Functionalized Solvents for Olefin Isomer Purification by Reactive Extractive Distillation

N.J.M. Kuipers, A.E. Wentink, A.B. de Haan, J. Scholtz, H. Mulder

Research output: Contribution to journalArticleAcademic

7 Citations (Scopus)

Abstract

Olefin isomer separations are difficult, energy intensive and thus expensive. An overview is presented to investigate the feasibility of metal–ligand complexes as functionalized solvents applied in a novel separation technology, reactive extractive distillation, for the separation and purification of α-olefins like 1-hexene from other C6-olefin isomers (internal, branched, cyclic and diolefins) and paraffins by using π-complexation. Functionalized metal–ligand complexes were synthesized based on commercial available ligands from hydrometallurgy. In screening experiments they were evaluated for ρ-complexation with ethylene. The best solvents were selected for evaluation of preferential complexation of 1-hexene relative to other olefin isomers. D2EHPA and DNNSA yield both stable metal–ligand complexes and triple the solubility of ethylene. Next, three different phosphoric acid ligands: D2EHPA, DBPA and MEHPA and two sulphonic acid ligands: DNNSA and DBSA, were investigated for a variety of C6-olefin isomers. The highest selectivities were obtained for silver-DBPA (20 wt% Ag, S/F = 3): 1.23 for 2-methyl-1-pentene and 1.42 for n-hexane. An equilibrium model is used to conceptually design a reactive extractive distillation column applying the functionalized solvent silver-D2EHPA. Such a column should be operated at a solvent to feed ratio of around 5(P = 0.2 bar, T = 311 K) for 99.5% purity and 99% recovery. Under these conditions, the minimum number of equilibrium trays (Nmin) to separate 1-hexene from 2-methyl-1-pentene is approximately 42, a dramatic decrease compared to Nmin of about 310 in the absence of silver.
Original languageEnglish
Pages (from-to)88-99
JournalChemical engineering research and design (Transactions of the Institution of Chemical Engineers, part A)
Volume85
Issue number1
DOIs
Publication statusPublished - 2007
EventIChemE Distillation and Absorption Conference 2006 - Rugby, United Kingdom
Duration: 4 Sep 20066 Sep 2006

Fingerprint

Alkenes
Distillation
Isomers
Olefins
Purification
Complexation
Silver
Ligands
Ethylene
Alkadienes
Hydrometallurgy
Sulfonic Acids
Distillation columns
Phosphoric acid
Hexane
Paraffin
Paraffins
Screening
Solubility
Recovery

Keywords

  • π-Complexation
  • Olefin isomer separation
  • Reactive extractive distillation
  • Ligands

Cite this

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title = "Functionalized Solvents for Olefin Isomer Purification by Reactive Extractive Distillation",
abstract = "Olefin isomer separations are difficult, energy intensive and thus expensive. An overview is presented to investigate the feasibility of metal–ligand complexes as functionalized solvents applied in a novel separation technology, reactive extractive distillation, for the separation and purification of α-olefins like 1-hexene from other C6-olefin isomers (internal, branched, cyclic and diolefins) and paraffins by using π-complexation. Functionalized metal–ligand complexes were synthesized based on commercial available ligands from hydrometallurgy. In screening experiments they were evaluated for ρ-complexation with ethylene. The best solvents were selected for evaluation of preferential complexation of 1-hexene relative to other olefin isomers. D2EHPA and DNNSA yield both stable metal–ligand complexes and triple the solubility of ethylene. Next, three different phosphoric acid ligands: D2EHPA, DBPA and MEHPA and two sulphonic acid ligands: DNNSA and DBSA, were investigated for a variety of C6-olefin isomers. The highest selectivities were obtained for silver-DBPA (20 wt{\%} Ag, S/F = 3): 1.23 for 2-methyl-1-pentene and 1.42 for n-hexane. An equilibrium model is used to conceptually design a reactive extractive distillation column applying the functionalized solvent silver-D2EHPA. Such a column should be operated at a solvent to feed ratio of around 5(P = 0.2 bar, T = 311 K) for 99.5{\%} purity and 99{\%} recovery. Under these conditions, the minimum number of equilibrium trays (Nmin) to separate 1-hexene from 2-methyl-1-pentene is approximately 42, a dramatic decrease compared to Nmin of about 310 in the absence of silver.",
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author = "N.J.M. Kuipers and A.E. Wentink and {de Haan}, A.B. and J. Scholtz and H. Mulder",
year = "2007",
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journal = "Chemical engineering research and design (Transactions of the Institution of Chemical Engineers, part A)",
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Functionalized Solvents for Olefin Isomer Purification by Reactive Extractive Distillation. / Kuipers, N.J.M.; Wentink, A.E.; de Haan, A.B.; Scholtz, J.; Mulder, H.

In: Chemical engineering research and design (Transactions of the Institution of Chemical Engineers, part A), Vol. 85, No. 1, 2007, p. 88-99.

Research output: Contribution to journalArticleAcademic

TY - JOUR

T1 - Functionalized Solvents for Olefin Isomer Purification by Reactive Extractive Distillation

AU - Kuipers, N.J.M.

AU - Wentink, A.E.

AU - de Haan, A.B.

AU - Scholtz, J.

AU - Mulder, H.

PY - 2007

Y1 - 2007

N2 - Olefin isomer separations are difficult, energy intensive and thus expensive. An overview is presented to investigate the feasibility of metal–ligand complexes as functionalized solvents applied in a novel separation technology, reactive extractive distillation, for the separation and purification of α-olefins like 1-hexene from other C6-olefin isomers (internal, branched, cyclic and diolefins) and paraffins by using π-complexation. Functionalized metal–ligand complexes were synthesized based on commercial available ligands from hydrometallurgy. In screening experiments they were evaluated for ρ-complexation with ethylene. The best solvents were selected for evaluation of preferential complexation of 1-hexene relative to other olefin isomers. D2EHPA and DNNSA yield both stable metal–ligand complexes and triple the solubility of ethylene. Next, three different phosphoric acid ligands: D2EHPA, DBPA and MEHPA and two sulphonic acid ligands: DNNSA and DBSA, were investigated for a variety of C6-olefin isomers. The highest selectivities were obtained for silver-DBPA (20 wt% Ag, S/F = 3): 1.23 for 2-methyl-1-pentene and 1.42 for n-hexane. An equilibrium model is used to conceptually design a reactive extractive distillation column applying the functionalized solvent silver-D2EHPA. Such a column should be operated at a solvent to feed ratio of around 5(P = 0.2 bar, T = 311 K) for 99.5% purity and 99% recovery. Under these conditions, the minimum number of equilibrium trays (Nmin) to separate 1-hexene from 2-methyl-1-pentene is approximately 42, a dramatic decrease compared to Nmin of about 310 in the absence of silver.

AB - Olefin isomer separations are difficult, energy intensive and thus expensive. An overview is presented to investigate the feasibility of metal–ligand complexes as functionalized solvents applied in a novel separation technology, reactive extractive distillation, for the separation and purification of α-olefins like 1-hexene from other C6-olefin isomers (internal, branched, cyclic and diolefins) and paraffins by using π-complexation. Functionalized metal–ligand complexes were synthesized based on commercial available ligands from hydrometallurgy. In screening experiments they were evaluated for ρ-complexation with ethylene. The best solvents were selected for evaluation of preferential complexation of 1-hexene relative to other olefin isomers. D2EHPA and DNNSA yield both stable metal–ligand complexes and triple the solubility of ethylene. Next, three different phosphoric acid ligands: D2EHPA, DBPA and MEHPA and two sulphonic acid ligands: DNNSA and DBSA, were investigated for a variety of C6-olefin isomers. The highest selectivities were obtained for silver-DBPA (20 wt% Ag, S/F = 3): 1.23 for 2-methyl-1-pentene and 1.42 for n-hexane. An equilibrium model is used to conceptually design a reactive extractive distillation column applying the functionalized solvent silver-D2EHPA. Such a column should be operated at a solvent to feed ratio of around 5(P = 0.2 bar, T = 311 K) for 99.5% purity and 99% recovery. Under these conditions, the minimum number of equilibrium trays (Nmin) to separate 1-hexene from 2-methyl-1-pentene is approximately 42, a dramatic decrease compared to Nmin of about 310 in the absence of silver.

KW - π-Complexation

KW - Olefin isomer separation

KW - Reactive extractive distillation

KW - Ligands

U2 - 10.1205/cherd06096

DO - 10.1205/cherd06096

M3 - Article

VL - 85

SP - 88

EP - 99

JO - Chemical engineering research and design (Transactions of the Institution of Chemical Engineers, part A)

JF - Chemical engineering research and design (Transactions of the Institution of Chemical Engineers, part A)

SN - 0263-8762

IS - 1

ER -