Method for preparing polybutene
Disclosed is a method for preparing a highly reactive polybutene of high quality having low fluorine content and high vinylidene content at high mileage of catalyst with economy. The method for preparing a polybutene includes: performing a selective hydrogenation reaction of diolefin among C4 hydrocarbon components produced from petroleum refineries or naphtha cracking centers, which involve cracking of crude oils, and simultaneously an isomerization reaction of 1-butene to 2-butene and then isolating an isobutene feedstock through fractional distillation; and polymerizing the isobutene feedstock obtained by the fractional distillation.
1. A method for preparing a polybutene, comprising:
performing a selective hydrogenation reaction of diolefin among C4 hydrocarbon components produced from petroleum refineries or naphtha cracking centers, which involve cracking crude oils, and simultaneously an isomerization reaction of 1-butene to 2-butene and then isolating an isobutene feedstock through fractional distillation;
polymerizing the isobutene feedstock in the presence of a polymerization catalyst to prepare the polybutene; and
recycling whole or part of unreacted isobutene feedstock, after the polymerization ion reaction, to the isomerization step thereby diluting the isobutene feedstock.
2. The method for preparing a polybutene as claimed in claim 1 , wherein the isobutene content in the isobutene feedstock or diluted isobutene feedstock is 25 to 65 wt %.
3. The method for preparing a polybutene as claimed in claim 1 , wherein the isobutene content in the unreacted isobutene feedstock, after the polybutene polymerization reaction, is 2 to 20 wt %.
4. The method for preparing a polybutene as claimed in claim 1 , wherein a product from the polybutene polymerization reaction is a conventional polybutene in which vinylidene positioned at the terminal of the polybutene is 70% or less, and the polymerization catalyst is aluminum trichloride.
5. The method for preparing a polybutene as claimed in claim 1 , wherein a product from the polybutene polymerization reaction is a high reactive polybutene in which vinylidene positioned at the terminal of the polybutene is more than 70% and whose number average molecular weight (Mn) is 300 to 5,000, and the polymerization catalyst includes boron trifluoride (BF 3 ) and a cocatalyst.
6. The method for preparing a polybutene as claimed in claim 5 , wherein the cocatalyst is a primary, secondary or tertiary alcohol having 1 to 4 carbon atoms or a primary, secondary or tertiary ether having 2 to 8 carbon atoms.
7. The method for preparing a polybutene as claimed in claim 1 , further comprising a step of removing an organic substance containing oxygen (O) atoms and a halogen acid from the recycling unreacted isobutene feedstock.
8. The method for preparing a polybutene as claimed in claim 7 , wherein the removal of the organic substance containing oxygen (O) atoms and halogen acid is carried out by making the recycling unreacted isobutene feedstock pass through an adsorbing tower charged with a adsorbent, and wherein the absorbent is one selected from the group consisting of Ca(OH) 2 , CaO, CaCO 3 , CaCl 2 , KOH, K 2 CO 3 , KHCO 3 , KCl, NaOH, Na 2 CO 3 , NaHCO 3 , solid silica, solid alumina, zeolite, anion exchange resin to which amine group is bonded, cation exchange resin to which sulfono-group is bonded and mixtures thereof.
9. The method for preparing a polybutene as claimed in claim 8 , wherein an adsorbing tower for removing the organic substance containing oxygen (O) atoms and an absorbing tower for removing the halogen acid are respectively mounted.
10. The method for preparing a polybutene as claimed in claim 1 , the polymerization temperature is −30 to 20° C., the polymerization pressure is 3 kg/cm 2 or above and the retention time is 5 to 100 minutes.
11. The method for preparing a polybutene as claimed in claim 1 , wherein the hydrogenation reaction of diolefin and the isomerization reaction of 1-butene are performed by supplying a hydrogen gas to the C4 hydrocarbon component in the presence of a metal catalyst.
12. The method for preparing a polybutene as claimed in claim 1 , wherein the fractional distillation step includes isolating the isobutene feedstock with 20 to 150 distillation columns under a fractional distillation temperature of 20 to 80° C. and a fractional distillation pressure of 2 to 10 atm.
13. The method for preparing a polybutene as claimed in claim 1 , further comprising a step of recycling part of the unreacted isobutene feedstock to the polybutene polymerization step.