Ethylene oligomerization process for making hydrocarbon liquids

Patent metadata

Field	Value
Publication number	US-2016289574-A1
Application number	US-201514674918-A
Country	US
Kind code	A1
Filing date	Mar 31, 2015
Priority date	Mar 31, 2015
Publication date	Oct 6, 2016
Grant date	—

Abstract

Provided herein are processes for ethylene oligomerization in the presence of an ionic liquid catalyst and a co-catalyst to produce a hydrocarbon product comprising C 10 -C 55 oligomers.

First claim

What is claimed is:

1 . A process for making a hydrocarbon product, comprising:
a. selecting a feed comprising an olefin, wherein the olefin comprises greater than 10 wt % ethylene and less than 10 wt % isoparaffins; b. charging the feed, an ionic liquid catalyst, and a co-catalyst comprising a halide to a reactor; wherein a molar ratio of the ethylene to the halide in the reactor is from 10 to 50; and c. oligomerizing the olefin in the reactor to produce a hydrocarbon product, wherein greater than 30 wt % of the ethylene is convened to the hydrocarbon product, and wherein greater than 40 wt % of the hydrocarbon product has a boiling point distribution from 250° F. to 700° F.

2 . The process of claim 1 , wherein the feed comprises an offgas from a refinery unit selected from an ethylene cracker, a fluid catalytic cracker, a coker, a naphtha cracker, a FT synthesis unit, an ethylene polymerization unit, and a pyrolysis unit.

3 . The process of claim 1 , wherein the feed comprises 20 wt % to 100 wt % of the ethylene.

4 . The process of claim 1 , wherein the feed comprises 0 to 5 wt % of the isoparaffins.

5 . The process of claim 1 , wherein a molar ratio of the isoparaffins to the ethylene in the reactor is less than 0.04.

6 . The process of claim 1 , wherein the hydrocarbon product has less than 2 mole % olefinic hydrogens by 1 H NMR.

7 . The process of claim 1 , wherein the hydrocarbon product has from 45 wt % to 90 wt % product boiling from 250° F. to 700° F.

8 . The process of claim 1 , wherein the hydrocarbon product has from 1 wt % to 15 wt % product boiling from 215° F. to 250° F.

9 . The process of claim 1 , wherein the hydrocarbon product has an average carbon number from 15 to 35.

10 . The process of claim 1 , wherein the hydrocarbon product has a branching index from 45 to 70%.

11 . The process of claim 1 , further comprising charging an n-paraffin solvent to the reactor.

12 . The process of claim 1 , wherein the co-catalyst is a hydrogen chloride or an organic chloride.

13 . The process of claim 1 , wherein the co-catalyst is an anhydrous hydrogen chloride.

14 . The process of claim 1 , wherein the molar ratio of the ethylene to the halide is from 10 to 40.

15 . The process of claim 1 , wherein the ionic liquid catalyst comprises a metal halide.

16 . The process of claim 1 , wherein the ionic liquid catalyst comprises an ammonium, a phosphonium, or a sulphonium cation.

17 . The process of claim 1 , wherein the ionic liquid catalyst is N-butylpyridinium chloroaluminate.

18 . The process of claim 1 , wherein the reactor contains 10 to 30 vol % of the ionic liquid catalyst.

19 . The process of claim 1 , wherein the oligomerizing step is conducted:
a. at a temperature from 50 OF to 300° F.; b. at a pressure of 100 to 1000 psig; c. with a reaction residence time of 15 to 150 minutes; and d. with a sufficient mixing to provide effective contact between the ionic liquid catalyst and the ethylene.

20 . The process of claim 1 , wherein 50 wt % to 90 wt % of the ethylene is converted to the hydrocarbon product.

21 . The process of claim 1 , further comprising distilling the hydrocarbon product to obtain one or more distillate fractions boiling from 250° F. to 700° F. and having a freeze point and a cloud point less than −40° F.

22 . A hydrocarbon product made by the process of claim 1 .

23 . The hydrocarbon product of claim 22 , wherein the product has less than 2 mole % olefinic hydrogens by 1 H NMR, less than 0.1 mole % aromatic hydrogens by 1 H NMR, an average carbon number from 15 to 40, and a branching index from 45 to 70.

24 . The hydrocarbon product of claim 22 , wherein from 1 wt % to 15 wt % of the hydrocarbon product has a boiling point distribution from 215° F. to 250° F.

25 . A hydrocarbon product having less than 2 mole % olefinic hydrogens by 1 H NMR, less than 0.1 mole % aromatic hydrogens by 1 H NMR, an average carbon number from 15 to 40, a branching index from 45 to 70, and wherein greater than 40 wt % of the hydrocarbon product has a boiling point distribution from 250° F. to 700° F.

Assignees

• Timken Hye-Kyung Cho
• Chang Bong-Kyu
• Campbell Curtis Bay
• Thomas Andrew Michael
• Fernandez Mark Anthony
• Sessions Madeleine
• Chevron Oronite Co
• Chevron Usa Inc

Inventors

• Timken Hye-Kyung Cho
• Chang Bong-Kyu
• Campbell Curtis Bay
• Thomas Andrew Michael
• Fernandez Mark Anthony
• Sessions Madeleine

Classifications

• C10L2270/026

  for diesel engines, e.g. automobiles, stationary, marine · CPC title

• C10L2270/04

  for turbines, planes, power generation · CPC title

• C10L2200/0446

  Diesel · CPC title

• C10L2290/543

  Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel · CPC title

• C10L1/08

  for compression ignition · CPC title