WO2016154528A1 - Procédés et systèmes d'oligomérisation d'une ou plusieurs oléfines - Google Patents

Procédés et systèmes d'oligomérisation d'une ou plusieurs oléfines Download PDF

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Publication number
WO2016154528A1
WO2016154528A1 PCT/US2016/024200 US2016024200W WO2016154528A1 WO 2016154528 A1 WO2016154528 A1 WO 2016154528A1 US 2016024200 W US2016024200 W US 2016024200W WO 2016154528 A1 WO2016154528 A1 WO 2016154528A1
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WIPO (PCT)
Prior art keywords
olefin
effluent
isoparaffin
unreacted
catalyst
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PCT/US2016/024200
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English (en)
Inventor
William M. CROSS Jr.
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Cross William M Jr
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Publication of WO2016154528A1 publication Critical patent/WO2016154528A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation

Definitions

  • Embodiments described generally relate to methods and systems for oligomerizing one or more olefins. More particularly, such embodiments relate to methods and systems for oligomerizing a first olefin to produce a second olefin and separating unreacted first olefin from the second olefin.
  • a high recovery of the unreacted olefins from the oligomer in the oligomer product is desired.
  • One method for separating the olefins from the oligomer product is distillation. The separation of the olefins from the oligomer to provide an oligomer product having a sufficiently low concentration of the olefin, while, at the same time, minimizing oligomer carry-over with the separated olefins, however, is both difficult and challenging from an energy perspective.
  • the method can include introducing a first olefin that can include ethylene, propylene, or a mixture thereof to a reactor.
  • the first olefin can be oligomerized in the presence of a catalyst within the reactor to produce an effluent that can include a second olefin and unreacted first olefin.
  • the effluent and an isoparaffin can be introduced to a separator.
  • the effluent can be initially contacted with the isoparaffin within the separator.
  • the isoparaffin can include isobutane, isopentane, 2-methyl-pentane, 2,2,4 trimethylpentane, or any mixture thereof.
  • the effluent can be separated within the separator to produce a second olefin product that can include the second olefin and a first portion of the isoparaffin and an unreacted first olefin product that can include the unreacted first olefin and a second portion of the isoparaffin. At least a portion of the unreacted first olefin product can be recycled to the reactor. At least a portion of unreacted first olefin product can be oligomerized in the presence of the catalyst and the first olefin to produce additional second olefin.
  • the method for oligomerizing one or more olefins can include introducing a first olefin that can include ethylene, propylene, or a mixture thereof, and a catalyst to a reactor.
  • the first olefin can be oligomerized in the presence of the catalyst to produce an effluent that can include unreacted first olefin, the catalyst, and a second olefin that can include one or more C4-C9 olefins.
  • At least a portion the effluent can be introduced to a wash unit to produce a catalyst-lean effluent.
  • the catalyst-lean effluent and an isoparaffin can be introduced to a first distillation column.
  • the catalyst- lean effluent can be initially contacted with the isoparaffin within the first distillation column.
  • the isoparaffin can include isobutane, isopentane, 2-methyl-pentane, 2,2,4 trimethylpentane, or any mixture thereof.
  • the isoparaffin can be introduced to the first distillation column above the catalyst-lean effluent.
  • the catalyst- lean effluent can be separated within the first distillation column to produce a second olefin product that can include the second olefin and a first portion of the isoparaffin and an overhead that can include the unreacted first olefin and a second portion of the isoparaffin.
  • the overhead can be introduced to a second distillation column.
  • the overhead can be separated into an unreacted first olefin product and an isoparaffin product. At least a portion of the isoparaffin product can be recycled to the first distillation column. At least a portion of the unreacted first olefin product can be recycled to the reactor. At least a portion of the unreacted first olefin product can be oligomerized in the presence of the catalyst and the first olefin to produce additional second olefin.
  • the system for oligomerizing one or more olefins can include a reactor configured to oligomerize a first olefin in the presence of a catalyst to produce an effluent that can include a second olefin and an unreacted first olefin.
  • the first olefin can include ethylene, propylene, or a mixture thereof.
  • the system can also include a separator configured to initially contact the effluent with an isoparaffin within the separator and to separate the effluent to produce a second olefin product that can include the second olefin and a first portion of the isoparaffin and an unreacted first olefin product that can include the unreacted first olefin and a second portion of the isoparaffin.
  • the system can also include a recycle line configured to recycle at least a portion of the unreacted first olefin product to the reactor.
  • Figure 1 depicts an illustrative oligomerization system that includes a distillation column configured to separate a second olefin product and an unreacted first olefin product from an effluent, according to one or more embodiments described.
  • Figure 2 depicts an illustrative oligomerization system that includes two distillation columns configured to separate a second olefin product and an unreacted first olefin product from an effluent, according to one or more embodiments described.
  • Figure 3 depicts another illustrative oligomerization system that includes two distillation columns configured to separate a second olefin product and an unreacted first olefin product from an effluent, according to one or more embodiments described.
  • One or more first olefins can be oligomerized, e.g. , dimerized and/or trimerized, in the presence of one or more catalysts to produce a crude oligomer product or "effluent" that can include one or more second olefins, i.e. , the oligomer(s), and unreacted first olefin(s).
  • the effluent can be separated to produce a second olefin product and an unreacted first olefin product. Separation of the effluent can include contacting the effluent with one or more isoparaffins to produce the second olefin product and the unreacted first olefin product.
  • the second olefin product can include the second olefin and a first portion of the isoparaffin.
  • the unreacted first olefin product can include the unreacted first olefin and a second portion of the isoparaffin.
  • Other compounds that can be present during oligomerization of the first olefin can be or include, but are not limited to, compounds in the effluent of which a portion can be recycled back to the oligomerization process, unreacted first olefin that can be recycled back to the oligomerization process after separation from the second olefin, one or more isoparaffins present in the unreacted first olefin that can be recycled back to the oligomerization process, or any mixture thereof.
  • the presence of the isoparaffin during separation of the effluent can also reduce or eliminate the need to compress any of the unreacted first olefin product that may be recycled back to the oligomerization process.
  • the presence of the isoparaffin can also enable operation of the oligomerization reactor in a mode in which a high rate of per pass conversion of the first olefin, e.g. , greater than 90%, is not required to achieve an overall energy efficient operation. This can allow for enhanced oligomer product selectivity at the same or substantially the same energy efficiency without requiring new catalyst improvements.
  • the effluent can be contacted with the isoparaffin after the first olefin has been oligomerized, e.g. , after removal from an oligomerization reactor.
  • the effluent can be initially contacted with the isoparaffin within a separator.
  • Illustrative separators can include, but are not limited to, one or more distillation columns, one or more vapor-liquid separators, one or more absorbers, or any combination thereof.
  • the second olefin product and the unreacted first olefin can be separated within a distillation column.
  • the second olefin product and the unreacted first olefin can be separated within two or more distillation columns.
  • the effluent and the isoparaffin can be introduced to a first distillation column to separate the effluent into a bottoms or second olefin product that can include the second olefin and a first portion of the isoparaffin and an overhead that can include the unreacted first olefin and a second portion of the isoparaffin.
  • the overhead can be introduced to a second distillation column to separate the overhead into the unreacted olefin product and an isoparaffin product.
  • the isoparaffin and the effluent can be separately introduced to the separator.
  • the isoparaffin can be introduced to the separator at a location above where the effluent is introduced to the separator.
  • the isoparaffin and the effluent can be mixed, blended, or otherwise combined with one another and introduced as a mixture to the separator.
  • the effluent can be recovered from the reactor as liquid, a gas, a mixture of a liquid and a gas, and/or a first portion of the effluent can be recovered as a gas and a second portion of the effluent can be recovered as a liquid.
  • the isoparaffin can be introduced to the separator at a location above where both the first effluent and the second effluent are introduced to the separator.
  • the isoparaffin can be introduced to the separator at a location between the first effluent and the second effluent, i.e. , below the second effluent and above the first effluent or below the first effluent and above the second effluent.
  • a weight ratio of the isoparaffin introduced to the separator to the first olefin introduced to the reactor can be from a low of about 1:350, about 1:200, about 1:100, about 1:50, about 1:25, about 1:10, about 1:7, or about 1:5 to a high of about 1:2, about 1:1, about 1.5:1, about 2:1, about 3:1, about 4:1, about 5:1, about 6:1, about 7:1, or about 8:1.
  • the weight ratio of the isoparaffin introduced to the separator to the first olefin introduced to the reactor can be from about 1:335 to about 1:1, about 1:100 to about 1:2, about 1:10 to about 1:3, about 1:300 to about 1:150, about 1:150 to about 1:50, about 1:55 to about 1:20, about 1:25 to about 1:5, or about 1:10 to about 1:1.
  • the weight ratio of the isoparaffin introduced to the separator to the first olefin introduced to the reactor can be from about 1:50 to about 8:1, about 1:10 to about 1:3.4, about 1:50 to about 5:1, about 1:40 to about 3:1, about 1:30 to about 2:1, or about 1:20 to about 1:1.
  • the weight ratio of the isoparaffin introduced to the separator to the first olefin introduced to the reactor can be at least 1:335, at least 1:200, at least 1:100, at least 1:50, at least 1:30, at least 1:20, or at least 1:10 and up to about 1:3.4, about 1:2, about 1:1, about 1.5:1, about 2:1, about 4:1, about 6:1, or about 8:1.
  • the weight ratio of the isoparaffin introduced to the separator, e.g. , a single distillation column, to the first olefin introduced to the reactor can be about 1:20 to about 2:1, or about 1:10 to about 1.5:1.
  • the weight ratio of the isoparaffin introduced to the separator can be about at least 1:350, at least 1:335, at least 1:290, at least 1:210, at least 1:170, at least 1:120, or at least 1:80 up to about 1:1, about 1:2, about 1:3, about 1:4, or about 1:5.
  • a weight ratio of the isoparaffin introduced to the separator to a total amount of the first olefin introduced to the reactor, i.e., fresh first olefin and any unreacted first olefin recycled to the reactor, can be from a low of about 1:600, about 1:500, about 1:400, about 1:300, about 1:200, about 1:100, about 1:50, or about 1:25 to a high of about 1:10, about 1:2, about 1:1, about 2:1, about 3:1, about 5:1, or about 7:1.
  • the weight ratio of the isoparaffin introduced to the separator, e.g., a single distillation column, to the total amount of the first olefin introduced to the reactor can be from about 1:50 to about 3:1, about 1:40 to about 2:1, about 1:30 to about 1.8:1, about 1:20 to about 1.6:1, about 1:15 to about 1.4:1, about 1:10 to about 1:1, or about 1:8 to about 1:2.
  • the weight ratio of the isoparaffin introduced to the separator, e.g., a two distillation column separator, to the total amount of the first olefin introduced to the reactor can be from about 1:6 to about 1:650, about 1:8 to about 1:600, about 1:20 to about 1:550, about 1:40 to about 1:400, or about 1:50 to about 1:450.
  • a weight ratio of the isoparaffin introduced to the separator to the unreacted first olefin introduced to the separator can be from a low of about 1:150, about 1:100, about 1:75, about 1:50, about 1:25, or about 1:10 to a high of about 1:5, about 1:1, about 5:1, about 15:1, about 25:1, about 30:1, about 32:1, about 35:1, or about 45:1.
  • the weight ratio of the isoparaffin introduced to the separator to the unreacted first olefin introduced to the separator can be from about 1:10 to about 10:1, about 1:5 to about 8:1, about 1:3.5 to about 7:1, about 1:2.5 to about 6:1, about 1:1.5 to about 4:1, about 1:1 to about 3:1, about 1:4 to about 1:1, or about 1:1 to about 5:1.
  • the weight ratio of the isoparaffin introduced to the separator to the unreacted first olefin introduced to the separator can be from about 1:1 to about 1:200, about 1:1.3 to about 1:150, about 1:1.3 to about 1:100, about 1:5 to about 1:50, about 1:40 to about 1:120, or about 1:2 to about 1:75.
  • a weight ratio of the second olefin in the effluent introduced to the separator to the isoparaffin introduced to the separator can be from a low of about 0.5:1, about 1:1, about 2:1, or about 5:1 to a high of about 30:1, about 50:1, about 75:1, or about 125:1.
  • the weight ratio of the second olefin to the isoparaffin introduced to the separator can be from about 1:1 to about 99:1, about 0.5:1 to about 25:1, about 15:1 to about 60:1, about 30:1 to about 80:1, or about 70:1 to about 110:1.
  • a weight ratio of the total amount of isoparaffin introduced to the separator, i.e. , weight of isoparaffin introduced to the separator and any isoparaffin present in the effluent introduced to the separator, to the unreacted first olefin introduced to the separator can be from a low of about 1:75, about 1:50, about 1:30, about 1:10, about 1:5, or about 1:1 to a high of about 2:1, about 10:1, about 40:1, about 60:1, about 80:1, about 100:1, about 125:1, or about 150:1.
  • the weight ratio of the total amount of isoparaffin introduced to the separator to the unreacted first olefin introduced to the separator can be from about 1 :50 to 100: 1, about 1 : 10 to about 50: 1, about 1:20 to about 10: 1, about 1: 1 to about 80: 1, about 40: 1 to about 100: 1, or about 1:25 to about 40: 1.
  • a weight ratio of the total amount of isoparaffin introduced to the separator, i.e. , weight of isoparaffin introduced to the separator and any isoparaffin present in the effluent introduced to the separator, to the second olefin introduced to the separator can be from a low of about 1:350, about 1:300, about 1:200, about 1: 100, or about 1:50 to a high of about 1 : 10, about 1: 1, about 3: 1, about 5: 1, about 9 : 1 , or about 12: 1.
  • the weight ratio of the total amount of isoparaffin introduced to the separator to the second olefin introduced to the separator can be from about 1:300 to 9: 1, about 1:250 to about 1 : 100, about 1:300 to about 1:200, about 1:200 to about 1 :50, about 1:60 to about 1 : 1 about 1 : 1 to about 3: 1, or about 2: 1 to about 9: 1.
  • the effluent can be separated into the second olefin product and the unreacted first olefin product at a temperature from a low of about 25 °C, about 40°C, about 60°C, about 90°C, about 110°C, or about 130°C to a high of about 180°C, about 200°C, about 230°C, about 270°C, about 300°C, or about 330°C.
  • the separator can be or include one or more distillation columns that can be operated under conditions sufficient to provide a temperature gradient from a first or bottom end to a second or top end thereof.
  • the effluent and the isoparaffin can be introduced to a distillation column operated to have a temperature of about 100°C to about 300°C at the bottom end and temperature of about 25 °C to about 200°C at the top end thereof, where the temperature at the top end is less than the temperature at the bottom end.
  • the effluent can be separated into the second olefin product and the unreacted first olefin product at a pressure from a low of about 101 kPa, about 170 kPa, about 350 kPa, about 500 kPa, about 800 kPa, or about 1,050 kPa to a high of about 1,500 kPa, about 2,000 kPa, about 2,500 kPa, about 3,000 kPa, about 3,500 kPa, about 4,000 kPa, or about 4,500 kPa.
  • the effluent can be separated into the second olefin product and the unreacted first olefin product under a pressure of about 170 kPa to about 4,250 kPa, about 400 kPa to about 1,600 kPa, about 900 kPa to about 2,600 kPa, about 1,400 kPa to about 3,600 kPa, about 680 kPa to about 3,900 kPa, or about 1,000 kPa to about 4,000 kPa.
  • the second olefin product can include from a low of about 10 wt%, about 12 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, or about 40 wt% to a high of about 60 wt%, about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 97 wt%, about 99 wt%, or about 99.99 wt% of the second olefin, based on the total weight of the second olefin product.
  • the second olefin product can include from about 12 wt% to about 99.95 wt%, about 12 wt% to about 50 wt%, about 30 wt% to about 75 wt%, about 45 wt% to about 85 wt%, about 50 wt% to about 99.5 wt%, about 65 wt% to about 90 wt%, about 80 wt% to about 99.9 wt%, or about 85 wt% to about 99.95 wt% of the second olefin, based on the total weight of the second olefin product.
  • the second olefin product can include from a low of about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, or about 80 wt% to a high of about 90 wt%, about 93 wt%, about 95 wt%, about 97 wt%, about 98 wt%, about 99 wt%, about 99.5 wt%, about 99.9 wt%, about 99.95 wt%, about 99.99 wt%, about 99.995 wt%, or about 99.999 wt% of the second olefin, based on the combined weight of the second olefin and the isoparaffin.
  • the second olefin product can include about 50 wt% to about 99.999 wt%, about 50 wt% to about 80 wt%, about 60 to about 85 wt%, about 75 wt% to about 95 wt%, about 60 wt% to about 95 wt%, or about 90 wt% to about 99.99 wt% of the second olefin, based on the combined weight of the second olefin and the isoparaffin.
  • the second olefin product can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 80 wt%, about 90 wt%, about 95 wt%, about 97 wt%, about 99 wt%, about 99.9 wt%, or about 99.99 wt% of the second olefin, based on the total weight of the second olefin product.
  • the second olefin product can include from a low of about 0.01 wt%, about 0.1 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 10 wt%, or about 20 wt% to a high of about 40 wt%, about 50 wt%, about 75 wt%, or about 88 wt% of the isoparaffin, based on the total weight of the second olefin product.
  • the second olefin product can be free or essentially free of any unreacted first olefin.
  • the second olefin product can include from a low of about 1 part per million by weight ("ppmw"), about 5 ppmw, about 10 ppmw, about 20 ppmw, about 40 ppmw, about 60 ppmw, about 80 ppmw or about 100 ppmw to a high of about 200 ppmw, about 350 ppmw, about 500 ppmw, about 600 ppmw, about 800 ppmw, or about 1,000 ppmw of the unreacted first olefin, based on the total weight of the second olefin product.
  • ppmw part per million by weight
  • the second olefin product can include less than 1,000 ppmw, less than 500 ppmw, less than 100 ppmw, less than 50 ppmw, less than 40 ppmw, less than 30 ppmw, less than 25 ppmw, less than 20 ppmw, less than 15 ppmw, less than 10 ppmw, or less than 5 ppmw of the unreacted first olefin, based on the total weight of the second olefin product.
  • the second olefin product can include from a low of about 1 ppmw, about 5 ppmw, about 10 ppmw, about 20 ppmw, about 40 ppmw, about 60 ppmw, about 80 ppmw or about 100 ppmw to a high of about 200 ppmw, about 350 ppmw, about 500 ppmw, about 600 ppmw, about 800 ppmw, or about 1,000 ppmw of the unreacted first olefin, based on a combined weight of the second olefin, the isoparaffin, and the unreacted first olefin.
  • the second olefin product can include less than 1,000 ppmw, less than 500 ppmw, less than 100 ppmw, less than 50 ppmw, less than 40 ppmw, less than 30 ppmw, less than 25 ppmw, less than 20 ppmw, less than 15 ppmw, less than 10 ppmw, or less than 5 ppmw of the unreacted first olefin, based on the combined weight of the second olefin, the isoparaffin, and the unreacted first olefin.
  • the unreacted first olefin product can include from a low of about 0.1 wt%, about 1 wt%, about 3 wt%, about 5 wt%, or about 7 wt% to a high of about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, or about 30 wt% of the unreacted first olefin, based on the total weight of the unreacted first olefin product.
  • the unreacted first olefin product can include about 0.5 wt% to about 5 wt%, about 1 wt% to about 15 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 20 wt%, or about 15 wt% to about 25 wt% of the unreacted first olefin, based on the total weight of the unreacted first olefin product.
  • the unreacted first olefin product can include from a low of about 0.25 wt%, about 1 wt%, about 3 wt%, about 5 wt%, or about 7 wt% to a high of about 10 wt%, about 13 wt%, about 15 wt%, about 18 wt%, about 20 wt%, about 23 wt%, about 25 wt%, about 27 wt%, about 30 wt%, or about 35 wt% of the unreacted first olefin, based on the combined weight of the unreacted first olefin and the isoparaffin.
  • the unreacted first olefin product can include about 0.5 wt% to about 5 wt%, about 1 wt% to about 15 wt%, about 5 wt% to about 20 wt%, about 10 wt% to about 20 wt%, or about 15 wt% to about 25 wt% of the unreacted first olefin, based on the combined weight of the unreacted first olefin and the isoparaffin.
  • the unreacted first olefin product can include from a low of about 5 wt%, about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 75 wt% to a high of about 85 wt%, about 90 wt%, about 95 wt%, or about 99 wt% of the isoparaffin, based on the total weight of the unreacted first olefin product.
  • the unreacted first olefin product can include about 10 wt% to about 30 wt%, about 25 wt% to about 55 wt%, about 50 wt% to about 95 wt%, about 70 wt% to about 90 wt%, about 75 wt% to about 95 wt%, about 80 wt% to about 97 wt%, or about 85 wt% to about 99 wt% of the isoparaffin, based on the total weight of the unreacted first olefin product.
  • the unreacted first olefin product can include from a low of about 5 wt%, about 10 wt%, about 20 wt%, about 30 wt% about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 75 wt% to a high of about 85 wt%, about 90 wt%, about 95 wt%, or about 99 wt% of the isoparaffin, based on the combined amount of the unreacted first olefin and the isoparaffin.
  • the unreacted first olefin product can include about 10 wt% to about 30 wt%, about 25 wt% to about 55 wt%, about 50 wt% to about 95 wt%, about 70 wt% to about 90 wt%, about 75 wt% to about 95 wt%, about 80 wt% to about 97 wt%, or about 85 wt% to about 99 wt% of the isoparaffin, based on the combined amount of the unreacted first olefin and the isoparaffin.
  • the unreacted first olefin product can be free or essentially free of any second olefin.
  • the unreacted first olefin product can include from a low of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, or about 5 wt% to a high of about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% of the second olefin, based on the total weight of the unreacted first olefin product.
  • the unreacted first olefin product can include less than 5 wt%, less than 3 wt%, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt% of the second olefin, based on the total weight of the unreacted first olefin product.
  • the unreacted first olefin product can be free or essentially free of or include from a low of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, or about 5 wt% to a high of about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, or about 10 wt% of the second olefin, based on the combined weight of the unreacted first olefin, the isoparaffin, and the second olefin.
  • the unreacted first olefin product can include less than 5 wt%, less than 3 wt%, less than 1 wt%, less than 0.5 wt%, or less than 0.1 wt% of the second olefin, based on the combined weight of the unreacted first olefin, the isoparaffin, and the second olefin.
  • the unreacted first olefin product can be at a temperature of from a low of about 10°C, about 35°C, or about 75°C to a high of about 100°C, about 125°C, or about 150°C.
  • the unreacted first olefin product can be at a temperature of about 30°C to about 50°C, about 40°C to about 85 °C, about 50°C to about 70°C, about 60°C to about 100°C, about 70°C to about 90°C, or about 85 °C to about 120°C.
  • the unreacted first olefin product can be at a pressure from a low of about 170 kPa, about 400 kPa, about 700 kPa, about 1,000 kPa, or about 1,300 kPa to a high of about 2,000 kPa, about 2,500 kPa, about 3,000 kPa, about 3,500 kPa, about 4,000 kPa, or about 4,500 kPa.
  • the unreacted first olefin product can be at a pressure of about 300 kPa to about 650 kPa, about 500 kPa to about 2,000 kPa, about 650 kPa to about 950 kPa, about 800 kPa to about 1,800 kPa, about 950 kPa to about 4,000 kPa, about 1,600 kPa to about 4,250 kPa, or about 2,800 kPa to about 3,600 kPa.
  • the unreacted first olefin product can be at a pressure of at least 170 kPa, at least 400 kPa, at least 800 kPa, or at least 1,100 kPa and up to about 2,000 kPa, about 3,000 kPa, or about 4,250 kPa.
  • the first olefin can be oligomerized in the presence of the catalyst within one or more reactors.
  • Illustrative reactors can be or include, but are not limited to, stirred tank reactors, loop reactors, bubble column reactors, fixed bed reactors, fluid bed reactors, radial flow reactors, reactors that include one or more internal heat exchange coils, catalytic distillation type reactors, or any combination thereof.
  • a loop reactor can be a shell-and-tube type reactor, where the first olefin and catalyst can be introduced to the tube-side and at least a portion of the effluent can be introduced to the shell-side.
  • the loop reactor can be a shell-and-tube style reactor, where the first olefin and catalyst can be introduced to the shell-side and at least a portion of the effluent can be introduced to the tube-side.
  • the oligomerization of the first olefin in the presence of the catalyst is an exothermic reaction and introduction of at least a portion of the effluent to the shell-side (or tube-side if the first olefin is introduced to the shell side) can be used to remove heat generated during oligomerization of the first olefin.
  • a weight ratio of the catalyst flowrate added into the dimerization process to a total amount of first olefin flowrate, i.e. , the first olefin and any unreacted first olefin recycled to the reactor, within the reactor can be from a low of about 1:500,000, about 1 :100,000, or about 1 :50,000 to a high of about 1: 10,000, about 1: 1,000, or about 1 : 100.
  • the catalyst quantity within the reactor can be from a low of about 2 ppmw, about 10 ppmw, about 20 ppmw, or about 50 ppmw to a high of about 0.1 wt%, about 0.5 wt%, about 1 wt%, about 3 wt%, or about 5 wt%.
  • a weight hourly space velocity of the first olefin ratio of the hourly flowrate of first olefin to the weight of the solid catalyst inside the reactor
  • a liquid hourly space velocity of the first olefin to liquid catalyst within the system (ratio of the hourly flowrate of the first olefin to the weight of the liquid catalyst within the reactor) can be from about 0.1 to about 20, about 0.5 to about 10, or about 1 to about 5.
  • a portion of the effluent and/or the unreacted first olefin product can also be introduced to the reactor.
  • the catalyst depending at least in part on the particular type of reactor, can also be introduced to the reactor, e.g. , a loop reactor, or can be contained within the reactor, e.g. , a fixed bed reactor.
  • the feeds or components that can be introduced to the reactor namely, the first olefin, the catalyst, the unreacted first olefin product, and/or a portion of the effluent, can be introduced separately or any two or more of the components can be mixed or otherwise combined with one another and introduced as a mixture to the reactor.
  • the unreacted first olefin product can include from about 40 wt% to about 99 wt% of the isoparaffin.
  • the first olefin i.e.
  • fresh first olefin and, optionally, unreacted first olefin from the unreacted first olefin product can be oligomerized in the presence of the catalyst, a portion of the effluent, and the isoparaffin that can be introduced as a component of the unreacted first olefin product and/or as a component of the effluent that can also be recycled back to the oligomerization process.
  • the first olefin can be oligomerized at a temperature from a low of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 50°C, about 60°C, or about 70°C to a high of about 120°C, about 140°C, about 160°C, about 180°C, about 200°C, or about 220°C.
  • the first olefin can be oligomerized at a temperature of about 25 °C to about 205 °C, about 30°C to about 130°C, about 35°C to about 120°C, or about 50°C to about 100°C.
  • the first olefin can be oligomerized at a temperature of less than 200°C, less than 175 °C, less than 150°C, less than 150°C, less than 135°C, or less than 125°C.
  • the first olefin can be oligomerized at a pressure from a low of about 950 kPa, about 1,000 kPa, about 1,100 kPa, about 1,250 kPa, about 1,400 kPa, about 1,700 kPa, or about 2,000 kPa to a high of about 3,500 kPa, about 4,000 kPa, about 4,500 kPa, about 5,000 kPa, about 5,500 kPa, or about 6,000 kPa.
  • the first olefin can be oligomerized at a pressure of about 1,035 kPa to about 5,515 kPa, about 1,150 kPa to about 3,200 kPa, about 1,800 kPa to about 3,600 kPa, about 2,600 kPa to about 4,800 kPa, or about 3,700 kPa to about 5,500 kPa.
  • the effluent can be recovered from the reactor in the form of a gas, a liquid, or a mixture of a gas and a liquid.
  • a gaseous effluent can be recovered as a first effluent and a liquid effluent can be recovered as a second effluent from the reactor. If a gaseous first effluent and a liquid second effluent are recovered as separate products from the reactor the first and second effluents can be mixed, blended, or otherwise combined with one another to produce a mixed effluent.
  • the amount of the first effluent can be from a low of about 1 wt%, about 5 wt%, about 10 wt%, or about 15 wt% to a high of about 25 wt%, about 35 wt%, about 45 wt%, or about 55 wt%, based on the total weight of the effluent, i.e. , the first effluent and the second effluent.
  • the effluent can include from about 1 wt% to about 50 wt%, about 10 wt% to about 30 wt%, about 20 wt% to about 40 wt%, or about 25 wt% to about 50 wt% of the first effluent, based on the total weight of the effluent, i.e. , the first effluent and the second effluent.
  • At least a portion of any catalyst in the effluent can be removed prior to separating the effluent into the second olefin product and the unreacted first olefin product.
  • at least a portion of any catalyst in the effluent can be removed by contacting the effluent with one or more wash fluids, by extraction via one or more liquid/liquid extraction units, by one or more membrane filters, and/or via fixed bed adsorption over one or more solid adsorbent materials.
  • Illustrative wash fluids can be or include, but are not limited to, one or more aqueous caustic solutions, one or more aqueous acid solutions, or any mixture thereof.
  • Illustrative aqueous caustic solutions can be or include, but are not limited to, sodium hydroxide, potassium hydroxide, one or more amines, water, or any mixture thereof.
  • Illustrative amines can include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, or any mixture thereof.
  • Illustrative aqueous acid solutions can be or include, but are not limited to, acetic acid, propionic acid, sulfuric acid, water, or any mixture thereof.
  • the effluent containing the catalyst can be contacted with the wash fluid at a temperature from a low of about -10°C, about 0°C, about 10°C, about 20°C, about 30°C, or about 40°C to a high of about 60°C, about 80°C, about 100°C, or about 120°C.
  • the effluent containing the catalyst can be contacted with the wash fluid at a temperature of about -5°C to about 95 °C, about 0°C to about 50°C, about -5°C to about 30°C, about 25 °C to about 60°C, or about 20°C to about 80°C.
  • the effluent containing the catalyst can be contacted with the wash fluid at a pressure from a low of about 400 kPa, about 800 kPa, about 1,200 kPa, or about 1,800 kPa to a high of about 3,000 kPa, about 4,500 kPa, or about 6,000 kPa.
  • the effluent can be contacted with the wash fluid within any suitable contactor.
  • An illustrative contactor can be or include a vessel.
  • the vessel can be empty, partially filled, or completely filled with one or more fill materials.
  • Illustrative fill materials can include, but are not limited to, structured materials, random packed materials, trays, coalescer and demister materials, or any combination thereof.
  • the effluent may or may not contain catalyst.
  • the gaseous effluent can be free or essentially free from any catalyst and the liquid effluent can include catalyst in a sufficient amount that removal of the catalyst may be desired.
  • the gaseous effluent can bypass the catalyst removal step while the liquid effluent undergoes the catalyst removal step.
  • the gaseous effluent can be mixed, blended, or otherwise combined with the liquid effluent and the combined mixture can be subjected to catalyst separation.
  • the gaseous effluent can be condensed before, during, and/or after combining with the liquid effluent.
  • the reactor is a fixed bed reactor the effluent recovered therefrom can be free or essentially free of any catalyst and catalyst removal can be unnecessary.
  • the effluent can be free from any catalyst when introduced to the separator.
  • the effluent can contain less than 100 ppmw, less than 50 ppmw, less than 30 ppmw, less than 10 ppmw, less than 5 ppmw, or less than 1 ppmw.
  • the effluent can include catalyst when introduced to the separator. Any catalyst contained in the unreacted first olefin product and/or the second olefin product can be removed after recovering the products from the separator.
  • Illustrative first olefins can be or include, but are not limited to, ethylene, propylene, or a mixture thereof.
  • the first olefin can include at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 99 wt%, at least 99.5 wt%, or at least 99.9 wt% of ethylene.
  • the first olefin can include at least 40 wt%, at least 60 wt%, at least 70 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, or at least 99.9 wt% of propylene. If the first olefin includes a mixture of two or more olefins, e.g. , a mixture of ethylene and propylene, the two or more olefins can be present in any amount with respect to one another.
  • the first olefin can include ethylene in an amount of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about 99 wt%, based on the total weight of the ethylene and the propylene.
  • the first olefin can include ethylene in an amount of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about 99 wt%, based on the total weight of the first olefin.
  • Illustrative second olefins can be or include, but are not limited to, one or more C 4 to C9 olefins.
  • the second olefin or oligomer product can be or include, but is not limited to, but-l-ene, (Z)-but-2-ene, (£)-but-2-ene, 2-methylpropene, hex-l-ene, (E)3-hexene, (Z)3-hexene, (E)2-hexene, (Z)2-hexene, 2-methyl-2-pentene, 3-methyl-2-pentene, dimethylbutenes, 1-octene, 2-methyl-l-pentene, 4-methyl-l-pentene, 3-methyl-2- pentene(E)(Z), 4-methyl-2-pentene(E)(Z), 3-octene, 4-octene, 2-octene, 2-methyl-l-heptene, 2,3 dimethy
  • the second olefin can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of but-l-ene, based on a total weight of the second olefin.
  • the second olefin can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of (Z)-but-2-ene, based on a total weight of the second olefin.
  • the second olefin can include from a low of 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of (£>but-2-ene, based on a total weight of the second olefin.
  • the second olefin can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of 2-methylpropene, based on a total weight of the second olefin.
  • the second olefin can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of hex- l-ene, based on a total weight of the second olefin.
  • the second olefin can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of tripropylene, based on a total weight of the second olefin.
  • the second olefin can include from a low of about 12 wt%, about 25 wt%, about 40 wt%, about 50 wt%, or about 60 wt% to a high of about 70 wt%, about 80 wt%, about 90 wt%, about 95 wt%, about 99 wt%, or about 99.99 wt% of Ce olefins, based on a total weight of the second olefin.
  • the second olefin can be or include (Z)-but-2-ene, (£ " )-but-2- ene, 1-butene, 1-hexene, (E)2-hexene, (Z)2-hexene, (E)3-hexene, (Z)3-hexene, other branched Ce olefins, or any mixture thereof, the first olefin can include ethylene, e.g.
  • the second olefin product can include at least 85 wt% of the second olefin, less than 15 wt% of the isoparaffin, less than 100 ppmw of the unreacted first olefin, and less than 10 wt% of Ce olefins.
  • the second olefin can be or include (Z)-but- 2-ene, (£ " )-but-2-ene, 1-butene, one or more Ce olefins, or any mixture thereof
  • the first olefin can include ethylene, e.g.
  • the second olefin product can include at least 60 wt% of the second olefin, less than 40 wt% of the isoparaffin, less than 100 ppmw of the unreacted first olefin, and less than 10 wt% of Ce olefins.
  • the second olefin can be or include 1-butene, one or more Ce olefins, or any mixture thereof
  • the first olefin can include ethylene, e.g.
  • At least 95 wt% of ethylene, and the second olefin product can include at least 99.5 wt% of the second olefin, less than 0.5 wt% of the isoparaffin, less than 100 ppmw of the unreacted first olefin, and less than 0.5 wt% of Ce olefins.
  • the first olefin can include propylene.
  • the first olefin can include at least 40 wt% propylene, with a substantial portion of propane.
  • the first olefin can include at least 60 wt% propylene.
  • the first olefin can include at least 70% propylene.
  • the produced second olefin can include linear or branched Ce olefins (dimers, such as dimethyl-butene isomers, and methyl-pentene isomers), branched C 9 olefins (trimers, such as isomers of nonene, dimethyl-heptene isomers, trimethyl-hexene isomers, methyl- octene isomers), C12 olefins (tetramers, such as isomers of dodecene), or any mixture thereof.
  • the second olefin can be or include 2-methyl-2-butene, 2-methyl-l- pentene, 3-methyl-2-pentene, 3-methyl-l-pentene, 3-methyl-2-pentene, 2,3 dimethyl- 1-butene, 2,3 dimethyl-2-butene, 4-methyl-2-pentene, C 9 branched olefins, or C12 branched olefins, or any mixture thereof, the first olefin can include, e.g.
  • At least 60 wt% of propylene, and the second olefin product can include at least 85 wt% of the second olefin, less than 15 wt% of the isoparaffin, less than 100 ppmw of the unreacted first olefin, and less than 10 wt% of C 9 olefins.
  • Illustrative isoparaffins that can be contacted with the effluent can be or include, but are not limited to, isobutane, isopentane, 2-methyl pentane, 2,3 dimethyl butane, 2,2,4 trimethylpentane, 2,3,4 trimethyl pentane, 2,3,3 trimethyl pentane, 2,4 dimethyl hexane, 2,3 dimethyl hexane, or any mixture thereof.
  • the isoparaffin can include at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 99 wt%, at least 99.5 wt%, or at least 99.9 wt% of isobutane.
  • the isoparaffin can include at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 99 wt%, at least 99.5 wt%, or at least 99.9 wt% of isopentane.
  • the isoparaffin includes a first isoparaffin and a second isoparaffin, e.g., isobutane and isopentane
  • the first isoparaffin and the second isoparaffin can be present in any amount with respect to one another.
  • the first isoparaffin can be present in an amount of about 1 wt%, about 5 wt%, about 10 wt%, about 15 wt%, about 20 wt%, about 25 wt%, about 30 wt%, about 35 wt%, about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, about 65 wt%, about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about 99 wt%, based on the total weight of the first isoparaffin and the second isoparaffin.
  • the isoparaffin can include a mixture isobutane and isopentane where the isobutane can be present in an amount of about 1 wt% to about 99 wt%, based on the total weight of the isobutane and the isopentane.
  • the isoparaffin can be derived from any suitable source or combination of sources.
  • the isoparaffin can be isobutane recovered from an alkylation unit deisobutanizer.
  • the separation of the effluent into the second olefin product and the unreacted first olefin can be integrated with an alkylation unit via the alkylation unit deisobutanizer.
  • the isobutane can be derived from field butanes, a mixture of n-butane and isobutane, using a deisobutanizer, or any combination thereof.
  • the isobutane or isopentane can be derived from an n-butane or n-pentane isomerization unit.
  • the isoparaffin 2,2,4 trimethylpentane can be derived from an alkylation unit.
  • the catalyst can be or include one or more homogeneous catalysts, one or more heterogeneous catalysts, or any mixture thereof.
  • the homogeneous catalyst can be or include one or more homogeneous metal complexes that can include soluble nickel compounds and/or titanate compounds with aluminum co-catalyst compounds that contain organic functionality. Suitable aluminum components can include alky, aryl, or other hydrocarbyl groups.
  • An illustrative titanate catalyst system can be or include a combination of tetrabutyltitanate and triethylaluminum.
  • the titanate catalyst system can include one or more alkytitanates, one or more ethers, and one or more organic alumina compounds.
  • the titanate can have the general formula, Ti(OR) 4 , where R can be a hydrocarbyl group.
  • Aluminum compounds can be or include trialkylaluminum compounds that can have the general formula AIR'3 or AIR 2H, where R' can be hydrocarbyl group.
  • An illustrative nickel catalyst system can be or include one or more nickel complexes with organic, e.g. , hydrocarbyl group, functionality with additional halide functionality.
  • the nickel catalyst system can include tri-n-butylphosphine nickel dichloride and ethyl aluminium dichloride. More particularly, the nickel catalyst system can include or be composed of: one or more organonickel(II) compounds, one or more phosphite compounds, and one or more alkyl aluminium compounds.
  • the phosphite compound can include organic functionality.
  • Illustrative phosphite compounds can include, but are not limited to, trimethylphosphite, triethylphosphite, triphenylposphite, tricyclohexyl phosphite, or any mixture thereof.
  • Illustrative organonickel(II) compounds can be or include, but are not limited to, bis(cyclopentadienyl) nickel(II), nickel(II) acetylacetonate, nickel(II) 2-ethylhexanoate, bis(pentamethylcyclopentadienyl) nickel(II), or any mixture thereof.
  • Illustrative aluminum compounds that can be included in the nickel catalyst system can be or include one or more trialkylaluminum compounds that can have the general formula AIR'3 or AIR 2H, where R' can be hydrocarbyl group.
  • Other nickel (non-phosphite) complexes can be or include a halide, e.g. , chloride, bromine, iodine, functionality and at least one of arsenic (As), phosphorous (P), pyridine, and phenanthroline.
  • suitable homogeneous catalyst systems can include an element of zirconium, vanadium, tantalum, and/or chromium having organic, e.g. , hydrocarbyl group, functionality in conjunction with a co-catalyst, such as one or more of the alkylaluminium compounds that can have the general formula AIR'3 or AIR 2H.
  • a zirconium catalyst system can include, but are not limited to, zirconium tetrapropylate and/or zirconium tetrabutylate.
  • the heterogeneous catalysts can include, but is not limited to, silica alumina, silica, or titania supported metal oxides.
  • Illustrative metal oxides can include, but are not limited to, metals of Group VIII and/or VI.
  • the metal oxide can be or include an oxide of metals such as nickel (Ni), cobalt (Co), chromium (Cr), vanadium (V), molybdenum (Mo), tungsten (W), or any mixture thereof.
  • Other useful metal oxides can include, but are not limited to, one or more metal oxides of Groups VIII or VI mixed with an oxide of palladium (Pd).
  • Other useful catalyst systems can be or include one or more ionic liquids.
  • the ionic liquid can be a supported ionic liquid.
  • a catalyst system based on one or more ionic liquids can be referred to or thought of as a hybrid catalyst system of homogenous materials on heterogeneous supports.
  • Supported ionic liquids can include, but are not limited to, one or more supports and one or more acidic ionic liquids.
  • the support can be a solid material.
  • the support can have any desired shape. Illustrative shapes suitable for the support can include, but are not limited to, spheres, pellets, granules, or flakes that can be composed of porous materials.
  • the support can be composed of silica, alumina, zirconia, titania, one or more tin oxides, or any mixture thereof.
  • Illustrative acidic ionic liquids can be or include, but are not limited to, one or more halides and one or more organic salts
  • Illustrative halides can include, but are not limited to, Group 3, 4, or 5 elements combined with halides, such as chlorides, bromides, and/or iodides.
  • Organic salts can be or include, but are not limited to, ammonium, phosphonium, iodium, and/or sulfonium organics.
  • a suitable catalyst can be a solid phosphoric acid (SPA) catalyst that can produce C 6 + oligomers.
  • the solid phosphoric acid catalyst can be or include, but is not limited to, an acid of phosphorous, e.g. , ortho, pyro, and/or tetra phosphoric acid, on a natural occurring support, e.g. , silica, kaolin, and/or diatomaceous earth.
  • Figure 1 depicts an illustrative oligomerization system 100 that includes a single distillation column 160 configured to separate a second olefin product and an unreacted first olefin product from an effluent, according to one or more embodiments.
  • the oligomerization system 100 can include, but is not limited to, one or more reactors 120, one or more heat exchangers (five are shown, 130, 140, 150, 170, and 180), one or more wash units 145, and the distillation column 160.
  • the reactor 120 can be a shell-and-tube type reactor.
  • the distillation column 160 can include one or more trays 162.
  • a first olefin via line 101 and a catalyst via line 103 can be combined with one another and introduced via line 105 to the tube side of the reactor 120.
  • the first olefin can be oligomerized, e.g. , dimerized and/or trimerized, in the presence of the catalyst within the reactor 120 to produce a crude oligomer product or effluent.
  • the effluent via line 121 can be recovered from the reactor 120.
  • a first portion of the effluent in line 121 can be introduced via line 123 to the first heat exchanger 130 to produce a cooled effluent via line 133 that can be recycled via line 133 to the reactor 120.
  • a second portion of the effluent in line 121 can be introduced via line 124 to the shell side of the reactor 120. Heat generated during oligomerization of the first olefin can be indirectly transferred to the second portion of the effluent introduced via line 124. As shown in Figure 1, a gaseous effluent via line 126 and a liquid effluent via line 128 can be recovered from the reactor 120.
  • the gaseous effluent via line 126 can be introduced to the second heat exchanger 140 to produce a cooled or condensed effluent via line 141.
  • the cooled effluent via line 141 can be combined with the liquid effluent in line 128 to produce a combined effluent via line 143.
  • the gaseous effluent via line 126 can be introduced directly to the distillation column 160 and/or the cooled effluent via line 141 can be introduced directly to the distillation column 160 rather than being combined with the liquid effluent in line 128.
  • the liquid effluent via line 128 or the combined effluent via line 143 and a wash fluid via line 144 can be introduced to the wash unit 145.
  • the effluent can be contacted with the wash fluid within wash unit 145 to remove at least a portion of any catalyst to produce a catalyst-rich liquid via line 146 and a catalyst-lean effluent via line 147.
  • the catalyst-lean effluent via line 147 can be introduced to the third heat exchanger 150 to produce a heated catalyst-lean effluent via line 151.
  • a second olefin product in line 182 can also be introduced to the third heat exchanger 150 and heat can be transferred from the second olefin product to the catalyst-lean effluent, to provide the heated catalyst-lean effluent or heated distillation column feed via line 151.
  • the heated catalyst- lean effluent via line 151 and an isoparaffin via line 153 can be introduced to the distillation column 160.
  • the catalyst-lean effluent via line 151 can be introduced to the distillation column 160 at a location below a location the isoparaffin via line 153 can be introduced to the distillation column 160.
  • the distillation column 160 can be operated under conditions sufficient to cause the unreacted first olefin to flow toward the top of the distillation column 160 and the second olefin to flow toward the bottom of the distillation column 160.
  • the isoparaffin can contact the catalyst- lean effluent within the distillation column 160 to facilitate separation of the unreacted first olefin from the second olefin.
  • a weight ratio of the isoparaffin introduced to the distillation column 160 via line 153 to the first olefin introduced via line 101 to the reactor 120 can be from a low of about 1:350, about 1:200, about 1:100, or about 1:50 to a high of about 1:25, about 1:10, about 1:7, about 1:5, about 1:3, about 1:2, or about 1.2:1.
  • the weight ratio of the isoparaffin introduced via line 153 to the distillation column 160 to the first olefin introduced via line 101 to the reactor can be from about 1:335 to about 1:1, about 1:100 to about 1:2, about 1:100 to about 1:50, about 1:40 to about 1:10, or about 1:15 to about 1:2.
  • a weight ratio of the isoparaffin introduced via line 153 to the distillation column 160 to a total amount of the first olefin introduced to the reactor 120, i.e., the first olefin introduced via line 101 and any unreacted first olefin recycled via lines 133 and/or 174 to the reactor 120, can be from a low of about 1:300, about 1:150, about 1:100, about 1:80, or about 1:60 to a high of about 1:40, about 1:20, about 1:10, about 1:5, about 1:2, about 1:1, or about 1.1:1.
  • a weight ratio of the isoparaffin introduced via line 153 to the distillation column 160 to the unreacted first olefin introduced via line 151 to the distillation column 160 can be from a low of about 1:600, about 1:500, about 1:400, about 1:300, about 1:200, about 1:100, about 1:50, or about 1:25 to a high of about 1:10, about 1:2, about 1:1, about 2:1, about 3:1, about 5:1, or about 7:1.
  • a weight ratio of the second olefin introduced via line 151 to the distillation column 160 to the isoparaffin introduced via line 153 to the distillation column 160 can be from a low of about 0.5:1, about 1:1, about 2:1, or about 5:1 to a high of about 30:1, about 50:1, about 75:1, or about 125:1.
  • a weight ratio of the total amount of isoparaffin introduced to the distillation column 160, i.e., the isoparaffin introduced via line 153 and any isoparaffin present in the effluent introduced via line 151 to the distillation column 160, to the unreacted first olefin introduced via line 151 to the distillation column 160 can be from a low of about 1:300, about 1:150, about 1:100, about 1:80, or about 1:60 to ahigh of about 1:20, about 1:10, about 1:5, about 1:2, about 1:1, about 1.5:1, about 2:1, or about 2.5:1.
  • the weight ratio of the total amount of isoparaffin introduced to the distillation column 160, i.e., the isoparaffin introduced via line 153 and any isoparaffin present in the effluent introduced via line 151 to the distillation column 160, to the unreacted first olefin introduced via line 151 to the distillation column 160 can be from 1:75, about 1:50, about 1:30, about 1:10, about 1:5, or about 1:1 to a high of about 2:1, about 10:1, about 40:1, about 60:1, about 80:1, about 100:1, about 125:1, or about 150:1.
  • a weight ratio of the total amount of isoparaffin introduced to the distillation column 160, i.e., the isoparaffin introduced via line 153 and any isoparaffin present in the effluent introduced via line 151 to the distillation column 160, to the second olefin introduced via line 151 to the distillation column 160 can be from a low of about 1:350, about 1:300, about 1:200, about 1:100, or about 1:50 to a high of about 1: 10, about 1:1, about 3:1, about 5: 1, about 9:1, or about 12:1.
  • An unreacted first olefin product or overhead via line 163 and a second olefin product or bottoms via line 165 can be recovered from the distillation column 160.
  • the unreacted first olefin product in line 163 can include at least a portion of the isoparaffin introduced via line 153 to the distillation column 160.
  • the second olefin product in line 165 can include at least a portion of the isoparaffin introduced via line 153 to the distillation column 160.
  • the unreacted first olefin can be introduced to the fourth heat exchanger 170 to produce a cooled unreacted first effluent via line 171.
  • the cooled unreacted first effluent in line 171 can be split into a first portion via line 172, a second portion via line 173, and a third portion via line 174.
  • the first portion of the cooled unreacted first effluent via line 172 can be recycled to the distillation column 160.
  • the second portion of the cooled unreacted first effluent via line 173 can be purged or otherwise removed from the system 100.
  • the third portion of the cooled unreacted first effluent via line 174 can be recycled to the reactor 120.
  • the third portion of the cooled unreacted first effluent via line 174 can be combined with the catalyst and the first olefin in line 105 and introduced to the reactor 120.
  • the third portion of the cooled unreacted first effluent in line 174 can be dried to remove at least a portion of any water contained therein prior to recycling to the reactor 120.
  • the unreacted first olefin product in line 171 can be at a temperature from a low of about 0°C, about 5°C, about 10°C, or about 20°C to a high of about 70°C, about 95°C, or about 120°C.
  • the unreacted first olefin product in line 171 can be at a pressure from a low of about 200 kPa, about 450 kPa, about 600 kPa, or about 1,100 kPa to a high of about 2,000 kPa, about 3,000 kPa, or about 4,000 kPa.
  • the second olefin product or bottoms via line 165 can be introduced to the fifth heat exchanger 180 to produce a heated second product via lines 181 and 182.
  • the heated second product via line 181 can be recycled to the distillation column 160 and the heated second product via line 182 can be introduced to the third heat exchanger 150 to produce a cooled second product via line 184.
  • the second product via line 184 can be introduced to an alkylation reactor.
  • the second product via line 184 can be alkylated to produce high octane gasoline blendstocks, having research and motor octane values above 85 RON and MON.
  • the second product via line 184 can be introduced to an aromatization reactor.
  • the second product in line 184 can be aromatized to produce benzene, toluene, ortho xylene, meta xylene, para xylene, or any mixture thereof.
  • Illustrative alkylation processes can include those discussed and described in U.S. Patent Nos.: 3,050,456; 3,502,369; 5,095,168, 5,841,014, 6,855,856; and 8,753,318 and U.S. Patent Application Publication No.: 2011/0319695.
  • Illustrative aromatization processes can include those discussed and described in U.S. Patent Nos.: 3,843,741 ; 4,861,932; 4,912,273; 4,855,522; and 6,617,275.
  • Figure 2 depicts an illustrative oligomerization system 200 that includes two distillation columns 260 and 285 configured to separate a second olefin product and an unreacted first olefin product from an effluent, according to one or more embodiments.
  • the oligomerization system 200 can include, but is not limited to, one or more reactors 220, one or more heat exchangers (eight are shown, 230, 240, 250, 270, 275, 280, 288, and 296), one or more wash units 245, and the distillation columns 260 and 285.
  • the reactor 220 can be a shell-and-tube type reactor.
  • the distillation columns 260 and 285 can include one or more trays 262 and 286, respectively.
  • a first olefin via line 201 and a catalyst via line 203 can be combined with one another and introduced via line 205 to the tube side of the reactor 220.
  • the first olefin can be oligomerized, e.g. , dimerized and/or trimerized, in the presence of the catalyst within the reactor 220 to produce a crude oligomer product or effluent.
  • the effluent via line 221 can be recovered from the reactor 220.
  • a first portion of the effluent in line 221 can be introduced via line 223 to the first heat exchanger 230 to produce a cooled effluent via line 233 that can be recycled via line 233 to the reactor 220.
  • a second portion of the effluent in line 221 can be introduced via line 224 to the shell side of the reactor 220. Heat generated during oligomerization of the first olefin can be indirectly transferred to the second portion of the effluent introduced via line 224. As shown in Figure 2, a gaseous effluent via line 226 and a liquid effluent via line 228 can be recovered from the reactor 220.
  • the gaseous effluent via line 226 can be introduced to the second heat exchanger 240 to produce a cooled or condensed effluent via line 241.
  • the cooled effluent via line 241 can be combined with the liquid effluent in line 228 to produce a combined effluent via line 243.
  • the gaseous effluent via line 226 can be introduced directly to the first distillation column 260 and/or the cooled effluent via line 241 can be introduced directly to the first distillation column 260 rather than being combined with the liquid effluent in line 228.
  • the liquid effluent via line 228 or the combined effluent via line 243 and a wash fluid via line 244 can be introduced to the wash unit 245.
  • the effluent can be contacted with the wash fluid within wash unit 245 to remove at least a portion of any catalyst to produce a catalyst-rich liquid via line 246 and a catalyst-lean effluent via line 247.
  • the catalyst-lean effluent via line 247 can be introduced to the third heat exchanger 250 to produce a heated catalyst-lean effluent via line 251.
  • a second olefin product in line 282 can also be introduced to the third heat exchanger 250 and heat can be transferred from the second olefin product to the catalyst-lean effluent.
  • the catalyst-lean effluent via line 251 and an isoparaffin via line 253 can be introduced to the first distillation column 260.
  • the catalyst-lean effluent via line 251 can be introduced to the first distillation column 260 at a location below a location the isoparaffin via line 253 can be introduced to the first distillation column 260.
  • the distillation column 260 can be operated under conditions sufficient to cause the unreacted first olefin to flow toward the top of the first distillation column 260 and the second olefin to flow toward the bottom of the first distillation column 260.
  • the isoparaffin can contact the catalyst-lean effluent within the first distillation column 260 to facilitate separation of the unreacted first olefin from the second olefin.
  • a weight ratio of the isoparaffin introduced via line 253 to the first distillation column 260 to the first olefin introduced via line 201 to the reactor 220 can be from a low of about 1 :350, about 1 :200, about 1 : 100, about 1:50, about 1 :25, about 1: 10, about 1:7, or about 1 :5 to a high of about 1 :2, about 1 : 1, about 1.5: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, or about 8: 1.
  • the weight ratio of the isoparaffin introduced via line 253 to the first distillation column 260 to the first olefin introduced via line 201 to the reactor 220 can be from about 1 :50 to about 8: 1, about 1 : 10 to about 1:3.4, about 1:20 to about 2: 1, about 1 : 15 to about 1 :2, or about 1:20 to about 1 :1.
  • a weight ratio of the isoparaffin introduced via line 253 to the first distillation column 260 to a total amount of the first olefin introduced to the reactor 220, i.e. , the first olefin introduced via line 201 and any unreacted first olefin recycled via lines 233 and/or 274 to the reactor 220 can be from a low of about 1:600, about 1 :500, about 1:400, about 1:300, about 1:200, about 1: 100, about 1:50, or about 1:25 to a high of about 1:10, about 1:2, about 1:1, about 2:1, about 3: 1, about 5:1, or about 7:1.
  • a weight ratio of the isoparaffin introduced via line 253 to the first distillation column 260 to the unreacted first olefin introduced via line 251 to the first distillation column 260 can be from a low of about 1:150, about 1:100, about 1:75, about 1:50, about 1:25, or about 1:10 to a high of about 1:5, about 1:1, about 5:1, about 15:1, about 25:1, about 30:1, about 32:1, about 35:1, or about 45:1.
  • a weight ratio of the second olefin introduced via line 251 to the first distillation column 260 to the isoparaffin introduced via line 253 to the first distillation column 260 can be from a low of about 0.5:1, about 1: 1, about 2:1, or about 5:1 to a high of about 30:1, about 50:1, about 75:1, or about 125:1.
  • a weight ratio of the total amount of isoparaffin introduced to the first distillation column 260, i.e. , the isoparaffin introduced via line 253 and any isoparaffin present in the effluent introduced via line 251 to the first distillation column 260, to the unreacted first olefin introduced via line 251 to the first distillation column 260 can be from a low of about 1:75, about 1:50, about 1:30, about 1: 10, about 1:5, or about 1:1 to a high of about 2: 1, about 10: 1, about 40:1, about 60:1, about 80:1, about 100: 1, about 125: 1, or about 150:1.
  • the isoparaffin introduced via line 253 and any isoparaffin present in the effluent introduced via line 251 to the distillation column 260, to the second olefin introduced via line 251 to the distillation column 260 can be from a low of about 1:350, about 1:300, about 1:200, about 1:100, or about 1:50 to a high of about 1: 10, about 1:1, about 3:1, about 5: 1, about 9:1, or about 12:1.
  • a first unreacted first olefin product or overhead via line 263 and a second olefin product or bottoms via line 265 can be recovered from the first distillation column 260.
  • the overhead in line 263 can include at least a portion of the isoparaffin introduced via line 253 to the first distillation column 260.
  • the second olefin product in line 265 can include at least a portion of the isoparaffin introduced via line 253 to the first distillation column 260.
  • the overhead via line 263 can be introduced to the fourth heat exchanger 270 to produce a cooled overhead via line 271.
  • the cooled overhead in line 271 can be split into a first portion via line 272 and a second portion via line 273.
  • the first portion of the cooled overhead via line 272 can be recycled to the first distillation column 260.
  • the second portion of the cooled overhead via line 273 can be introduced to the fifth heat exchanger 275 to produce a preheated feed via line 277 that can be introduced to the second distillation column 285.
  • a bottoms product or isoparaffin product via line 298 recovered from the second distillation column 285 can be introduced to the fifth heat exchanger 275 and heat can be indirectly transferred from the isoparaffin product to the cooled overhead in line 273 to produce a preheated feed via line 277.
  • the preheated feed via line 277 can be introduced to the second distillation column 285.
  • a cooled isoparaffin product via line 299 can be recovered from the fifth heat exchanger 275.
  • the cooled isoparaffin via line 299 can be recycled to the first distillation column 260 by mixing with the isoparaffin in line 253, as shown, and/or directly (not shown).
  • all or a portion of the heated isoparaffin via line 299 can be purged or otherwise removed from the system 200.
  • the second olefin product via line 265 can be introduced to the sixth heat exchanger 280 to produce a heated second product via lines 281 and 282.
  • the heated second product via line 281 can be recycled to the first distillation column 260 and the heated second product via line 282 can be introduced to the third heat exchanger 250 to produce a cooled second product via line 284.
  • the second product via line 284 can be introduced to an alkylation reactor.
  • the second product via line 284 can be alkylated to produce high octane gasoline blendstocks, having research and motor octane values above 85 RON & MON.
  • the second product via line 284 can be introduced to an aromatization reactor.
  • the second product in line 284 can be aromatized to produce benzene, toluene, ortho xylene, meta xylene, para xylene, or any mixture thereof.
  • the preheated feed via line 277 introduced to the second distillation column 285 can be separated into the isoparaffin product or bottoms product via line 295 and an overhead or unreacted first olefin product via line 287.
  • the unreacted first olefin product in line 287 can be introduced to the seventh heat exchanger 288 and separated to produce a first unreacted first olefin product via line 291, a second unreacted first olefin product via line 290, and a third unreacted first olefin product via line 289.
  • the second unreacted first olefin product via line 290 can be purged or otherwise removed from the system 200.
  • the third unreacted first olefin product via line 289 can be recycled back to the second distillation column 285.
  • the first unreacted first olefin product via line 291 can be introduced to the drier 292 to produce a dried unreacted first olefin product via line 294 and a waste water via line 293.
  • the dried unreacted first olefin in line 294 can be combined with the catalyst and the first olefin in line 205 and recycled to the reactor 220, recycled directly to the tube-side of the reactor 120 (not shown), and/or combined with the cooled first effluent in line 233 and recycled to the reactor 220 (not shown).
  • the first unreacted first olefin product via line 291 can be recycled to the reactor 220 without drying.
  • the drier 292 can be or include one or more molecular sieves.
  • the drier 292 can be or include a molecular sieve bed configured to remove at least a portion of any water that can be present in the first unreacted first olefin product in line 291.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being compressed.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being further cooled.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being pumped.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being compressed or cooled.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being compressed or pumped.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being cooled or pumped.
  • the first unreacted first olefin in line 291 can be recycled to the reactor 220 without being further compressed, cooled, or pumped.
  • the line 291 that can recycle the first unreacted first olefin to the reactor 220 can be free from at least one, at least two, or all three of a compressor, a pump, and a cooler.
  • the isoparaffin product via line 295 can be introduced to the eighth heat exchanger 296 to produce a first heated isoparaffin product via line 297 and a second heated isoparaffin product via line 298.
  • the first heated isoparaffin product via line 297 can be recycled to the second distillation column 285.
  • the second heated isoparaffin product via line 298 can be introduced to the fifth heat exchanger 275 to produce the heated isoparaffin product via line 299.
  • Figure 3 depicts another illustrative oligomerization system 300 that includes two distillation columns 360 and 385 configured to separate a second olefin product and an unreacted first olefin product from an effluent, according to one or more embodiments.
  • the oligomerization system 300 can include, but is not limited to, one or more reactors 320, one or more heat exchangers (seven are shown, 330, 350, 370, 375, 380, 388, and 396), one or more wash units 345, and the distillation columns 360 and 385.
  • the reactor 320 can be a shell-and-tube type reactor.
  • the distillation columns 360 and 385 can include one or more trays 362, and 386, respectively.
  • a first olefin via line 301 and a catalyst via line 303 can be combined with one another and introduced via line 305 to the tube-side of the reactor 320.
  • An effluent via line 321 can be recovered from the reactor 320.
  • a first portion of the effluent in line 321 can be introduced via line 323 to the first heat exchanger 330 to produce a cooled effluent via line 333 that can be recycled to the reactor 320 via line 305.
  • a second portion of the effluent in line 321 can be introduced via line 324 to the shell side of the reactor 320.
  • Heat generated during oligomerization of the first olefin can be indirectly transferred to the second portion of the effluent introduced via line 324.
  • a gaseous effluent via line 326 and a liquid effluent via line 328 can be recovered from the reactor 320.
  • the gaseous effluent via line 326 can be introduced to the first distillation column 362.
  • the liquid effluent via line 328 can be split into a first portion via line 329 and a second portion via line 331.
  • the first portion of the liquid effluent via line 329 can be recycled to the reactor 320 by combining with the first olefin and catalyst in line 305 and/or recycled directly to the reactor 320 (not shown).
  • the second portion of the liquid effluent via line 331 and a wash fluid via line 344 can be introduced to the wash unit 345.
  • the effluent can be contacted with the wash fluid within wash unit 345 to remove at least a portion of any catalyst to produce a catalyst-rich liquid via line 346 and a catalyst-lean effluent via line 347.
  • the catalyst-lean effluent via line 347 can be introduced to the third heat exchanger 350 to produce a heated catalyst-lean effluent via line 351.
  • a second olefin product in line 382 can also be introduced to the third heat exchanger 350 and heat can be transferred from the second olefin product to the catalyst-lean effluent.
  • the catalyst-lean effluent via line 351 and an isoparaffin via line 353 can be introduced to the first distillation column 360.
  • the catalyst-lean effluent via line 351 can be introduced to the first distillation column 360 at a location below a location the isoparaffin via line 353 can be introduced to the first distillation column 360.
  • the first distillation column 360 can be operated under conditions sufficient to cause the unreacted first olefin to flow toward the top of the first distillation column 360 and the second olefin to flow toward the bottom of the first distillation column 360.
  • the isoparaffin can contact the catalyst-lean effluent within the first distillation column 360 to facilitate separation of the unreacted first olefin from the second olefin.
  • An unreacted first olefin product or overhead via line 363 and a second olefin product or bottoms via line 365 can be recovered from the first distillation column 360.
  • the overhead via line 363 can be introduced to the fourth heat exchanger 370 to produce a first cooled overhead via line 371.
  • the first cooled overhead in line 371 can be split into a first portion via line 372 and a second portion via line 373.
  • the first portion of the first cooled overhead via line 372 can be recycled to the first distillation column 360.
  • the second portion of the first cooled overhead via line 373 can be introduced to the fifth heat exchanger 375 to produce a preheated feed, line 377, for distillation column 385.
  • a bottoms product or isoparaffin product via line 398 recovered from the second distillation column 385 can be introduced to the fifth heat exchanger 375 and heat can be indirectly transferred from the isoparaffin product to the first cooled overhead in line 373 to produce a preheated feed via line 377.
  • the preheated feed in line 377 can be introduced to the second distillation column 385.
  • a cooled isoparaffin product via line 399 can be recovered from the fifth heat exchanger 375.
  • the cooled isoparaffin product via line 399 can be recycled to the first distillation column 360 by mixing with the isoparaffin in line 353, as shown, and/or directly (not shown).
  • all or a portion of the cooled isoparaffin via line 399 can be purged or otherwise removed from the system 300.
  • the second olefin product via line 365 can be introduced to the sixth heat exchanger 380 to produce a heated second product via lines 381 and 382.
  • the heated second product via line 381 can be recycled to the first distillation column 360 and the heated second product via line 382 can be introduced to the third heat exchanger 350 to produce a cooled second product via line 384.
  • the second product via line 384 can be introduced to an alkylation reactor.
  • the second product via line 384 can be alkylated to produce high octane gasoline blendstocks, having research and motor octane values above 85 RON and MON.
  • the second product via line 384 can be introduced to an aromatization reactor.
  • the second product in line 384 can be aromatized to produce benzene, toluene, ortho xylene, meta xylene, para xylene, or any mixture thereof.
  • the second cooled overhead via line 377 that can be introduced to the second distillation column 385 can be separated into the isoparaffin product or bottoms product via line 395 and an overhead or unreacted first olefin product via line 387.
  • the unreacted first olefin product in line 387 can be introduced to the seventh heat exchanger 388 and separated to produce a first unreacted first olefin product via line 391, a second unreacted first olefin product via line 390, and a third unreacted first olefin product via line 389.
  • the second unreacted first olefin product via line 390 can be purged or otherwise removed from the system 300.
  • the third unreacted first olefin product via line 389 can be recycled back to the second distillation column 385.
  • the first unreacted first olefin product via line 391 can be introduced to the drier 392 to produce a dried unreacted first olefin product via line 394 and a waste water via line 393.
  • the dried unreacted first olefin in line 394 can be combined with the catalyst and the first olefin in line 305 and recycled to the reactor 320, recycled directly to the tube-side of the reactor 320 (not shown), and/or combined with the cooled first effluent in line 333 and recycled to the reactor 320 (not shown).
  • the isoparaffin product via line 395 can be introduced to the eighth heat exchanger 396 to produce a first heated isoparaffin product via line 397 and a second heated isoparaffin product via line 398.
  • the first heated isoparaffin product via line 397 can be recycled to the second distillation column 385.
  • the second heated isoparaffin product via line 398 can be introduced to the fifth heat exchanger 375 to produce the heated isoparaffin product via line 399.
  • Example 1 is a simulated method for dimerizing ethylene that uses a single distillation column for separating the dimerized ethylene from the unreacted ethylene, according to one or more embodiments discussed and described above with reference to Figure 1.
  • Table 1 shows the simulated process conditions and results.
  • the simulated data in Table 1 shows that a second distillation column is not required when the isobutane content in the reactor 120 is allowed to further increase in content. More importantly, the simulated data in Table 1 shows that a compressor is not required to compress the unreacted first olefin product in line 174 prior to recycling to the reactor 120.
  • Increasing the isobutane concentration helps the oligomerization of the ethylene from the standpoint of product, e.g. , dimer, selectivity, but increasing the isobutane concentration can also decrease the per pass conversion within the reactor 120. As such, there is a balance or trade-off on how high the isoparaffin concentration should go.
  • the amount of isobutane in the effluent recycle (133) is approximately 12 wt% versus 4 wt% as provided in Example 2 below.
  • Example 2 is a simulated method for dimerizing ethylene that uses two distillation columns for separating the dimerized ethylene from the unreacted ethylene, according to one or more embodiments discussed and described above with reference to Figure 2.
  • Table 2 shows the simulated process conditions and results.
  • Isobutane is introduced via line 253 to the first distillation column 260.
  • the isobutane is mixed with the isobutane product in line 299 that is recovered from the second distillation column 285.
  • the bottoms or second olefin product via line 282 from the first distillation column 260 exits the process as the second olefin product via line 284 and can be used as an alkylation feedstock and/or an aromatization feedstock, for example.
  • the second olefin product in line 284 contains a significant amount of isobutane, i.e. , about 31 wt% in this example.
  • the second olefin product in line 284 contains both butenes and hexenes. Although only butenes are conventionally alkylated, feedstocks that include hexenes from a dimerization unit are considered acceptable feedstocks for alkylation and aromatization processes.
  • the unreacted first olefin product via line 287 from the second distillation column 285 is essentially free of C 4 olefins and primarily contains ethylene, ethane, and isobutane.
  • the condensing temperature on the second distillation column 285 allows the use of cooling water.
  • About 65 wt% of the unreacted first olefin product (dried) in line 294 is isobutane.
  • the unreacted first olefin product via line 294 is recycled back to the reactor 220 by mixing the unreacted first olefin product with the ethylene and catalyst in line 205.
  • the effluent recycle via line 233 contains less than 5 wt% isobutane.
  • One means by which recycling of isobutane can be made more economical, is through the integration of the first and second distillation columns 260 and 360, respectively, with an alkylation unit deisobutanizer.
  • integration between an alkylation unit deisobutanizer and the first distillation column 260 can be useful.
  • integrating the first distillation column 260 with an alkylation unit deisobuanizer verses using the fresh isobutane via line 253, a portion of deisobutanizer overhead reflux can be used to wash C 4+ olefins from the ethylene within the first distillation column 260.
  • the quantity of isobutane available from an alkylation unit deisobutanizer is more than sufficient for integration with the process.
  • isobutane to the C 4 olefins in the product can be available.
  • Example 1 Of commonality to both Example 1 and Example 2, is the use of two distillation feed points. More particularly, the isobutane via lines 153 and 253 are introduced to the distillation column 160 and the first distillation column 260, respectively, at a location above where the effluents via lines 151 and 251, respectively are introduced.
  • Example 2 allows for independent operation of the isoparaffin content within the reactor 220.
  • Such a design is used to bottle up a portion of isoparaffin between the first distillation column overhead 263 and the second distillation column bottoms 295. This can be useful from the standpoint of being able to independently control or reduce the quantity of isoparaffins within the unreacted first olefin recycled via line 294 to the reactor 220.
  • Embodiments of the present disclosure further relate to any one or more of the following paragraphs:
  • a method for oligomerizing one or more olefins comprising: introducing a first olefin comprising ethylene, propylene, or a mixture thereof to a reactor; oligomerizing the first olefin in the presence of a catalyst within the reactor to produce an effluent comprising a second olefin and an unreacted first olefin; introducing the effluent and an isoparaffin to a separator, wherein the effluent is initially contacted with the isoparaffin within the separator, and wherein the isoparaffin comprises isobutane, isopentane, 2-methyl-pentane, 2,2,4 trimethylpentane, or any mixture thereof; separating the effluent within the separator to produce a second olefin product comprising the second olefin and a first portion of the isoparaffin and an unreacted first olefin product comprising the unreacted first ole
  • a method for oligomerizing one or more olefins comprising: introducing a first olefin comprising ethylene, propylene, or a mixture thereof, and a catalyst to a reactor; oligomerizing the first olefin in the presence of the catalyst to produce an effluent comprising unreacted first olefin, the catalyst, and a second olefin comprising one or more C4-C9 olefins; introducing at least a portion of the effluent to a wash unit to produce a catalyst-lean effluent; introducing the catalyst-lean effluent and an isoparaffin to a distillation column, wherein the catalyst-lean effluent is initially contacted with the isoparaffin within the distillation column, wherein the isoparaffin comprises isobutane, isopentane, 2-methyl-pentane, 2,2,4 trimethylpentane, or any mixture thereof, and wherein the
  • a method for oligomerizing one or more olefins comprising: introducing a first olefin comprising ethylene, propylene, or a mixture thereof, and a catalyst to a reactor; oligomerizing the first olefin in the presence of the catalyst to produce an effluent comprising unreacted first olefin, the catalyst, and a second olefin comprising one or more C4-C9 olefins; introducing at least a portion of the effluent to a wash unit to produce a catalyst-lean effluent; introducing the catalyst-lean effluent and an isoparaffin to a first distillation column, wherein the catalyst-lean effluent is initially contacted with the isoparaffin within the first distillation column, wherein the isoparaffin comprises isobutane, isopentane, 2-methyl-pentane, 2,2,4 trimethylpentane, or any mixture thereof, and where
  • the second olefin comprises but-l-ene, (Z)-but-2-ene, (E")-but-2-ene, 2-methylpropene, 1-hexene, 2-hexene, 3- hexene, 2-methyl-2-pentene, 2-methyl-l-pentene, 2,3 dimethyl-2-butene, 2,3-dimethyl-l- butene, 3,3-dimethyl-l-butene, 3 -methyl- 1-butene, 1-octene, or any mixture thereof.
  • the first olefin comprises at least 95 wt% of ethylene
  • the second olefin comprises (Z)-but-2-ene, (E)-but-2- ene, 1-butene, C 6 olefins, or any mixture thereof
  • the second olefin product comprises at least 85 wt% of the second olefin, less than 15 wt% of the isoparaffin, less than 100 ppmw of the unreacted first olefin, and less than 10 wt% of C 6 olefins.
  • the first olefin comprises at least 95 wt% of ethylene
  • the second olefin comprises (Z)-but-2-ene, (£)-but-2- ene, 1-butene, C 6 olefins, or any mixture thereof
  • the second olefin product comprises at least 60 wt% of the second olefin, less than 40 wt% of the isoparaffin, less than 100 ppmw of the unreacted first olefin, and less than 10 wt% of C 6 olefins.
  • the reactor comprises one or more stirred tank reactors, one or more loop reactors, one or more bubble column reactors, one or more fixed bed reactors, one or more fluid bed reactors, one or more radial flow reactors, one or more reactors that includes one or more internal heat exchange coils, one or more catalytic distillation type reactors, or any combination thereof.
  • a system for oligomerizing one or more olefins comprising: a reactor configured to oligomerize a first olefin in the presence of a catalyst to produce an effluent comprising a second olefin and an unreacted first olefin, wherein the first olefin comprises ethylene, propylene, or a mixture thereof; a separator configured to initially contact the effluent with an isoparaffin within the separator and to separate the effluent to produce a second olefin product comprising the second olefin and a first portion of the isoparaffin and an unreacted first olefin product comprising the unreacted first olefin and a second portion of the isoparaffin; and a recycle line configured to recycle at least a portion of the unreacted first olefin product to the reactor.
  • the catalyst comprises one or more heterogeneous
  • the reactor comprises one or more stirred tank reactors, one or more loop reactors, one or more bubble column reactors, one or more fixed bed reactors, one or more fluid bed reactors, one or more radial flow reactors, one or more reactors that includes one or more internal heat exchange coils, one or more catalytic distillation type reactors, or any combination thereof.
  • first distillation column is configured to operate at a pressure of about 1,000 kPa to about 1,400 kPa
  • second distillation column is configured to operate at a pressure of about 1,700 kPa to about 3,500 kPa
  • the reactor is configured to operate at a pressure that is less than second distillation column is configured to operate at.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne des procédés et des systèmes permettant l'oligomérisation d'une ou plusieurs oléfines. Le procédé peut consister à introduire une première oléfine dans un réacteur. La première oléfine peut être oligomérisée en présence d'un catalyseur dans le réacteur pour produire un effluent qui peut comprendre une seconde oléfine et la première oléfine n'ayant pas réagi. L'effluent et une isoparaffine peuvent être introduits dans un séparateur. L'effluent peut être initialement mis en contact avec l'isoparaffine à l'intérieur du séparateur. L'effluent peut être séparé à l'intérieur du séparateur pour produire un second produit à base d'oléfine et un produit à base d'oléfine n'ayant pas réagi. Au moins une partie du produit à base de la première oléfine n'ayant pas réagi peut être recyclée vers le réacteur. Au moins une partie du produit à base de la première oléfine n'ayant pas réagi peut être oligomérisée en présence du catalyseur et de la première oléfine pour produire la seconde oléfine supplémentaire.
PCT/US2016/024200 2015-03-26 2016-03-25 Procédés et systèmes d'oligomérisation d'une ou plusieurs oléfines WO2016154528A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022140184A1 (fr) * 2020-12-22 2022-06-30 Kellogg Brown & Root Llc Récupération d'oléfines légères à partir de gaz d'hydrocarbures secs provenant de procédés de production pétrochimique et de raffinerie pour la production d'alkylat

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005084772A1 (fr) * 2004-03-03 2005-09-15 Chevron Phillips Chemical Company Lp Procede et appareil de separation d'un effluent de reacteur d'oligomerisation
US20070142685A1 (en) * 2005-12-20 2007-06-21 Chevron U.S.A. Inc. Process for making and composition of superior lubricant or lubricant blendstock
WO2008022212A1 (fr) * 2006-08-16 2008-02-21 Catalytic Distillation Technologies Alkylation de la paraffine
KR20140097400A (ko) * 2011-11-21 2014-08-06 바스프 에스이 부텐의 올리고머의 제조 방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005084772A1 (fr) * 2004-03-03 2005-09-15 Chevron Phillips Chemical Company Lp Procede et appareil de separation d'un effluent de reacteur d'oligomerisation
US20070142685A1 (en) * 2005-12-20 2007-06-21 Chevron U.S.A. Inc. Process for making and composition of superior lubricant or lubricant blendstock
WO2008022212A1 (fr) * 2006-08-16 2008-02-21 Catalytic Distillation Technologies Alkylation de la paraffine
KR20140097400A (ko) * 2011-11-21 2014-08-06 바스프 에스이 부텐의 올리고머의 제조 방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022140184A1 (fr) * 2020-12-22 2022-06-30 Kellogg Brown & Root Llc Récupération d'oléfines légères à partir de gaz d'hydrocarbures secs provenant de procédés de production pétrochimique et de raffinerie pour la production d'alkylat
US11905241B2 (en) 2020-12-22 2024-02-20 Kellogg Brown & Root Llc Recovery of light olefins from dry hydrocarbon gas from refinery and petrochemical production processes for production of alkylate

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