claim 1, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules of at least 0.7. 5. The method of claim 1, wherein a portion of the branched olefins comprises methyl and ethyl branches. 6. The method of claim 1, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules of less than 2.5. 7. The method of claim 1, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules from about 0.7 to about 2.2. 8. The method of claim 1, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules of from about 1.0 to about 2.2. 9. The method of claim 1, wherein greater than 50 percent of the branched groups on the branched olefins are methyl groups. 10. The method of claim 1, wherein less than 30 percent of the branched groups on the branched olefins are ethyl groups. 11. The method of claim 1, wherein less than 10 percent of the branched groups on the branched olefins are neither methyl or ethyl groups. 12. The method of claim 1, wherein the branched olefins have less than 0.5 percent aliphatic quaternary carbon atoms. 13. The method of claim 1, wherein the branched olefins have less than 0.3 percent aliphatic quaternary carbon atoms. 14. The method of claim 1, further comprising: introducing at least a portion of the second hydrocarbon stream into a separation unit, wherein the separation unit is configured to separate at least a portion of the branched olefins from linear olefins and paraffins to form a linear olefins and paraffins stream and a branched olefins stream; combining at least a portion of the linear olefins and paraffins stream with the Fischer-Tropsch hydrocarbon stream upstream of the dehydrogenation-isomerization unit; and combining at least a portion of the branched olefins stream with the second hydrocarbon stream upstream of the hydroformylation unit. 15. The method of claim 1, wherein the aliphatic alcohols produced by the hydroformylation unit comprise greater than 50 percent of the total hydrocarbon content of the hydroformylation reaction stream. 16. The method of claim 1, wherein the hydroformylation unit is operated at a reaction temperature from about 100�� C. to about 300�� C. 17. The method of claim 1, further comprising adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by adding at least a portion of a third hydrocarbon stream into the hydroformylation unit. 18. The method of claim 1, further comprising adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by adding at least a portion of a third hydrocarbon stream into the hydroformylation unit, wherein the third hydrocarbon stream comprises greater than 80 percent olefins by weight. 19. The method of claim 1, further comprising adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit and introducing the combined stream into the hydroformylation unit. 20. The method of claim 1, further comprising: adjusting a ratio of olefins to paraffins introduced into the hydroformylation unit by combining at least a portion of a third hydrocarbon stream with at least a portion of the second hydrocarbon stream upstream of the hydroformylation unit, wherein the third hydrocarbon stream comprises greater than 80 percent olefins by weight; and introducing the mixed stream into the hydroformylation unit. 21. The method of claim 1, wherein the branched alkyl groups of the aliphatic alcohols comprise 0.5 percent or less aliphatic quaternary carbon atoms, and an average number of branches per alkyl group of at least 0.7, the branches comprising methyl and ethyl branching. 22. The method of claim 1, further comprising: separating aliphatic alcohols from the hydroformylation reaction stream to produce at least a paraffins and unreacted olefins stream and an aliphatic alcohols product stream; and introducing at least a portion of the paraffins and unreacted olefins stream into the dehydrogenation-isomerization unit. 23. The method of claim 22, wherein introducing at least a portion of the paraffins and unreacted olefins stream into the dehydrogenation-isomerization unit comprises: combining at least a portion of the paraffins and unreacted olefins stream with at least a portion of the Fischer-Tropsch hydrocarbon stream to produce a combined stream upstream of the dehydrogenation-isomerization unit; and introducing at least a portion of the combined stream into the dehydrogenation-isomerization unit. 24. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a dehydrogenation-isomerization catalyst which additionally comprises a binder, a coke-oxidizing compound, and a paraffin dehydrogenation promoting compound. 25. The method of claim 24, wherein the coke-oxidizing compound comprises chrome oxide, iron oxide, noble metals, or mixtures thereof. 26. The method of claim 24, wherein the coke-oxidizing compound comprises a platinum, palladium, iridium, ruthenium, osmium, rhodium, or mixtures thereof. 27. The method of claim 24, wherein the coke-oxidizing compound is a noble metal. 28. The method of claim 24, wherein the paraffin dehydrogenation promoting compound is a noble metal. 29. The method of claim 24, wherein the paraffin dehydrogenation promoting compound is platinum. 30. The method of claim 24, wherein the binder is selected from natural clays, alumina, and silica-alumina. 31. The method of claim 24, wherein the binder is alumina. 32. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, and wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins, and wherein at least a portion of the unreacted components of the Fischer-Tropsch hydrocarbon stream and at least a portion of the products of the dehydrogenation and isomerization reactions form a second hydrocarbon stream. 33. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the first reaction zone is operated at a temperature of between about 300�� C. and about 600�� C. 34. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the first reaction zone is operated at a temperature of between about 450�� C. and about 550�� C. 35. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the first reaction zone is operated at a total reaction pressure between about 0.01 atmospheres and about 25.0 atmospheres. 36. The method of claim 1, further comprising introducing hydrogen into the Fischer-Tropsch hydrocarbon stream. 37. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, and wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins. 38. The method of claim 37, further comprising introducing at least a portion of the first hydrocarbon stream exiting the first reaction zone into a heat exchanger, wherein the heat exchanger is configured to remove heat from a portion of the Fischer-Tropsch hydrocarbon stream before it enters the second reaction zone. 39. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the second reaction zone is operated at a temperature range from about 200�� C. to about 500�� C. 40. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the second reaction zone is operated at a hydrocarbon partial pressure of from about 0.1 atmosphere to about 10 atmospheres. 41. The method of claim 1, wherein the dehydrogenation-isomerization unit comprises a stacked bed catalyst configuration, wherein the stacked bed comprises a dehydrogenation catalyst and an isomerization catalyst. 42. The method of claim 1, further comprising introducing at least a portion of the produced aliphatic alcohols into a sulfation unit, wherein the sulfation unit is configured to sulfate at least a portion of the produced aliphatic alcohols to produce aliphatic sulfates, and wherein at least a portion of the aliphatic sulfates produced comprise branched aliphatic sulfates. 43. The method of claim 1, further comprising introducing at least a portion of the produced aliphatic alcohols into an oxyalkylation unit, wherein the oxyalkylation unit is configured to oxyalkylate at least a portion of the produced aliphatic alcohols to produce oxyalkyl alcohols, wherein at least a portion of the oxyalkyl alcohols produced comprises branched oxyalkyl alcohols. 44. The method of claim 1, further comprising: forming an hydroformylation reaction stream wherein the hydroformylation reaction stream comprises at least a portion of the unreacted components of the second hydrocarbon stream and at least a portion of the produced aliphatic alcohols; and separating produced aliphatic alcohols from the hydroformylation reaction stream to produce a paraffins and unreacted olefins stream and an aliphatic alcohol product stream. 45. The method of claim 44, further comprising introducing at least a portion of the paraffins and unreacted olefins stream into the dehydrogenation-isomerization unit. 46. A method for the production of aliphatic alcohols comprising: introducing a Fischer-Tropsch hydrocarbon stream comprising olefins and paraffins, said Fischer-Tropsch hydrocarbon stream containing from 5 to 80 percent olefins having an average carbon number of from 10 to 17, into a hydrogenation unit, wherein the hydrogenation unit is configured to hydrogenate at least a portion of olefins in the first hydrocarbon stream to paraffins, and wherein at least a portion of the unreacted components of the Fischer-Tropsch hydrocarbon stream and at least a portion of the hydrogenated olefins form a second hydrocarbon stream, introducing the second hydrocarbon stream into a dehydrogenation-isomerization unit, wherein the dehydrogenation-isomerization unit is configured to dehydrogenate at least a portion of the paraffins in the second hydrocarbon stream to olefins, and wherein the dehydrogenation-isomerization unit is further configured to isomerize at least a portion of linear olefins to branched olefins in the presence of a dehydrogenation-isomerization catalyst comprising a hydrogen form of a zeolite having a ferrierite isotypic framework structure, and wherein the residence time is such that the conversion of paraffins to olefins is below 40 mole percent, and wherein at least a portion of the unreacted components of the second hydrocarbon stream and at least a portion of the products of the dehydrogenation and isomerization reactions form a third hydrocarbon stream, the third hydrocarbon stream comprising olefins and paraffins, and wherein at least a portion of the olefins in the third hydrocarbon stream are branched olefins; and introducing at least a portion of the third hydrocarbon stream into a hydroformylation unit, wherein the hydroformylation unit is configured to hydroformylate at least a portion of the olefins in the third hydrocarbon stream to produce aliphatic alcohols having an average carbon number of from 11 to 18, and wherein at least a portion of the produced aliphatic alcohols comprises a branched alkyl group. 47. The method of claim 46, wherein the hydrogenation unit is operated at a temperature range from about 175�� C. to about 250�� C. 48. The method of claim 46, wherein the hydrogenation unit is operated at a hydrogen flow rate between about 250 NL/L/hr and about 5000 NL/L/hr. 49. The method of claim 46, wherein the hydrogenation unit is operated at a pressure range from about 10 atmospheres to about 50 atmospheres. 50. The method of claim 46, wherein the dehydrogenation-isomerization unit is operated at a temperature range from about 300�� C. to about 500�� C. 51. The method of claim 46, wherein the dehydrogenation-isomerization unit is configured to operate at a pressure range from about 0.010 atmosphere to about 15 atmospheres. 52. The method of claim 46, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules of at least 0.7. 53. The method of claim 46, wherein a portion of the branched olefins comprises methyl and ethyl branches. 54. The method of claim 46, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules of less than 2.5. 55. The method of claim 46, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules from about 0.7 to about 2.2. 56. The method of claim 46, wherein a portion of the branched olefins comprises an average number of branches per total olefin molecules from about 1.0 to about 2.2. 57. The method of claim 46, wherein greater than 50 percent of the branched groups on the branched olefins are methyl groups. 58. The method of claim 46, wherein less than 30 percent of the branched groups on the branched olefins are ethyl groups. 59. The method of claim 46, wherein less than 10 percent of the branched groups on the branched olefins are neither methyl or ethyl groups. 60. The method of claim 46, wherein the branched olefins have less than 0.5 percent aliphatic quaternary carbon atoms. 61. The method of claim 46, wherein the branched olefins have less than 0.3 percent aliphatic quaternary carbon atoms. 62. The method of claim 46, wherein the hydroformylation unit is configured to produce greater than 50 percent of aliphatic alcohols. 63. The method of claim 46, wherein the hydroformylation unit is configured to produce greater than 95 percent of aliphatic alcohols. 64. The method of claim 46, wherein the hydroformylation unit is operated at a reaction temperature range from about 100�� C. to about 300�� C. 65. The method of claim 46, wherein the branched alkyl groups of the aliphatic alcohols comprise about 0.5 percent or less aliphatic quaternary carbon atoms, and an average number of branches per alkyl group of at least 0.7, the branches comprising methyl and ethyl branching. 66. The method of claim 46, further comprising: forming a hydroformylation reaction stream comprising at least a portion of the unreacted components of the third hydrocarbon stream, and at least a portion of the produced aliphatic alcohol; separating aliphatic alcohols from the hydroformylation reaction stream to produce a paraffins and unreacted olefins stream and an aliphatic alcohol product stream; introducing at least a portion of the paraffins and unreacted olefins stream into the dehydrogenation-isomerization unit. 67. The method of claim 66, wherein introducing at least a portion of the paraffins and unreacted olefins stream into the dehydrogenation-isomerization unit comprises combining at least a portion of the paraffins and unreacted olefins stream with at least a portion of the second hydrocarbon stream to produce a combined stream upstream of the dehydrogenation-isomerization unit and introducing at least a portion of the combined stream into the dehydrogenation-isomerization unit. 68. The method of claim 46, further comprising introducing at least a portion of the produced aliphatic alcohols into a sulfation unit, wherein the sulfation unit is configured to sulfate at least a portion of the aliphatic alcohols to produce aliphatic sulfates; wherein at least a portion of the aliphatic sulfates produced comprises branched aliphatic sulfates. 69. The method of claim 46, further comprising introducing at least a portion of the produced aliphatic alcohols into an oxyalkylation unit, wherein the oxyalkylation unit is configured to oxyalkylate at least a portion of the produced aliphatic alcohols to produce oxyalkyl alcohols, wherein at least a portion of the oxyalkyl alcohols produced comprises branched oxyalkyl alcohols. 70. The method of claim 46, further comprising: introducing at least a portion of the produced aliphatic alcohols into an oxyalkylation unit, wherein the oxyalkylation unit is configured to oxyalkylate at least a portion of the produced aliphatic alcohols to produce an oxyalkyl alcohol stream, wherein at least a portion of the oxyalkyl alcohols produced comprises branched oxyalkyl alcohols; and introducing at least a portion of the oxyalkyl alcohol stream into a sulfation unit, wherein the sulfation unit is configured to sulfate at least a portion of the oxyalkyl alcohols in the oxyalkyl alcohol stream to produce oxyalkyl sulfates, wherein at least a portion of the oxyalkyl sulfates produced comprises branched oxyalkyl sulfates. 71. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a dehydrogenation-isomerization catalyst additionally comprising a binder, a coke-oxidizing compound, and a paraffin dehydrogenation promoting compound. 72. The method of claim 71, wherein the coke-oxidizing compound comprises chrome oxide, iron oxide, noble metals, or mixtures thereof. 73. The method of claim 71, wherein the coke-oxidizing compound comprises a platinum, palladium, iridium, ruthenium, osmium, rhodium, or mixtures thereof. 74. The method of claim 71, wherein the coke-oxidizing compound is a noble metal. 75. The method of claim 71, wherein the paraffin dehydrogenation promoting compound is a noble metal. 76. The method of claim 71, wherein the paraffin dehydrogenation promoting compound is platinum. 77. The method of claim 71, wherein the binder is selected from natural clays, alumina, and silica-alumina. 78. The method of claim 71, wherein the binder is alumina. 79. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, and wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins, and wherein at least a portion of the unreacted components of the first hydrocarbon stream and at least a portion of the products of the dehydrogenation and isomerization reactions form a second hydrocarbon stream. 80. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, and wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the first reaction zone is operated in a temperature range of from about 300�� C. to about 600�� C. 81. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, and wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins, and wherein the first reaction zone is operated in a temperature range of from about 450�� C. to about 550�� C. 82. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, and wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins and wherein the first reaction zone is operated at a total reaction pressure between about 0.01 atmospheres and about 25.0 atmospheres. 83. The method of claim 46, further comprising introducing hydrogen into the first hydrocarbon stream. 84. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins. 85. The method of claim 84, further comprising introducing at least a portion of the first hydrocarbon stream exiting the first reaction zone into a heat exchanger, wherein the heat exchanger is configured to remove heat from a portion of said hydrocarbon stream exiting the first reaction zone before it enters the second reaction zone. 86. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the second reaction zone is operated in a temperature range of from about 200�� C. to about 500�� C. 87. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a plurality of zones, wherein the plurality of zones comprises a first reaction zone and a second reaction zone, wherein the first reaction zone is configured to dehydrogenate at least a portion of paraffins to olefins, wherein the second reaction zone is configured to isomerize at least a portion of linear olefins to branched olefins; and wherein the second reaction zone is operated at a hydrocarbon partial pressure between about 0.1 atmosphere and about 10 atmospheres. 88. The method of claim 46, wherein the dehydrogenation-isomerization unit comprises a stacked bed catalyst configuration, wherein the stacked bed catalyst comprises a dehydrogenation catalyst and an isomerization catalyst.